Metabolic stratification driven by surface and subsurface interactions in a terrestrial mud volcano

PubMed Central

Cheng, Ting-Wen; Chang, Yung-Hsin; Tang, Sen-Lin; Tseng, Ching-Hung; Chiang, Pei-Wen; Chang, Kai-Ti; Sun, Chih-Hsien; Chen, Yue-Gau; Kuo, Hung-Chi; Wang, Chun-Ho; Chu, Pao-Hsuan; Song, Sheng-Rong; Wang, Pei-Ling; Lin, Li-Hung

2012-01-01

Terrestrial mud volcanism represents the prominent surface geological feature, where fluids and hydrocarbons are discharged along deeply rooted structures in tectonically active regimes. Terrestrial mud volcanoes (MVs) directly emit the major gas phase, methane, into the atmosphere, making them important sources of greenhouse gases over geological time. Quantification of methane emission would require detailed insights into the capacity and efficiency of microbial metabolisms either consuming or producing methane in the subsurface, and establishment of the linkage between these methane-related metabolisms and other microbial or abiotic processes. Here we conducted geochemical, microbiological and genetic analyses of sediments, gases, and pore and surface fluids to characterize fluid processes, community assemblages, functions and activities in a methane-emitting MV of southwestern Taiwan. Multiple lines of evidence suggest that aerobic/anaerobic methane oxidation, sulfate reduction and methanogenesis are active and compartmentalized into discrete, stratified niches, resembling those in marine settings. Surface evaporation and oxidation of sulfide minerals are required to account for the enhanced levels of sulfate that fuels subsurface sulfate reduction and anaerobic methanotrophy. Methane flux generated by in situ methanogenesis appears to alter the isotopic compositions and abundances of thermogenic methane migrating from deep sources, and to exceed the capacity of microbial consumption. This metabolic stratification is sustained by chemical disequilibria induced by the mixing between upward, anoxic, methane-rich fluids and downward, oxic, sulfate-rich fluids. PMID:22739492

Mechanistic modeling of microbial interactions at pore to profile scale resolve methane emission dynamics from permafrost soil

NASA Astrophysics Data System (ADS)

Ebrahimi, Ali; Or, Dani

2017-05-01

The sensitivity of polar regions to raising global temperatures is reflected in rapidly changing hydrological processes associated with pronounced seasonal thawing of permafrost soil and increased biological activity. Of particular concern is the potential release of large amounts of soil carbon and stimulation of other soil-borne greenhouse gas emissions such as methane. Soil methanotrophic and methanogenic microbial communities rapidly adjust their activity and spatial organization in response to permafrost thawing and other environmental factors. Soil structural elements such as aggregates and layering affect oxygen and nutrient diffusion processes thereby contributing to methanogenic activity within temporal anoxic niches (hot spots). We developed a mechanistic individual-based model to quantify microbial activity dynamics in soil pore networks considering transport processes and enzymatic activity associated with methane production in soil. The model was upscaled from single aggregates to the soil profile where freezing/thawing provides macroscopic boundary conditions for microbial activity at different soil depths. The model distinguishes microbial activity in aerate bulk soil from aggregates (or submerged profile) for resolving methane production and oxidation rates. Methane transport pathways by diffusion and ebullition of bubbles vary with hydration dynamics. The model links seasonal thermal and hydrologic dynamics with evolution of microbial community composition and function affecting net methane emissions in good agreement with experimental data. The mechanistic model enables systematic evaluation of key controlling factors in thawing permafrost and microbial response (e.g., nutrient availability and enzyme activity) on long-term methane emissions and carbon decomposition rates in the rapidly changing polar regions.

First determination of volume changes and enthalpies of the high-pressure decomposition reaction of the structure H methane hydrate to the cubic structure I methane hydrate and fluid methane.

PubMed

Ogienko, Andrey G; Tkacz, Marek; Manakov, Andrey Yu; Lipkowski, Janusz

2007-11-08

Pressure-temperature (P-T) conditions of the decomposition reaction of the structure H high-pressure methane hydrate to the cubic structure I methane hydrate and fluid methane were studied with a piston-cylinder apparatus at room temperature. For the first time, volume changes accompanying this reaction were determined. With the use of the Clausius-Clapeyron equation the enthalpies of the decomposition reaction of the structure H high-pressure methane hydrate to the cubic structure I methane hydrate and fluid methane have been calculated.

Template-Assisted Wet-Combustion Synthesis of Fibrous Nickel-Based Catalyst for Carbon Dioxide Methanation and Methane Steam Reforming.

PubMed

Aghayan, M; Potemkin, D I; Rubio-Marcos, F; Uskov, S I; Snytnikov, P V; Hussainova, I

2017-12-20

Efficient capture and recycling of CO 2 enable not only prevention of global warming but also the supply of useful low-carbon fuels. The catalytic conversion of CO 2 into an organic compound is a promising recycling approach which opens new concepts and opportunities for catalytic and industrial development. Here we report about template-assisted wet-combustion synthesis of a one-dimensional nickel-based catalyst for carbon dioxide methanation and methane steam reforming. Because of a high temperature achieved in a short time during reaction and a large amount of evolved gases, the wet-combustion synthesis yields homogeneously precipitated nanoparticles of NiO with average particle size of 4 nm on alumina nanofibers covered with a NiAl 2 O 4 nanolayer. The as-synthesized core-shell structured fibers exhibit outstanding activity in steam reforming of methane and sufficient activity in carbon dioxide methanation with 100% selectivity toward methane formation. The as-synthesized catalyst shows stable operation under the reaction conditions for at least 50 h.

Water-Gas Shift and Methane Reactivity on Reducible Perovskite-Type Oxides

PubMed Central

2015-01-01

Comparative (electro)catalytic, structural, and spectroscopic studies in hydrogen electro-oxidation, the (inverse) water-gas shift reaction, and methane conversion on two representative mixed ionic–electronic conducting perovskite-type materials La0.6Sr0.4FeO3−δ (LSF) and SrTi0.7Fe0.3O3−δ (STF) were performed with the aim of eventually correlating (electro)catalytic activity and associated structural changes and to highlight intrinsic reactivity characteristics as a function of the reduction state. Starting from a strongly prereduced (vacancy-rich) initial state, only (inverse) water-gas shift activity has been observed on both materials beyond ca. 450 °C but no catalytic methane reforming or methane decomposition reactivity up to 600 °C. In contrast, when starting from the fully oxidized state, total methane oxidation to CO2 was observed on both materials. The catalytic performance of both perovskite-type oxides is thus strongly dependent on the degree/depth of reduction, on the associated reactivity of the remaining lattice oxygen, and on the reduction-induced oxygen vacancies. The latter are clearly more reactive toward water on LSF, and this higher reactivity is linked to the superior electrocatalytic performance of LSF in hydrogen oxidation. Combined electron microscopy, X-ray diffraction, and Raman measurements in turn also revealed altered surface and bulk structures and reactivities. PMID:26045733

Enhanced activity and stability of La-doped CeO2 monolithic catalysts for lean-oxygen methane combustion.

PubMed

Zhu, Wenjun; Jin, Jianhui; Chen, Xiao; Li, Chuang; Wang, Tonghua; Tsang, Chi-Wing; Liang, Changhai

2018-02-01

Effective utilization of coal bed methane is very significant for energy utilization and environment protection. Catalytic combustion of methane is a promising way to eliminate trace amounts of oxygen in the coal bed methane and the key to this technology is the development of high-efficiency catalysts. Herein, we report a series of Ce 1-x La x O 2-δ (x = 0-0.8) monolithic catalysts for the catalytic combustion of methane, which are prepared by citric acid method. The structural characterization shows that the substitution of La enhance the oxygen vacancy concentration and reducibility of the supports and promote the migration of the surface oxygen, as a result improve the catalytic activity of CeO 2 . M-Ce 0.8 La 0.2 O 2-δ (monolithic catalyst, Ce 0.8 La 0.2 O 2-δ coated on cordierite honeycomb) exhibits outstanding activity for methane combustion, and the temperature for 10 and 90% methane conversion are 495 and 580 °C, respectively. Additionally, Ce 0.8 La 0.2 O 2-δ monolithic catalyst presents excellent stability at high temperature. These Ce 1-x La x O 2-δ monolithic materials with a small amount of La incorporation therefore show promises as highly efficient solid solution catalysts for lean-oxygen methane combustion. Graphical abstract ᅟ.

Mechanistic modeling of thermo-hydrological processes and microbial interactions at pore to profile scales resolve methane emission dynamics from permafrost soil

NASA Astrophysics Data System (ADS)

Ebrahimi, Ali; Or, Dani

2017-04-01

The sensitivity of the Earth's polar regions to raising global temperatures is reflected in rapidly changing hydrological processes with pronounced seasonal thawing of permafrost soil and increased biological activity. Of particular concern is the potential release of large amounts of soil carbon and the stimulation of other soil-borne GHG emissions such as methane. Soil methanotrophic and methanogenic microbial communities rapidly adjust their activity and spatial organization in response to permafrost thawing and a host of other environmental factors. Soil structural elements such as aggregates and layering and hydration status affect oxygen and nutrient diffusion processes thereby contributing to methanogenic activity within temporal anoxic niches (hotspots or hot-layers). We developed a mechanistic individual based model to quantify microbial activity dynamics within soil pore networks considering, hydration, temperature, transport processes and enzymatic activity associated with methane production in soil. The model was the upscaled from single aggregates (or hotspots) to quantifying emissions from soil profiles in which freezing/thawing processes provide macroscopic boundary conditions for microbial activity at different soil depths. The model distinguishes microbial activity in aerate bulk soil from aggregates (or submerged parts of the profile) for resolving methane production and oxidation rates. Methane transport pathways through soil by diffusion and ebullition of bubbles vary with hydration dynamics and affect emission patterns. The model links seasonal thermal and hydrologic dynamics with evolution of microbial community composition and function affecting net methane emissions in good agreement with experimental data. The mechanistic model enables systematic evaluation of key controlling factors in thawing permafrost and microbial response (e.g., nutrient availability, enzyme activity, PH) on long term methane emissions and carbon decomposition rates in the rapidly changing polar regions.

Structural characterization of a non-heme iron active site in zeolites that hydroxylates methane

DOE PAGES

Snyder, Benjamin E. R.; Bottger, Lars H.; Bols, Max L.; ...

2018-04-02

Iron-containing zeolites exhibit unprecedented reactivity in the low-temperature hydroxylation of methane to form methanol. Reactivity occurs at a mononuclear ferrous active site, α-Fe(II), that is activated by N 2O to form the reactive intermediate α-O. This has been defined as an Fe(IV)=O species. Using nuclear resonance vibrational spectroscopy coupled to X-ray absorption spectroscopy, we probe the bonding interaction between the iron center, its zeolite lattice-derived ligands, and the reactive oxygen. α-O is found to contain an unusually strong Fe(IV)=O bond resulting from a constrained coordination geometry enforced by the zeolite lattice. As a result, density functional theory calculations clarify howmore » the experimentally determined geometric structure of the active site leads to an electronic structure that is highly activated to perform H-atom abstraction.« less

Structural characterization of a non-heme iron active site in zeolites that hydroxylates methane

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

Snyder, Benjamin E. R.; Bottger, Lars H.; Bols, Max L.

Iron-containing zeolites exhibit unprecedented reactivity in the low-temperature hydroxylation of methane to form methanol. Reactivity occurs at a mononuclear ferrous active site, α-Fe(II), that is activated by N 2O to form the reactive intermediate α-O. This has been defined as an Fe(IV)=O species. Using nuclear resonance vibrational spectroscopy coupled to X-ray absorption spectroscopy, we probe the bonding interaction between the iron center, its zeolite lattice-derived ligands, and the reactive oxygen. α-O is found to contain an unusually strong Fe(IV)=O bond resulting from a constrained coordination geometry enforced by the zeolite lattice. As a result, density functional theory calculations clarify howmore » the experimentally determined geometric structure of the active site leads to an electronic structure that is highly activated to perform H-atom abstraction.« less

Theoretical Investigation of Methane Hydroxylation over Isoelectronic [FeO]2+- and [MnO]+-Exchanged Zeolites Activated by N2O.

PubMed

Mahyuddin, M Haris; Shiota, Yoshihito; Staykov, Aleksandar; Yoshizawa, Kazunari

2017-09-05

While the most likely structure of the active site in iron-containing zeolites has been recently identified as [FeO] 2+ (Snyder et al. Nature 2016, 536, 317-321), the mechanism for the direct conversion of methane to methanol over this active species is still debatable between the direct-radical-rebound or nonradical (concerted) mechanism. Using density functional theory on periodic systems, we calculated the two reaction mechanisms over two d 4 isoelectronic systems, [FeO] 2+ and [MnO] + zeolites. We found that [FeO] 2+ zeolites favor the direct-radical-rebound mechanism with low CH 4 activation energies, while [MnO] + zeolites prefer the nonradical mechanism with higher CH 4 activation energies. These contrasts, despite their isoelectronic structures, are mainly due to the differences in the metal coordination number and O α (oxo) spin density. Moreover, molecular orbital analyses suggest that the zeolite steric hindrance further degrades the reactivity of [MnO] + zeolites toward methane. Two types of zeolite frameworks, i.e., medium-pore ZSM-5 (MFI framework) and small-pore SSZ-39 (AEI framework) zeolites, were evaluated, but no significant differences in the reactivity were found. The rate-determining reaction step is found to be methanol desorption instead of methane activation. Careful examination of the most stable sites hosting the active species and calculation for N 2 O decomposition over [Fe] 2+ -MFI and -AEI zeolites were also performed.

Composition and structural features of condensed tannins from Texas legumes exhibiting methane abatement activity during in vitro rumen digestion

USDA-ARS?s Scientific Manuscript database

Previous studies showed that a series of purified condensed tannins (CTs) from warm-season perennial legumes exhibited high variability in their modulation of methane production during in vitro rumen digestion. The molecular weight difference of these CTs did not provide correlation with either the ...

Effects of Zinc on Particulate Methane Monooxygenase Activity and Structure*

PubMed Central

Sirajuddin, Sarah; Barupala, Dulmini; Helling, Stefan; Marcus, Katrin; Stemmler, Timothy L.; Rosenzweig, Amy C.

2014-01-01

Particulate methane monooxygenase (pMMO) is a membrane-bound metalloenzyme that oxidizes methane to methanol in methanotrophic bacteria. Zinc is a known inhibitor of pMMO, but the details of zinc binding and the mechanism of inhibition are not understood. Metal binding and activity assays on membrane-bound pMMO from Methylococcus capsulatus (Bath) reveal that zinc inhibits pMMO at two sites that are distinct from the copper active site. The 2.6 Å resolution crystal structure of Methylocystis species strain Rockwell pMMO reveals two previously undetected bound lipids, and metal soaking experiments identify likely locations for the two zinc inhibition sites. The first is the crystallographic zinc site in the pmoC subunit, and zinc binding here leads to the ordering of 10 previously unobserved residues. A second zinc site is present on the cytoplasmic side of the pmoC subunit. Parallels between these results and zinc inhibition studies of several respiratory complexes suggest that zinc might inhibit proton transfer in pMMO. PMID:24942740

Methane Oxidation to Methanol Catalyzed by Cu-Oxo Clusters Stabilized in NU-1000 Metal-Organic Framework.

PubMed

Ikuno, Takaaki; Zheng, Jian; Vjunov, Aleksei; Sanchez-Sanchez, Maricruz; Ortuño, Manuel A; Pahls, Dale R; Fulton, John L; Camaioni, Donald M; Li, Zhanyong; Ray, Debmalya; Mehdi, B Layla; Browning, Nigel D; Farha, Omar K; Hupp, Joseph T; Cramer, Christopher J; Gagliardi, Laura; Lercher, Johannes A

2017-08-02

Copper oxide clusters synthesized via atomic layer deposition on the nodes of the metal-organic framework (MOF) NU-1000 are active for oxidation of methane to methanol under mild reaction conditions. Analysis of chemical reactivity, in situ X-ray absorption spectroscopy, and density functional theory calculations are used to determine structure/activity relations in the Cu-NU-1000 catalytic system. The Cu-loaded MOF contained Cu-oxo clusters of a few Cu atoms. The Cu was present under ambient conditions as a mixture of ∼15% Cu + and ∼85% Cu 2+ . The oxidation of methane on Cu-NU-1000 was accompanied by the reduction of 9% of the Cu in the catalyst from Cu 2+ to Cu + . The products, methanol, dimethyl ether, and CO 2 , were desorbed with the passage of 10% water/He at 135 °C, giving a carbon selectivity for methane to methanol of 45-60%. Cu oxo clusters stabilized in NU-1000 provide an active, first generation MOF-based, selective methane oxidation catalyst.

Methane related changes in prokaryotic activity along geochemical profiles in sediments of Lake Kinneret (Israel)

NASA Astrophysics Data System (ADS)

Bar Or, I.; Ben-Dov, E.; Kushmaro, A.; Eckert, W.; Sivan, O.

2014-06-01

Microbial methane oxidation process (methanotrophy) is the primary control on the emission of the greenhouse gas methane (CH4) to the atmosphere. In terrestrial environments, aerobic methanotrophic bacteria are mainly responsible for oxidizing the methane. In marine sediments the coupling of the anaerobic oxidation of methane (AOM) with sulfate reduction, often by a consortium of anaerobic methanotrophic archaea (ANME) and sulfate reducing bacteria, was found to consume almost all the upward diffusing methane. Recently, we showed geochemical evidence for AOM driven by iron reduction in Lake Kinneret (LK) (Israel) deep sediments and suggested that this process can be an important global methane sink. The goal of the present study was to link the geochemical gradients found in the porewater (chemical and isotope profiles) with possible changes in microbial community structure. Specifically, we examined the possible shift in the microbial community in the deep iron-driven AOM zone and its similarity to known sulfate driven AOM populations. Screening of archaeal 16S rRNA gene sequences revealed Thaumarchaeota and Euryarchaeota as the dominant phyla in the sediment. Thaumarchaeota, which belongs to the family of copper containing membrane-bound monooxgenases, increased with depth while Euryarchaeota decreased. This may indicate the involvement of Thaumarchaeota, which were discovered to be ammonia oxidizers but whose activity could also be linked to methane, in AOM in the deep sediment. ANMEs sequences were not found in the clone libraries, suggesting that iron-driven AOM is not through sulfate. Bacterial 16S rRNA sequences displayed shifts in community diversity with depth. Proteobacteria and Chloroflexi increased with depth, which could be connected with their different dissimilatory anaerobic processes. The observed changes in microbial community structure suggest possible direct and indirect mechanisms for iron-driven AOM in deep sediments.

Biomimetic methane oxidation

NASA Astrophysics Data System (ADS)

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

1992-06-01

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

Understanding trends in C-H bond activation in heterogeneous catalysis.

PubMed

Latimer, Allegra A; Kulkarni, Ambarish R; Aljama, Hassan; Montoya, Joseph H; Yoo, Jong Suk; Tsai, Charlie; Abild-Pedersen, Frank; Studt, Felix; Nørskov, Jens K

2017-02-01

While the search for catalysts capable of directly converting methane to higher value commodity chemicals and liquid fuels has been active for over a century, a viable industrial process for selective methane activation has yet to be developed. Electronic structure calculations are playing an increasingly relevant role in this search, but large-scale materials screening efforts are hindered by computationally expensive transition state barrier calculations. The purpose of the present letter is twofold. First, we show that, for the wide range of catalysts that proceed via a radical intermediate, a unifying framework for predicting C-H activation barriers using a single universal descriptor can be established. Second, we combine this scaling approach with a thermodynamic analysis of active site formation to provide a map of methane activation rates. Our model successfully rationalizes the available empirical data and lays the foundation for future catalyst design strategies that transcend different catalyst classes.

Understanding trends in C–H bond activation in heterogeneous catalysis

DOE PAGES

Latimer, Allegra A.; Kulkarni, Ambarish R.; Aljama, Hassan; ...

2016-10-10

While the search for catalysts capable of directly converting methane to higher value commodity chemicals and liquid fuels has been active for over a century, a viable industrial process for selective methane activation has yet to be developed1. Electronic structure calculations are playing an increasingly relevant role in this search, but large-scale materials screening efforts are hindered by computationally expensive transition state barrier calculations. The purpose of the present letter is twofold. First, we show that, for the wide range of catalysts that proceed via a radical intermediate, a unifying framework for predicting C–H activation barriers using a single universalmore » descriptor can be established. Second, we combine this scaling approach with a thermodynamic analysis of active site formation to provide a map of methane activation rates. Lastly, our model successfully rationalizes the available empirical data and lays the foundation for future catalyst design strategies that transcend different catalyst classes.« less

Understanding trends in C-H bond activation in heterogeneous catalysis

NASA Astrophysics Data System (ADS)

Latimer, Allegra A.; Kulkarni, Ambarish R.; Aljama, Hassan; Montoya, Joseph H.; Yoo, Jong Suk; Tsai, Charlie; Abild-Pedersen, Frank; Studt, Felix; Nørskov, Jens K.

2017-02-01

While the search for catalysts capable of directly converting methane to higher value commodity chemicals and liquid fuels has been active for over a century, a viable industrial process for selective methane activation has yet to be developed. Electronic structure calculations are playing an increasingly relevant role in this search, but large-scale materials screening efforts are hindered by computationally expensive transition state barrier calculations. The purpose of the present letter is twofold. First, we show that, for the wide range of catalysts that proceed via a radical intermediate, a unifying framework for predicting C-H activation barriers using a single universal descriptor can be established. Second, we combine this scaling approach with a thermodynamic analysis of active site formation to provide a map of methane activation rates. Our model successfully rationalizes the available empirical data and lays the foundation for future catalyst design strategies that transcend different catalyst classes.

Ecosystem Modelling for Impact Assessment of Possible Methane Leakage during Methane Hydrate Utilization

NASA Astrophysics Data System (ADS)

Yamazaki, T.; Nakano, Y.; Monoe, D.; Oomi, T.; Doi, T.; Nakata, K.; Fukushima, T.

2005-05-01

Natural methane hydrate has been scientifically studied as a carbon reservoir globally. However, in Japan, the potential for energy resource has been industrially highlighted. There is less domestic oil and natural gas resources in Japan, but many potential deposition areas for methane hydrate in ocean around Japan are the reasons. Less CO2 discharge from methane compared with coal, oil and conventional natural gas when the same calorie value we get is considered as the advantage for energy resource. However, because methane hydrate distributes in shallower sediment layer in ocean floor, accidental leakage of methane may occur while we utilize methane hydrate. Methane itself has 21-times impact on the greenhouse effect, if it reaches the atmosphere. Therefore, it is necessary to estimate the behavior in the environment after the leakage, if we want to use methane hydrate as energy resource. The mass balance after leakage of methane on seafloor and in water column is numerically studied through the analyses of methane emissions from natural cold seepages and hydrothermal activities in this research. The outline structure of mass balance ecosystem model creating is introduced and some preliminary examination results from the test calculation are discussed.

Diversity and potential activity of methanotrophs in high methane-emitting permafrost thaw ponds

PubMed Central

Vincent, Warwick F.; Comte, Jérôme; Matveev, Alex; Lovejoy, Connie

2017-01-01

Lakes and ponds derived from thawing permafrost are strong emitters of carbon dioxide and methane to the atmosphere, but little is known about the methane oxidation processes in these waters. Here we investigated the distribution and potential activity of aerobic methanotrophic bacteria in thaw ponds in two types of eroding permafrost landscapes in subarctic Québec: peatlands and mineral soils. We hypothesized that methanotrophic community composition and potential activity differ regionally as a function of the landscape type and permafrost degradation stage, and locally as a function of depth-dependent oxygen conditions. Our analysis of pmoA transcripts by Illumina amplicon sequencing and quantitative PCR showed that the communities were composed of diverse and potentially active lineages. Type I methanotrophs, particularly Methylobacter, dominated all communities, however there was a clear taxonomic separation between the two landscape types, consistent with environmental control of community structure. In contrast, methanotrophic potential activity, measured by pmoA transcript concentrations, did not vary with landscape type, but correlated with conductivity, phosphorus and total suspended solids. Methanotrophic potential activity was also detected in low-oxygen bottom waters, where it was inversely correlated with methane concentrations, suggesting methane depletion by methanotrophs. Methanotrophs were present and potentially active throughout the water column regardless of oxygen concentration, and may therefore be resilient to future mixing and oxygenation regimes in the warming subarctic. PMID:29182670

Diversity and potential activity of methanotrophs in high methane-emitting permafrost thaw ponds.

PubMed

Crevecoeur, Sophie; Vincent, Warwick F; Comte, Jérôme; Matveev, Alex; Lovejoy, Connie

2017-01-01

Lakes and ponds derived from thawing permafrost are strong emitters of carbon dioxide and methane to the atmosphere, but little is known about the methane oxidation processes in these waters. Here we investigated the distribution and potential activity of aerobic methanotrophic bacteria in thaw ponds in two types of eroding permafrost landscapes in subarctic Québec: peatlands and mineral soils. We hypothesized that methanotrophic community composition and potential activity differ regionally as a function of the landscape type and permafrost degradation stage, and locally as a function of depth-dependent oxygen conditions. Our analysis of pmoA transcripts by Illumina amplicon sequencing and quantitative PCR showed that the communities were composed of diverse and potentially active lineages. Type I methanotrophs, particularly Methylobacter, dominated all communities, however there was a clear taxonomic separation between the two landscape types, consistent with environmental control of community structure. In contrast, methanotrophic potential activity, measured by pmoA transcript concentrations, did not vary with landscape type, but correlated with conductivity, phosphorus and total suspended solids. Methanotrophic potential activity was also detected in low-oxygen bottom waters, where it was inversely correlated with methane concentrations, suggesting methane depletion by methanotrophs. Methanotrophs were present and potentially active throughout the water column regardless of oxygen concentration, and may therefore be resilient to future mixing and oxygenation regimes in the warming subarctic.

Differences in the Nature of Active Sites for Methane Dry Reforming and Methane Steam Reforming over Nickel Aluminate Catalysts

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

Rogers, Jessica L.; Mangarella, Michael C.; D’Amico, Andrew D.

In this paper, the Pechini synthesis was used to prepare nickel aluminate catalysts with the compositions NiAl 4O 7, NiAl 2O 4, and Ni 2Al 2O 5. The samples have been characterized by N 2 physisorption, temperature-programmed reduction (TPR), temperature-programmed oxidation (TPO), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and X-ray absorption spectroscopy (XAS). Characterization results indicate unique structural properties and excellent regeneration potential of nickel aluminates. Prepared samples were tested when unreduced and reduced prior to reaction for methane dry reforming and methane steam reforming reactivity. NiAl 2O 4 in the reduced and unreduced statemore » as well as NiAl 4O 7 in the reduced state are active and stable for methane dry reforming due to the presence of 4-fold coordinated oxidized nickel. The limited amount of metallic nickel in these samples minimizes carbon deposition. Finally, on the other hand, the presence of metallic nickel is required for methane steam reforming. Ni 2Al 2O 5 in the reduced and unreduced states and NiAl 2O 4 in the reduced state are found to be active for methane steam reforming due to the presence of sufficiently small nickel nanoparticles that catalyze the reaction without accumulating carbonaceous deposits.« less

Differences in the Nature of Active Sites for Methane Dry Reforming and Methane Steam Reforming over Nickel Aluminate Catalysts

DOE PAGES

Rogers, Jessica L.; Mangarella, Michael C.; D’Amico, Andrew D.; ...

2016-07-20

In this paper, the Pechini synthesis was used to prepare nickel aluminate catalysts with the compositions NiAl 4O 7, NiAl 2O 4, and Ni 2Al 2O 5. The samples have been characterized by N 2 physisorption, temperature-programmed reduction (TPR), temperature-programmed oxidation (TPO), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and X-ray absorption spectroscopy (XAS). Characterization results indicate unique structural properties and excellent regeneration potential of nickel aluminates. Prepared samples were tested when unreduced and reduced prior to reaction for methane dry reforming and methane steam reforming reactivity. NiAl 2O 4 in the reduced and unreduced statemore » as well as NiAl 4O 7 in the reduced state are active and stable for methane dry reforming due to the presence of 4-fold coordinated oxidized nickel. The limited amount of metallic nickel in these samples minimizes carbon deposition. Finally, on the other hand, the presence of metallic nickel is required for methane steam reforming. Ni 2Al 2O 5 in the reduced and unreduced states and NiAl 2O 4 in the reduced state are found to be active for methane steam reforming due to the presence of sufficiently small nickel nanoparticles that catalyze the reaction without accumulating carbonaceous deposits.« less

Systematic Structure–Property Relationship Studies in Palladium-Catalyzed Methane Complete Combustion

DOE PAGES

Willis, Joshua J.; Gallo, Alessandro; Sokaras, Dimosthenis; ...

2017-10-09

To limit further rising levels in methane emissions from stationary and mobile sources and to enable promising technologies based on methane, the development of efficient combustion catalysts that completely oxidize CH 4 to CO 2 and H 2O at low temperatures in the presence of high steam concentrations is required. Palladium is widely considered as one of the most promising materials for this reaction, and a better understanding of the factors affecting its activity and stability is crucial to design even more improved catalysts that efficiently utilize this precious metal. Here we report a study of the effect of threemore » important variables (particle size, support, and reaction conditions including water) on the activity of supported Pd catalysts. We use uniform palladium nanocrystals as catalyst precursors to prepare a library of well-defined catalysts to systematically describe structure–property relationships with help from theory and in situ X-ray absorption spectroscopy. With this approach, we confirm that PdO is the most active phase and that small differences in reaction rates as a function of size are likely due to variations in the surface crystal structure. We further demonstrate that the support exerts a limited influence on the PdO activity, with inert (SiO 2), acidic (Al 2O 3), and redox-active (Ce 0.8Zr 0.2O 2) supports providing similar rates, while basic (MgO) supports show remarkably lower activity. Finally, we show that the introduction of steam leads to a considerable decrease in rates that is due to coverage effects, rather than structural and/or phase changes. Altogether, the data suggest that to further increase the activity and stability of Pd-based catalysts for methane combustion, increasing the surface area of supported PdO phases while avoiding strong adsorption of water on the catalytic surfaces is required. Furthermore, this study clarifies contrasting reports in the literature about the active phase and stability of Pd-based materials for methane combustion.« less

Systematic Structure–Property Relationship Studies in Palladium-Catalyzed Methane Complete Combustion

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

Willis, Joshua J.; Gallo, Alessandro; Sokaras, Dimosthenis

To limit further rising levels in methane emissions from stationary and mobile sources and to enable promising technologies based on methane, the development of efficient combustion catalysts that completely oxidize CH 4 to CO 2 and H 2O at low temperatures in the presence of high steam concentrations is required. Palladium is widely considered as one of the most promising materials for this reaction, and a better understanding of the factors affecting its activity and stability is crucial to design even more improved catalysts that efficiently utilize this precious metal. Here we report a study of the effect of threemore » important variables (particle size, support, and reaction conditions including water) on the activity of supported Pd catalysts. We use uniform palladium nanocrystals as catalyst precursors to prepare a library of well-defined catalysts to systematically describe structure–property relationships with help from theory and in situ X-ray absorption spectroscopy. With this approach, we confirm that PdO is the most active phase and that small differences in reaction rates as a function of size are likely due to variations in the surface crystal structure. We further demonstrate that the support exerts a limited influence on the PdO activity, with inert (SiO 2), acidic (Al 2O 3), and redox-active (Ce 0.8Zr 0.2O 2) supports providing similar rates, while basic (MgO) supports show remarkably lower activity. Finally, we show that the introduction of steam leads to a considerable decrease in rates that is due to coverage effects, rather than structural and/or phase changes. Altogether, the data suggest that to further increase the activity and stability of Pd-based catalysts for methane combustion, increasing the surface area of supported PdO phases while avoiding strong adsorption of water on the catalytic surfaces is required. Furthermore, this study clarifies contrasting reports in the literature about the active phase and stability of Pd-based materials for methane combustion.« less

Methane release from sediment seeps to the atmosphere is counteracted by highly active Methylococcaceae in the water column of deep oligotrophic Lake Constance.

PubMed

Bornemann, Maren; Bussmann, Ingeborg; Tichy, Lucas; Deutzmann, Jörg; Schink, Bernhard; Pester, Michael

2016-08-01

Methane emissions from freshwater environments contribute substantially to global warming but are under strong control of aerobic methane-oxidizing bacteria. Recently discovered methane seeps (pockmarks) in freshwater lake sediments have the potential to bypass this control by their strong outgassing activity. Whether this is counteracted by pelagic methanotrophs is not well understood yet. We used a (3)H-CH4-radiotracer technique and pmoA-based molecular approaches to assess the activity, abundance and community structure of pelagic methanotrophs above active pockmarks in deep oligotrophic Lake Constance. Above profundal pockmarks, methane oxidation rates (up to 458 nmol CH4 l(-1) d(-1)) exceeded those of the surrounding water column by two orders of magnitude and coincided with maximum methanotroph abundances of 0.6% of the microbial community. Phylogenetic analysis indicated a dominance of members of the Methylococcaceae in the water column of both, pockmark and reference sites, with most of the retrieved sequences being associated with a water-column specific clade. Communities at pockmark and reference locations also differed in parts, which was likely caused by entrainment of sediment-hosted methanotrophs at pockmark sites. Our results show that the release of seep-derived methane to the atmosphere is counteracted by a distinct methanotrophic community with a pronounced activity throughout bottom waters. © FEMS 2016. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Methane Oxidation on Pd-Ceria. A DFT Study of the Combustion Mechanism over Pd, PdO and Pd-ceria Sites

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

Mayernick, Adam D.; Janik, Michael J.

2010-12-24

Palladium/ceria exhibits unique catalytic activity for hydrocarbon oxidation; however, the chemical and structural properties of active sites on the palladium–ceria surface are difficult to characterize. Strong interactions between palladium and the ceria support stabilize oxidized Pd δ+ species, which may contribute to the significant activity of Pd/ceria for methane oxidation. We present a density functional theory (DFT + U) investigation into methane oxidation over Pd/ceria and quantify the activity of the Pd xCe 1-xO 2(1 1 1) mixed oxide surface in comparison with the PdO(1 0 0) and Pd(1 1 1) surfaces. The methane activation barrier is lowest over themore » Pd xCe 1-xO 2(1 1 1) surface, even lower than over the Pd(1 1 1) surface or low coordinated stepped or kinked Pd sites. Subsequent reaction steps in complete oxidation, including product desorption and vacancy refilling, are considered to substantiate that methane activation remains the rate-limiting step despite the low barrier over Pd xCe 1-xO 2(1 1 1). The low barrier over the Pd xCe 1-xO 2(1 1 1) surface demonstrates that mixed ceria-noble metal oxides offer the potential for improved hydrocarbon oxidation performance with respect to dispersed noble metal particles on ceria.« less

Methane oxidation on Pd–Ceria: A DFT study of the mechanism over PdxCe1-xO2, Pd, and PdO

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

Mayernick, Adam D.; Janik, Michael J.

2011-02-14

Palladium/ceria exhibits unique catalytic activity for hydrocarbon oxidation; however, the chemical and structural properties of active sites on the palladium–ceria surface are difficult to characterize. Strong interactions between palladium and the ceria support stabilize oxidized Pdδ+ species, which may contribute to the significant activity of Pd/ceria for methane oxidation. We present a density functional theory (DFT + U) investigation into methane oxidation over Pd/ceria and quantify the activity of the Pd xCe 1-xO 2(1 1 1) mixed oxide surface in comparison with the PdO(1 0 0) and Pd(1 1 1) surfaces. The methane activation barrier is lowest over the Pdmore » xCe 1-xO 2(1 1 1) surface, even lower than over the Pd(1 1 1) surface or low coordinated stepped or kinked Pd sites. Subsequent reaction steps in complete oxidation, including product desorption and vacancy refilling, are considered to substantiate that methane activation remains the rate-limiting step despite the low barrier over Pd xCe 1-xO 2(1 1 1). The low barrier over the Pd xCe 1-xO 2(1 1 1) surface demonstrates that mixed ceria-noble metal oxides offer the potential for improved hydrocarbon oxidation performance with respect to dispersed noble metal particles on ceria.« less

Methane Oxidation to Methanol Catalyzed by Cu-Oxo Clusters Stabilized in NU-1000 Metal–Organic Framework

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

Ikuno, Takaaki; Zheng, Jian; Vjunov, Aleksei

The catalyzed conversion of shale gas-derived light hydrocarbons, e.g. methane to methanol, for further application as automotive fuels and/or bulk chemicals is especially attractive in light of improved methods of hydrocarbon extraction. MOF based catalysts have previously been demonstrated to be active for a range of catalytic reactions. In this work we used Cu-NU1000 as a methane-to-methanol oxidation catalyst. In addition to product studies, in-situ X-ray Absorption Spectroscopic (XAS) experiments are performed under catalytic conditions in order to follow the modification of the Cu-species and directly probe the structure/activity properties of the Cu-NU1000 system. The insights reported herein serve asmore » a first look at metal-organic framework materials as catalysts for methane oxidation and be the basis for development of the subsequent generations of materials.« less

Spatial Structure and Activity of Sedimentary Microbial Communities Underlying a Beggiatoa spp. Mat in a Gulf of Mexico Hydrocarbon Seep

PubMed Central

Lloyd, Karen G.; Albert, Daniel B.; Biddle, Jennifer F.; Chanton, Jeffrey P.; Pizarro, Oscar; Teske, Andreas

2010-01-01

Background Subsurface fluids from deep-sea hydrocarbon seeps undergo methane- and sulfur-cycling microbial transformations near the sediment surface. Hydrocarbon seep habitats are naturally patchy, with a mosaic of active seep sediments and non-seep sediments. Microbial community shifts and changing activity patterns on small spatial scales from seep to non-seep sediment remain to be examined in a comprehensive habitat study. Methodology/Principal Findings We conducted a transect of biogeochemical measurements and gene expression related to methane- and sulfur-cycling at different sediment depths across a broad Beggiatoa spp. mat at Mississippi Canyon 118 (MC118) in the Gulf of Mexico. High process rates within the mat (∼400 cm and ∼10 cm from the mat's edge) contrasted with sharply diminished activity at ∼50 cm outside the mat, as shown by sulfate and methane concentration profiles, radiotracer rates of sulfate reduction and methane oxidation, and stable carbon isotopes. Likewise, 16S ribosomal rRNA, dsrAB (dissimilatory sulfite reductase) and mcrA (methyl coenzyme M reductase) mRNA transcripts of sulfate-reducing bacteria (Desulfobacteraceae and Desulfobulbaceae) and methane-cycling archaea (ANME-1 and ANME-2) were prevalent at the sediment surface under the mat and at its edge. Outside the mat at the surface, 16S rRNA sequences indicated mostly aerobes commonly found in seawater. The seep-related communities persisted at 12–20 cm depth inside and outside the mat. 16S rRNA transcripts and V6-tags reveal that bacterial and archaeal diversity underneath the mat are similar to each other, in contrast to oxic or microoxic habitats that have higher bacterial diversity. Conclusions/Significance The visual patchiness of microbial mats reflects sharp discontinuities in microbial community structure and activity over sub-meter spatial scales; these discontinuities have to be taken into account in geochemical and microbiological inventories of seep environments. In contrast, 12–20 cm deep in the sediments microbial communities performing methane-cycling and sulfate reduction persist at lower metabolic rates regardless of mat cover, and may increase activity rapidly when subsurface flow changes. PMID:20090951

An efficient method to improve the production of methane from anaerobic digestion of waste activated sludge.

PubMed

Li, Xiaolan; Xu, Xueqin; Huang, Shansong; Zhou, Yun; Jia, Haijiang

2017-10-01

Methane production from waste activated sludge (WAS) anaerobic digestion is always low due to slow hydrolysis rate and inappropriate ratio of carbon to nitrogen (C/N). In this work, a novel approach, i.e., co-digestion of WAS and tobacco waste (TW) using ozone pretreatment, to greatly enhance the production of methane is reported. Experimental results showed the optimal C/N and ozone dosage for methane production was 24:1 and 90 mg/g suspended solids, and the corresponding methane production was 203.6 mL/g volatile suspended solids, which was 1.3-fold that in mono-WAS digestion. Further investigation showed the co-digestion of WAS and TW was beneficial to the consumptions of protein and cellulose; also, the presence of ozone enhanced the disruption of organic substrates and production of short chain fatty acids, which provided sufficient digestion substrates for methane generation. Analysis of microbial community structure suggested that members of the phyla Bacteroidetes and Firmicutes were the dominant species when ozone pretreatment was applied. The findings obtained in this work might be of great importance for the treatment of WAS and TW.

Electronic Structure of the [Cu 3 (μ-O) 3] 2+ Cluster in Mordenite Zeolite and Its Effects on the Methane to Methanol Oxidation

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

Vogiatzis, Konstantinos D.; Li, Guanna; Hensen, Emiel J. M.

Identifying Cu-exchanged zeolites able to activate C–H bonds and selectively convert methane to methanol is a challenge in the field of biomimetic heterogeneous catalysis. Recent experiments point to the importance of trinuclear [Cu 3(μ-O) 3] 2+ complexes inside the micropores of mordenite (MOR) zeolite for selective oxo-functionalization of methane. The electronic structures of these species, namely, the oxidation state of Cu ions and the reactive character of the oxygen centers, are not yet fully understood. In this study, we performed a detailed analysis of the electronic structure of the [Cu 3(μ-O) 3] 2+ site using multiconfigurational wave-function-based methods and densitymore » functional theory. The calculations reveal that all Cu sites in the cluster are predominantly present in the Cu(II) formal oxidation state with a minor contribution from Cu(III), whereas two out of three oxygen anions possess a radical character. These electronic properties, along with the high accessibility of the out-of-plane oxygen center, make this oxygen the preferred site for the homolytic C–H activation of methane by [Cu 3(μ-O) 3] 2+. These new insights aid in the construction of a theoretical framework for the design of novel catalysts for oxyfunctionalization of natural gas and suggest further spectroscopic examination.« less

Electronic Structure of the [Cu 3 (μ-O) 3] 2+ Cluster in Mordenite Zeolite and Its Effects on the Methane to Methanol Oxidation

DOE PAGES

Vogiatzis, Konstantinos D.; Li, Guanna; Hensen, Emiel J. M.; ...

2017-09-28

Identifying Cu-exchanged zeolites able to activate C–H bonds and selectively convert methane to methanol is a challenge in the field of biomimetic heterogeneous catalysis. Recent experiments point to the importance of trinuclear [Cu 3(μ-O) 3] 2+ complexes inside the micropores of mordenite (MOR) zeolite for selective oxo-functionalization of methane. The electronic structures of these species, namely, the oxidation state of Cu ions and the reactive character of the oxygen centers, are not yet fully understood. In this study, we performed a detailed analysis of the electronic structure of the [Cu 3(μ-O) 3] 2+ site using multiconfigurational wave-function-based methods and densitymore » functional theory. The calculations reveal that all Cu sites in the cluster are predominantly present in the Cu(II) formal oxidation state with a minor contribution from Cu(III), whereas two out of three oxygen anions possess a radical character. These electronic properties, along with the high accessibility of the out-of-plane oxygen center, make this oxygen the preferred site for the homolytic C–H activation of methane by [Cu 3(μ-O) 3] 2+. These new insights aid in the construction of a theoretical framework for the design of novel catalysts for oxyfunctionalization of natural gas and suggest further spectroscopic examination.« less

Methane seep events of the southern Joetsu Knoll since middle Pleistocene based on benthic foraminifera

NASA Astrophysics Data System (ADS)

Oi, T.; Akiba, F.; Matsumoto, R.; Kakuwa, Y.

2016-12-01

Gas hydrates were collected at several sites off Joetsu which presented anomalous seismic structures. "Gas chimneys", major host structures for shallow gas hydrates, were recognized ROV off Joetsu in eastern margin of the Japan Sea, as were a number of active methane seeps. The assemblage components and carbon isotope of benthic foraminifera, which are ubiquitous in global marine settings, can indicate methane seep environments (Akimoto et al., 1994; Bhaumik and Gupta, 2007). Preliminary work by Oi et al. (2015) documented the obvious occurrences of methane related foraminifera, Rutherfordoides sp., in three core sediments recovered from Umitaka Spur, west Oki Trough and north Mogami Trough in the eastern margin of the Japan Sea, and found them to comprise the early part of the MIS 2, calculated to 28-25ka. These records suggest that active methane seep events might occur at the same time during early MIS 2, but were confined within the last 100ka. In this study, we analyzed benthic foraminiferal fossils from drilling core J04RB (core length 122 m; one of the gas hydrate bearing sites at a southern part of the Joetsu Knoll) in order to document methane seep events during the last 500ka. Firstly, we estimated sedimentation ages from diatom biostratigraphy and identification of Aso-1 tephra. Based on diatom components, we recognized a boundary between NPD (Neogene North Pacific diatom Zonations) 12 and NPD11, estimated at 300 ka (MIS8/9; Yanagisawa and Akiba, 1998). The bottom age was estimated to almost 530-560 ka (around MIS14) especially from the alternation with warm and cold diatom zones (Akiba et al., 2014). Secondary, we could suppose the paleoenvironments from benthic foraminifera as below. 1. The rare benthic foraminifera during the cold stages (MIS8, MIS10, and MIS12) indicate anoxic bottom conditions characteristic of falling sea level, just as with MIS 2. 2. We recognized the continuous distributions of tiny methane related specimens of Rutherfordoides sp. during MIS10. In order to confirm new records of active methane seep events in the Joetsu Knoll, we need to measure isotope records of this species. This study was conducted under the commission from AIST as a part of the methane hydrate research project of METI (the Ministry of Economy, Trade and Industry, Japan).

Microbial eukaryotic distributions and diversity patterns in a deep-sea methane seep ecosystem.

PubMed

Pasulka, Alexis L; Levin, Lisa A; Steele, Josh A; Case, David H; Landry, Michael R; Orphan, Victoria J

2016-09-01

Although chemosynthetic ecosystems are known to support diverse assemblages of microorganisms, the ecological and environmental factors that structure microbial eukaryotes (heterotrophic protists and fungi) are poorly characterized. In this study, we examined the geographic, geochemical and ecological factors that influence microbial eukaryotic composition and distribution patterns within Hydrate Ridge, a methane seep ecosystem off the coast of Oregon using a combination of high-throughput 18S rRNA tag sequencing, terminal restriction fragment length polymorphism fingerprinting, and cloning and sequencing of full-length 18S rRNA genes. Microbial eukaryotic composition and diversity varied as a function of substrate (carbonate versus sediment), activity (low activity versus active seep sites), sulfide concentration, and region (North versus South Hydrate Ridge). Sulfide concentration was correlated with changes in microbial eukaryotic composition and richness. This work also revealed the influence of oxygen content in the overlying water column and water depth on microbial eukaryotic composition and diversity, and identified distinct patterns from those previously observed for bacteria, archaea and macrofauna in methane seep ecosystems. Characterizing the structure of microbial eukaryotic communities in response to environmental variability is a key step towards understanding if and how microbial eukaryotes influence seep ecosystem structure and function. © 2016 Society for Applied Microbiology and John Wiley & Sons Ltd.

Transition mechanism of sH to filled-ice Ih structure of methane hydrate under fixed pressure condition

NASA Astrophysics Data System (ADS)

Kadobayashi, H.; Hirai, H.; Ohfuji, H.; Kojima, Y.; Ohishi, Y.; Hirao, N.; Ohtake, M.; Yamamoto, Y.

2017-10-01

The phase transition mechanism of methane hydrate from sH to filled-ice Ih structure was examined using a combination of time-resolved X-ray diffractometry (XRD) and Raman spectroscopy in conjunction with charge-coupled device (CCD) camera observation under fixed pressure conditions. Prior to time-resolved Raman experiments, the typical C-H vibration modes and their pressure dependence of three methane hydrate structures, fluid methane and solid methane were measured using Raman spectroscopy to distinguish the phase transitions of methane hydrates from decomposition to solid methane and ice VI or VII. Experimental results by XRD, Raman spectroscopy and CCD camera observation revealed that the structural transition of sH to filled-ice Ih occurs through a collapse of the sH framework followed by the release of fluid methane that is then gradually incorporated into the filled-ice Ih to reconstruct its structure. These observations suggest that the phase transition of sH to filled-ice Ih takes place by a typical reconstructive mechanism.

Fine-Scale Community Structure Analysis of ANME in Nyegga Sediments with High and Low Methane Flux

PubMed Central

Roalkvam, Irene; Dahle, Håkon; Chen, Yifeng; Jørgensen, Steffen Leth; Haflidason, Haflidi; Steen, Ida Helene

2012-01-01

To obtain knowledge on how regional variations in methane seepage rates influence the stratification, abundance, and diversity of anaerobic methanotrophs (ANME), we analyzed the vertical microbial stratification in a gravity core from a methane micro-seeping area at Nyegga by using 454-pyrosequencing of 16S rRNA gene tagged amplicons and quantitative PCR. These data were compared with previously obtained data from the more active G11 pockmark, characterized by higher methane flux. A down core stratification and high relative abundance of ANME were observed in both cores, with transition from an ANME-2a/b dominated community in low-sulfide and low methane horizons to ANME-1 dominance in horizons near the sulfate-methane transition zone. The stratification was over a wider spatial region and at greater depth in the core with lower methane flux, and the total 16S rRNA copy numbers were two orders of magnitude lower than in the sediments at G11 pockmark. A fine-scale view into the ANME communities at each location was achieved through operational taxonomical units (OTU) clustering of ANME-affiliated sequences. The majority of ANME-1 sequences from both sampling sites clustered within one OTU, while ANME-2a/b sequences were represented in unique OTUs. We suggest that free-living ANME-1 is the most abundant taxon in Nyegga cold seeps, and also the main consumer of methane. The observation of specific ANME-2a/b OTUs at each location could reflect that organisms within this clade are adapted to different geochemical settings, perhaps due to differences in methane affinity. Given that the ANME-2a/b population could be sustained in less active seepage areas, this subgroup could be potential seed populations in newly developed methane-enriched environments. PMID:22715336

Spectroscopic Identification of the Carbyne Hydride Structure of the Dehydrogenation Product of Methane Activation by Osmium Cations

NASA Astrophysics Data System (ADS)

Armentrout, P. B.; Kuijpers, Stach E. J.; Lushchikova, Olga V.; Hightower, Randy L.; Boles, Georgia C.; Bakker, Joost M.

2018-04-01

The present work explores the structures of species formed by dehydrogenation of methane (CH4) and perdeuterated methane (CD4) by the 5d transition metal cation osmium (Os+). Using infrared multiple photon dissociation (IRMPD) action spectroscopy and density functional theory (DFT), the structures of the [Os,C,2H]+ and [Os,C,2D]+ products are explored. This study complements previous work on the related species formed by dehydrogenation of methane by four other 5d transition metal cations (M+ = Ta+, W+, Ir+, and Pt+). Osmium cations are formed in a laser ablation source, react with methane pulsed into a reaction channel downstream, and the resulting products spectroscopically characterized through photofragmentation using the Free-Electron Laser for IntraCavity Experiments (FELICE) in the 300-1800 cm-1 range. Photofragmentation was monitored by the loss of H2/D2. Comparison of the experimental spectra and DFT calculated spectra leads to identification of the ground state carbyne hydride, HOsCH+ (2A') as the species formed, as previously postulated theoretically. Further, a full description of the systematic spectroscopic shifts observed for deuterium labeling of these complexes, some of the smallest systems to be studied using IRMPD action spectroscopy, is achieved. A full rotational contour analysis explains the observed linewidths as well as the observation of doublet structures in several bands, consistent with previous observations for HIrCH+ (2A'). [Figure not available: see fulltext.

Implementing the "Curriculum and Evaluation Standards."

ERIC Educational Resources Information Center

Pacyga, Robert

1994-01-01

Describes two activities to analyze unit-cell structures from a geometric viewpoint and invite students to apply their mathematical understanding to scientific phenomena. Students form models of the simple cube, a building block of crystalline structures, and a methane molecule. (MDH)

Theoretical Insights into Methane C–H Bond Activation on Alkaline Metal Oxides

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

Aljama, Hassan; Nørskov, Jens K.; Abild-Pedersen, Frank

Here, we investigate the role of alkaline metal oxides (AMO) (MgO, CaO, and SrO) in activating the C–H bond in methane. We also use Density Functional Theory (DFT) and microkinetic modeling to study the catalytic elementary steps in breaking the C–H bond in methane and creating the methyl radical, a precursor prior to creating C2 products. We also study the effects of surface geometry on the catalytic activity of AMO by examining terrace and step sites. We observe that the process of activating methane depends strongly on the structure of the AMO. When the AMO surface is doped with anmore » alkali metal, the transition state (TS) structure has a methyl radical-like behavior, where the methyl radical interacts weakly with the AMO surface. In this case, the TS energy scales with the hydrogen binding energy. On pure AMO, the TS interacts with AMO surface oxygen as well as the metal atom on the surface, and consequently the TS energy scales with the binding energy of hydrogen and methyl. We study the activity of AMO using a mean-field microkinetic model. The results indicate that terrace sites have similar catalytic activity, with the exception of MgO(100). Step sites bind hydrogen more strongly, making them more active, and this confirms previously reported experimental results. We map the catalytic activity of AMO using a volcano plot with two descriptors: the methyl and the hydrogen binding energies, with the latter being a more significant descriptor. The microkinetic model results suggest that C–H bond dissociation is not always the rate-limiting step. At weak hydrogen binding, the reaction is limited by C–H bond activation. At strong hydrogen binding, the reaction is limited due to poisoning of the active site. We found an increase in activity of AMO as the basicity increased. Finally, the developed microkinetic model allows screening for improved catalysts using simple calculations of the hydrogen binding energy.« less

Theoretical Insights into Methane C–H Bond Activation on Alkaline Metal Oxides

DOE PAGES

Aljama, Hassan; Nørskov, Jens K.; Abild-Pedersen, Frank

2017-07-17

Here, we investigate the role of alkaline metal oxides (AMO) (MgO, CaO, and SrO) in activating the C–H bond in methane. We also use Density Functional Theory (DFT) and microkinetic modeling to study the catalytic elementary steps in breaking the C–H bond in methane and creating the methyl radical, a precursor prior to creating C2 products. We also study the effects of surface geometry on the catalytic activity of AMO by examining terrace and step sites. We observe that the process of activating methane depends strongly on the structure of the AMO. When the AMO surface is doped with anmore » alkali metal, the transition state (TS) structure has a methyl radical-like behavior, where the methyl radical interacts weakly with the AMO surface. In this case, the TS energy scales with the hydrogen binding energy. On pure AMO, the TS interacts with AMO surface oxygen as well as the metal atom on the surface, and consequently the TS energy scales with the binding energy of hydrogen and methyl. We study the activity of AMO using a mean-field microkinetic model. The results indicate that terrace sites have similar catalytic activity, with the exception of MgO(100). Step sites bind hydrogen more strongly, making them more active, and this confirms previously reported experimental results. We map the catalytic activity of AMO using a volcano plot with two descriptors: the methyl and the hydrogen binding energies, with the latter being a more significant descriptor. The microkinetic model results suggest that C–H bond dissociation is not always the rate-limiting step. At weak hydrogen binding, the reaction is limited by C–H bond activation. At strong hydrogen binding, the reaction is limited due to poisoning of the active site. We found an increase in activity of AMO as the basicity increased. Finally, the developed microkinetic model allows screening for improved catalysts using simple calculations of the hydrogen binding energy.« less

The occurrence of macro- and mesoscopic methane hydrate in the eastern margin of Japan Sea

NASA Astrophysics Data System (ADS)

Matsumoto, R.; Kakuwa, Y.; Tanahashi, M.; Hiruta, A.

2016-12-01

Shallow methane hydrate is known to occur in muddy sediments that were deposited in the eastern margin of Japan Sea. In such settings, the hydrate occurs just below the seabed or is exposed directly on the seabed. Its presence is quite different from the pore-filling type of hydrate typically found in sandstone of the Pacific Ocean side of the Japanese islands. This presentation focuses on categorizing the distribution of gas hydrate in Japan Sea which, until recently, has been poorly understood. Macroscopic occurrence: Numerous gas chimney structures, which are characterized by an acoustic blanking on sub-bottom profiler images, have been discovered in the eastern margin of Japan Sea. We carried out seafloor drilling at several topographic highs that showed gas chimney structures. The results confirm that, while methane hydrate does not occur in the well-stratified part of SBP images, it does occur uniquely in the gas chimney structure-bearing mounds and pockmarks. Several horizons of methane hydrate-concentrated layers are identified by our LWD data and are traceable over lateral distances of as much as a kilometer.. In another case, the methane hydrate-concentrated layers occur stratigraphically in a regular manner with methane-derived carbonate nodules. We interpret the second case as one in which methane gas was supplied by regularly repeated movements of active fault(s). Mesoscopic occurrence: Methane hydrate is classified into 5 types that are readily observable in drilled cores: granular, nodular, platy, veiny and massive. The granular type is common over shallower intervals, while platy and veiny types are more common in the deeper intervals. Nevertheless, a significant fraction of the granular type may have possibly originated from the destruction and dissociation of other types during drilling and recovery. The massive type hydrate that characterizes highly-concentrated layers transitions to other types laterally as methane hydrate becomes poorly concentrated. This study was conducted under the commission from AIST as a part of the methane hydrate research project funded by METI (the Ministry of Economy, Trade and Industry, Japan).

ELECTROCHEMISTRY AND ON-CELL REFORMATION MODELING FOR SOLID OXIDE FUEL CELL STACKS

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

Recknagle, Kurtis P.; Jarboe, Daniel T.; Johnson, Kenneth I.

2007-01-16

ABSTRACT Providing adequate and efficient cooling schemes for solid-oxide-fuel-cell (SOFC) stacks continues to be a challenge coincident with the development of larger, more powerful stacks. The endothermic steam-methane reformation reaction can provide cooling and improved system efficiency when performed directly on the electrochemically active anode. Rapid kinetics of the endothermic reaction typically causes a localized temperature depression on the anode near the fuel inlet. It is desirable to extend the endothermic effect over more of the cell area and mitigate the associated differences in temperature on the cell to alleviate subsequent thermal stresses. In this study, modeling tools validated formore » the prediction of fuel use, on-cell methane reforming, and the distribution of temperature within SOFC stacks, are employed to provide direction for modifying the catalytic activity of anode materials to control the methane conversion rate. Improvements in thermal management that can be achieved through on-cell reforming is predicted and discussed. Two operating scenarios are considered: one in which the methane fuel is fully pre-reformed, and another in which a substantial percentage of the methane is reformed on-cell. For the latter, a range of catalytic activity is considered and the predicted thermal effects on the cell are presented. Simulations of the cell electrochemical and thermal performance with and without on-cell reforming, including structural analyses, show a substantial decrease in thermal stresses for an on-cell reforming case with slowed methane conversion.« less

Making Connections by Using Molecular Models in Geometry.

ERIC Educational Resources Information Center

Pacyga, Robert

1995-01-01

Describes two activities to analyze unit-cell structures from a geometric viewpoint and invites students to apply their mathematical understanding to scientific phenomena. Students form models of the simple cube, a building block of crystalline structures, and a methane molecule. (MKR)

Gas hydrate and spatial venting variations in the continental margin offshore Southwestern Taiwan

NASA Astrophysics Data System (ADS)

Lin, S.; Lim, Y.; Hsieh, W.; Yang, T.; Wang, Y.

2006-12-01

Strong BSR, high methane contents and rapid sulfate reduction were found in the continental margin sediments offshore southwestern Taiwan. In order to identify the venting phenomena and its relationship with gas hydrate, this research investigate sea floor vent features using WHOI?|s Towcam system as well as piston core in the study region. A total of 10 dives were conducted on board the r/v OR-1. Pore water sulfate, dissolved sulfide, methane, chloride, del O18 ratio, sediment organic carbon, carbonate content and carbonate del C13 ratio, pyrite-S were measured Large spatial variations were found based on pictures obtained from Towcam system and piston cores. Active venting features include bacteria mat, live dense bivalve patches, gas plume, temperature and salinity fluctuations, rapid sulfate reduction and high concentrations of methane in sediments. In addition, vent chimney, pockmark and large authigenic carbonate buildup were also observed in the active venting area. In contrast, in some areas without active venting features, scatter dead chimney, semi- buried carbonate structures, and dead bivalves were found. Total sulfate depletion was found at depth as shallow as 1 meter below sediment water interface in area near active vent whereas almost no sulfate depletion was observed in areas without any vent feature. Stages of carbonate build up existed, with initial phase dominated by small tube, chimney, and later with massive carbonate structures protruding the sea floor. The appearances of massive carbonate buildup structures seemed to indicate the end stage of gas hydrate venting phenomena.

Composition of methane-oxidizing bacterial communities as a function of nutrient loading in the Florida everglades.

PubMed

Chauhan, Ashvini; Pathak, Ashish; Ogram, Andrew

2012-10-01

Agricultural runoff of phosphorus (P) in the northern Florida Everglades has resulted in several ecosystem level changes, including shifts in the microbial ecology of carbon cycling, with significantly higher methane being produced in the nutrient-enriched soils. Little is, however, known of the structure and activities of methane-oxidizing bacteria (MOB) in these environments. To address this, 0 to 10 cm plant-associated soil cores were collected from nutrient-impacted (F1), transition (F4), and unimpacted (U3) areas, sectioned in 2-cm increments, and methane oxidation rates were measured. F1 soils consumed approximately two-fold higher methane than U3 soils; additionally, most probable numbers of methanotrophs were 4-log higher in F1 than U3 soils. Metabolically active MOB containing pmoA sequences were characterized by stable-isotope probing using 10 % (v/v) (13)CH(4). pmoA sequences, encoding the alpha subunit of methane monooxygenase and related to type I methanotrophs, were identified from both impacted and unimpacted soils. Additionally, impacted soils also harbored type II methanotrophs, which have been shown to exhibit preferences for high methane concentrations. Additionally, across all soils, novel pmoA-type sequences were also detected, indicating presence of MOB specific to the Everglades. Multivariate statistical analyses confirmed that eutrophic soils consisted of metabolically distinct MOB community that is likely driven by nutrient enrichment. This study enhances our understanding on the biological fate of methane being produced in productive wetland soils of the Florida Everglades and how nutrient-enrichment affects the composition of methanotroph bacterial communities.

Trace Elements Affect Methanogenic Activity and Diversity in Enrichments from Subsurface Coal Bed Produced Water

PubMed Central

Ünal, Burcu; Perry, Verlin Ryan; Sheth, Mili; Gomez-Alvarez, Vicente; Chin, Kuk-Jeong; Nüsslein, Klaus

2012-01-01

Microbial methane from coal beds accounts for a significant and growing percentage of natural gas worldwide. Our knowledge of physical and geochemical factors regulating methanogenesis is still in its infancy. We hypothesized that in these closed systems, trace elements (as micronutrients) are a limiting factor for methanogenic growth and activity. Trace elements are essential components of enzymes or cofactors of metabolic pathways associated with methanogenesis. This study examined the effects of eight trace elements (iron, nickel, cobalt, molybdenum, zinc, manganese, boron, and copper) on methane production, on mcrA transcript levels, and on methanogenic community structure in enrichment cultures obtained from coal bed methane (CBM) well produced water samples from the Powder River Basin, Wyoming. Methane production was shown to be limited both by a lack of additional trace elements as well as by the addition of an overly concentrated trace element mixture. Addition of trace elements at concentrations optimized for standard media enhanced methane production by 37%. After 7 days of incubation, the levels of mcrA transcripts in enrichment cultures with trace element amendment were much higher than in cultures without amendment. Transcript levels of mcrA correlated positively with elevated rates of methane production in supplemented enrichments (R2 = 0.95). Metabolically active methanogens, identified by clone sequences of mcrA mRNA retrieved from enrichment cultures, were closely related to Methanobacterium subterraneum and Methanobacterium formicicum. Enrichment cultures were dominated by M. subterraneum and had slightly higher predicted methanogenic richness, but less diversity than enrichment cultures without amendments. These results suggest that varying concentrations of trace elements in produced water from different subsurface coal wells may cause changing levels of CBM production and alter the composition of the active methanogenic community. PMID:22590465

Analysis of Decomposition for Structure I Methane Hydrate by Molecular Dynamics Simulation

NASA Astrophysics Data System (ADS)

Wei, Na; Sun, Wan-Tong; Meng, Ying-Feng; Liu, An-Qi; Zhou, Shou-Wei; Guo, Ping; Fu, Qiang; Lv, Xin

2018-05-01

Under multi-nodes of temperatures and pressures, microscopic decomposition mechanisms of structure I methane hydrate in contact with bulk water molecules have been studied through LAMMPS software by molecular dynamics simulation. Simulation system consists of 482 methane molecules in hydrate and 3027 randomly distributed bulk water molecules. Through analyses of simulation results, decomposition number of hydrate cages, density of methane molecules, radial distribution function for oxygen atoms, mean square displacement and coefficient of diffusion of methane molecules have been studied. A significant result shows that structure I methane hydrate decomposes from hydrate-bulk water interface to hydrate interior. As temperature rises and pressure drops, the stabilization of hydrate will weaken, decomposition extent will go deep, and mean square displacement and coefficient of diffusion of methane molecules will increase. The studies can provide important meanings for the microscopic decomposition mechanisms analyses of methane hydrate.

Characterization of Methane Emission Sources Using Genetic Algorithms and Atmospheric Transport Modeling

NASA Astrophysics Data System (ADS)

Cao, Y.; Cervone, G.; Barkley, Z.; Lauvaux, T.; Deng, A.; Miles, N.; Richardson, S.

2016-12-01

Fugitive methane emission rates for the Marcellus shale area are estimated using a genetic algorithm that finds optimal weights to minimize the error between simulated and observed concentrations. The overall goal is to understand the relative contribution of methane due to Shale gas extraction. Methane sensors were installed on four towers located in northeastern Pennsylvania to measure atmospheric concentrations since May 2015. Inverse Lagrangian dispersion model runs are performed from each of these tower locations for each hour of 2015. Simulated methane concentrations at each of the four towers are computed by multiplying the resulting footprints from the atmospheric simulations by thousands of emission sources grouped into 11 classes. The emission sources were identified using GIS techniques, and include conventional and unconventional wells, different types of compressor stations, pipelines, landfills, farming and wetlands. Initial estimates for each source are calculated based on emission factors from EPA and few regional studies. A genetic algorithm is then used to identify optimal emission rates for the 11 classes of methane emissions and to explore extreme events and spatial and temporal structures in the emissions associated with natural gas activities.

Exploring bis-(indolyl)methane moiety as an alternative and innovative CAP group in the design of histone deacetylase (HDAC) inhibitors.

PubMed

Giannini, Giuseppe; Marzi, Mauro; Marzo, Maria Di; Battistuzzi, Gianfranco; Pezzi, Riccardo; Brunetti, Tiziana; Cabri, Walter; Vesci, Loredana; Pisano, Claudio

2009-05-15

In order to gather further knowledge about the structural requirements on histone deacetylase inhibitors (HDACi), starting from the schematic model of the common pharmacophore that characterizes this class of molecules (surface recognition CAP group-connection unit-linker region-Zinc Binding Group), we designed and synthesized a series of hydroxamic acids containing a bis-(indolyl)methane moiety. HDAC inhibition profile and antiproliferative activity were evaluated.

Methane Recovery from Gaseous Mixtures Using Carbonaceous Adsorbents

NASA Astrophysics Data System (ADS)

Buczek, Bronisław

2016-06-01

Methane recovery from gaseous mixtures has both economical and ecological aspect. Methane from different waste gases like mine gases, nitrogenated natural gases and biogases can be treated as local source for production electric and heat energy. Also occurs the problem of atmosphere pollution with methane that shows over 20 times more harmful environmental effect in comparison to carbon dioxide. One of the ways utilisation such gases is enrichment of methane in the PSA technique, which requires appropriate adsorbents. Active carbons and carbon molecular sieve produced by industry and obtained in laboratory scale were examined as adsorbent for methane recuperation. Porous structure of adsorbents was investigated using densimetry measurements and adsorption of argon at 77.5K. On the basis of adsorption data, the Dubinin-Radushkevich equation parameters, micropore volume (Wo) and characteristics of energy adsorption (Eo) as well as area micropores (Smi) and BET area (SBET) were determined. The usability of adsorbents in enrichment of the methane was evaluated in the test, which simulate the basic stages of PSA process: a) adsorbent degassing, b) pressure raise in column by feed gas, c) cocurrent desorption with analysis of out flowing gas. The composition of gas phase was accepted as the criterion of the suitability of adsorbent for methane separation from gaseous mixtures. The relationship between methane recovery from gas mixture and texture parameters of adsorbents was found.

Spatial and temporal dependencies of structure II to structure I methane hydrate transformation in porous media under moderate pressure and temperature conditions

NASA Astrophysics Data System (ADS)

Dong, T.; Lin, J. F.; Gu, J. T.; Polito, P. J.; O'Connell, J.; Flemings, P. B.

2017-12-01

We used Raman spectroscopy to monitor methane hydrates transforming from structure II to structure I at the pore scale as a function of space and time. It is well documented that structure I hydrate is the thermodynamically stable phase for pure methane hydrate (<100 MPa, < 20 °C), but due to kinetic limitation, initial methane hydrate formation produces a mixture of structure I and structure II hydrates. We observed that the structure transformation originated around the porous medium grains and over time slowly migrated into the pore space. We synthesized methane hydrates in spherical glass beads (210-297 µm in diameter) in a pressure cell with a sapphire window to integrate optical observations with Raman measurements. We injected CH4 vapor into the cell and supplied only deionized water thereafter to maintain a constant pressure of 14.6 MPa at 3.5 °C, with 14.5 °C subcooling. We used Raman spectroscopy to map the methane hydrates in pore spaces at 5-25 µm resolution, in order to monitor the occupancy ratio of CH4 in large cages to CH4 in small cages, by their Raman peak intensity ratio, i.e., I( 2905 cm-1)/I( 2915 cm-1). We identified 3 stages of hydrate formation at the pore scale: (1) after the initial hydrate formation, Raman mapping revealed that the occupancy ratio ranged from 0.5 to 3, indicating a mixture of structure I and II hydrates; (2) within 1 week, we observed that all structure I hydrates occurred on the glass bead surfaces and structure II hydrates occupied the pore spaces; (3) over the following 2 weeks, structure II hydrates gradually recrystallized into structure I hydrates from glass bead surfaces towards the pore space. These results imply that (1) due to kinetics, the formation of methane hydrate in porous media is more complex than previously thought, and (2) the bulk physical and chemical properties of laboratory-synthesized methane hydrates in porous media may drift over time, as methane hydrates recrystallize from a metastable phase (structure II) to the thermodynamically stable phase (structure I).

Crystal structure and DNA repair activities of the AP endonuclease from Leishmania major.

PubMed

Vidal, Antonio E; Harkiolaki, Maria; Gallego, Claribel; Castillo-Acosta, Victor M; Ruiz-Pérez, Luis M; Wilson, Keith; González-Pacanowska, Dolores

2007-11-02

Apurinic/apyrimidinic endonucleases initiate the repair of abasic sites produced either spontaneously, from attack of bases by reactive oxygen species or as intermediates during base excision repair. The catalytic properties and crystal structure of Leishmania major apurinic/apyrimidinic endonuclease are described and compared with those of human APE1 and bacterial exonuclease III. The purified enzyme is shown to possess apurinic/apyrimidinic endonuclease activity of the same order as eukaryotic and prokaryotic counterparts and an equally robust 3'-phosphodiesterase activity. Consistent with this, expression of the L. major endonuclease confers resistance to both methyl methane sulphonate and H2O2 in Escherichia coli repair-deficient mutants while expression of the human homologue only reverts methyl methane sulphonate sensitivity. Structural analyses and modelling of the enzyme-DNA complex demonstrates a high degree of conservation to previously characterized homologues, although subtle differences in the active site geometry might account for the high 3'-phosphodiesterase activity. Our results confirm that the L. major's enzyme is a key element in mediating repair of apurinic/apyrimidinic sites and 3'-blocked termini and therefore must play an important role in the survival of kinetoplastid parasites after exposure to the highly oxidative environment within the host macrophage.

Experimental investigations about the effect of trace amount of propane on the formation of mixed hydrates of methane and propane

NASA Astrophysics Data System (ADS)

Cai, W.; Lu, H.; Huang, X.

2016-12-01

In natural gas hydrates, some heavy hydrocarbons are always detected in addition to methane. However, it is still not well understood how the trace amount of heavy gas affect the hydrate properties. Intensive studies have been carried out to study the thermodynamic properties and structure types of mixed gases hydrates, but comparatively few investigations have been carried out on the cage occupancies of guest molecules in mixed gases hydrates. For understanding how trace amount of propane affects the formation of mixed methane-propane hydrates, X-ray diffraction, Raman spectroscopy, and gas chromatography were applied to the synthesized mixed methane-propane hydrate specimens, to get their structural characteristics (structure type, structural parameters, cage occupancy, etc.) and gas compositions. The mixed methane-propane hydrates were prepared by reacting fine ice powders with various gas mixtures of methane and propane. When the propane content was below 0.4%, the hydrates synthesized were found containing both sI methane hydrate and sII methane-propane hydrate; while the hydrates were found always sII when propane was over certain content. Detail studies about the cage occupancies of propane and methane in sII hydrate revealed that: 1) with the increase in propane content of methane-propane mixture, the occupancy of propane in large cage increased as accompanied with the decrease in methane occupancy in large cage, however the occupancy of methane in small cage didn't experience significant change; 2) temperature and pressure seemed no obvious influence on cage occupancy.

Methane emissions from different coastal wetlands in New England, US

NASA Astrophysics Data System (ADS)

Wang, F.; Tang, J.; Kroeger, K. D.; Gonneea, M. E.

2017-12-01

According to the IPCC, methane have 25 times warming effect than CO2, and natural wetlands contribute 20-39 % to the global emission of methane. Although most of these methane was from inland wetlands, there was still large uncertain in the methane emissions in coastal wetlands. In the past three years, we have investigated methane emissions in coastal wetlands in MA, USA. Contrary to previous assumptions, we have observed relative larger methane flux in some salt marshes than freshwater wetlands. We further detect the methane source, and found that plant activities played an important role in methane flux, for example, the growth of S. aterniflora, the dominate plants in salt marsh, could enhance methane emission, while in an fresh water wetland that was dominated by cattail, plant activity oxided methane and reduced total flux. Phragmite, an invasive plant at brackish marsh, have the highest methane flux among all coastal wetland investigated. This study indicated that coastal wetland could still emit relatively high amount of methane even under high water salinity condiations, and plant activity played an important role in methane flux, and this role was highly species-specific.

Methane Production and Methanogenic Archaea in the Digestive Tracts of Millipedes (Diplopoda)

PubMed Central

Šustr, Vladimír; Chroňáková, Alica; Semanová, Stanislava; Tajovský, Karel; Šimek, Miloslav

2014-01-01

Methane production by intestinal methanogenic Archaea and their community structure were compared among phylogenetic lineages of millipedes. Tropical and temperate millipedes of 35 species and 17 families were investigated. Species that emitted methane were mostly in the juliform orders Julida, Spirobolida, and Spirostreptida. The irregular phylogenetic distribution of methane production correlated with the presence of the methanogen-specific mcrA gene. The study brings the first detailed survey of methanogens’ diversity in the digestive tract of millipedes. Sequences related to Methanosarcinales, Methanobacteriales, Methanomicrobiales and some unclassified Archaea were detected using molecular profiling (DGGE). The differences in substrate preferences of the main lineages of methanogenic Archaea found in different millipede orders indicate that the composition of methanogen communities may reflect the differences in available substrates for methanogenesis or the presence of symbiotic protozoa in the digestive tract. We conclude that differences in methane production in the millipede gut reflect differences in the activity and proliferation of intestinal methanogens rather than an absolute inability of some millipede taxa to host methanogens. This inference was supported by the general presence of methanogenic activity in millipede faecal pellets and the presence of the 16S rRNA gene of methanogens in all tested taxa in the two main groups of millipedes, the Helminthophora and the Pentazonia. PMID:25028969

Structural control of coalbed methane production in Alabama

USGS Publications Warehouse

Pashin, J.C.; Groshong, R.H.

1998-01-01

Thin-skinned structures are distributed throughout the Alabama coalbed methane fields, and these structures affect the production of gas and water from coal-bearing strata. Extensional structures in Deerlick Creek and Cedar Cove fields include normal faults and hanging-wall rollovers, and area balancing indicates that these structures are detached in the Pottsville Formation. Compressional folds in Gurnee and Oak Grove fields, by comparison, are interpreted to be detachment folds formed above decollements at different stratigraphic levels. Patterns of gas and water production reflect the structural style of each field and further indicate that folding and faulting have affected the distribution of permeability and the overall success of coalbed methane operations. Area balancing can be an effective way to characterize coalbed methane reservoirs in structurally complex regions because it constrains structural geometry and can be used to determine the distribution of layer-parallel strain. Comparison of calculated requisite strain and borehole expansion data from calliper logs suggests that strain in coalbed methane reservoirs is predictable and can be expressed as fracturing and small-scale faulting. However, refined methodology is needed to analyze heterogeneous strain distributions in discrete bed segments. Understanding temporal variation of production patterns in areas where gas and water production are influenced by map-scale structure will further facilitate effective management of coalbed methane fields.Thin-skinned structures are distributed throughout the Alabama coalbed methane fields, and these structures affect the production of gas and water from coal-bearing strata. Extensional structures in Deerlick Creek and Cedar Cove fields include normal faults and hanging-wall rollovers, and area balancing indicates that these structures are detached in the Pottsville Formation. Compressional folds in Gurnee and Oak Grove fields, by comparison, are interpreted to be detachment folds formed above decollements at different stratigraphic levels. Patterns of gas and water production reflect the structural style of each field and further indicate that folding and faulting have affected the distribution of permeability and the overall success of coalbed methane operations. Area balancing can be an effective way to characterize coalbed methane reservoirs in structurally complex regions because it constrains structural geometry and can be used to determine the distribution of layer-parallel strain. Comparison of calculated requisite strain and borehole expansion data from calliper logs suggests that strain in coalbed methane reservoirs is predictable and can be expressed as fracturing and small-scale faulting. However, refined methodology is needed to analyze heterogeneous strain distributions in discrete bed segments. Understanding temporal variation of production patterns in areas where gas and water production are influenced by map-scale structure will further facilitate effective management of coalbed methane fields.

Structural stability of methane hydrate at high pressures

USGS Publications Warehouse

Shu, J.; Chen, X.; Chou, I-Ming; Yang, W.; Hu, Jiawen; Hemley, R.J.; Mao, Ho-kwang

2011-01-01

The structural stability of methane hydrate under pressure at room temperature was examined by both in-situ single-crystal and powder X-ray diffraction techniques on samples with structure types I, II, and H in diamond-anvil cells. The diffraction data for types II (sII) and H (sH) were refined to the known structures with space groups Fd3m and P63/mmc, respectively. Upon compression, sI methane hydrate transforms to the sII phase at 120 MPa, and then to the sH phase at 600 MPa. The sII methane hydrate was found to coexist locally with sI phase up to 500 MPa and with sH phase up to 600 MPa. The pure sH structure was found to be stable between 600 and 900 MPa. Methane hydrate decomposes at pressures above 3 GPa to form methane with the orientationally disordered Fm3m structure and ice VII (Pn3m). The results highlight the role of guest (CH4)-host (H2O) interactions in the stabilization of the hydrate structures under pressure.

Thermo-alkaline pretreatment of waste activated sludge at low-temperatures: effects on sludge disintegration, methane production, and methanogen community structure.

PubMed

Kim, Jaai; Yu, Youngseob; Lee, Changsoo

2013-09-01

Low-temperature thermo-alkaline pretreatment of waste activated sludge (WAS) was studied, within the region of 0-0.2 M NaOH and 60-90°C, for the effects of NaOH concentration and temperature on sludge degradability in anaerobic digestion (AD). Significant disintegration of sludge solids (up to 75.6%) and an increase in methane production (up to 70.6%) were observed in the pretreatment trials. Two quadratic models were successfully generated by response surface analysis (R(2)>0.9, p<0.05) to approximate how the degree of sludge disintegration (SD) and methane production (MP) respond to changes in the pretreatment conditions. The maximum responses of SD (77.8%) and MP (73.9% increase over the control) were shown at [0.16 M NaOH, 90°C] and [0.10 M NaOH, 73.7°C], respectively. NaOH addition showed a significant influence on the evolution of methanogen community structure during AD, whereas temperature did not. Aceticlastic Methanosaeta and Methanosarcina speceies were likely the major methanogens. Copyright © 2013 Elsevier Ltd. All rights reserved.

Transformations in methane hydrates

USGS Publications Warehouse

Chou, I.-Ming; Sharma, A.; Burruss, R.C.; Shu, J.; Mao, Ho-kwang; Hemley, R.J.; Goncharov, A.F.; Stern, L.A.; Kirby, S.H.

2000-01-01

Detailed study of pure methane hydrate in a diamond cell with in situ optical, Raman, and x-ray microprobe techniques reveals two previously unknown structures, structure II and structure H, at high pressures. The structure II methane hydrate at 250 MPa has a cubic unit cell of a = 17.158(2) A?? and volume V = 5051.3(13) A??3; structure H at 600 MPa has a hexagonal unit cell of a = 11.980(2) A??, c = 9.992(3) A??, and V = 1241.9(5) A??3. The compositions of these two investigated phases are still not known. With the effects of pressure and the presence of other gases in the structure, the structure II phase is likely to dominate over the known structure I methane hydrate within deep hydrate-bearing sediments underlying continental margins.

In silico design of porous polymer networks: high-throughput screening for methane storage materials.

PubMed

Martin, Richard L; Simon, Cory M; Smit, Berend; Haranczyk, Maciej

2014-04-02

Porous polymer networks (PPNs) are a class of advanced porous materials that combine the advantages of cheap and stable polymers with the high surface areas and tunable chemistry of metal-organic frameworks. They are of particular interest for gas separation or storage applications, for instance, as methane adsorbents for a vehicular natural gas tank or other portable applications. PPNs are self-assembled from distinct building units; here, we utilize commercially available chemical fragments and two experimentally known synthetic routes to design in silico a large database of synthetically realistic PPN materials. All structures from our database of 18,000 materials have been relaxed with semiempirical electronic structure methods and characterized with Grand-canonical Monte Carlo simulations for methane uptake and deliverable (working) capacity. A number of novel structure-property relationships that govern methane storage performance were identified. The relationships are translated into experimental guidelines to realize the ideal PPN structure. We found that cooperative methane-methane attractions were present in all of the best-performing materials, highlighting the importance of guest interaction in the design of optimal materials for methane storage.

Molecular dynamics study of structure H clathrate hydrates of methane and large guest molecules.

PubMed

Susilo, Robin; Alavi, Saman; Ripmeester, John A; Englezos, Peter

2008-05-21

Methane storage in structure H (sH) clathrate hydrates is attractive due to the relatively higher stability of sH as compared to structure I methane hydrate. The additional stability is gained without losing a significant amount of gas storage density as happens in the case of structure II (sII) methane clathrate. Our previous work has showed that the selection of a specific large molecule guest substance (LMGS) as the sH hydrate former is critical in obtaining the optimum conditions for crystallization kinetics, hydrate stability, and methane content. In this work, molecular dynamics simulations are employed to provide further insight regarding the dependence of methane occupancy on the type of the LMGS and pressure. Moreover, the preference of methane molecules to occupy the small (5(12)) or medium (4(3)5(6)6(3)) cages and the minimum cage occupancy required to maintain sH clathrate mechanical stability are examined. We found that thermodynamically, methane occupancy depends on pressure but not on the nature of the LMGS. The experimentally observed differences in methane occupancy for different LMGS may be attributed to the differences in crystallization kinetics and/or the nonequilibrium conditions during the formation. It is also predicted that full methane occupancies in both small and medium clathrate cages are preferred at higher pressures but these cages are not fully occupied at lower pressures. It was found that both small and medium cages are equally favored for occupancy by methane guests and at the same methane content, the system suffers a free energy penalty if only one type of cage is occupied. The simulations confirm the instability of the hydrate when the small and medium cages are empty. Hydrate decomposition was observed when less than 40% of the small and medium cages are occupied.

[Methanotrophic bacteria in cold seeps of the floodplains of northern rivers].

PubMed

Belova, S É; Oshkin, I Iu; Glagolev, M V; Lapshina, E D; Maksiutov, Sh Sh; Dedysh, S N

2013-01-01

Small mud volcanoes (cold seeps), which are common in the floodplains of northern rivers, are a potentially important, although poorly studied sources of atmospheric methane. Field research on the cold seeps of the Mukhrina River (Khanty-Mansiysk Autonomous okrug, Russia) revealed methane fluxes from these structures to be orders of magnitude higher than from equivalent areas of the mid-taiga bogs. Microbial communities developing around the seeps were formed under conditions of high methane concentrations, low temperatures (3-5 degrees C), and near-neutral pH. Molecular identification of methane-oxidizing bacteria from this community by analysis of the pmoA gene encoding particulate methane monooxygenase revealed both type I and type II methanotrophs (classes Gammaproteobacteria and Alphaproteobacteria, respectively), with predomination of type I methanotrophs. Among the latter, microorganisms related to Methylobacterpsychrophilus and Methylobacter tundripaludum, Crenothrix polyspora (a stagnant water dweller), and a number of methanotrophs belonging to unknown taxa were detected. Growth characteristics of two isolates were determined. Methylobactersp. CMS7 exhibited active growth at 4-10 degrees C, while Methylocystis sp. SB12 grew better at 20 degrees C. Experimental results confirmed the major role ofmethanotrophic gammaproteobacteria in controlling the methane emission from cold river seeps.

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

PubMed

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

2014-12-01

Methane is a potent greenhouse gas and its emission from municipal wastewater treatment plants (WWTPs) should be prevented. One way to do this is to promote the biological conversion of dissolved methane over stripping in aeration tanks. In this study, the well-established Activated Sludge Model n°1 (ASM1) and Benchmark Simulation Model n°1 (BSM1) were extended to study the influence of process design and operating parameters on biological methane oxidation. The aeration function used in BSM 1 was upgraded to more accurately describe gas-liquid transfer of oxygen and methane in aeration tanks equipped with subsurface aeration. Dissolved methane could be effectively removed in an aeration tank at an aeration rate that is in agreement with optimal effluent quality. Subsurface bubble aeration proved to be better than surface aeration, while a CSTR configuration was superior to plug flow conditions in avoiding methane emissions. The conversion of methane in the activated sludge tank benefits from higher methane concentrations in the WWTP's influent. Finally, if an activated sludge tank is aerated with methane containing off-gas, a limited amount of methane is absorbed and converted in the mixed liquor. This knowledge helps to stimulate the methane oxidizing capacity of activated sludge in order to abate methane emissions from wastewater treatment to the atmosphere. Copyright © 2014 Elsevier Ltd. All rights reserved.

The Synthesis and Characterization of Tetrakis [(p - amino phenoxy) methyl] methane

NASA Astrophysics Data System (ADS)

Peng, Yongli; Zou, Qian

2017-06-01

In order to solve the shortcomings of the cured epoxy resin poor toughness, this paper proceeded from the structural design of curing agent to synthesize a special curing agent tetrakis [(p-aminophenoxy) methyl] methane which containing both Benzene ring and amino group. A Symmetric compound of tetrakis [(p - acetamidophenoxy) methyl] methane was prepared by using simple and easy to get pentaerythritoltetratosylate and acetaminophen for raw materials, after Williamson etherification reaction intermediates for synthesis of a symmetrical structure of the compound tetrakis [(p-acetamido phenoxy) methyl] methane, then hydrolysed under acidic conditions it can be tetrakis [(p-amino phenoxy) methyl] methane. The influence of reaction time, reaction temperature and reactant ratio to production yield of tetrakis [(p - acetamidophenoxy) methyl] methane was studied by orthogonal experiment of three factors and three levels, and get the optimal process parameters: the reaction time: 16 h, the reaction temperature: 170 °C, reactant ratio, 1:5. The Structure of tetrakis [(p - acetamidophenoxy) methyl] methane and tetrakis [(p-amino phenoxy) methyl] methane were characterized by infrared and 1H-NMR.

High Coke-Resistance Pt/Mg1-xNixO Catalyst for Dry Reforming of Methane

PubMed Central

Al-Doghachi, Faris A. J.; Islam, Aminul; Zainal, Zulkarnain; Saiman, Mohd Izham; Embong, Zaidi; Taufiq-Yap, Yun Hin

2016-01-01

A highly active and stable nano structured Pt/Mg1-xNixO catalysts was developed by a simple co-precipitation method. The obtained Pt/Mg1-xNixO catalyst exhibited cubic structure nanocatalyst with a size of 50–80 nm and realized CH4 and CO2 conversions as high as 98% at 900°C with excellent stability in the dry reforming of methane. The characterization of catalyst was performed using various kinds of analytical techniques including XRD, BET, XRF, TPR-H2, TGA, TEM, FESEM, FT-IR, and XPS analyses. Characterization of spent catalyst further confirms that Pt/Mg1-xNixO catalyst has high coke-resistance for dry reforming. Thus, the catalyst demonstrated in this study, offers a promising catalyst for resolving the dilemma between dispersion and reducibility of supported metal, as well as activity and stability during high temperature reactions. PMID:26745623

Illumina sequencing-based analysis of a microbial community enriched under anaerobic methane oxidation condition coupled to denitrification revealed coexistence of aerobic and anaerobic methanotrophs.

PubMed

Siniscalchi, Luciene Alves Batista; Leite, Laura Rabelo; Oliveira, Guilherme; Chernicharo, Carlos Augusto Lemos; de Araújo, Juliana Calabria

2017-07-01

Methane is produced in anaerobic environments, such as reactors used to treat wastewaters, and can be consumed by methanotrophs. The composition and structure of a microbial community enriched from anaerobic sewage sludge under methane-oxidation condition coupled to denitrification were investigated. Denaturing gradient gel electrophoresis (DGGE) analysis retrieved sequences of Methylocaldum and Chloroflexi. Deep sequencing analysis revealed a complex community that changed over time and was affected by methane concentration. Methylocaldum (8.2%), Methylosinus (2.3%), Methylomonas (0.02%), Methylacidiphilales (0.45%), Nitrospirales (0.18%), and Methanosarcinales (0.3%) were detected. Despite denitrifying conditions provided, Nitrospirales and Methanosarcinales, known to perform anaerobic methane oxidation coupled to denitrification (DAMO) process, were in very low abundance. Results demonstrated that aerobic and anaerobic methanotrophs coexisted in the reactor together with heterotrophic microorganisms, suggesting that a diverse microbial community was important to sustain methanotrophic activity. The methanogenic sludge was a good inoculum to enrich methanotrophs, and cultivation conditions play a selective role in determining community composition.

Authigenic carbonates from methane seeps of the Congo deep-sea fan

NASA Astrophysics Data System (ADS)

Pierre, Catherine; Fouquet, Yves

2007-06-01

Submersible investigations with the ROV Victor 6000 of some pockmark structures on the seafloor of the Congo deep-sea fan have shown that they are active venting sites of methane-rich fluids, associated with abundant fauna and carbonate crusts. Moreover, methane hydrates have been observed both outcropping and deep in the sediments in the centre of the “Regab” giant pockmark. Authigenic carbonates, mostly calcite sometimes mixed with aragonite, are cementing the sedimentary matrix components and fauna; diatoms are abundant but only as moulds, indicating that biogenic silica dissolution occurred in situ synchronous with carbonate precipitation. The occurrence of diagenetic barite and pyrite in some carbonate crusts demonstrates that they can be formed either within the sulphate/methane transition zone or deeper in sulphate-depleted sediments. The oxygen isotopic compositions of the diagenetic carbonates (3.17 6.01‰ V-PDB) indicate that precipitation occurred with bottom seawater mixed with a variable contribution of water from gas hydrate decomposition. The very low carbon isotopic compositions of the diagenetic carbonates (-57.1 to -27.75‰ V-PDB) demonstrate that carbon derives mostly from the microbial oxidation of methane.

Perchlorate bioreduction linked to methane oxidation in a membrane biofilm reactor: Performance and microbial community structure.

PubMed

Xie, Ting; Yang, Qi; Winkler, Mari K H; Wang, Dongbo; Zhong, Yu; An, Hongxue; Chen, Fei; Yao, Fubin; Wang, Xiaolin; Wu, Jiawei; Li, Xiaoming

2018-06-05

Perchlorate bioreduction coupled to methane oxidation was successfully achieved without the addition of nitrate or nitrite in a membrane biofilm reactor (MBfR) inoculated with a mixture of freshwater sediments and anaerobic digester sludge as well as return activated sludge. The reactor was operated at different methane pressures (60, 40 and 20 Kpa) and influent perchlorate concentrations (1, 5 and 10 mg/L) to evaluate the biochemical process of perchlorate bioreduction coupled to methane oxidation. Perchlorate was completely reduced with a higher removal flux of 92.75 mg/m 2 ·d using methane as the sole carbon source and electron donor, other than hydrogen or other limiting organics. Quantitative real-time PCR showed that bacteria prevailed over archaea and the abundances of mcrA, pMMO, pcrA, and nirS genes were correlated with the influent perchlorate flux. High-throughput sequencing of 16S rRNA genes demonstrated that the functional community consisted of methanotrophs, methylotrophs, perchlorate-reducing bacteria, as well as various denitrifiers. Copyright © 2018 Elsevier B.V. All rights reserved.

Mechanistic insights into heterogeneous methane activation

DOE PAGES

Latimer, Allegra A.; Aljama, Hassan; Kakekhani, Arvin; ...

2017-01-11

While natural gas is an abundant chemical fuel, its low volumetric energy density has prompted a search for catalysts able to transform methane into more useful chemicals. This search has often been aided through the use of transition state (TS) scaling relationships, which estimate methane activation TS energies as a linear function of a more easily calculated descriptor, such as final state energy, thus avoiding tedious TS energy calculations. It has been shown that methane can be activated via a radical or surface-stabilized pathway, both of which possess a unique TS scaling relationship. Herein, we present a simple model tomore » aid in the prediction of methane activation barriers on heterogeneous catalysts. Analogous to the universal radical TS scaling relationship introduced in a previous publication, we show that a universal TS scaling relationship that transcends catalysts classes also seems to exist for surface-stabilized methane activation if the relevant final state energy is used. We demonstrate that this scaling relationship holds for several reducible and irreducible oxides, promoted metals, and sulfides. By combining the universal scaling relationships for both radical and surface-stabilized methane activation pathways, we show that catalyst reactivity must be considered in addition to catalyst geometry to obtain an accurate estimation for the TS energy. Here, this model can yield fast and accurate predictions of methane activation barriers on a wide range of catalysts, thus accelerating the discovery of more active catalysts for methane conversion.« less

Mechanistic insights into heterogeneous methane activation

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

Latimer, Allegra A.; Aljama, Hassan; Kakekhani, Arvin

While natural gas is an abundant chemical fuel, its low volumetric energy density has prompted a search for catalysts able to transform methane into more useful chemicals. This search has often been aided through the use of transition state (TS) scaling relationships, which estimate methane activation TS energies as a linear function of a more easily calculated descriptor, such as final state energy, thus avoiding tedious TS energy calculations. It has been shown that methane can be activated via a radical or surface-stabilized pathway, both of which possess a unique TS scaling relationship. Herein, we present a simple model tomore » aid in the prediction of methane activation barriers on heterogeneous catalysts. Analogous to the universal radical TS scaling relationship introduced in a previous publication, we show that a universal TS scaling relationship that transcends catalysts classes also seems to exist for surface-stabilized methane activation if the relevant final state energy is used. We demonstrate that this scaling relationship holds for several reducible and irreducible oxides, promoted metals, and sulfides. By combining the universal scaling relationships for both radical and surface-stabilized methane activation pathways, we show that catalyst reactivity must be considered in addition to catalyst geometry to obtain an accurate estimation for the TS energy. Here, this model can yield fast and accurate predictions of methane activation barriers on a wide range of catalysts, thus accelerating the discovery of more active catalysts for methane conversion.« less

Biogeochemical processes controlling authigenic carbonate formation within the sediment column from the Okinawa Trough

NASA Astrophysics Data System (ADS)

Li, Jiwei; Peng, Xiaotong; Bai, Shijie; Chen, Zhiyan; Van Nostrand, Joy D.

2018-02-01

Authigenic carbonates are one type of conspicuous manifestation in seep environments that can provide long-term archives of past seepage activity and methane cycling in the oceans. Comprehensive investigations of the microbial community functional structure and their roles in the process of carbonate formation are, however, lacking. In this study, the mineralogical, geochemical, and microbial functional composition were examined in seep carbonate deposits collected from the west slope of the northern section of the Okinawa Trough (OT). The aim of this work was to explore the correspondence between the mineralogical phases and microbial metabolism during carbonate deposit formation. The mineralogical analyses indicated that authigenic carbonate minerals (aragonite, magnesium-rich calcite, dolomite, ankerite and siderite) and iron-bearing minerals (limonite, chlorite, and biotite) were present in these carbonate samples. The carbon and oxygen isotopic values of the carbonate samples varied between -51.1‰ to -4.7‰ and -4.8‰ to 3.7‰, respectively. A negative linear correlation between carbon and oxygen isotopic compositions was found, indicating a mixture of methane-derived diagenetic (low δ13C/high 18O) carbonates and detrital origin (high δ13C/low 18O) carbonates at the OT. GeoChip analyses suggested that various metabolic activities of microorganisms, including methanogenesis, methane oxidation, sulfite oxidation, sulfate reduction, and metal biotransformations, all occurred during the formation process. On the basis of these findings, the following model for the methane cycle and seep carbonate deposit formation in the sediment column at the OT is proposed: (1) in the upper oxidizing zone, aerobic methane oxidation was the main way of methane consumption; (2) in the sulfate methane transition zone, sulfate-dependent AOM (anaerobic oxidation of methane) consumes methane, and authigenic minerals such as aragonite, magnesium-calcite, and sulfide minerals precipitate; (3) in the underlying sulfate depleted zone, the presence of iron-oxides supplied by hydrothermal fluids and terrestrial inputs created thermodynamically favorable conditions for Fe-dependent AOM to consume methane, and dolomite and siderite/ankerite precipitate in this zone.

Stratigraphy and structure of coalbed methane reservoirs in the United States: an overview

USGS Publications Warehouse

Pashin, J.C.

1998-01-01

Stratigraphy and geologic structure determine the shape, continuity and permeability of coal and are therefore critical considerations for designing exploration and production strategies for coalbed methane. Coal in the United states is dominantly of Pennsylvanian, Cretaceous and Tertiary age, and to date, more than 90% of the coalbed methane produced is from Pennsylvanian and cretaceous strata of the Black Warrior and San Juan Basins. Investigations of these basins establish that sequence stratigraphy is a promising approach for regional characterization of coalbed methane reservoirs. Local stratigraphic variation within these strata is the product of sedimentologic and tectonic processes and is a consideration for selecting completion zones. Coalbed methane production in the United States is mainly from foreland and intermontane basins containing diverse compression and extensional structures. Balanced structural models can be used to construct and validate cross sections as well as to quantify layer-parallel strain and predict the distribution of fractures. Folds and faults influence gas and water production in diverse ways. However, interwell heterogeneity related to fractures and shear structures makes the performance of individual wells difficult to predict.Stratigraphy and geologic structure determine the shape, continuity and permeability of coal and are therefore critical considerations for designing exploration and production strategies for coalbed methane. Coal in the United States is dominantly of Pennsylvanian, Cretaceous and Tertiary age, and to date, more than 90% of the coalbed methane produced is from Pennsylvanian and Cretaceous strata of the Black Warrior and San Juan Basins. Investigations of these basins establish that sequence stratigraphy is a promising approach for regional characterization of coalbed methane reservoirs. Local stratigraphic variation within these strata is the product of sedimentologic and tectonic processes and is a consideration for selecting completion zones. Coalbed methane production in the United States is mainly from foreland and intermontane basins containing diverse compressional and extensional structures. Balanced structural models can be used to construct and validate cross sections as well as to quantify layer-parallel strain and predict the distribution of fractures. Folds and faults influence gas and water production in diverse ways. However, interwell heterogeneity related to fractures and shear structures makes the performance of individual wells difficult to predict.

Controlled surface segregation leads to efficient coke-resistant nickel/platinum bimetallic catalysts for the dry reforming of methane

DOE PAGES

Li, Lidong; Zhou, Lu; Ould-Chikh, Samy; ...

2015-02-03

Surface composition and structure are of vital importance for heterogeneous catalysts, especially for bimetallic catalysts, which often vary as a function of reaction conditions (known as surface segregation). The preparation of bimetallic catalysts with controlled metal surface composition and structure is very challenging. In this study, we synthesize a series of Ni/Pt bimetallic catalysts with controlled metal surface composition and structure using a method derived from surface organometallic chemistry. The evolution of the surface composition and structure of the obtained bimetallic catalysts under simulated reaction conditions is investigated by various techniques, which include CO-probe IR spectroscopy, high-angle annular dark-field scanningmore » transmission electron microscopy, energy-dispersive X-ray spectroscopy, extended X-ray absorption fine structure analysis, X-ray absorption near-edge structure analysis, XRD, and X-ray photoelectron spectroscopy. It is demonstrated that the structure of the bimetallic catalyst is evolved from Pt monolayer island-modified Ni nanoparticles to core–shell bimetallic nanoparticles composed of a Ni-rich core and a Ni/Pt alloy shell upon thermal treatment. As a result, these catalysts are active for the dry reforming of methane, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure.« less

Relating Anaerobic Digestion Microbial Community and Process Function.

PubMed

Venkiteshwaran, Kaushik; Bocher, Benjamin; Maki, James; Zitomer, Daniel

2015-01-01

Anaerobic digestion (AD) involves a consortium of microorganisms that convert substrates into biogas containing methane for renewable energy. The technology has suffered from the perception of being periodically unstable due to limited understanding of the relationship between microbial community structure and function. The emphasis of this review is to describe microbial communities in digesters and quantitative and qualitative relationships between community structure and digester function. Progress has been made in the past few decades to identify key microorganisms influencing AD. Yet, more work is required to realize robust, quantitative relationships between microbial community structure and functions such as methane production rate and resilience after perturbations. Other promising areas of research for improved AD may include methods to increase/control (1) hydrolysis rate, (2) direct interspecies electron transfer to methanogens, (3) community structure-function relationships of methanogens, (4) methanogenesis via acetate oxidation, and (5) bioaugmentation to study community-activity relationships or improve engineered bioprocesses.

Copper enhances the activity and salt resistance of mixed methane-oxidizing communities.

PubMed

van der Ha, David; Hoefman, Sven; Boeckx, Pascal; Verstraete, Willy; Boon, Nico

2010-08-01

Effluents of anaerobic digesters are an underestimated source of greenhouse gases, as they are often saturated with methane. A post-treatment with methane-oxidizing bacterial consortia could mitigate diffuse emissions at such sites. Semi-continuously fed stirred reactors were used as model systems to characterize the influence of the key parameters on the activity of these mixed methanotrophic communities. The addition of 140 mg L(-1) NH (4) (+) -N had no significant influence on the activity nor did a temperature increase from 28 degrees C to 35 degrees C. On the other hand, addition of 0.64 mg L(-1) of copper(II) increased the methane removal rate by a factor of 1.5 to 1.7 since the activity of particulate methane monooxygenase was enhanced. The influence of different concentrations of NaCl was also tested, as effluents of anaerobic digesters often contain salt levels up to 10 g NaCl L(-1). At a concentration of 11 g NaCl L(-1), almost no methane-oxidizing activity was observed in the reactors without copper addition. Yet, reactors with copper addition exhibited a sustained activity in the presence of NaCl. A colorimetric test based on naphthalene oxidation showed that soluble methane monooxygenase was inhibited by copper, suggesting that the particulate methane monooxygenase was the active enzyme and thus more salt resistant. The results obtained demonstrate that the treatment of methane-saturated effluents, even those with increased ammonium (up to 140 mg L(-1) NH (4) (+) -N) and salt levels, can be mitigated by implementation of methane-oxidizing microbial consortia.

Effect of structural carbohydrates and lignin content on the anaerobic digestion of paper and paper board materials by anaerobic granular sludge.

PubMed

Gonzalez-Estrella, Jorge; Asato, Caitlin M; Jerke, Amber C; Stone, James J; Gilcrease, Patrick C

2017-05-01

Anaerobic digestion (AD) of lignocellulosic materials is commonly limited by the hydrolysis step. Unlike unprocessed lignocellulosic materials, paper and paper board (PPB) are processed for their fabrication. Such modifications may affect their methane yields and methane production rates. Previous studies have investigated the correlation between lignin and biomethane yields of unprocessed lignocellulosic materials; nevertheless, there is limited knowledge regarding the relationship between the AD kinetic parameters and composition of PPB. This study evaluated correlations of methane yields and Monod and Gompertz kinetic parameters with structural carbohydrates, lignin, and ash concentration of five types of PPBs. All components were used as single and combined independent variables in linear regressions to predict methane yield, maximum specific methanogenic activity (SMA max ), saturation constant (K s ), and lag phase (λ). Additionally, microbial community profiles were obtained for each PPB assay. Results showed methane yields ranging from 69.2 ± 8.61 to 97.2 ± 2.29% of PPB substrates provided. The highest correlation coefficients were obtained for SMA max as function of hemicellulose/(lignin + ash) (R 2  = 0.86) and for λ as a function of lignin + cellulose (R 2  = 0.85). All other parameters exhibited weaker correlations (R 2  ≤ 0.77). Relative abundance analyses revealed no major changes in the community profile for each of the substrates evaluated. The overall findings of this study are: (i) combinations of structural carbohydrates, lignin, and ash used as ratios of degradable to either non-degradable or slowly degradable fractions predict AD kinetic parameters of PPB materials better than single independent variables; and (ii) other components added during their fabrication may also influence both methane yield and kinetic parameters. Biotechnol. Bioeng. 2017;114: 951-960. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Enhancing methane production from waste activated sludge using a novel indigenous iron activated peroxidation pre-treatment process.

PubMed

Zhou, Xu; Wang, Qilin; Jiang, Guangming

2015-04-01

Methane production from anaerobic digestion of waste activated sludge (WAS) is limited by the slow hydrolysis rate and/or poor methane potential of WAS. This study presents a novel pre-treatment strategy based on indigenous iron (in WAS) activated peroxidation to enhance methane production from WAS. Pre-treatment of WAS for 30 min at 50mg H2O2/g total solids (dry weight) and pH 2.0 (iron concentration in WAS was 7 mg/g TS) substantially enhanced WAS solubilization. Biochemical methane potential tests demonstrated that methane production was improved by 10% at a digestion time of 16d after incorporating the indigenous iron activated peroxidation pre-treatment. Model-based analysis indicated that indigenous iron activated peroxidation pre-treatment improved the methane potential by 13%, whereas the hydrolysis rate was not significantly affected. The economic analysis showed that the proposed pre-treatment method can save the cost by $112,000 per year in a treatment plant with a population equivalent of 300,000. Copyright © 2015 Elsevier Ltd. All rights reserved.

Impact of hydrology on methane flux patterns in a permafrost-affected floodplain in Northeast Siberia

NASA Astrophysics Data System (ADS)

Kwon, Min Jung; Beulig, Felix; Kuesel, Kirsten; Wildner, Marcus; Heimann, Martin; Zimov, Nikita; Zimov, Sergei; Goeckede, Mathias

2015-04-01

A large fraction of organic carbon stored in Arctic permafrost soil is at risk to be decomposed and released to the atmosphere under climate change. Thawing of ice-rich permafrost will re-structure the surface topography, with potentially significant effects on hydrology: water table depth (WTD) of depressed areas will increase, while that of the surrounding area will decrease. Changes in hydrology will trigger modifications in soil and vegetation, e.g. soil temperature, vegetation and microbial community structure. All of these secondary effects will alter carbon cycle processes, with the magnitude and even sign of the net effect yet unknown. The objective of this study is to investigate effects of drainage on methane fluxes in a floodplain of the Kolyma River near Cherskii, Northeast Siberia. The study site is separated into two areas, one that has been drained since 2004, and a nearby reference site. Methane flux was measured for ~16 weeks during summer and early winter of 2013, and summer of 2014. In addition, to separate different methane emission pathways, plant-mediated methane transport (through aerenchyma) as well as the proportion of ebullition were measured in 2014. Vegetation and microbial community structures were investigated and compared. After a decade of drainage history that lowered WTD by about 20cm in the drained area, Eriophorum (cotton grass) that previously dominated have to a large part been replaced by Carex (tussock-forming sedge) and shrub species. While WTD primarily influenced the methane flux rate, this vegetation change indirectly altered the flux as well in a way that sites with Eriophorum emitted more methane. Concerning the microbial community structure, the relative abundance of methanogen and ratio of methanotrophs to methanogens were well correlated with methane flux rates, implying that the methane flux is highly influenced by microorganisms. As a consequence of these changes, in the drained area less amount of methane was produced in the first place due to less anaerobic condition, and subsequently most of it was oxidized while being transported to the atmosphere through diffusion. In fall, however, methane emission was higher in the drained site, potentially originating from stored methane during growing season or freshly produced methane in deep, relatively warmer soil layers. To summarize all effects of WTD, the drainage changed vegetation and microbial community structure, which in turn altered net methane emissions in growing season with significantly less amount of methane emission in drained site.

Rice Cluster I, an Important Group of Archaea Producing Methane in Rice Fields

NASA Astrophysics Data System (ADS)

Conrad, R.

2006-12-01

Rice fields are an important source for the greenhouse gas methane. Methane is a major degradation product of organic matter in the anoxic soil, is partially oxidized in the rhizosphere and is emitted into the atmosphere through the aerenchyma system of the plants. Anaerobic degradation of organic matter by fermenting bacteria eventually results in the production of acetate and hydrogen, the two major substrates for microbial methanogenesis. The community of methanogenic archaea consists of several major orders or families including hydrogen-utilizing Rice Cluster-I (RC-I). Environmental conditions affect the methanogenic degradation process and the community structure of the methanogenic archaea in soil and rhizosphere. For example, populations of acetoclastic Methanosaetaceae and Methanosarcinaceae are enhanced by low and high acetate concentrations, respectively. Stable isotope probing of 16S rRNA showed that RC-I methanogens are mainly active on rice roots and at low H2 concentrations. Growth and population size is largely consistent with energetic conditions. RC-I methanogens on roots seem to be responsible for methane production from plant photosynthates that account for a major part of the emitted methane. Populations of RC-I methanogens in rice field soil are also enhanced at elevated temperatures (40-50°C). Moderately thermophilic members of RC-I methanogens or other methanogenic families were found to be ubiquitously present in soils from rice fields and river marshes. The genome of a RC-I methanogen was completely sequenced out of an enrichment culture using a metagenome approach. Genes found are consistent with life in the rhizosphere and in temporarily drained, oxic soil. We found that the methanogenic community structure on the rice roots is mainly determined by the respective community structure of the soil, but is in addition affected by the rice cultivar. Rice microcosms in which soil and rice roots are mainly colonized by RC-I methanogens produce and emit more methane than when inhabited by Methanomicrobiales, indicating that the methanogenic archaeal community is an important factor for methane emission from rice fields.

Raman studies of methane-ethane hydrate metastability.

PubMed

Ohno, Hiroshi; Strobel, Timothy A; Dec, Steven F; Sloan, E Dendy; Koh, Carolyn A

2009-03-05

The interconversion of methane-ethane hydrate from metastable to stable structures was studied using Raman spectroscopy. sI and sII hydrates were synthesized from methane-ethane gas mixtures of 65% or 93% methane in ethane and water, both with and without the kinetic hydrate inhibitor, poly(N-vinylcaprolactam). The observed faster structural conversion rate in the higher methane concentration atmosphere can be explained in terms of the differences in driving force (difference in chemical potential of water in sI and sII hydrates) and kinetics (mass transfer of gas and water rearrangement). The kinetic hydrate inhibitor increased the conversion rate at 65% methane in ethane (sI is thermodynamically stable) but retards the rate at 93% methane in ethane (sII is thermodynamically stable), implying there is a complex interaction between the polymer, water, and hydrate guests at crystal surfaces.

Dynamics of the microbial community during continuous methane fermentation in continuously stirred tank reactors.

PubMed

Tang, Yue-Qin; Shigematsu, Toru; Morimura, Shigeru; Kida, Kenji

2015-04-01

Methane fermentation is an attractive technology for the treatment of organic wastes and wastewaters. However, the process is difficult to control, and treatment rates and digestion efficiency require further optimization. Understanding the microbiology mechanisms of methane fermentation is of fundamental importance to improving this process. In this review, we summarize the dynamics of microbial communities in methane fermentation chemostats that are operated using completely stirred tank reactors (CSTRs). Each chemostat was supplied with one substrate as the sole carbon source. The substrates include acetate, propionate, butyrate, long-chain fatty acids, glycerol, protein, glucose, and starch. These carbon sources are general substrates and intermediates of methane fermentation. The factors that affect the structure of the microbial community are discussed. The carbon source, the final product, and the operation conditions appear to be the main factors that affect methane fermentation and determine the structure of the microbial community. Understanding the structure of the microbial community during methane fermentation will guide the design and operation of practical wastewater treatments. Copyright © 2014 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Methane combustion reactivity during the metal→metallic oxide transformation of Pd-Pt catalysts: Effect of oxygen pressure

NASA Astrophysics Data System (ADS)

Qi, Wenjie; Ran, Jingyu; Zhang, Zhien; Niu, Juntian; Zhang, Peng; Fu, Lijuan; Hu, Bo; Li, Qilai

2018-03-01

Density functional theory combined with kinetic models were used to probe different kinetics consequences by which methane activation on different oxygen chemical potential surfaces as oxygen pressure increased. The metallic oxide → metal transformation temperature of Pd-Pt catalysts increased with the increase of the Pd content or/and O2 pressure. The methane conversion rate on Pt catalyst increased and then decreased to a constant value when increasing the O2 pressure, and Pd catalyst showed a poor activity performance in the case of low O2 pressure. Moreover, its activity increased as the oxygen chemical potential for O2 pressure increased in the range of 2.5-10 KPa. For metal clusters, the Csbnd H bond and Odbnd O bond activation steps occurred predominantly on *-* site pairs. The methane conversion rate was determined by O2 pressure because the adsorbed O atoms were rapidly consumed by other adsorbed species in this kinetic regime. As the O2 pressure increased, the metallic active sites for methane activation were decreased and there was no longer lack of adsorbed O atoms, resulting in the decrease of the methane conversion rate. Furthermore, when the metallic surfaces were completely covered by adsorbed oxygen atoms at higher oxygen chemical potentials, Pt catalyst showed a poor activity due to a high Csbnd H bond activation barrier on O*sbnd O*. In the case of high O2 pressure, Pd atoms preferred to segregate to the active surface of Pd-Pt catalysts, leading to the formation of PdO surfaces. The increase of Pd segregation promoted a subsequent increase in active sites and methane conversion rate. The PdO was much more active than metallic and O* saturated surfaces for methane activation, inferred from the theory and experimental study. Pd-rich bimetallic catalyst (75% molar Pd) showed a dual high methane combustion activity on O2-poor and O2-rich conditions.

Dissociation behavior of methane--ethane mixed gas hydrate coexisting structures I and II.

PubMed

Kida, Masato; Jin, Yusuke; Takahashi, Nobuo; Nagao, Jiro; Narita, Hideo

2010-09-09

Dissociation behavior of methane-ethane mixed gas hydrate coexisting structures I and II at constant temperatures less than 223 K was studied with use of powder X-ray diffraction and solid-state (13)C NMR techniques. The diffraction patterns at temperatures less than 203 K showed both structures I and II simultaneously convert to Ih during the dissociation, but the diffraction pattern at temperatures greater than 208 K showed different dissociation behavior between structures I and II. Although the diffraction peaks from structure II decreased during measurement at constant temperatures greater than 208 K, those from structure I increased at the initial step of dissociation and then disappeared. This anomalous behavior of the methane-ethane mixed gas hydrate coexisting structures I and II was examined by using the (13)C NMR technique. The (13)C NMR spectra revealed that the anomalous behavior results from the formation of ethane-rich structure I. The structure I hydrate formation was associated with the dissociation rate of the initial methane-ethane mixed gas hydrate.

Investigating Microbial Activity in Diazotrophic Methane Seep Sediment via Transcript Analysis and Single-Cell FISH-NanoSIMS

NASA Astrophysics Data System (ADS)

Dekas, A. E.; Connon, S. A.; Chadwick, G.; Orphan, V. J.

2012-12-01

Methane seep microbial ecosystems are phylogenetically diverse and physiologically complex, and require culture-independent techniques to accurately investigate metabolic activity. In the present study we combine an RNA analysis of four key microbial genes with FISH-NanoSIMS analysis of single cells to determine the diversity of nitrogen fixing microorganisms (diazotrophs) present at a deep-sea methane-seeping site, as well as investigate the methane-dependency of a variety of community members. Recently, methane-dependent nitrogen fixation was observed in Mound 12 Costa Rica sediments, and was spatially correlated with the abundance of aggregates of anaerobic methanotrophic archaea (ANME) and sulfate reducing bacterial symbionts (SRB). Combined with the detection of 15N uptake from 15N2 in these aggregates, this suggested that the ANME-SRB aggregates are the primary diazotrophs in seep sediment. However, the diversity of dinitrogenase reductase (nifH) sequences recovered from several deep-sea locales, including Mound 12, suggests a greater diversity of diazotrophs in marine sediment. To investigate the activity of these potential diazotrophs in Mound 12 sediment, we investigated a suite of RNA transcripts in 15N2 incubations in both the presence and absence of methane: nifH, bacterial 16S rRNA, methyl coenzyme M reductase A (mcrA), and adenosine-5'-phosposulfate reductase alpha subunit (aprA). No nifH transcripts were recovered in incubations without methane, consistent with previous measurements lacking 15N2 uptake in the same sediments. The activity of the bacterial community in general, assessed by variable transcription, was also greatly affected by the presence or absence of methane. Single-cell fluorescence in situ hybridization coupled to nanoscale secondary ion mass spectrometry (FISH-NanoSIMS) was employed to confirm diazotrophic activity (15N2 uptake) and protein synthesis (15NH4+ uptake) of particular species implicated as ecologically important by the pattern of transcripts recovered in the mesocosm experiments. This analysis revealed 15N enrichment in free-living (i.e. non-ANME associated) members of the Desulfobulbaceae in 15N2 incubations with methane, while free-living Desulfosarcina/Desulfococcus cells, as well as nearly 40 unidentified DAPI-stained cells, were not 15N enriched. However, further NanoSIMS analyses of DSB in a variety of incubation conditions suggests that this enrichment may be due to N sharing between the ANME and DSB while in tight physical association, and then subsequent dissociation, rather than nitrogen fixation by the DSB. If true, this is an excellent example of the potential pitfalls of single cell stable isotope labeling experiments, and potential false positives due to the recycling of labeled material between (even transiently) closely associated symbionts. This work highlights both the utility of transcript analysis as a hypothesis-generator for direct analyses of microbial activity via stable isotope labeling, as well as the need to contextualize labeling experiments with investigations of microbial community structure.

[In situ Raman spectroscopic observation of micro-processes of methane hydrate formation and dissociation].

PubMed

Liu, Chang-Ling; Ye, Yu-Guang; Meng, Qing-Guo; Lü, Wan-Jun; Wang, Fei-Fei

2011-06-01

Micro laser Raman spectroscopic technique was used for in situ observation of the micro-processes of methane hydrate formed and decomposed in a high pressure transparent capillary. The changes in clathrate structure of methane hydrate were investigated during these processes. The results show that, during hydrate formation, the Raman peak (2 917 cm(-1)) of methane gas gradually splits into two peaks (2 905 and 2 915 cm(-1)) representing large and small cages, respectively, suggesting that the dissolved methane molecules go into two different chemical environments. In the meantime, the hydrogen bonds interaction is strengthened because water is changing from liquid to solid state gradually. As a result, the O-H stretching vibrations of water shift to lower wavenumber. During the decomposition process of methane hydrates, the Raman peaks of the methane molecules both in the large and small cages gradually clear up, and finally turn into a single peak of methane gas. The experimental results show that laser Raman spectroscopy can accurately demonstrate some relevant information of hydrate crystal structure changes during the formation and dissociation processes of methane hydrate.

Theoretical and Experimental Approaches towards study of Methane Occupation Dynamics within Gas Hydrates

NASA Astrophysics Data System (ADS)

Mendonca, P.; Shemella, P.; Nayak, S.; Sharma, A.

2006-12-01

Hydrate structures of hydrocarbon (commonly methane hydrates) within the continental shelf regions are considered a huge energy resource since they are a significant reservoir for terrestrial carbon. Any changes, abrupt or continual, will have an impact on the carbon (as well as water) cycle. However, tapping into this reservoir for energy resource has been challenging from both technical and scientific fronts primarily because any rapid release of methane (CH4) will likely have serious impact on the global climate of Earth as well as the stability of the continental shelf. While fossil fuel combustion derived CO2 in the atmosphere is considered a major contributor to global warming, the massive amounts of methane release from the gas hydrates has been a point of debate for its impact on the global climate. Due to the lack of a clear physical mechanism for such structural destabilization, environmental changes within the ocean setting (viz. temperature, salinity or biology) are typically assigned as possible causes. A good kinetic model that ties into structural instability of these essentially non-stoichiometric compounds at both the macromolecular (thermodynamic) and nanometric scale is essential. Preliminary experiments on single crystal methane hydrate high pressure phase (~1.0GPa) indicate a measurable kinetics of methane diffusion upon bringing structural disorder to the single crystal. Although there have been several kinetic studies of gas-hydrate nucleation and dissociation, systematic study of kinetics (and dynamics) of diffusion based changes within the gas hydrates has been lacking. In addition to experimental data on single crystal methane hydrates, we will present a first principle study on the structure, energetic, and dynamics of sI phase methane hydrate. We use density functional theory to study the energetic effect of the occupancy of neighboring cages in a cluster model system consisting of two sI gas hydrates. In this situation there can be two, one, or no methane, and we find that the binding for the first methane is exothermic. The second methane binding is endothermic, suggesting that the stability of a methane molecule is determined by the occupancy of adjacent cages. Using these results, we will present the calculated binding energies of a periodic system based on crystal structure data and compare them to the cluster method. This combined experimental and theoretical investigation is aimed at generating fundamental dataset that can be tested for the broader impact of such processes on the global carbon cycle.

Combined free nitrous acid and hydrogen peroxide pre-treatment of waste activated sludge enhances methane production via organic molecule breakdown

PubMed Central

Zhang, Tingting; Wang, Qilin; Ye, Liu; Batstone, Damien; Yuan, Zhiguo

2015-01-01

This study presents a novel pre-treatment strategy using combined free nitrous acid (FNA i.e. HNO2) and hydrogen peroxide (H2O2) to enhance methane production from WAS, with the mechanisms investigated bio-molecularly. WAS from a full-scale plant was treated with FNA alone (1.54 mg N/L), H2O2 alone (10–80 mg/g TS), and their combinations followed by biochemical methane potential tests. Combined FNA and H2O2 pre-treatment substantially enhanced methane potential of WAS by 59–83%, compared to 13–23% and 56% with H2O2 pre-treatment alone and FNA pre-treatment alone respectively. Model-based analysis indicated the increased methane potential was mainly associated with up to 163% increase in rapidly biodegradable fraction with combined pre-treatment. The molecular weight distribution and chemical structure analyses revealed the breakdown of soluble macromolecules with the combined pre-treatment caused by the deamination and oxidation of the typical functional groups in proteins, polysaccharides and phosphodiesters. These changes likely improved the biodegradability of WAS. PMID:26565653

Relationships between structure and function: System structure matters whether you are in a wetland or a college classroom

NASA Astrophysics Data System (ADS)

Andrews, Sarah Elizabeth

Part I of this dissertation describes two research projects I undertook to understand how structure influences function in freshwater wetlands. In the first study I tested the hypothesis that wetland structure (created versus natural) would influence function (methane cycling). Created wetlands had reduced rates of potential methane production and potential methane oxidation compared to natural wetlands; this was most likely explained by differences in edaphic factors that characterized each wetland, particularly soil moisture and soil organic matter. In the second study (Andrews et al. 2013), I tested the hypothesis that plant community structure (functional group composition, richness, presence/absence) would influence function (methane and iron cycling) in wetland mesocosms. Plant functional group richness was less important than the type of vegetation present: the presence of perennial vegetation (reeds or tussocks) led to increased rates of potential iron reduction compared to when only annual vegetation was present. Part II of this dissertation describes research I undertook to understand how structure influences function in an undergraduate soil science course. In the first study I tested the hypothesis that course structure (traditional versus studio) would influence function (student performance) in the course. Students in the studio course outperformed students in the traditional course; there was also a decrease in the fail rate. In the second study I looked at students' perspectives on their learning and experiences (function) in the studio course and asked whether students' epistemological development influenced this function. Interviews with students revealed that active learning, the integrated nature of the course, community, and variety of learning and assessment methods helped student learning. Students' epistemological development (interpreted from the Measure of Epistemological Reflection) permeated much of what they spoke about during the interviews. There was also evidence that the studio structure may help promote epistemological growth via "sneaky learning" and an expanded role of peers. The studies in Part I show that differences in structure affect function in freshwater wetland systems and the studies in Part II show that structure affects function in an undergraduate introductory soil science course. Thus, system structure matters whether you are in a wetland or a college classroom.

Reconstructing the Aliso Canyon natural gas leak incident

NASA Astrophysics Data System (ADS)

Duren, R. M.; Yadav, V.; Verhulst, K. R.; Thorpe, A. K.; Hopkins, F. M.; Prasad, K.; Kuai, L.; Thompson, D. R.; Wong, C.; Sander, S. P.; Mueller, K. L.; Nehrkorn, T.; Lee, M.; Hulley, G. C.; Johnson, W. R.; Aubrey, A. D.; Whetstone, J. R.; Miller, C. E.

2016-12-01

Natural gas is a key energy source and presents significant policy challenges including energy reliability and the potential for fugitive methane emissions. The well blowout reported in October 2015 at the Aliso Canyon underground gas storage facility near Porter Ranch, California and subsequent uncontrolled venting was the largest single anthropogenic methane source known to date. Multiple independent estimates indicate that this super-emitter source rivaled the normal methane flux of the entire South Coast Air Basin (SoCAB) for several months until the well was plugged. The complexity of the event and logistical challenges - particularly in the initial weeks - presented significant barriers to estimating methane losses. Additionally, accounting for total gas lost is necessary but not sufficient for understanding the sequence of events and the controlling physical processes. We used a tiered system of observations to assess methane emissions from the Aliso Canyon incident. To generate a complete flux time-series, we applied tracer-transport models and tracer-tracer techniques to persistent, multi-year atmospheric methane observations from a network of surface in-situ and remote-sensing instruments. To study the fine spatio-temporal structure of methane plumes and understand the changing source morphology, we conducted intensive mobile surface campaigns, deployed airborne imaging spectrometers, requested special observations from two satellites, and employed large eddy simulations. Through a synthesis analysis we assessed methane fluxes from Aliso Canyon before, during and after the reported incident. We compared our fine scale spatial data with bottom-up data and reports of activity at the facility to better understand the controlling processes. We coordinated with California stakeholder agencies to validate and interpret these results and to consider the potential broader implications on underground gas storage and future priorities for methane monitoring.

The close relation between Lactococcus and Methanosaeta is a keystone for stable methane production from molasses wastewater in a UASB reactor.

PubMed

Kim, Tae Gwan; Yun, Jeonghee; Cho, Kyung-Suk

2015-10-01

The up-flow anaerobic sludge blanket (UASB) reactor is a promising method for the treatment of high-strength industrial wastewaters due to advantage of its high treatment capacity and settleable suspended biomass retention. Molasses wastewater as a sugar-rich waste is one of the most valuable raw material for bioenergy production due to its high organic strength and bioavailability. Interpretation for complex interactions of microbial community structures and operational parameters can help to establish stable biogas production. RNA-based approach for biogas production systems is recommended for analysis of functionally active community members which are significantly underestimated. In this study, methane production and active microbial community were characterized in an UASB reactor using molasses wastewater as feedstock. The UASB reactor achieved a stable process performance at an organic loading rate of 1.7~13.8-g chemical oxygen demand (COD,·L(-1) day(-1); 87-95 % COD removal efficiencies), and the maximum methane production rate was 4.01 L-CH4·at 13.8 g-COD L(-1) day(-1). Lactococcus and Methanosaeta were comprised up to 84 and 80 % of the active bacterial and archaeal communities, respectively. Network analysis of reactor performance and microbial community revealed that Lactococcus and Methanosaeta were network hub nodes and positively correlated each other. In addition, they were positively correlated with methane production and organic loading rate, and they shared the other microbial hub nodes as neighbors. The results indicate that the close association between Lactococcus and Methanosaeta is responsible for the stable production of methane in the UASB reactor using molasses wastewater.

Bioaugmentation of anaerobic sludge digestion with iron-reducing bacteria: process and microbial responses to variations in hydraulic retention time.

PubMed

Baek, Gahyun; Kim, Jaai; Shin, Seung Gu; Lee, Changsoo

2016-01-01

Although anaerobic digestion (AD) is a widely used option to manage waste activated sludge (WAS), there are some drawbacks related to its slow reaction rate and low energy productivity. This study examined an anaerobic WAS digester, augmented with an iron-reducing microbial consortium, relative to changes in microbial community structure and process performance at decreasing hydraulic retention times (HRTs) of 20 to 10 days. The enhanced methanation performance (approximately 40 % increase in methane yield) by the bioaugmentation was sustained until the HRT was decreased to 12.5 days, under Fe(3+)-rich conditions (ferric oxyhydroxide, 20 mM Fe). Enhanced iron-reducing activity was evidenced by the increased Fe(2+) to total Fe ratio maintained above 50 % during the stable operational phases. A further decrease in HRT to 10 days resulted in a significant performance deterioration, along with a drop in the Fe(2+) to total Fe ratio to <35 %, after four turnovers of operation. Prevailing existence of putative iron-reducing bacteria (IRBs) was identified by denaturing gradient gel electrophoresis (DGGE), with Spirochaetaceae- and Thauera-related organisms being dominant members, and clear dominance shifts among them with respect to decrease in HRT were observed. Lowering HRT led to evident shifts in bacterial community structure likely associated with washout of IRBs, leading to decreases in iron respiration activity and AD performance at a lower HRT. The bacterial community structure shifted dynamically over phases, and the community transitions correlated well with the changes in process performance. Overall, the combined biostimulation and bioaugmentation investigated in this study proved effective for enhanced methane recovery from anaerobic WAS digestion, which suggests an interesting potential for high-rate AD.

Changes in methane emission and microbial community structure in a Phragmites australis-expanding tidal marsh of a temperature region

NASA Astrophysics Data System (ADS)

Kim, J.; Lee, J.; Kang, H.

2017-12-01

Phragmites australis is one of the representative vegetation of coastal wetlands which is distributed in North America, East Asia and European Countries. In North America, P. australis has invaded large areas of coastal wetlands, which causes various ecological problems such as increases in methane emission and reduction in biodiversity. In South Korea, P. australis is rapidly expanded in tidal marshes in Suncheon Bay. The expansion of P. australis enhanced methane emission by increasing dissolved organic carbon and soil moisture, and changing in relative abundances of methanogen, methanotroph, and sulfate reducing bacteria. Microbial community structure might be also shifted and affect methane cycle, but accurate observation on microbial community structure has not been fully illustrated yet. Therefore, we tried to monitor the changing microbial community structure due to P. australis expansion by using Next Generation Sequencing (NGS). NGS results showed that microbial community was substantially changed with the expansion. We also observed seasonal variations and chronosequence of microbial community structures along the expansion of P. australis, which showed distinctive changing patterns. P. australis expansion substantially affected microbial community structure in tidal marsh which may play an important role in methane cycle in tidal marshes.

Activity and interactions of methane seep microorganisms assessed by parallel transcription and FISH-NanoSIMS analyses

PubMed Central

Dekas, Anne E; Connon, Stephanie A; Chadwick, Grayson L; Trembath-Reichert, Elizabeth; Orphan, Victoria J

2016-01-01

To characterize the activity and interactions of methanotrophic archaea (ANME) and Deltaproteobacteria at a methane-seeping mud volcano, we used two complimentary measures of microbial activity: a community-level analysis of the transcription of four genes (16S rRNA, methyl coenzyme M reductase A (mcrA), adenosine-5′-phosphosulfate reductase α-subunit (aprA), dinitrogenase reductase (nifH)), and a single-cell-level analysis of anabolic activity using fluorescence in situ hybridization coupled to nanoscale secondary ion mass spectrometry (FISH-NanoSIMS). Transcript analysis revealed that members of the deltaproteobacterial groups Desulfosarcina/Desulfococcus (DSS) and Desulfobulbaceae (DSB) exhibit increased rRNA expression in incubations with methane, suggestive of ANME-coupled activity. Direct analysis of anabolic activity in DSS cells in consortia with ANME by FISH-NanoSIMS confirmed their dependence on methanotrophy, with no 15NH4+ assimilation detected without methane. In contrast, DSS and DSB cells found physically independent of ANME (i.e., single cells) were anabolically active in incubations both with and without methane. These single cells therefore comprise an active ‘free-living' population, and are not dependent on methane or ANME activity. We investigated the possibility of N2 fixation by seep Deltaproteobacteria and detected nifH transcripts closely related to those of cultured diazotrophic Deltaproteobacteria. However, nifH expression was methane-dependent. 15N2 incorporation was not observed in single DSS cells, but was detected in single DSB cells. Interestingly, 15N2 incorporation in single DSB cells was methane-dependent, raising the possibility that DSB cells acquired reduced 15N products from diazotrophic ANME while spatially coupled, and then subsequently dissociated. With this combined data set we address several outstanding questions in methane seep microbial ecosystems and highlight the benefit of measuring microbial activity in the context of spatial associations. PMID:26394007

Activity and interactions of methane seep microorganisms assessed by parallel transcription and FISH-NanoSIMS analyses

DOE PAGES

Dekas, Anne E.; Connon, Stephanie A.; Chadwick, Grayson L.; ...

2015-09-22

To characterize the activity and interactions of methanotrophic archaea (ANME) and Deltaproteo-bacteria at a methane-seeping mud volcano, we used two complimentary measures of microbial activity: a community-level analysis of the transcription of four genes (16S rRNA, methyl coenzyme M reductase A (mcrA), adenosine-5'-phosphosulfate reductase α-subunit (aprA), dinitrogenase reductase (nifH)), and a single-cell-level analysis of anabolic activity using fluorescence in situ hybridization coupled to nanoscale secondary ion mass spectrometry (FISH-NanoSIMS). Transcript analysis revealed that members of the deltaproteobacterial groups Desulfosarcina/Desulfococcus (DSS) and Desulfobulbaceae (DSB) exhibit increased rRNA expression in incubations with methane, suggestive of ANME-coupled activity. Direct analysis of anabolic activity in DSS cells in consortia with ANME by FISH-NanoSIMS confirmed their dependence on methanotrophy, with no 15NHmore » $$+\\atop{4}$$ assimilation detected without methane. In contrast, DSS and DSB cells found physically independent of ANME (i.e., single cells) were anabolically active in incubations both with and without methane. These single cells therefore comprise an active ‘free-living’ population, and are not dependent on methane or ANME activity. We investigated the possibility of N 2 fixation by seep Deltaproteobacteria and detected nifH transcripts closely related to those of cultured diazotrophic Deltaproteobacteria. However, nifH expression was methane-dependent. 15N 2 incorporation was not observed in single DSS cells, but was detected in single DSB cells. Interestingly, 15N 2 incorporation in single DSB cells was methane-dependent, raising the possibility that DSB cells acquired reduced 15N products from diazotrophic ANME while spatially coupled, and then subsequently dissociated. In conclusion, with this combined data set we address several outstanding questions in methane seep microbial ecosystems and highlight the benefit of measuring microbial activity in the context of spatial associations.« less

Single cell activity reveals direct electron transfer in methanotrophic consortia

NASA Astrophysics Data System (ADS)

McGlynn, Shawn E.; Chadwick, Grayson L.; Kempes, Christopher P.; Orphan, Victoria J.

2015-10-01

Multicellular assemblages of microorganisms are ubiquitous in nature, and the proximity afforded by aggregation is thought to permit intercellular metabolic coupling that can accommodate otherwise unfavourable reactions. Consortia of methane-oxidizing archaea and sulphate-reducing bacteria are a well-known environmental example of microbial co-aggregation; however, the coupling mechanisms between these paired organisms is not well understood, despite the attention given them because of the global significance of anaerobic methane oxidation. Here we examined the influence of interspecies spatial positioning as it relates to biosynthetic activity within structurally diverse uncultured methane-oxidizing consortia by measuring stable isotope incorporation for individual archaeal and bacterial cells to constrain their potential metabolic interactions. In contrast to conventional models of syntrophy based on the passage of molecular intermediates, cellular activities were found to be independent of both species intermixing and distance between syntrophic partners within consortia. A generalized model of electric conductivity between co-associated archaea and bacteria best fit the empirical data. Combined with the detection of large multi-haem cytochromes in the genomes of methanotrophic archaea and the demonstration of redox-dependent staining of the matrix between cells in consortia, these results provide evidence for syntrophic coupling through direct electron transfer.

Co-aromatization of olefin and methane over Ag-Ga/ZSM-5 catalyst at low temperature

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

He, Peng; Gatip, Richard; Yung, Matthew

The massive exploitation of shale gas in the past decade has boosted the production of natural gas and reduced its price dramatically. The methane activation and following conversion into more valuable fuels and chemicals have thus become more and more attractive, while the introduction of hydrocarbons to enhance the methane activation at mild conditions represents a promising approach. In the present work, the co-aromatization of methane with propylene has been studied at 400 °C. The presence of methane would increase the toluene to benzene ratio as well as the average carbon number of the formed liquid aromatic products compared tomore » its propylene alone counterpart. Among the gas products, the formations of C 3H 8, C 4H 8 and C 4H 10 also get promoted when methane is present. The incorporation of methane into the product molecules is also directly evidenced by the 1H, 2D and 13C NMR spectroscopy of the liquid products obtained from the reaction between propylene (or styrene) and isotope labelled methane. Hydrogen from methane would contribute a large portion of the hydrogen in the product molecules, while the benzylic and aromatic hydrogen sites are favored compared with those on the alkyl side chains. The activation of methane is also observed in the DRIFT spectra when deuterium enriched methane is engaged as the methane source and evidenced by the escalated exothermic feature when olefin aromatization takes place under methane environment. The excellent catalytic performance of Ag-Ga/ZSM-5 might be because of the better dispersion of Ag and Ga on the ZSM-5 surface and moderate amount of strong Brosted and Lewis surface acid sites. All the observations suggest that methane might be activated nonoxidatively and converted into aromatics if suitable catalyst is charged under the assistance of co-existing olefin. In conclusion, the reported synergetic effect could potentially lead to the more economic utilization of abundant natural gas and petrochemical intermediates.« less

Co-aromatization of olefin and methane over Ag-Ga/ZSM-5 catalyst at low temperature

DOE PAGES

He, Peng; Gatip, Richard; Yung, Matthew; ...

2017-04-22

The massive exploitation of shale gas in the past decade has boosted the production of natural gas and reduced its price dramatically. The methane activation and following conversion into more valuable fuels and chemicals have thus become more and more attractive, while the introduction of hydrocarbons to enhance the methane activation at mild conditions represents a promising approach. In the present work, the co-aromatization of methane with propylene has been studied at 400 °C. The presence of methane would increase the toluene to benzene ratio as well as the average carbon number of the formed liquid aromatic products compared tomore » its propylene alone counterpart. Among the gas products, the formations of C 3H 8, C 4H 8 and C 4H 10 also get promoted when methane is present. The incorporation of methane into the product molecules is also directly evidenced by the 1H, 2D and 13C NMR spectroscopy of the liquid products obtained from the reaction between propylene (or styrene) and isotope labelled methane. Hydrogen from methane would contribute a large portion of the hydrogen in the product molecules, while the benzylic and aromatic hydrogen sites are favored compared with those on the alkyl side chains. The activation of methane is also observed in the DRIFT spectra when deuterium enriched methane is engaged as the methane source and evidenced by the escalated exothermic feature when olefin aromatization takes place under methane environment. The excellent catalytic performance of Ag-Ga/ZSM-5 might be because of the better dispersion of Ag and Ga on the ZSM-5 surface and moderate amount of strong Brosted and Lewis surface acid sites. All the observations suggest that methane might be activated nonoxidatively and converted into aromatics if suitable catalyst is charged under the assistance of co-existing olefin. In conclusion, the reported synergetic effect could potentially lead to the more economic utilization of abundant natural gas and petrochemical intermediates.« less

Activities That Reduce Global Anthropogenic Methane Emissions Grant - Closed Announcement FY 2012

EPA Pesticide Factsheets

Grant to fund eligible projects for activities that advance near-term, cost-effective methane abatement or recovery and use as a clean energy source, and support the goals of of theGlobal Methane Initiative.

Distribution and Rate of Methane Oxidation in Sediments of the Florida Everglades †

PubMed Central

King, Gary M.; Roslev, Peter; Skovgaard, Henrik

1990-01-01

Rates of methane emission from intact cores were measured during anoxic dark and oxic light and dark incubations. Rates of methane oxidation were calculated on the basis of oxic incubations by using the anoxic emissions as an estimate of the maximum potential flux. This technique indicated that methane oxidation consumed up to 91% of the maximum potential flux in peat sediments but that oxidation was negligible in marl sediments. Oxygen microprofiles determined for intact cores were comparable to profiles measured in situ. Thus, the laboratory incubations appeared to provide a reasonable approximation of in situ activities. This was further supported by the agreement between measured methane fluxes and fluxes predicted on the basis of methane profiles determined by in situ sampling of pore water. Methane emissions from peat sediments, oxygen concentrations and penetration depths, and methane concentration profiles were all sensitive to light-dark shifts as determined by a combination of field and laboratory analyses. Methane emissions were lower and oxygen concentrations and penetration depths were higher under illuminated than under dark conditions; the profiles of methane concentration changed in correspondence to the changes in oxygen profiles, but the estimated flux of methane into the oxic zone changed negligibly. Sediment-free, root-associated methane oxidation showed a pattern similar to that for methane oxidation in the core analyses: no oxidation was detected for roots growing in marl sediment, even for roots of Cladium jamaicense, which had the highest activity for samples from peat sediments. The magnitude of the root-associated oxidation rates indicated that belowground plant surfaces may not markedly increase the total capacity for methane consumption. However, the data collectively support the notion that the distribution and activity of methane oxidation have a major impact on the magnitude of atmospheric fluxes from the Everglades. PMID:16348299

Rain increases methane production and methane oxidation in a boreal thermokarst bog

NASA Astrophysics Data System (ADS)

Neumann, R. B.; Moorberg, C.; Turner, J.; Wong, A.; Waldrop, M. P.; Euskirchen, E. S.; Edgar, C.; Turetsky, M. R.

2017-12-01

Bottom-up biogeochemical models of wetland methane emissions simulate the response of methane production, oxidation and transport to wetland conditions and environmental forcings. One reason for mismatches between bottom-up and top-down estimates of emissions is incomplete knowledge of factors and processes that control microbial rates and methane transport. To advance mechanistic understanding of wetland methane emissions, we conducted a multi-year field investigation and plant manipulation experiment in a thermokarst bog located near Fairbanks, Alaska. The edge of the bog is experiencing active permafrost thaw, while the center of the bog thawed 50 to 100 years ago. Our study, which captured both an average year and two of the wettest years on record, revealed how rain interacts with vascular vegetation and recently thawed permafrost to affect methane emissions. In the floating bog, rain water warmed and oxygenated the subsurface, but did not alter soil saturation. The warmer peat temperatures increased both microbial methane production and plant productivity at the edge of the bog near the actively thawing margin, but minimally altered microbial and plant activity in the center of the bog. These responses indicate processes at the edge of the bog were temperature limited while those in the center were not. The compounding effect of increased microbial activity and plant productivity at the edge of the bog doubled methane emissions from treatments with vascular vegetation during rainy years. In contrast, methane emissions from vegetated treatments in the center of the bog did not change with rain. The oxygenating influence of rain facilitated greater methane oxidation in treatments without vascular vegetation, which offset warming-induced increases in methane production at the edge of the bog and decreased methane emissions in the center of the bog. These results elucidate the complex and spatially variable response of methane production and oxidation in thermokarst bogs to energy and oxygen inputs from rain, and have implications for how boreal wetland methane emissions may respond in the future to altered precipitation patterns. Advective delivery of energy and oxygen to wetland subsoils via rainwater is not currently a mechanism included in bottom-up wetland methane models.

Effects of Nitrogen Load on the Function and Diversity of Methanotrophs in the Littoral Wetland of a Boreal Lake

PubMed Central

Siljanen, Henri M. P.; Saari, Anne; Bodrossy, Levente; Martikainen, Pertti J.

2012-01-01

Methane is the second most abundant greenhouse gas in the atmosphere. A major part of the total methane emissions from lake ecosystems is emitted from littoral wetlands. Methane emissions are significantly reduced by methanotrophs, as they use methane as their sole energy and carbon source. Methanotrophic activity can be either activated or inhibited by nitrogen. However, the effects of nitrogen on methanotrophs in littoral wetlands are unknown. Here we report how nitrogen loading in situ affected the function and diversity of methanotrophs in a boreal littoral wetland. Methanotrophic community composition and functional diversity were analyzed with a particulate methane monooxygenase (pmoA) gene targeted microarray. Nitrogen load had no effects on methane oxidation potential and methane fluxes. Nitrogen load activated pmoA gene transcription of type I (Methylobacter, Methylomonas, and LW21-freshwater phylotypes) methanotrophs, but decreased the relative abundance of type II (Methylocystis, Methylosinus trichosporium, and Methylosinus phylotypes) methanotrophs. Hence, the overall activity of a methanotroph community in littoral wetlands is not affected by nitrogen leached from the catchment area. PMID:22363324

Dry reforming of methane on a highly-active Ni-CeO 2 catalyst: Effects of metal-support interactions on C–H bond breaking

DOE PAGES

Liu, Zongyuan; Grinter, David C.; Lustemberg, Pablo G.; ...

2016-05-04

Ni-CeO 2 is a highly efficient, stable and non-expensive catalyst for methane dry reforming at relative low temperatures (700 K). The active phase of the catalyst consists of small nanoparticles of nickel dispersed on partially reduced ceria. Experiments of ambient pressure XPS indicate that methane dissociates on Ni/CeO 2 at temperatures as low as 300 K, generating CH x and CO x species on the surface of the catalyst. Strong metal–support interactions activate Ni for the dissociation of methane. The results of density-functional calculations show a drop in the effective barrier for methane activation from 0.9 eV on Ni(111) tomore » only 0.15 eV on Ni/CeO 2–x(111). At 700 K, under methane dry reforming conditions, no signals for adsorbed CH x or C species are detected in the C1s XPS region. As a result, the reforming of methane proceeds in a clean and efficient way.« less

30 CFR 77.201-1 - Tests for methane; qualified person; use of approved device.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Tests for methane; qualified person; use of... WORK AREAS OF UNDERGROUND COAL MINES Surface Installations § 77.201-1 Tests for methane; qualified person; use of approved device. Tests for methane in structures, enclosures, or other facilities, in...

30 CFR 77.201-1 - Tests for methane; qualified person; use of approved device.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 30 Mineral Resources 1 2011-07-01 2011-07-01 false Tests for methane; qualified person; use of... WORK AREAS OF UNDERGROUND COAL MINES Surface Installations § 77.201-1 Tests for methane; qualified person; use of approved device. Tests for methane in structures, enclosures, or other facilities, in...

Coalbed Methane Outreach Program

EPA Pesticide Factsheets

Coalbed Methane Outreach Program, voluntary program seeking to reduce methane emissions from coal mining activities. CMOP promotes profitable recovery/use of coal mine methane (CMM), addressing barriers to using CMM instead of emitting it to atmosphere.

Synthesis of ZSM-5 zeolite from coal fly ash and rice husk: characterization and application for partial oxidation of methane to methanol

NASA Astrophysics Data System (ADS)

Krisnandi, Y. K.; Yanti, F. M.; Murti, S. D. S.

2017-04-01

Indonesian fly ash (SiO2/Al2O3 mole ratio = 3.59) was used together with rice husk (SiO2 92%) as raw material for mesoporous ZSM-5 zeolite synthesis. Prior being used, coal fly ash and rice husk were subjected to pre-treatment in order to extract silicate (SiO4 4-) and aluminate (AlO4 5-) and to remove the impurities. Then the ZSM-5 zeolite were synthesized through hydrothermal treatment using two types of templates (TPAOH and PDDA). The as-synthesized ZSM-5 was characterized using FTIR, XRD, SEM-EDX, and BET. The result of FTIR showed peaks at 1250-950 cm-1 (v asymetric T-O), 820-650 cm-1 (v symetric T-O), and at 650-500 cm-1 confirming the presence of the five number ring of the pentasil structure. The result of XRD showed the appearance of certain peaks in the position 2 theta between 7-9° and 22-25° indicative of ZSM-5 structure, but also showed the pattern of low intensity magnetite and hematite. The SEM image showed the rough surface of hexagonal crystals from ZSM-5 structure, indicative of mesoporosity in the structure. EDX result showed Si/Al ratio of 20, while surface area analysis gave SA of 43.16. The ZSM-5 zeolites then was modified with cobalt oxide through impregnation method. The catalytic activity as heterogeneous catalysts in partial oxidation of methane was tested. The result showed that hence the catalytic activity of ZSM-5 and Co/ZSM-5 from fly ash and rice husk were still inferior compared to the pro-analysis sourced-counterpart, they were potential to be used as catalyst in the partial oxidation of methane to methanol.

Methane seepage along the Hikurangi Margin offshore New Zealand: 6 years of multidisciplinary studies

NASA Astrophysics Data System (ADS)

Greinert, J.; Bialas, J.; Klaucke, I.; Crutchley, G.; Dale, A.; Linke, P.; Sommer, S.; Bowden, D.; Rowden, A.; de Haas, H.; de Stigter, H.; Faure, K.

2012-12-01

Detailed studies in 2006, 2007 and 2011 along the east coast of New Zealand's North Island highlighted the close link of sub-bottom fluid pathways and seafloor expressions of methane seepage such as clam fields, carbonate build-ups, tubeworms, bacterial mats and methane release (Marine Geology 272). Prior to our studies, only accidental observations of hydroacoustic anomalies, recoveries of calyptogena shells and methane-derived carbonate chimneys indicated active seepage. Wide areas of the sub-seafloor show BSR structures, gas migration pathways, gas chimneys and blanking zones, which are closely linked to actual seep sites. Sidescan surveys showed four prominent seep areas at Omakere Ridge in 1120m water depth, three of them perfectly matching the shapes and locations of faults seen in high resolution 3D-seismic surveys. The fourth seep, Bear's Paw, on its western side represents an old seep which developed into a cold water coral habitat. At the actively seeping eastern part, gas hydrates could be retrieved and bubble release was observed hydroacoustically and confirmed by high dissolved methane values (380nM). No strong microbial oxidation effects could be found in δ13C values plotting along a mixing curve between pure seep (-70 ‰PDB) and atmospheric methane (-47 ‰PDB). Lander deployments show a tide-influenced gas discharge with sometimes eruptive bubble release with possible plume development transporting methane-charged water higher up into the water column. Rock Garden, with just above 600m water depth at its top outside the gas hydrate stability zone, hosts two main seep areas. ROV observations at Faure Site document eruptive releases of free gas from decimeter-wide craters at the seafloor. Flux estimates show peak releases of 420ml/min with bubbles up to 9mm in diameter. Concentrations of dissolved methane reach up to 3500nM close to the bottom, but higher concentrations are limited to below 400m of water depth; here, methane is transported towards the sea surface or even into the mixed layer. Faure site is just at the limit of the gas hydrate phase boundary, where relatively high-permeable sediment layers act as preferred pathway for fluids from below a shallow BSR. Seismic studies at the seep site LM-3 show gas chimneys as main fluid migration pathways in the sub-seafloor. Opouawe Bank has the densest occurrence of seeps. In water depths between 800 and 1200m, seeps of different ages and appearances exist in close proximity. North and South Tower resemble old structures with massive aragonitic carbonate blocks paving the seafloor, tube worms, bacterial mats, clams and beds of ampharetid polychaetes. These patchy polychaetes habitats have a very high total oxygen uptake of up to 83.7 mmol m^-2 day^-1) feeding from organic carbon generated via aerobic methane oxidation. Hydroacoustic flares at the 1200m deep Towers rise more than 600m into the water column above, which the dissolved gas concentrations quickly drop to background. In contrast, the isolated Takahe seep only 2 miles away shows no carbonates at the seafloor surface despite a well developed acoustic gas chimney and surface-near gas hydrates. This seep represents a much younger seep which highlights the great spatial and temporal variability in seep occurrences and activity, which can also be found in fossil seeps on land.

Carbon monoxide and methane adsorption of crude oil refinery using activated carbon from palm shells as biosorbent

NASA Astrophysics Data System (ADS)

Yuliusman; Afdhol, M. K.; Sanal, Alristo

2018-03-01

Carbon monoxide and methane gas are widely present in oil refineries. Off-potential gas is used as raw material for the petrochemical industry. In order for this off-gas to be utilized, carbon monoxide and methane must be removed from off-gas. This study aims to adsorb carbon monoxide and methane using activated carbon of palm shells and commercial activated carbon simultaneously. This research was conducted in 2 stages: 1) Preparation and characterization of activated carbon, 2) Carbon monoxide and methane adsorption test. The activation experiments using carbon dioxide at a flow rate of 150 ml/min yielded a surface area of 978.29 m2/g, Nitrogen at flow rate 150 ml/min yielded surface area 1241.48 m2/g, and carbon dioxide and nitrogen at a flow rate 200 ml/min yielded a surface area 300.37 m2/g. Adsorption of carbon monoxide and methane on activated carbon of palm shell systems yielded results in the amount of 0.5485 mg/g and 0.0649 mg/g and using commercial activated carbon yielded results in the amount of 0.5480 mg/g and 0.0650 mg/g

Elimination of methane in exhaust gas from biogas upgrading process by immobilized methane-oxidizing bacteria.

PubMed

Wu, Ya-Min; Yang, Jing; Fan, Xiao-Lei; Fu, Shan-Fei; Sun, Meng-Ting; Guo, Rong-Bo

2017-05-01

Biogas upgrading is essential for the comprehensive utilization of biogas as substitute of natural gas. However, the methane in the biogas can be fully recovered during the upgrading process of biogas, and the exhaust gas produced during biogas upgrading may contain a very low concentration of methane. If the exhaust gas with low concentration methane releases to atmosphere, it will be harmful to environment. In addition, the utilization of large amounts of digestate produced from biogas plant is another important issue for the development of biogas industry. In this study, solid digestate was used to produce active carbon, which was subsequently used as immobilized material for methane-oxidizing bacteria (MOB) in biofilter. Biofilter with MOB immobilized on active carbon was used to eliminate the methane in exhaust gas from biogas upgrading process. Results showed porous active carbon was successfully made from solid digestate. The final methane elimination capacity of immobilized MOB reached about 13molh -1 m -3 , which was more 4 times higher than that of MOB without immobilization. Copyright © 2017 Elsevier Ltd. All rights reserved.

Geological Characteristics of Active Methane Expulsion In Accretionary Prism Kaoping Slope Off SW Taiwan

NASA Astrophysics Data System (ADS)

Huang, C.; Chien, C.; Yang, T. F.; Lin, S.

2005-12-01

The Kaoping Slope off SW Taiwan represents the syn-collision accretionary prism characterized by active NW-trending folding - thrusting structures and high sedimentation rate favoring the formation of gas hydrate. For an assessment of gas hydrate potential in the Kaoping Slope off SW Taiwan, sedimentology, paleontology and geochemistry in box cores and piston cores were studied. BSRs are commonly found in seismic profiles in 400-600 m below seafloor of water depth 2500-1000 m. Active expulsions of methane were found along active thrust faults where sulfate/methane interface could be as shallow as 30 cm and the methane concentration of dissolved gases in bottom water and in pore-space of drilled core samples could be three-four order higher than the normal marine environments. Occurrences of authigenic carbonate and elongated pyrite tubes are correlated with shallow SMI depth and high methane content in bottom water and pore-space of sediment cores. Authigenic carbonates were found in seafloor surface and in 20-25 meters below seafloor. The authigenic carbonate nodules are characterized by irregular shape, whitish color, no visible microfossil, containing native sulfur, pyrites, gypsum, small open spaces, and very depleted carbon isotope (-54 ~ -43 per mil PDB). Tiny native sulfur and gypsum crystals were commonly found either on surface of foraminiferal tests and elongated pyrite tubes or in the authigenic carbonate nodules. Morphological measurements of elongated pyrite tubes show that they could represent pseudomorphs after three types of Pogonophora tube worm. Foraminifers are commonly filled by rhomboidal pyrites or cemented by pyrite crystals. Normal marine benthic foraminifers predominated by calcareous tests of slope fauna are associated with authigenic carbonate nodules in the study area, suggesting no major geochemistry effect on distribution of benthic foraminifers. Integrating sedimentology, paleontology and geochemistry characters, there could be high potential to have gas hydrate in the accretionary prism off SW Taiwan.

Methane Activation by 5 d Transition Metals: Energetics, Mechanisms, and Periodic Trends.

PubMed

Armentrout, Peter B

2017-01-01

Although it has been known for almost three decades that several 5d transition-metal cations will activate methane at room temperature, a more detailed examination of these reactions across the periodic table has only recently been completed. In this Minireview, we compare and contrast studies of the kinetic energy dependence of these reactions as studied using guided-ion-beam tandem mass spectrometry. Thermochemistry for the various products observed (MH + , MH 2 + , MC + , MCH + , MCH 2 + , and MCH 3 + ) are collected and periodic trends evaluated and discussed. The mechanisms for the reactions as elucidated by synergistic quantum chemical calculations are also reviewed. Recent spectroscopic evidence for the structures of the MCH 2 + dehydrogenation products are discussed as well. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel microbial communities of the Haakon Mosby mud volcano and their role as a methane sink.

PubMed

Niemann, Helge; Lösekann, Tina; de Beer, Dirk; Elvert, Marcus; Nadalig, Thierry; Knittel, Katrin; Amann, Rudolf; Sauter, Eberhard J; Schlüter, Michael; Klages, Michael; Foucher, Jean Paul; Boetius, Antje

2006-10-19

Mud volcanism is an important natural source of the greenhouse gas methane to the hydrosphere and atmosphere. Recent investigations show that the number of active submarine mud volcanoes might be much higher than anticipated (for example, see refs 3-5), and that gas emitted from deep-sea seeps might reach the upper mixed ocean. Unfortunately, global methane emission from active submarine mud volcanoes cannot be quantified because their number and gas release are unknown. It is also unclear how efficiently methane-oxidizing microorganisms remove methane. Here we investigate the methane-emitting Haakon Mosby Mud Volcano (HMMV, Barents Sea, 72 degrees N, 14 degrees 44' E; 1,250 m water depth) to provide quantitative estimates of the in situ composition, distribution and activity of methanotrophs in relation to gas emission. The HMMV hosts three key communities: aerobic methanotrophic bacteria (Methylococcales), anaerobic methanotrophic archaea (ANME-2) thriving below siboglinid tubeworms, and a previously undescribed clade of archaea (ANME-3) associated with bacterial mats. We found that the upward flow of sulphate- and oxygen-free mud volcano fluids restricts the availability of these electron acceptors for methane oxidation, and hence the habitat range of methanotrophs. This mechanism limits the capacity of the microbial methane filter at active marine mud volcanoes to <40% of the total flux.

Structural transformations of sVI tert-butylamine hydrates to sII binary hydrates with methane.

PubMed

Prasad, Pinnelli S R; Sugahara, Takeshi; Sloan, E Dendy; Sum, Amadeu K; Koh, Carolyn A

2009-10-22

Binary clathrate hydrates with methane (CH(4), 4.36 A) and tert-butylamine (t-BuNH(2), 6.72 A) as guest molecules were synthesized at different molar concentrations of t-BuNH(2) (1.00-9.31 mol %) with methane at 7.0 MPa and 250 K, and were characterized by powder X-ray diffraction (PXRD) and Raman microscopy. A structural transformation from sVI to sII of t-BuNH(2) hydrate was clearly observed on pressurizing with methane. The PXRD showed sII signatures and the remnant sVI signatures were insignificant, implying the metastable nature of sVI binary hydrates. Raman spectroscopic data on these binary hydrates suggest that the methane molecules occupy the small cages and vacant large cages. The methane storage capacity in this system was nearly doubled to approximately 6.86 wt % for 5.56 mol % > t-BuNH(2) > 1.0 mol %.

Possible Peroxo State of the Dicopper Site of Particulate Methane Monooxygenase from Combined Quantum Mechanics and Molecular Mechanics Calculations.

PubMed

Itoyama, Shuhei; Doitomi, Kazuki; Kamachi, Takashi; Shiota, Yoshihito; Yoshizawa, Kazunari

2016-03-21

Enzymatic methane hydroxylation is proposed to efficiently occur at the dinuclear copper site of particulate methane monooxygenase (pMMO), which is an integral membrane metalloenzyme in methanotrophic bacteria. The resting state and a possible peroxo state of the dicopper active site of pMMO are discussed by using combined quantum mechanics and molecular mechanics calculations on the basis of reported X-ray crystal structures of the resting state of pMMO by Rosenzweig and co-workers. The dicopper site has a unique structure, in which one copper is coordinated by two histidine imidazoles and another is chelated by a histidine imidazole and primary amine of an N-terminal histidine. The resting state of the dicopper site is assignable to the mixed-valent Cu(I)Cu(II) state from a computed Cu-Cu distance of 2.62 Å from calculations at the B3LYP-D/TZVP level of theory. A μ-η(2):η(2)-peroxo-Cu(II)2 structure similar to those of hemocyanin and tyrosinase is reasonably obtained by using the resting state structure and dioxygen. Computed Cu-Cu and O-O distances are 3.63 and 1.46 Å, respectively, in the open-shell singlet state. Structural features of the dicopper peroxo species of pMMO are compared with those of hemocyanin and tyrosinase and synthetic dicopper model compounds. Optical features of the μ-η(2):η(2)-peroxo-Cu(II)2 state are calculated and analyzed with TD-DFT calculations.

Genomic insights into the metabolic potential and interactions between marine methanotrophic ANME archaea and associated bacteria

NASA Astrophysics Data System (ADS)

Orphan, V. J.; Skennerton, C.; Chadwick, G.; Haroon, F.; Tyson, G. W.; Leu, A.; Hatzenpichler, R.; Woyke, T.; Malmstrom, R.; Yu, H.; Scheller, S.

2015-12-01

Cooperative metabolic interactions between multiple groups of methanotrophic 'ANME' archaea and sulfate-reducing bacteria represent the primary sink for methane within continental margin sediments. These syntrophic associations are frequently observed as structured multi-celled consortia in methane seeps, often comprising a substantial proportion of the microbial biomass within near seafloor seep sediments. Since their discovery nearly 15 years ago, a number of distinct ANME groups and multiple sulfate-reducing bacterial partners have been described from seep environments worldwide. Attempts to reconstruct the genomes of some ANME organisms have been reported, however the ecological physiology and metabolic interactions of distinct ANME lineages and their bacterial partners remains poorly understood. Here, we used a fluorescence azide-alkyne click chemistry technique known as BONCAT combined with FAC sorting to examine patterns in microbial membership and the genomes of single, metabolically active ANME-bacterial consortia recovered from methane seep sediments. This targeted consortia-level sequencing approach revealed significant diversity in the ANME-bacterial associations in situ as well as insights into the potential syntrophic mechanisms underpinning these enigmatic methane-fueled partnerships.

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

NASA Astrophysics Data System (ADS)

Weidhaas, Jennifer; Dupont, R. Ryan

2013-07-01

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

NC10 bacteria in marine oxygen minimum zones

PubMed Central

Padilla, Cory C; Bristow, Laura A; Sarode, Neha; Garcia-Robledo, Emilio; Gómez Ramírez, Eddy; Benson, Catherine R; Bourbonnais, Annie; Altabet, Mark A; Girguis, Peter R; Thamdrup, Bo; Stewart, Frank J

2016-01-01

Bacteria of the NC10 phylum link anaerobic methane oxidation to nitrite denitrification through a unique O2-producing intra-aerobic methanotrophy pathway. A niche for NC10 in the pelagic ocean has not been confirmed. We show that NC10 bacteria are present and transcriptionally active in oceanic oxygen minimum zones (OMZs) off northern Mexico and Costa Rica. NC10 16S rRNA genes were detected at all sites, peaking in abundance in the anoxic zone with elevated nitrite and methane concentrations. Phylogenetic analysis of particulate methane monooxygenase genes further confirmed the presence of NC10. rRNA and mRNA transcripts assignable to NC10 peaked within the OMZ and included genes of the putative nitrite-dependent intra-aerobic pathway, with high representation of transcripts containing the unique motif structure of the nitric oxide (NO) reductase of NC10 bacteria, hypothesized to participate in O2-producing NO dismutation. These findings confirm pelagic OMZs as a niche for NC10, suggesting a role for this group in OMZ nitrogen, methane and oxygen cycling. PMID:26918666

A case study of methane gas migration through sealed mine GOB into active mine workings

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

Garcia, F.; McCall, F.E.; Trevits, M.A.

1995-12-31

The U.S. Bureau of Mines investigated the influence of atmospheric pressure changes on methane gas migration through mine seals at a mine site located in the Pittsburgh Coalbed. The mine gained access to a coal reserve through part of an abandoned mine and constructed nine seals to isolate the extensive old workings from the active mine area. Underground problems were experienced when atmospheric pressure fell, causing methane gas to migrate around the seals and into the active workings. During mining operations, methane gas levels exceeded legal limits and coal production was halted until the ventilation system could be improved. Whenmore » mining resumed with increased air flow, methane gas concentrations occasionally exceeded the legal limits and production had to be halted until the methane level fell within the mandated limit. To assist the ventilation system, a pressure relief borehole located in the abandoned workings near the mine seals was proposed. Preliminary estimates by a gob gas simulator (computer model) suggested that a 0.76 m (2.5 ft) diameter pressure relief borehole with an exhaust fan would be necessary to remove enough methane from the abandoned area so that the ventilation system could dilute the gas in the active workings. However, by monitoring methane gas emissions and seal pressure, during periods of low atmospheric pressure, the amount of methane gas that migrated into the active mine workings was calculated. Researchers then determined that a relief borehole, 20.3 cm (8-in) with an exhaust fan could remove at least twice the maximum measured volume of migrating methane gas. Because gas concentrations in the abandoned workings could potentially reach explosive limits, it was proposed that the mine eliminate the exhaust fan. Installation of the recommended borehole and enlarging two other ventilation boreholes located In the abandoned area reduced methane gas leakage through the seals by at least 63%.« less

Temperature-Induced Increase in Methane Release from Peat Bogs: A Mesocosm Experiment

PubMed Central

van Winden, Julia F.; Reichart, Gert-Jan; McNamara, Niall P.; Benthien, Albert; Damsté, Jaap S. Sinninghe.

2012-01-01

Peat bogs are primarily situated at mid to high latitudes and future climatic change projections indicate that these areas may become increasingly wetter and warmer. Methane emissions from peat bogs are reduced by symbiotic methane oxidizing bacteria (methanotrophs). Higher temperatures and increasing water levels will enhance methane production, but also methane oxidation. To unravel the temperature effect on methane and carbon cycling, a set of mesocosm experiments were executed, where intact peat cores containing actively growing Sphagnum were incubated at 5, 10, 15, 20, and 25°C. After two months of incubation, methane flux measurements indicated that, at increasing temperatures, methanotrophs are not able to fully compensate for the increasing methane production by methanogens. Net methane fluxes showed a strong temperature-dependence, with higher methane fluxes at higher temperatures. After removal of Sphagnum, methane fluxes were higher, increasing with increasing temperature. This indicates that the methanotrophs associated with Sphagnum plants play an important role in limiting the net methane flux from peat. Methanotrophs appear to consume almost all methane transported through diffusion between 5 and 15°C. Still, even though methane consumption increased with increasing temperature, the higher fluxes from the methane producing microbes could not be balanced by methanotrophic activity. The efficiency of the Sphagnum-methanotroph consortium as a filter for methane escape thus decreases with increasing temperature. Whereas 98% of the produced methane is retained at 5°C, this drops to approximately 50% at 25°C. This implies that warming at the mid to high latitudes may be enhanced through increased methane release from peat bogs. PMID:22768100

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

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

Abichou, Tarek, E-mail: abichou@eng.fsu.edu; Mahieu, Koenraad; Chanton, Jeff

2011-05-15

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

A trimodal porous carbon as an effective catalyst for hydrogen production by methane decomposition.

PubMed

Shen, Yi; Lua, Aik Chong

2016-01-15

A new type of porous carbon with an interconnected trimodal pore system is synthesized by a nanocasting method using nanoparticulated bimodal micro-mesoporous silica particles as the template. The synthesized template and carbon material are characterized using transmission electron microscopy (TEM), field emission electron scanning microscopy (FESEM) and nitrogen adsorption-desorption test. The synthesized carbon material has an extremely high surface area, a large pore volume and an interconnected pore structure, which could provide abundant active sites and space for chemical reactions and minimize the diffusion resistance of the reactants. The resulting carbon is used as the catalyst for hydrogen production by the thermal decomposition of methane. The catalytic results show that the as-synthesized carbon in this study produces much higher methane conversion and hydrogen yield than the commercial carbon materials. Copyright © 2015 Elsevier Inc. All rights reserved.

Monocopper active site for partial methane oxidation in Cu-exchanged 8MR zeolites

DOE PAGES

Kulkarni, Ambarish R.; Zhao, Zhi -Jian; Siahrostami, Samira; ...

2016-08-17

Direct conversion of methane to methanol using oxygen is experiencing renewed interest owing to the availability of new natural gas resources. Copper-exchanged zeolites such as mordenite and ZSM-5 have shown encouraging results, and di- and tri-copper species have been suggested as active sites. Recently, small eight-membered ring (8MR) zeolites including SSZ-13, -16, and -39 have been shown to be active for methane oxidation, but the active sites and reaction mechanisms in these 8MR zeolites are not known. In this work, we use density functional theory (DFT) calculations to systematically evaluate monocopper species as active sites for the partial methane oxidationmore » reaction in Cu-exchanged SSZ-13. On the basis of kinetic and thermodynamic arguments, we suggest that [Cu IIOH] + species in the 8MR are responsible for the experimentally observed activity. Furthermore, our results successfully explain the available spectroscopic data and experimental observations including (i) the necessity of water for methanol extraction and (ii) the effect of Si/Al ratio on the catalyst activity. Monocopper species have not yet been suggested as an active site for the partial methane oxidation reaction, and our results suggest that [Cu IIOH] + active site may provide complementary routes for methane activation in zeolites in addition to the known [Cu–O–Cu] 2+ and Cu 3O 3 motifs.« less

Demonstration of Technologies for Remote and in Situ Sensing of Atmospheric Methane Abundances - a Controlled Release Experiment

NASA Astrophysics Data System (ADS)

Aubrey, A. D.; Thorpe, A. K.; Christensen, L. E.; Dinardo, S.; Frankenberg, C.; Rahn, T. A.; Dubey, M.

2013-12-01

It is critical to constrain both natural and anthropogenic sources of methane to better predict the impact on global climate change. Critical technologies for this assessment include those that can detect methane point and concentrated diffuse sources over large spatial scales. Airborne spectrometers can potentially fill this gap for large scale remote sensing of methane while in situ sensors, both ground-based and mounted on aerial platforms, can monitor and quantify at small to medium spatial scales. The Jet Propulsion Laboratory (JPL) and collaborators recently conducted a field test located near Casper, WY, at the Rocky Mountain Oilfield Test Center (RMOTC). These tests were focused on demonstrating the performance of remote and in situ sensors for quantification of point-sourced methane. A series of three controlled release points were setup at RMOTC and over the course of six experiment days, the point source flux rates were varied from 50 LPM to 2400 LPM (liters per minute). During these releases, in situ sensors measured real-time methane concentration from field towers (downwind from the release point) and using a small Unmanned Aerial System (sUAS) to characterize spatiotemporal variability of the plume structure. Concurrent with these methane point source controlled releases, airborne sensor overflights were conducted using three aircraft. The NASA Carbon in Arctic Reservoirs Vulnerability Experiment (CARVE) participated with a payload consisting of a Fourier Transform Spectrometer (FTS) and an in situ methane sensor. Two imaging spectrometers provided assessment of optical and thermal infrared detection of methane plumes. The AVIRIS-next generation (AVIRIS-ng) sensor has been demonstrated for detection of atmospheric methane in the short wave infrared region, specifically using the absorption features at ~2.3 μm. Detection of methane in the thermal infrared region was evaluated by flying the Hyperspectral Thermal Emission Spectrometer (HyTES), retrievals which interrogate spectral features in the 7.5 to 8.5 μm region. Here we discuss preliminary results from the JPL activities during the RMOTC controlled release experiment, including capabilities of airborne sensors for total columnar atmospheric methane detection and comparison to results from ground measurements and dispersion models. Potential application areas for these remote sensing technologies include assessment of anthropogenic and natural methane sources over wide spatial scales that represent significant unconstrained factors to the global methane budget.

Natural gas storage with activated carbon from a bituminous coal

USGS Publications Warehouse

Sun, Jielun; Rood, M.J.; Rostam-Abadi, M.; Lizzio, A.A.

1996-01-01

Granular activated carbons ( -20 + 100 mesh; 0.149-0.84 mm) were produced by physical activation and chemical activation with KOH from an Illinois bituminous coal (IBC-106) for natural gas storage. The products were characterized by BET surface area, micropore volume, bulk density, and methane adsorption capacities. Volumetric methane adsorption capacities (Vm/Vs) of some of the granular carbons produced by physical activation are about 70 cm3/cm3 which is comparable to that of BPL, a commercial activated carbon. Vm/Vs values above 100 cm3/cm3 are obtainable by grinding the granular products to - 325 mesh (<0.044 mm). The increase in Vm/Vs is due to the increase in bulk density of the carbons. Volumetric methane adsorption capacity increases with increasing pore surface area and micropore volume when normalizing with respect to sample bulk volume. Compared with steam-activated carbons, granular carbons produced by KOH activation have higher micropore volume and higher methane adsorption capacities (g/g). Their volumetric methane adsorption capacities are lower due to their lower bulk densities. Copyright ?? 1996 Elsevier Science Ltd.

Fugitive greenhouse gas emissions from shale gas activities - a case study of Dish, TX

NASA Astrophysics Data System (ADS)

Khan, A.; Roscoe, B.; Lary, D.; Schaefer, D.; Tao, L.; Sun, K.; Brian, A.; DiGangi, J.; Miller, D. J.; Zondlo, M. A.

2012-12-01

We evaluate new findings on aerial (horizontal and vertical) mapping of methane emissions in the atmospheric boundary layer region to help study fugitive methane emissions from extraction, transmission, and storage of natural gas and oil in Dish, Texas. Dish is located in the Barnett Shale which has seen explosive development of hydraulic fracking activities in recent years. The aerial measurements were performed with a new laser-based methane sensor developed specifically for an unmanned aerial vehicle (UAV). The vertical cavity surface emitting laser (VCSEL) methane sensor, with a mass of 2.5 kg and a precision of < 20 ppbv methane at 1 Hz, was flown on the UT-Dallas ARC Payload Master electronic aircraft at two sites in Texas: one representative of urban emissions of the Dallas-Fort Worth area in Richardson, Texas and another in Dish, Texas, closer to gas and oil activities. Methane mixing ratios at Dish were ubiquitously in the 3.5 - 4 ppmv range which was 1.5 - 2 ppmv higher than methane levels immediately downwind of Dallas. During the flight measurements at Dish, narrow methane plumes exceeding 20 ppmv were frequently observed at altitudes from the surface to 130 m above the ground. Based on the wind speed at the sampling location, the horizontal widths of large methane plumes were of the order of 100 m. The locations of the large methane plumes were variable in space and time over a ~ 1 km2 area sampled from the UAV. Spatial mapping over larger scales (10 km) by ground-based measurements showed similar methane levels as the UAV measurements. To corroborate our measurements, alkane and other hydrocarbon mixing ratios from an on-site TCEQ environmental monitoring station were analyzed and correlated with methane measurements to fingerprint the methane source. We show that fugitive methane emissions at Dish are a significant cause of the large and ubiquitous methane levels on the 1-10 km scale.

A theoretical study of the dissociation of the sI methane hydrate induced by an external electric field

NASA Astrophysics Data System (ADS)

Luis, D. P.; Herrera-Hernández, E. C.; Saint-Martin, H.

2015-11-01

Molecular dynamics simulations in the equilibrium isobaric—isothermal (NPT) ensemble were used to examine the strength of an external electric field required to dissociate the methane hydrate sI structure. The water molecules were modeled using the four-site TIP4P/Ice analytical potential and methane was described as a simple Lennard-Jones interaction site. A series of simulations were performed at T = 260 K with P = 80 bars and at T = 285 K with P = 400 bars with an applied electric field ranging from 1.0 V nm-1 to 5.0 V nm-1. For both (T,P) conditions, applying a field greater than 1.5 V nm-1 resulted in the orientation of the water molecules such that an ice Ih-type structure was formed, from which the methane was segregated. When the simulations were continued without the external field, the ice-like structures became disordered, resulting in two separate phases: gas methane and liquid water.

A hierarchical examination of methane uptake: field patterns, lab physiology, community composition and biogeography

NASA Astrophysics Data System (ADS)

von Fischer, J. C.; Koyama, A.; Johnson, N. G.; Webb, C. T.

2015-12-01

Scaling problems abound in biogeochemistry. At the finest scale, soil microbes experience habitats and environmental changes that affect the chemical transformations of interest. We collect the DNA of these organisms from sites across landscapes and note differences in who is there, and we seek to evaluate why group membership changes in space (biogeography) and why activity rates change over time (physiology). The goal of efforts at finer scales is often to better predict patterns at larger scales. We conducted such a hierarchical examination of methane uptake in the Great Plains grasslands of North America, gathering data from 22 plots at 8 field locations, scattered from South Dakota to New Mexico and Colorado to Kansas. Our work provides insight into methanotroph biogeochemistry at all of these scales. For example, we found that methane uptake rates vary mostly due to the methanotroph activity, and less so due to diffusivity. A combination of field and lab observations reveal that methanotroph communities differ in their sensitivity to soil moisture and to ammonium (an inhibitor of methanotrophy). Examination of methanotroph community composition reveals tantalizing patterns in composition, dominance and richness across sites, that appears to be structured by patterns of precipitation and soil texture. We anticipate that greater synthesis of these hierarchical findings will paint a richer picture of methanotroph life and enable improved prediction of methane uptake at regional scales.

77 FR 4297 - Agency Information Collection Activities; Proposed Collection; Comment Request; Reporting Under...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-01-27

... Activities; Proposed Collection; Comment Request; Reporting Under EPA's Landfill Methane Outreach Program...; and other landfill gas energy stakeholders. Title: Reporting Under EPA's Landfill Methane Outreach... Landfill Methane Outreach Program (LMOP), created by EPA as part of the Climate Change Action Plan, is a...

Structures of the dehydrogenation products of methane activation by 5d transition metal cations revisited: Deuterium labeling and rotational contours

NASA Astrophysics Data System (ADS)

Owen, Cameron J.; Boles, Georgia C.; Chernyy, Valeriy; Bakker, Joost M.; Armentrout, P. B.

2018-01-01

A previous infrared multiple photon dissociation (IRMPD) action spectroscopy and density functional theory (DFT) study explored the structures of the [M,C,2H]+ products formed by dehydrogenation of methane by four, gas-phase 5d transition metal cations (M+ = Ta+, W+, Ir+, and Pt+). Complicating the analysis of these spectra for Ir and Pt was observation of an extra band in both spectra, not readily identified as a fundamental vibration. In an attempt to validate the assignment of these additional peaks, the present work examines the gas phase [M,C,2D]+ products of the same four metal ions formed by reaction with perdeuterated methane (CD4). As before, metal cations are formed in a laser ablation source and react with methane pulsed into a reaction channel downstream, and the resulting products are spectroscopically characterized through photofragmentation using the free-electron laser for intracavity experiments in the 350-1800 cm-1 range. Photofragmentation was monitored by the loss of D for [Ta,C,2D]+ and [W,C,2D]+ and of D2 in the case of [Pt,C,2D]+ and [Ir,C,2D]+. Comparison of the experimental spectra and DFT calculated spectra leads to structural assignments for all [M,C,2H/2D]+ systems that are consistent with previous identifications and allows a full description of the systematic spectroscopic shifts observed for deuterium labeling of these complexes, some of the smallest systems to be studied using IRMPD action spectroscopy. Further, full rotational contours are simulated for each vibrational band and explain several observations in the present spectra, such as doublet structures in several bands as well as the observed linewidths. The prominent extra bands in the [Pt,C,2D/2H]+ spectra appear to be most consistent with an overtone of the out-of-plane bending vibration of the metal carbene cation structure.

Analysis of past recurrent methane seep activity using radiocarbon dating of Calyptogena spp. shells in the eastern Nankai subduction zone, Japan

NASA Astrophysics Data System (ADS)

Yagasaki, Kazuhiro; Ashi, Juichiro; Yokoyama, Yusuke; Miyairi, Yosuke; Kuramoto, Shin'ichi

2016-04-01

Fault activity around subduction zones have been widely studied and monitored through drilling of oceanic plates, studying piston cores, use of monitoring equipment or through visual analysis using submersible vehicles. Yet the understanding of how small scale faults near shallow regions of the seabed behave in relation to cold seep vent activity is still vague, especially determining when they were active in the past. In tectonically active margins such as the Nankai and Tokai regions off Japan, dense methane hydrate reservoirs have been identified. Cold seeps releasing methane rich hydrocarbon fluids are common here, supporting a wide variety of biological species that hold a symbiotic relationship with the chemosynthetic bacteria. In 1998 a large dead Calyptogena spp. bivalve colony (over 400m2 in size) was discovered off Tokai, Japan. It is unusual for a bivalve colony this size to mostly be dead, raising questions as to what caused their death. In this study we document the radiocarbon 14C age of these bivalve shells to attempt analysing the possible methane seep bahaviour in the past. The measured 14C age ranged in three age groups of 1396±36-1448±34, 1912±31-1938±35 and 5975±34. The 14C age of shells that were alive upon collection and the dissolved inorganic carbon (DIC) in seawater show little difference (˜100 14C age) indicating that shells are not heavily affected by the dead carbon effect from cold seeps that is of biogenic or thermogenic origin, which can make the age to become considerably older than the actual age. Thus the novel calibration model used was based on the seawater DIC collected above the Calyptogena spp. colony site (1133±31), which resulted in the dead shells to be clustered around 1900 Cal AD. This proves to be interesting as the predicted epicenter of the Ansei-Tokai earthquake (M 8.4) in 1854 is extremely close to the bibalve colony site. Using geological data obtained using visual analysis and sub-seafloor structural analysis that show multiple shallow faults and chaotic sediment structure below the colony site, the Calyptogena spp. shells have a strong connection to the coseismic faulting activity and could show potential for radiocarbon dating to be applied on marine samples providing the necessary calibration tools are available.

Experimental and modeling study on decomposition kinetics of methane hydrates in different media.

PubMed

Liang, Minyan; Chen, Guangjin; Sun, Changyu; Yan, Lijun; Liu, Jiang; Ma, Qinglan

2005-10-13

The decomposition kinetic behaviors of methane hydrates formed in 5 cm3 porous wet activated carbon were studied experimentally in a closed system in the temperature range of 275.8-264.4 K. The decomposition rates of methane hydrates formed from 5 cm3 of pure free water and an aqueous solution of 650 g x m(-3) sodium dodecyl sulfate (SDS) were also measured for comparison. The decomposition rates of methane hydrates in seven different cases were compared. The results showed that the methane hydrates dissociate more rapidly in porous activated carbon than in free systems. A mathematical model was developed for describing the decomposition kinetic behavior of methane hydrates below ice point based on an ice-shielding mechanism in which a porous ice layer was assumed to be formed during the decomposition of hydrate, and the diffusion of methane molecules through it was assumed to be one of the control steps. The parameters of the model were determined by correlating the decomposition rate data, and the activation energies were further determined with respect to three different media. The model was found to well describe the decomposition kinetic behavior of methane hydrate in different media.

Structural changes and preferential cage occupancy of ethane hydrate and methane-ethane mixed gas hydrate under very high pressure.

PubMed

Hirai, Hisako; Takahara, Naoya; Kawamura, Taro; Yamamoto, Yoshitaka; Yagi, Takehiko

2008-12-14

High-pressure experiments of ethane hydrate and methane-ethane mixed hydrates with five compositions were performed using a diamond anvil cell in a pressure range of 0.1-2.8 GPa at room temperature. X-ray diffractometry and Raman spectroscopy showed structural changes as follows. The initial structure, structure I (sI), of ethane hydrate was retained up to 2.1 GPa without any structural change. For the mixed hydrates, sI was widely distributed throughout the region examined except for the methane-rich and lower pressure regions. For the ethane-rich and intermediate composition regions (73 mol % ethane sample and 53% sample), sI was maintained up to 2.1 GPa. With increasing methane component (34% and 30% samples), sI existed at pressures from 0.1 to about 1.0 GPa. Hexagonal structure (sH) appeared in addition to sI at 1.3 GPa for the 34% sample and at 1.1 GPa for the 30% sample. By further increasing the methane component (22% sample), structure II (sII) existed solely up to 0.3 GPa. From 0.3 to 0.6 GPa, sII and sI coexisted, and from 0.6 to 1.0 GPa only sI existed. At 1.2 GPa sH appeared, and sH and sI coexisted up to 2.1 GPa. Above 2.1 GPa, ethane hydrate and all of the mixed hydrates decomposed into ice VI and ethane fluid or methane-ethane fluid, respectively. The Raman study revealed that occupation of the small cages by ethane molecules occurred above 0.1 GPa in ethane hydrate and continued up to decomposition at 2.1 GPa, although it is thought that ethane molecules are contained only in the large cage.

Correlating methane production to microbiota in anaerobic digesters fed synthetic wastewater.

PubMed

Venkiteshwaran, K; Milferstedt, K; Hamelin, J; Fujimoto, M; Johnson, M; Zitomer, D H

2017-03-01

A quantitative structure activity relationship (QSAR) between relative abundance values and digester methane production rate was developed. For this, 50 triplicate anaerobic digester sets (150 total digesters) were each seeded with different methanogenic biomass samples obtained from full-scale, engineered methanogenic systems. Although all digesters were operated identically for at least 5 solids retention times (SRTs), their quasi steady-state function varied significantly, with average daily methane production rates ranging from 0.09 ± 0.004 to 1 ± 0.05 L-CH 4 /L R -day (L R  = Liter of reactor volume) (average ± standard deviation). Digester microbial community structure was analyzed using more than 4.1 million partial 16S rRNA gene sequences of Archaea and Bacteria. At the genus level, 1300 operational taxonomic units (OTUs) were observed across all digesters, whereas each digester contained 158 ± 27 OTUs. Digester function did not correlate with typical biomass descriptors such as volatile suspended solids (VSS) concentration, microbial richness, diversity or evenness indices. However, methane production rate did correlate notably with relative abundances of one Archaeal and nine Bacterial OTUs. These relative abundances were used as descriptors to develop a multiple linear regression (MLR) QSAR equation to predict methane production rates solely based on microbial community data. The model explained over 66% of the variance in the experimental data set based on 149 anaerobic digesters with a standard error of 0.12 L-CH 4 /L R -day. This study provides a framework to relate engineered process function and microbial community composition which can be further expanded to include different feed stocks and digester operating conditions in order to develop a more robust QSAR model. Copyright © 2016 Elsevier Ltd. All rights reserved.

Self-preservation and structural transition of gas hydrates during dissociation below the ice point: an in situ study using Raman spectroscopy

NASA Astrophysics Data System (ADS)

Zhong, Jin-Rong; Zeng, Xin-Yang; Zhou, Feng-He; Ran, Qi-Dong; Sun, Chang-Yu; Zhong, Rui-Qin; Yang, Lan-Ying; Chen, Guang-Jin; Koh, Carolyn A.

2016-12-01

The hydrate structure type and dissociation behavior for pure methane and methane-ethane hydrates at temperatures below the ice point and atmospheric pressure were investigated using in situ Raman spectroscopic analysis. The self-preservation effect of sI methane hydrate is significant at lower temperatures (268.15 to 270.15 K), as determined by the stable C-H region Raman peaks and AL/AS value (Ratio of total peak area corresponding to occupancies of guest molecules in large cavities to small cavities) being around 3.0. However, it was reduced at higher temperatures (271.15 K and 272.15 K), as shown from the dramatic change in Raman spectra and fluctuations in AL/AS values. The self-preservation effect for methane-ethane double hydrate is observed at temperatures lower than 271.15 K. The structure transition from sI to sII occurred during the methane-ethane hydrate decomposition process, which was clearly identified by the shift in peak positions and the change in relative peak intensities at temperatures from 269.15 K to 271.15 K. Further investigation shows that the selectivity for self-preservation of methane over ethane leads to the structure transition; this kind of selectivity increases with decreasing temperature. This work provides new insight into the kinetic behavior of hydrate dissociation below the ice point.

Electron acceptors for anaerobic oxidation of methane drive microbial community structure and diversity in mud volcanoes.

PubMed

Ren, Ge; Ma, Anzhou; Zhang, Yanfen; Deng, Ye; Zheng, Guodong; Zhuang, Xuliang; Zhuang, Guoqiang; Fortin, Danielle

2018-04-06

Mud volcanoes (MVs) emit globally significant quantities of methane into the atmosphere, however, methane cycling in such environments is not yet fully understood, as the roles of microbes and their associated biogeochemical processes have been largely overlooked. Here, we used data from high-throughput sequencing of microbial 16S rRNA gene amplicons from six MVs in the Junggar Basin in northwest China to quantify patterns of diversity and characterize the community structure of archaea and bacteria. We found anaerobic methanotrophs and diverse sulfate- and iron-reducing microbes in all of the samples, and the diversity of both archaeal and bacterial communities was strongly linked to the concentrations of sulfate, iron and nitrate, which could act as electron acceptors in anaerobic oxidation of methane (AOM). The impacts of sulfate/iron/nitrate on AOM in the MVs were verified by microcosm experiments. Further, two representative MVs were selected to explore the microbial interactions based on phylogenetic molecular ecological networks. The sites showed distinct network structures, key species and microbial interactions, with more complex and numerous linkages between methane-cycling microbes and their partners being observed in the iron/sulfate-rich MV. These findings suggest that electron acceptors are important factors driving the structure of microbial communities in these methane-rich environments. © 2018 The Authors. Environmental Microbiology published by Society for Applied Microbiology and John Wiley & Sons Ltd.

Effect of methane partial pressure on the performance of a membrane biofilm reactor coupling methane-dependent denitrification and anammox.

PubMed

Cai, Chen; Hu, Shihu; Chen, Xueming; Ni, Bing-Jie; Pu, Jiaoyang; Yuan, Zhiguo

2018-10-15

Complete nitrogen removal has recently been demonstrated by integrating anaerobic ammonium oxidation (anammox) and denitrifying anaerobic methane oxidation (DAMO) processes. In this work, the effect of methane partial pressure on the performance of a membrane biofilm reactor (MBfR) consisting of DAMO and anammox microorganisms was evaluated. The activities of DAMO archaea and DAMO bacteria in the biofilm increased significantly with increased methane partial pressure, from 367 ± 9 and 58 ± 22 mg-N L -1 d -1 to 580 ± 12 and 222 ± 22 mg-N L -1 d -1 , respectively, while the activity of anammox bacteria only increased slightly, when the methane partial pressure was elevated from 0.24 to 1.39 atm in the short-term batch tests. The results were supported by a long-term (seven weeks) continuous test, when the methane partial pressure was dropped from 1.39 to 0.78 atm. The methane utilization efficiency was always above 96% during both short-term and long-term tests. Taken together, nitrogen removal rate (especially the nitrate reduction rate by DAMO archaea) and methane utilization efficiency could be maintained at high levels in a broad range of methane partial pressure (0.24-1.39 atm in this study). In addition, a previously established DAMO/anammox biofilm model was used to analyze the experimental data. The observed impacts of methane partial pressure on biofilm activity were well explained by the modeling results. These results suggest that methane partial pressure can potentially be used as a manipulated variable to control reaction rates, ultimately to maintain high nitrogen removal efficiency, according to nitrogen loading rate. Copyright © 2018 Elsevier B.V. All rights reserved.

Crystal structure, stability and spectroscopic properties of methane and CO2 hydrates.

PubMed

Martos-Villa, Ruben; Francisco-Márquez, Misaela; Mata, M Pilar; Sainz-Díaz, C Ignacio

2013-07-01

Methane hydrates are highly present in sea-floors and in other planets and their moons. Hence, these compounds are of great interest for environment, global climate change, energy resources, and Cosmochemistry. The knowledge of stability and physical-chemical properties of methane hydrate crystal structure is important for evaluating some new green becoming technologies such as, strategies to produce natural gas from marine methane hydrates and simultaneously store CO2 as hydrates. However, some aspects related with their stability, spectroscopic and other chemical-physical properties of both hydrates are not well understood yet. The structure and stability of crystal structure of methane and CO2 hydrates have been investigated by means of calculations with empirical interatomic potentials and quantum-mechanical methods based on Hartree-Fock and Density Functional Theory (DFT) approximations. Molecular Dynamic simulations have been also performed exploring different configurations reproducing the experimental crystallographic properties. Spectroscopic properties have also been studied. Frequency shifts of the main vibration modes were observed upon the formation of these hydrates, confirming that vibration stretching peaks of C-H at 2915cm(-1) and 2905cm(-1) are due to methane in small and large cages, respectively. Similar effect is observed in the CO2 clathrates. The guest-host binding energy in these clathrates calculated with different methods are compared and discussed in terms of adequacy of empirical potentials and DFT methods for describing the interactions between gas guest and the host water cage, proving an exothermic nature of methane and CO2 hydrates formation process. Copyright © 2013 Elsevier Inc. All rights reserved.

Bioassay for estimating the biogenic methane-generating potential of coal samples

USGS Publications Warehouse

Jones, Elizabeth J.P.; Voytek, Mary A.; Warwick, Peter D.; Corum, Margo D.; Cohn, Alexander G.; Bunnell, Joseph E.; Clark, Arthur C.; Orem, William H.

2008-01-01

Generation of secondary biogenic methane in coal beds is likely controlled by a combination of factors such as the bioavailability of coal carbon, the presence of a microbial community to convert coal carbon to methane, and an environment supporting microbial growth and methanogenesis. A set of treatments and controls was developed to bioassay the bioavailability of coal for conversion to methane under defined laboratory conditions. Treatments included adding a well-characterized consortium of bacteria and methanogens (enriched from modern wetland sediments) and providing conditions to support endemic microbial activity. The contribution of desorbed methane in the bioassays was determined in treatments with bromoethane sulfonic acid, an inhibitor of microbial methanogenesis. The bioassay compared 16 subbituminous coal samples collected from beds in Texas (TX), Wyoming (WY), and Alaska (AK), and two bituminous coal samples from Pennsylvania (PA). New biogenic methane was observed in several samples of subbituminous coal with the microbial consortium added, but endemic activity was less commonly observed. The highest methane generation [80 µmol methane/g coal (56 scf/ton or 1.75 cm3/g)] was from a south TX coal sample that was collected from a non-gas-producing well. Subbituminous coals from the Powder River Basin, WY and North Slope Borough, AK contained more sorbed (original) methane than the TX coal sample and generated 0–23 µmol/g (up to 16 scf/ton or 0.5 cm3/g) new biogenic methane in the bioassay. Standard indicators of thermal maturity such as burial depth, nitrogen content, and calorific value did not explain differences in biogenic methane among subbituminous coal samples. No original methane was observed in two bituminous samples from PA, nor was any new methane generated in bioassays of these samples. The bioassay offers a new tool for assessing the potential of coal for biogenic methane generation, and provides a platform for studying the mechanisms involved in this economically important activity.

Diindolylmethane Derivatives: Potent Agonists of the Immunostimulatory Orphan G Protein-Coupled Receptor GPR84.

PubMed

Pillaiyar, Thanigaimalai; Köse, Meryem; Sylvester, Katharina; Weighardt, Heike; Thimm, Dominik; Borges, Gleice; Förster, Irmgard; von Kügelgen, Ivar; Müller, Christa E

2017-05-11

The G i protein-coupled receptor GPR84, which is activated by (hydroxy)fatty acids, is highly expressed on immune cells. Recently, 3,3'-diindolylmethane was identified as a heterocyclic, nonlipid-like GPR84 agonist. We synthesized a broad range of diindolylmethane derivatives by condensation of indoles with formaldehyde in water under microwave irradiation. The products were evaluated at the human GPR84 in cAMP and β-arrestin assays. Structure-activity relationships (SARs) were steep. 3,3'-Diindolylmethanes bearing small lipophilic residues at the 5- and/or 7-position of the indole rings displayed the highest activity in cAMP assays, the most potent agonists being di(5-fluoro-1H-indole-3-yl)methane (38, PSB-15160, EC 50 80.0 nM) and di(5,7-difluoro-1H-indole-3-yl)methane (57, PSB-16671, EC 50 41.3 nM). In β-arrestin assays, SARs were different, indicating biased agonism. The new compounds were selective versus related fatty acid receptors and the arylhydrocarbon receptor. Selected compounds were further investigated and found to display an ago-allosteric mechanism of action and increased stability in comparison to the lead structure.

77 FR 24488 - Agency Information Collection Activities; Submission to OMB for Review and Approval; Comment...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-04-24

... Activities; Submission to OMB for Review and Approval; Comment Request; Landfill Methane Outreach Program... the electronic docket, go to www.regulations.gov . Title: Landfill Methane Outreach Program (Renewal... consolidated in 40 CFR part 9. Abstract: The Landfill Methane Outreach Program (LMOP), created by EPA as part...

Methanogenic activity and diversity in the centre of the Amsterdam Mud Volcano, Eastern Mediterranean Sea.

PubMed

Lazar, Cassandre Sara; John Parkes, R; Cragg, Barry A; L'Haridon, Stephane; Toffin, Laurent

2012-07-01

Marine mud volcanoes are geological structures emitting large amounts of methane from their active centres. The Amsterdam mud volcano (AMV), located in the Anaximander Mountains south of Turkey, is characterized by intense active methane seepage produced in part by methanogens. To date, information about the diversity or the metabolic pathways used by the methanogens in active centres of marine mud volcanoes is limited. (14)C-radiotracer measurements showed that methylamines/methanol, H(2)/CO(2) and acetate were used for methanogenesis in the AMV. Methylotrophic methanogenesis was measured all along the sediment core, Methanosarcinales affiliated sequences were detected using archaeal 16S PCR-DGGE and mcrA gene libraries, and enrichments of methanogens showed the presence of Methanococcoides in the shallow sediment layers. Overall acetoclastic methanogenesis was higher than hydrogenotrophic methanogenesis, which is unusual for cold seep sediments. Interestingly, acetate porewater concentrations were extremely high in the AMV sediments. This might be the result of organic matter cracking in deeper hotter sediment layers. Methane was also produced from hexadecanes. For the most part, the methanogenic community diversity was in accordance with the depth distribution of the H(2)/CO(2) and acetate methanogenesis. These results demonstrate the importance of methanogenic communities in the centres of marine mud volcanoes. © 2012 Federation of European Microbiological Societies. Published by Blackwell Publishing Ltd. All rights reserved.

Multi-scale monitoring of a marine geologic methane source in the Santa Barbara Channel using imaging spectrometry, ARCTAS-CARB in situ sampling and coastal hourly total hydrocarbon measurements

NASA Astrophysics Data System (ADS)

Bradley, E. S.; Leifer, I.; Roberts, D.; Dennison, P. E.; Margolis, J.; Moritsch, M.; Diskin, G. S.; Sachse, G. W.

2009-12-01

The Coal Oil Point (COP) hydrocarbon seep field off the coast of Santa Barbara, CA is one of the most active and best-studied marine geologic methane sources in the world and contributes to elevated terrestrial methane concentrations downwind. In this study, we investigate the spatiotemporal variability of this local source and the influence of meteorological conditions on transport and concentration. A methane plume emanating from Trilogy Seep was mapped with the Airborne Visible Infrared Imaging Spectrometer at a 7.5 m resolution with a short-wave infrared band ratio technique. This structure agrees with the local wind speed and direction and is orthogonal to the surface currents. ARCTAS-CARB aircraft in situ sampling of lower-troposphere methane is compared to sub-hour total hydrocarbon concentration (THC) measurements from the Santa Barbara Air Pollution Control District (SBAPCD) station located near COP. Hourly SBAPCD THC values from 1980-2008 demonstrate a decrease in seep source strength until the late 1990s, followed by a consistent increase. The occurrence of elevated SBAPCD THC values for onshore wind conditions as well as numerous positive outliers as high as 17 ppm suggests that seep field emissions are both quasi-steady state and transient, direct (bubble) and diffuse (outgassing). As demonstrated for the COP seeps, the combination of imaging spectrometry, aircraft in situ sampling, and ground-based monitoring provides a powerful approach for understanding local methane sources and transport processes.

Properties of planar structures based on Policluster films of diamond and AlN

NASA Astrophysics Data System (ADS)

Belyanin, A. F.; Luchnikov, A. P.; Nalimov, S. A.; Bagdasarian, A. S.

2018-01-01

AlN films doped with zinc were grown on Si substrates by RF magnetron reactive sputtering of a compound target. Policluster films of diamond doped with boron were formed on layered Si/AlN substrates from the gas phase hydrogen and methane, activated arc discharge. By electron microscopy, X-ray diffraction and Raman spectroscopy the composition and structure of synthetic policluster films of diamond and AlN films were studied. Photovoltaic devices based on the AlN/PFD layered structure are presented.

Aerated biofilters with multiple-level air injection configurations to enhance biological treatment of methane emissions.

PubMed

Farrokhzadeh, Hasti; Hettiaratchi, J Patrick A; Jayasinghe, Poornima; Kumar, Sunil

2017-09-01

Aiming to improve conventional methane biofilter performance, a multiple-level aeration biofilter design is proposed. Laboratory flow-through column experiments were conducted to evaluate three actively-aerated methane biofilter configurations. Columns were aerated at one, two, and three levels of the bed depth, with air introduced at flow rates calculated from methane oxidation reaction stoichiometry. Inlet methane loading rates were increased in five stages between 6 and 18mL/min. The effects of methane feeding rate, levels of aeration, and residence time on methane oxidation rates were determined. Samples collected after completion of flow-through experiments were used to determine methane oxidation kinetic parameters, V max , K m , and methanotrophic community distribution across biofilter columns. Results obtained from mixed variances analysis and response surfaces, as well as methanotrophic activity data, suggested that, biofilter column with two aeration levels has the most even performance over time, maintaining 85.1% average oxidation efficiency over 95days of experiments. Copyright © 2017 Elsevier Ltd. All rights reserved.

Simultaneous enhancement of methane production and methane content in biogas from waste activated sludge and perennial ryegrass anaerobic co-digestion: The effects of pH and C/N ratio.

PubMed

Dai, Xiaohu; Li, Xiaoshuai; Zhang, Dong; Chen, Yinguang; Dai, Lingling

2016-09-01

It is necessary to find an appropriate strategy to simultaneously enhance the methane production and methane content in biogas from waste activated sludge (WAS) and grass co-digestion. In this study an efficient strategy, i.e., adjusting the initial pH 12 and C/N ratio 17/1, for simultaneous enhancement of methane production and methane content in biogas from WAS and perennial ryegrass co-digestion was reported. Experimental results indicated that the maximal methane production was 310mL/gVSadd at the optimum conditions after 30-d anaerobic digestion, which was, respectively, about 1.5- and 3.8-fold of the sole WAS and sole perennial ryegrass anaerobic digestion. Meanwhile, the methane content in biogas was about 74%, which was much higher than that of sole WAS (64%) or sole perennial ryegrass (54%) anaerobic digestion. Copyright © 2016 Elsevier Ltd. All rights reserved.

Methane hydrate formation and decomposition: structural studies via neutron diffraction and empirical potential structure refinement.

PubMed

Thompson, Helen; Soper, Alan K; Buchanan, Piers; Aldiwan, Nawaf; Creek, Jefferson L; Koh, Carolyn A

2006-04-28

Neutron diffraction studies with hydrogen/deuterium isotope substitution measurements are performed to investigate the water structure at the early, medium, and late periods of methane clathrate hydrate formation and decomposition. These measurements are coupled with simultaneous gas consumption measurements to track the formation of methane hydrate from a gas/water mixture, and then the complete decomposition of hydrate. Empirical potential structure refinement computer simulations are used to analyze the neutron diffraction data and extract from the data the water structure in the bulk methane hydrate solution. The results highlight the significant changes in the water structure of the remaining liquid at various stages of hydrate formation and decomposition, and give further insight into the way in which hydrates form. The results also have important implications on the memory effect, suggesting that the water structure in the presence of hydrate crystallites is significantly different at equivalent stages of forming compared to decomposing. These results are in sharp contrast to the previously reported cases when all remaining hydrate crystallites are absent from the solution. For these systems there is no detectable change in the water structure or the methane hydration shell before hydrate formation and after decomposition. Based on the new results presented in this paper, it is clear that the local water structure is affected by the presence of hydrate crystallites, which may in turn be responsible for the "history" or "memory" effect where the production of hydrate from a solution of formed and then subsequently melted hydrate is reportedly much quicker than producing hydrate from a fresh water/gas mixture.

Evidence for methane in Martian meteorites

PubMed Central

Blamey, Nigel J. F.; Parnell, John; McMahon, Sean; Mark, Darren F.; Tomkinson, Tim; Lee, Martin; Shivak, Jared; Izawa, Matthew R. M.; Banerjee, Neil R.; Flemming, Roberta L.

2015-01-01

The putative occurrence of methane in the Martian atmosphere has had a major influence on the exploration of Mars, especially by the implication of active biology. The occurrence has not been borne out by measurements of atmosphere by the MSL rover Curiosity but, as on Earth, methane on Mars is most likely in the subsurface of the crust. Serpentinization of olivine-bearing rocks, to yield hydrogen that may further react with carbon-bearing species, has been widely invoked as a source of methane on Mars, but this possibility has not hitherto been tested. Here we show that some Martian meteorites, representing basic igneous rocks, liberate a methane-rich volatile component on crushing. The occurrence of methane in Martian rock samples adds strong weight to models whereby any life on Mars is/was likely to be resident in a subsurface habitat, where methane could be a source of energy and carbon for microbial activity. PMID:26079798

Variations in Gas and Water Pulses at an Arctic Seep: Fluid Sources and Methane Transport

NASA Astrophysics Data System (ADS)

Hong, W.-L.; Torres, M. E.; Portnov, A.; Waage, M.; Haley, B.; Lepland, A.

2018-05-01

Methane fluxes into the oceans are largely dependent on the methane phase as it migrates upward through the sediments. Here we document decoupled methane transport by gaseous and aqueous phases in Storfjordrenna (offshore Svalbard) and propose a three-stage evolution model for active seepage in the region where gas hydrates are present in the shallow subsurface. In a preactive seepage stage, solute diffusion is the primary transport mechanism for methane in the dissolved phase. Fluids containing dissolved methane have high 87Sr/86Sr ratios due to silicate weathering in the microbial methanogenesis zone. During the active seepage stage, migration of gaseous methane results in near-seafloor gas hydrate formation and vigorous seafloor gas discharge with a thermogenic fingerprint. In the postactive seepage stage, the high concentration of dissolved lithium points to the contribution of a deeper-sourced aqueous fluid, which we postulate advects upward following cessation of gas discharge.

Evidence for methane in Martian meteorites.

PubMed

Blamey, Nigel J F; Parnell, John; McMahon, Sean; Mark, Darren F; Tomkinson, Tim; Lee, Martin; Shivak, Jared; Izawa, Matthew R M; Banerjee, Neil R; Flemming, Roberta L

2015-06-16

The putative occurrence of methane in the Martian atmosphere has had a major influence on the exploration of Mars, especially by the implication of active biology. The occurrence has not been borne out by measurements of atmosphere by the MSL rover Curiosity but, as on Earth, methane on Mars is most likely in the subsurface of the crust. Serpentinization of olivine-bearing rocks, to yield hydrogen that may further react with carbon-bearing species, has been widely invoked as a source of methane on Mars, but this possibility has not hitherto been tested. Here we show that some Martian meteorites, representing basic igneous rocks, liberate a methane-rich volatile component on crushing. The occurrence of methane in Martian rock samples adds strong weight to models whereby any life on Mars is/was likely to be resident in a subsurface habitat, where methane could be a source of energy and carbon for microbial activity.

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

USGS Publications Warehouse

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

2015-01-01

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

Analyses of geological and hydrodynamic controls on methane emissions experienced in a Lower Kittanning coal mine

PubMed Central

Karacan, C. Özgen; Goodman, Gerrit V.R.

2015-01-01

This paper presents a study assessing potential factors and migration paths of methane emissions experienced in a room-and-pillar mine in Lower Kittanning coal, Indiana County, Pennsylvania. Methane emissions were not excessive at idle mining areas, but significant methane was measured during coal mining and loading. Although methane concentrations in the mine did not exceed 1% limit during operation due to the presence of adequate dilution airflow, the source of methane and its migration into the mine was still a concern. In the course of this study, structural and depositional properties of the area were evaluated to assess complexity and sealing capacity of roof rocks. Composition, gas content, and permeability of Lower Kittanning coal, results of flotation tests, and geochemistry of groundwater obtained from observation boreholes were studied to understand the properties of coal and potential effects of old abandoned mines within the same area. These data were combined with the data obtained from exploration boreholes, such as depths, elevations, thicknesses, ash content, and heat value of coal. Univariate statistical and principal component analyses (PCA), as well as geostatistical simulations and co-simulations, were performed on various spatial attributes to reveal interrelationships and to establish area-wide distributions. These studies helped in analyzing groundwater quality and determining gas-in-place (GIP) of the Lower Kittanning seam. Furthermore, groundwater level and head on the Lower Kittanning coal were modeled and flow gradients within the study area were examined. Modeling results were interpreted with the structural geology of the Allegheny Group of formations above the Lower Kittanning coal to understand the potential source of gas and its migration paths. Analyses suggested that the source of methane was likely the overlying seams such as the Middle and Upper Kittanning coals and Freeport seams of the Allegheny Group. Simulated ground-water water elevations, gradients of groundwater flow, and the presence of recharge and discharge locations at very close proximity to the mine indicated that methane likely was carried with groundwater towards the mine entries. Existing fractures within the overlying strata and their orientation due to the geologic conditions of the area, and activation of slickensides between shale and sandstones due to differential compaction during mining, were interpreted as the potential flow paths. PMID:26478644

Methane Emissions from Landfill: Isotopic Evidence for Low Percentage of Oxidation from Gas Wells, Active and Closed Cells

NASA Astrophysics Data System (ADS)

Lowry, David; Fisher, Rebecca; Zazzeri, Giulia; al-Shalaan, Aalia; France, James; Lanoisellé, Mathias; Nisbet, Euan

2017-04-01

Large landfill sites remain a significant source of methane emissions in developed and developing countries, with a global estimated flux of 29 Tg / yr in the EDGAR 2008 database. This is significantly lower than 20 years ago due to the introduction of gas extraction systems, but active cells still emit significant amounts of methane before the gas is ready for extraction. Historically the methane was either passively oxidized through topsoil layers or flared. Oxidation is still the primary method of methane removal in many countries, and covered, remediated cells across the world continue to emit small quantities of methane. The isotopic signatures of methane from landfill gas wells, and that emitted from active and closed cells have been characterized for more than 20 UK landfills since 2011, with more recent work in Kuwait and Hong Kong. Since 2013 the emission plumes have been identified by a mobile measurement system (Zazzeri et al., 2015). Emissions in all 3 countries have a characteristic δ13C signature of -58 ± 3 ‰ dominated by emissions from the active cells, despite the hot, dry conditions of Kuwait and the hot, humid conditions of Hong Kong. Gas well samples define a similar range. Surface emissions from closed cells and closed landfills are mostly in the range -56 to -52 ‰Ṫhese are much more depleted values than those observed in the 1990s (up to -35 ) when soil oxidation was the dominant mechanism of methane removal. Calculations using isotopic signatures of the amount of methane oxidised in these closed areas before emission to atmosphere range from 5 to 15%, but average less than 10%, and are too small to calculate from the high-emitting active cells. Compared to other major methane sources, landfills have the most consistent isotopic signature globally, and are distinct from the more 13C-enriched natural gas, combustion and biomass burning sources. Zazzeri, G. et al. (2015) Plume mapping and isotopic characterization of anthropogenic methane sources, Atmospheric Environment, 110, 151-162, doi.org/10.1016/j.atmosenv.2015.03.029.

Microbial community structure and soil pH correspond to methane production in Arctic Alaska soils.

PubMed

Wagner, Robert; Zona, Donatella; Oechel, Walter; Lipson, David

2017-08-01

While there is no doubt that biogenic methane production in the Arctic is an important aspect of global methane emissions, the relative roles of microbial community characteristics and soil environmental conditions in controlling Arctic methane emissions remains uncertain. Here, relevant methane-cycling microbial groups were investigated at two remote Arctic sites with respect to soil potential methane production (PMP). Percent abundances of methanogens and iron-reducing bacteria correlated with increased PMP, while methanotrophs correlated with decreased PMP. Interestingly, α-diversity of the methanogens was positively correlated with PMP, while β-diversity was unrelated to PMP. The β-diversity of the entire microbial community, however, was related to PMP. Shannon diversity was a better correlate of PMP than Simpson diversity across analyses, while rarefied species richness was a weak correlate of PMP. These results demonstrate the following: first, soil pH and microbial community structure both probably control methane production in Arctic soils. Second, there may be high functional redundancy in the methanogens with regard to methane production. Third, iron-reducing bacteria co-occur with methanogens in Arctic soils, and iron-reduction-mediated effects on methanogenesis may be controlled by α- and β-diversity. And finally, species evenness and rare species abundances may be driving relationships between microbial groups, influencing Arctic methane production. © 2017 Society for Applied Microbiology and John Wiley & Sons Ltd.

Methanogenic community composition in an organic waste mixture in an anaerobic bioreactor

NASA Astrophysics Data System (ADS)

Gryta, Agata; Oszust, Karolina; Brzezińska, Małgorzata; Ziemiński, Krzysztof; Bilińska-Wielgus, Nina; Frąc, Magdalena

2017-07-01

The aim of the study was to elucidate the substantial relationship between the compositions of methanogen community that assembles in the anaerobic digester mass and link it to methane production activity. The results of the metagenomic studies were used to evaluate how the methanogen structure changes during an anaerobic digestion process under various waste retention times (21, 23, 25, 29, 33, 39, 47 and 61 days). Phylogenetically coherent populations of methanogens were assessed by 16S rRNA gene next-generation sequencing and terminal restriction fragment length polymorphism fingerprinting of a specific molecular marker, the mcrA gene. The results indicated multiple phylogenetically diverse methanogen populations associated with the various steps of anaerobic digestion. The stages of the anaerobic digestion process and waste retention times determine the microbial composition. The most dominant and acclimated microbial communities in all samples belonged to the genera Methanosaeta and Methanobacterium. The methane yield was consistent with the results of the microbial community structure, which indicated that acetotrophic Methanosaeta was the most active and most important during the methanogenic stage.

Niche differentiation in nitrogen metabolism among methanotrophs within an operational taxonomic unit

PubMed Central

2014-01-01

Background The currently accepted thesis on nitrogenous fertilizer additions on methane oxidation activity assumes niche partitioning among methanotrophic species, with activity responses to changes in nitrogen content being dependent on the in situ methanotrophic community structure Unfortunately, widely applied tools for microbial community assessment only have a limited phylogenetic resolution mostly restricted to genus level diversity, and not to species level as often mistakenly assumed. As a consequence, intragenus or intraspecies metabolic versatility in nitrogen metabolism was never evaluated nor considered among methanotrophic bacteria as a source of differential responses of methane oxidation to nitrogen amendments. Results We demonstrated that fourteen genotypically different Methylomonas strains, thus distinct below the level at which most techniques assign operational taxonomic units (OTU), show a versatile physiology in their nitrogen metabolism. Differential responses, even among strains with identical 16S rRNA or pmoA gene sequences, were observed for production of nitrite and nitrous oxide from nitrate or ammonium, nitrogen fixation and tolerance to high levels of ammonium, nitrate, and hydroxylamine. Overall, reduction of nitrate to nitrite, nitrogen fixation, higher tolerance to ammonium than nitrate and tolerance and assimilation of nitrite were general features. Conclusions Differential responses among closely related methanotrophic strains to overcome inhibition and toxicity from high nitrogen loads and assimilation of various nitrogen sources yield competitive fitness advantages to individual methane-oxidizing bacteria. Our observations proved that community structure at the deepest phylogenetic resolution potentially influences in situ functioning. PMID:24708438

Niche differentiation in nitrogen metabolism among methanotrophs within an operational taxonomic unit.

PubMed

Hoefman, Sven; van der Ha, David; Boon, Nico; Vandamme, Peter; De Vos, Paul; Heylen, Kim

2014-04-04

The currently accepted thesis on nitrogenous fertilizer additions on methane oxidation activity assumes niche partitioning among methanotrophic species, with activity responses to changes in nitrogen content being dependent on the in situ methanotrophic community structure Unfortunately, widely applied tools for microbial community assessment only have a limited phylogenetic resolution mostly restricted to genus level diversity, and not to species level as often mistakenly assumed. As a consequence, intragenus or intraspecies metabolic versatility in nitrogen metabolism was never evaluated nor considered among methanotrophic bacteria as a source of differential responses of methane oxidation to nitrogen amendments. We demonstrated that fourteen genotypically different Methylomonas strains, thus distinct below the level at which most techniques assign operational taxonomic units (OTU), show a versatile physiology in their nitrogen metabolism. Differential responses, even among strains with identical 16S rRNA or pmoA gene sequences, were observed for production of nitrite and nitrous oxide from nitrate or ammonium, nitrogen fixation and tolerance to high levels of ammonium, nitrate, and hydroxylamine. Overall, reduction of nitrate to nitrite, nitrogen fixation, higher tolerance to ammonium than nitrate and tolerance and assimilation of nitrite were general features. Differential responses among closely related methanotrophic strains to overcome inhibition and toxicity from high nitrogen loads and assimilation of various nitrogen sources yield competitive fitness advantages to individual methane-oxidizing bacteria. Our observations proved that community structure at the deepest phylogenetic resolution potentially influences in situ functioning.

Methane oxidation coupled to oxygenic photosynthesis in anoxic waters

PubMed Central

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

2015-01-01

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

Molar tooth carbonates and benthic methane fluxes in Proterozoic oceans.

PubMed

Shen, Bing; Dong, Lin; Xiao, Shuhai; Lang, Xianguo; Huang, Kangjun; Peng, Yongbo; Zhou, Chuanming; Ke, Shan; Liu, Pengju

2016-01-07

Molar tooth structures are ptygmatically folded and microspar-filled structures common in early- and mid-Proterozoic (∼2,500-750 million years ago, Ma) subtidal successions, but extremely rare in rocks <750 Ma. Here, on the basis of Mg and S isotopes, we show that molar tooth structures may have formed within sediments where microbial sulphate reduction and methanogenesis converged. The convergence was driven by the abundant production of methyl sulphides (dimethyl sulphide and methanethiol) in euxinic or H2S-rich seawaters that were widespread in Proterozoic continental margins. In this convergence zone, methyl sulphides served as a non-competitive substrate supporting methane generation and methanethiol inhibited anaerobic oxidation of methane, resulting in the buildup of CH4, formation of degassing cracks in sediments and an increase in the benthic methane flux from sediments. Precipitation of crack-filling microspar was driven by methanogenesis-related alkalinity accumulation. Deep ocean ventilation and oxygenation around 750 Ma brought molar tooth structures to an end.

Molar tooth carbonates and benthic methane fluxes in Proterozoic oceans

PubMed Central

Shen, Bing; Dong, Lin; Xiao, Shuhai; Lang, Xianguo; Huang, Kangjun; Peng, Yongbo; Zhou, Chuanming; Ke, Shan; Liu, Pengju

2016-01-01

Molar tooth structures are ptygmatically folded and microspar-filled structures common in early- and mid-Proterozoic (∼2,500–750 million years ago, Ma) subtidal successions, but extremely rare in rocks <750 Ma. Here, on the basis of Mg and S isotopes, we show that molar tooth structures may have formed within sediments where microbial sulphate reduction and methanogenesis converged. The convergence was driven by the abundant production of methyl sulphides (dimethyl sulphide and methanethiol) in euxinic or H2S-rich seawaters that were widespread in Proterozoic continental margins. In this convergence zone, methyl sulphides served as a non-competitive substrate supporting methane generation and methanethiol inhibited anaerobic oxidation of methane, resulting in the buildup of CH4, formation of degassing cracks in sediments and an increase in the benthic methane flux from sediments. Precipitation of crack-filling microspar was driven by methanogenesis-related alkalinity accumulation. Deep ocean ventilation and oxygenation around 750 Ma brought molar tooth structures to an end. PMID:26739600

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

Roberts, F. Sloan; Kuhl, Kendra P.; Nilsson, Anders

The activity and selectivity for CO 2/CO reduction over copper electrodes is strongly dependent on the local surface structure of the catalyst and the pH of the electrolyte. Here we investigate a unique, copper nanocube surface (CuCube) as a CO reduction electrode under neutral and basic pH, using online electrochemical mass spectroscopy (OLEMS) to determine the onset potentials and relative intensities of methane and ethylene production. To relate the unique selectivity to the surface structure, the CuCube surface reactivity is compared to polycrystalline copper and three single crystals under the same reaction conditions. Here, we find that the high selectivitymore » for ethylene over the CuCube surface is most comparable to the Cu(100) surface, which has the cubic unit cell. However, the suppression of methane production over CuCube is unique to that particular surface. Basic pH is also shown to enhance ethylene selectivity on all surfaces, again with the CuCube surface being unique.« less

Ammonia clathrate hydrates as new solid phases for Titan, Enceladus, and other planetary systems.

PubMed

Shin, Kyuchul; Kumar, Rajnish; Udachin, Konstantin A; Alavi, Saman; Ripmeester, John A

2012-09-11

There is interest in the role of ammonia on Saturn's moons Titan and Enceladus as the presence of water, methane, and ammonia under temperature and pressure conditions of the surface and interior make these moons rich environments for the study of phases formed by these materials. Ammonia is known to form solid hemi-, mono-, and dihydrate crystal phases under conditions consistent with the surface of Titan and Enceladus, but has also been assigned a role as water-ice antifreeze and methane hydrate inhibitor which is thought to contribute to the outgassing of methane clathrate hydrates into these moons' atmospheres. Here we show, through direct synthesis from solution and vapor deposition experiments under conditions consistent with extraterrestrial planetary atmospheres, that ammonia forms clathrate hydrates and participates synergistically in clathrate hydrate formation in the presence of methane gas at low temperatures. The binary structure II tetrahydrofuran + ammonia, structure I ammonia, and binary structure I ammonia + methane clathrate hydrate phases synthesized have been characterized by X-ray diffraction, molecular dynamics simulation, and Raman spectroscopy methods.

Ammonia clathrate hydrates as new solid phases for Titan, Enceladus, and other planetary systems

PubMed Central

Shin, Kyuchul; Kumar, Rajnish; Udachin, Konstantin A.; Alavi, Saman; Ripmeester, John A.

2012-01-01

There is interest in the role of ammonia on Saturn’s moons Titan and Enceladus as the presence of water, methane, and ammonia under temperature and pressure conditions of the surface and interior make these moons rich environments for the study of phases formed by these materials. Ammonia is known to form solid hemi-, mono-, and dihydrate crystal phases under conditions consistent with the surface of Titan and Enceladus, but has also been assigned a role as water-ice antifreeze and methane hydrate inhibitor which is thought to contribute to the outgassing of methane clathrate hydrates into these moons’ atmospheres. Here we show, through direct synthesis from solution and vapor deposition experiments under conditions consistent with extraterrestrial planetary atmospheres, that ammonia forms clathrate hydrates and participates synergistically in clathrate hydrate formation in the presence of methane gas at low temperatures. The binary structure II tetrahydrofuran + ammonia, structure I ammonia, and binary structure I ammonia + methane clathrate hydrate phases synthesized have been characterized by X-ray diffraction, molecular dynamics simulation, and Raman spectroscopy methods. PMID:22908239

Microbial diversity and methanogenic activity of Antrim Shale formation waters from recently fractured wells

PubMed Central

Wuchter, Cornelia; Banning, Erin; Mincer, Tracy J.; Drenzek, Nicholas J.; Coolen, Marco J. L.

2013-01-01

The Antrim Shale in the Michigan Basin is one of the most productive shale gas formations in the U.S., but optimal resource recovery strategies must rely on a thorough understanding of the complex biogeochemical, microbial, and physical interdependencies in this and similar systems. We used Illumina MiSeq 16S rDNA sequencing to analyze the diversity and relative abundance of prokaryotic communities present in Antrim shale formation water of three closely spaced recently fractured gas-producing wells. In addition, the well waters were incubated with a suite of fermentative and methanogenic substrates in an effort to stimulate microbial methane generation. The three wells exhibited substantial differences in their community structure that may arise from their different drilling and fracturing histories. Bacterial sequences greatly outnumbered those of archaea and shared highest similarity to previously described cultures of mesophiles and moderate halophiles within the Firmicutes, Bacteroidetes, and δ- and ε-Proteobacteria. The majority of archaeal sequences shared highest sequence similarity to uncultured euryarchaeotal environmental clones. Some sequences closely related to cultured methylotrophic and hydrogenotrophic methanogens were also present in the initial well water. Incubation with methanol and trimethylamine stimulated methylotrophic methanogens and resulted in the largest increase in methane production in the formation waters, while fermentation triggered by the addition of yeast extract and formate indirectly stimulated hydrogenotrophic methanogens. The addition of sterile powdered shale as a complex natural substrate stimulated the rate of methane production without affecting total methane yields. Depletion of methane indicative of anaerobic methane oxidation (AMO) was observed over the course of incubation with some substrates. This process could constitute a substantial loss of methane in the shale formation. PMID:24367357

Search for memory effects in methane hydrate: structure of water before hydrate formation and after hydrate decomposition.

PubMed

Buchanan, Piers; Soper, Alan K; Thompson, Helen; Westacott, Robin E; Creek, Jefferson L; Hobson, Greg; Koh, Carolyn A

2005-10-22

Neutron diffraction with HD isotope substitution has been used to study the formation and decomposition of the methane clathrate hydrate. Using this atomistic technique coupled with simultaneous gas consumption measurements, we have successfully tracked the formation of the sI methane hydrate from a water/gas mixture and then the subsequent decomposition of the hydrate from initiation to completion. These studies demonstrate that the application of neutron diffraction with simultaneous gas consumption measurements provides a powerful method for studying the clathrate hydrate crystal growth and decomposition. We have also used neutron diffraction to examine the water structure before the hydrate growth and after the hydrate decomposition. From the neutron-scattering curves and the empirical potential structure refinement analysis of the data, we find that there is no significant difference between the structure of water before the hydrate formation and the structure of water after the hydrate decomposition. Nor is there any significant change to the methane hydration shell. These results are discussed in the context of widely held views on the existence of memory effects after the hydrate decomposition.

30 CFR 77.201-2 - Methane accumulations; change in ventilation.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 30 Mineral Resources 1 2011-07-01 2011-07-01 false Methane accumulations; change in ventilation... OF UNDERGROUND COAL MINES Surface Installations § 77.201-2 Methane accumulations; change in ventilation. If, at any time, the air in any structure, enclosure or other facility contains 1.0 volume per...

Thinking Like a Wildcatter: Prospecting for Methane in Arabia Terra, Mars

NASA Technical Reports Server (NTRS)

Allen, C. C.; Oehler, D. Z.

2005-01-01

Methane has been detected in the martian atmosphere at a concentration of approximately 10 ppb. The lifetime of such methane against decomposition by solar radiation is approximately 300 years, strongly suggesting that methane is currently being released to the atmosphere. By analogy to Earth, possible methane sources on Mars include active volcanism, hot springs, frozen methane clathrates, thermally-matured sedimentary organic matter, and extant microbial metabolism. The discovery of any one of these sources would revolutionize our understanding of Mars.

Diamond-anvil cell observations of a new methane hydrate phase in the 100-MPa pressure range

USGS Publications Warehouse

Chou, I.-Ming; Sharma, A.; Burruss, R.C.; Hemley, R.J.; Goncharov, A.F.; Stern, L.A.; Kirby, S.H.

2001-01-01

A new high-pressure phase of methane hydrate has been identified based on its high optical relief, distinct pressure-temperature phase relations, and Raman spectra. In-situ optical observations were made in a hydrothermal diamond-anvil cell at temperatures between -40?? and 60 ??C and at pressures up to 900 MPa. Two new invariant points were located at -8.7 ??C and 99 MPa for the assemblage consisting of the new phase, structure I methane hydrate, ice Ih, and water, and at 35.3 ??C and 137 MPa for the new phase-structure I methane hydrate-water-methane vapor. Existence of the new phase is critical for understanding the phase relations among the hydrates at low to moderate pressures, and may also have important implications for understanding the hydrogen bonding in H2O and the behavior of water in the planetary bodies, such as Europa, of the outer solar system.

Temporal variation of aerobic methane oxidation over a tidal cycle in a wetland of northern Taiwan.

NASA Astrophysics Data System (ADS)

Lee, T. Y.; Wang, P. L.; Lin, L. H.

2017-12-01

Aerobic methanotrophy plays an important role in controlling methane emitted from wetlands. However, the activity of aerobic methanotrophy regulated by temporal fluctuation of oxygen and methane supply in tidal wetlands is not well known. This study aims to examine the dynamics of methane fluxes and potential aerobic methane consumption rates in a tidal wetland of northern Taiwan, where the variation of environmental characteristics, such as sulfate and methane concentration in pore water has been demonstrated during a tidal cycle. Two field campaigns were carried out in December of 2016 and March of 2017. Fluxes of methane emission, methane concentrations in surface sediments and oxygen profiles were measured at different tidal phases. Besides, batch incubations were conducted on surface sediments in order to quantify potential microbial methane consumption rates and to derive the kinetic parameters for aerobic methanotrophy. Our results demonstrated temporal changes of the surface methane concentration and the methane emission flux during a tidal cycle, while the oxygen flux into the sediment was kept at a similar magnitude. The methane flux was low when the surface was exposed for both shortest and longest periods of time. The potential aerobic methane oxidation rate was high for sample collected from the surface sediments exposed the longest. No correlation could be found between the potential aerobic methane oxidation rate and either the oxygen downward flux or methane emission flux. The decoupled relationships between these observed rates and fluxes suggest that, rather than aerobic methanotrophy, heterotrophic respirations exert a profound control on oxygen flux, and the methane emission is not only been affected by methane consumption but also methane production at depths. The maximum potential rate and the half saturation concentration determined from the batch incubations were high for the surface sediments collected in low tide, suggesting that aerobic methanotrophy could be modulated to reach peak activity once the influence of saline water is reduced to a low level.

Mechanical instability of monocrystalline and polycrystalline methane hydrates

PubMed Central

Wu, Jianyang; Ning, Fulong; Trinh, Thuat T.; Kjelstrup, Signe; Vlugt, Thijs J. H.; He, Jianying; Skallerud, Bjørn H.; Zhang, Zhiliang

2015-01-01

Despite observations of massive methane release and geohazards associated with gas hydrate instability in nature, as well as ductile flow accompanying hydrate dissociation in artificial polycrystalline methane hydrates in the laboratory, the destabilising mechanisms of gas hydrates under deformation and their grain-boundary structures have not yet been elucidated at the molecular level. Here we report direct molecular dynamics simulations of the material instability of monocrystalline and polycrystalline methane hydrates under mechanical loading. The results show dislocation-free brittle failure in monocrystalline hydrates and an unexpected crossover from strengthening to weakening in polycrystals. Upon uniaxial depressurisation, strain-induced hydrate dissociation accompanied by grain-boundary decohesion and sliding destabilises the polycrystals. In contrast, upon compression, appreciable solid-state structural transformation dominates the response. These findings provide molecular insight not only into the metastable structures of grain boundaries, but also into unusual ductile flow with hydrate dissociation as observed during macroscopic compression experiments. PMID:26522051

Self-preservation and structural transition of gas hydrates during dissociation below the ice point: an in situ study using Raman spectroscopy

PubMed Central

Zhong, Jin-Rong; Zeng, Xin-Yang; Zhou, Feng-He; Ran, Qi-Dong; Sun, Chang-Yu; Zhong, Rui-Qin; Yang, Lan-Ying; Chen, Guang-Jin; Koh, Carolyn A.

2016-01-01

The hydrate structure type and dissociation behavior for pure methane and methane-ethane hydrates at temperatures below the ice point and atmospheric pressure were investigated using in situ Raman spectroscopic analysis. The self-preservation effect of sI methane hydrate is significant at lower temperatures (268.15 to 270.15 K), as determined by the stable C-H region Raman peaks and AL/AS value (Ratio of total peak area corresponding to occupancies of guest molecules in large cavities to small cavities) being around 3.0. However, it was reduced at higher temperatures (271.15 K and 272.15 K), as shown from the dramatic change in Raman spectra and fluctuations in AL/AS values. The self-preservation effect for methane-ethane double hydrate is observed at temperatures lower than 271.15 K. The structure transition from sI to sII occurred during the methane-ethane hydrate decomposition process, which was clearly identified by the shift in peak positions and the change in relative peak intensities at temperatures from 269.15 K to 271.15 K. Further investigation shows that the selectivity for self-preservation of methane over ethane leads to the structure transition; this kind of selectivity increases with decreasing temperature. This work provides new insight into the kinetic behavior of hydrate dissociation below the ice point. PMID:27941857

Self-preservation and structural transition of gas hydrates during dissociation below the ice point: an in situ study using Raman spectroscopy.

PubMed

Zhong, Jin-Rong; Zeng, Xin-Yang; Zhou, Feng-He; Ran, Qi-Dong; Sun, Chang-Yu; Zhong, Rui-Qin; Yang, Lan-Ying; Chen, Guang-Jin; Koh, Carolyn A

2016-12-12

The hydrate structure type and dissociation behavior for pure methane and methane-ethane hydrates at temperatures below the ice point and atmospheric pressure were investigated using in situ Raman spectroscopic analysis. The self-preservation effect of sI methane hydrate is significant at lower temperatures (268.15 to 270.15 K), as determined by the stable C-H region Raman peaks and A L /A S value (Ratio of total peak area corresponding to occupancies of guest molecules in large cavities to small cavities) being around 3.0. However, it was reduced at higher temperatures (271.15 K and 272.15 K), as shown from the dramatic change in Raman spectra and fluctuations in A L /A S values. The self-preservation effect for methane-ethane double hydrate is observed at temperatures lower than 271.15 K. The structure transition from sI to sII occurred during the methane-ethane hydrate decomposition process, which was clearly identified by the shift in peak positions and the change in relative peak intensities at temperatures from 269.15 K to 271.15 K. Further investigation shows that the selectivity for self-preservation of methane over ethane leads to the structure transition; this kind of selectivity increases with decreasing temperature. This work provides new insight into the kinetic behavior of hydrate dissociation below the ice point.

Changes in deep-sea carbonate-hosted microbial communities associated with high and low methane flux

NASA Astrophysics Data System (ADS)

Case, D. H.; Steele, J. A.; Chadwick, G.; Mendoza, G. F.; Levin, L. A.; Orphan, V. J.

2012-12-01

Methane seeps on continental shelves are rich in authigenic carbonates built of methane-derived carbon. These authigenic carbonates are home to micro- and macroscopic communities whose compositions are thus far poorly constrained but are known to broadly depend on local methane flux. The formation of authigenic carbonates is itself a result of microbial metabolic activity, as associations of anaerobic methane oxidizing archaea (ANME) and sulfate reducing bacteria (SRB) in the sediment subsurface increase both dissolved inorganic carbon (DIC) and alkalinity in pore waters. This 1:1 increase in DIC and alkalinity promotes the precipitation of authigenic carbonates. In this study, we performed in situ manipulations to test the response of micro- and macrofaunal communities to a change in methane flux. Methane-derived authigenic carbonates from two locations at Hydrate Ridge, OR, USA (depth range 595-604 mbsl), were transplanted from "active" cold seep sites (high methane flux) to "inactive" background sites (low methane flux), and vise versa, for one year. Community diversity surveys using T-RFLP and 16S rRNA clone libraries revealed how both bacterial and archaeal assemblages respond to this change in local environment, specifically demonstrating reproducible shifts in different ANME groups (ANME-1 vs. ANME-2). Animal assemblage composition also shifted during transplantation; gastropod representation increased (relative to control rocks) when substrates were moved from inactive to active sites and polychaete, crustacean and echinoderm representation increased when substrates were moved from active to inactive sites. Combined with organic and inorganic carbon δ13C measurements and mineralogy, this unique in situ experiment demonstrates that authigenic carbonates are viable habitats, hosting microbial and macrofaunal communities capable of responding to changes in external environment over relatively short time periods.

Correction: Conceptual design of tetraazaporphyrin- and subtetraazaporphyrin-based functional nanocarbon materials: electronic structures, topologies, optical properties, and methane storage capacities.

PubMed

Belosludov, Rodion V; Rhoda, Hannah M; Zhdanov, Ravil K; Belosludov, Vladimir R; Kawazoe, Yoshiyuki; Nemykin, Victor N

2017-08-02

Correction for 'Conceptual design of tetraazaporphyrin- and subtetraazaporphyrin-based functional nanocarbon materials: electronic structures, topologies, optical properties, and methane storage capacities' by Rodion V. Belosludov et al., Phys. Chem. Chem. Phys., 2016, 18, 13503-13518.

Impact of Peat Mining and Restoration on Methane Turnover Potential and Methane-Cycling Microorganisms in a Northern Bog.

PubMed

Reumer, Max; Harnisz, Monika; Lee, Hyo Jung; Reim, Andreas; Grunert, Oliver; Putkinen, Anuliina; Fritze, Hannu; Bodelier, Paul L E; Ho, Adrian

2018-02-01

Ombrotrophic peatlands are a recognized global carbon reservoir. Without restoration and peat regrowth, harvested peatlands are dramatically altered, impairing their carbon sink function, with consequences for methane turnover. Previous studies determined the impact of commercial mining on the physicochemical properties of peat and the effects on methane turnover. However, the response of the underlying microbial communities catalyzing methane production and oxidation have so far received little attention. We hypothesize that with the return of Sphagnum spp. postharvest, methane turnover potential and the corresponding microbial communities will converge in a natural and restored peatland. To address our hypothesis, we determined the potential methane production and oxidation rates in natural (as a reference), actively mined, abandoned, and restored peatlands over two consecutive years. In all sites, the methanogenic and methanotrophic population sizes were enumerated using quantitative PCR (qPCR) assays targeting the mcrA and pmoA genes, respectively. Shifts in the community composition were determined using Illumina MiSeq sequencing of the mcrA gene and a pmoA -based terminal restriction fragment length polymorphism (t-RFLP) analysis, complemented by cloning and sequence analysis of the mmoX gene. Peat mining adversely affected methane turnover potential, but the rates recovered in the restored site. The recovery in potential activity was reflected in the methanogenic and methanotrophic abundances. However, the microbial community composition was altered, being more pronounced for the methanotrophs. Overall, we observed a lag between the recovery of the methanogenic/methanotrophic activity and the return of the corresponding microbial communities, suggesting that a longer duration (>15 years) is needed to reverse mining-induced effects on the methane-cycling microbial communities. IMPORTANCE Ombrotrophic peatlands are a crucial carbon sink, but this environment is also a source of methane, an important greenhouse gas. Methane emission in peatlands is regulated by methane production and oxidation catalyzed by methanogens and methanotrophs, respectively. Methane-cycling microbial communities have been documented in natural peatlands. However, less is known of their response to peat mining and of the recovery of the community after restoration. Mining exerts an adverse impact on potential methane production and oxidation rates and on methanogenic and methanotrophic population abundances. Peat mining also induced a shift in the methane-cycling microbial community composition. Nevertheless, with the return of Sphagnum spp. in the restored site after 15 years, methanogenic and methanotrophic activity and population abundance recovered well. The recovery, however, was not fully reflected in the community composition, suggesting that >15 years are needed to reverse mining-induced effects. Copyright © 2018 American Society for Microbiology.

Methane rising from the Deep: Hydrates, Bubbles, Oil Spills, and Global Warming

NASA Astrophysics Data System (ADS)

Leifer, I.; Rehder, G. J.; Solomon, E. A.; Kastner, M.; Asper, V. L.; Joye, S. B.

2011-12-01

Elevated methane concentrations in near-surface waters and the atmosphere have been reported for seepage from depths of nearly 1 km at the Gulf of Mexico hydrate observatory (MC118), suggesting that for some methane sources, deepsea methane is not trapped and can contribute to atmospheric greenhouse gas budgets. Ebullition is key with important sensitivity to the formation of hydrate skins and oil coatings, high-pressure solubility, bubble size and bubble plume processes. Bubble ROV tracking studies showed survival to near thermocline depths. Studies with a numerical bubble propagation model demonstrated that consideration of structure I hydrate skins transported most methane only to mid-water column depths. Instead, consideration of structure II hydrates, which are stable to far shallower depths and appropriate for natural gas mixtures, allows bubbles to survive to far shallower depths. Moreover, model predictions of vertical methane and alkane profiles and bubble size evolution were in better agreement with observations after consideration of structure II hydrate properties as well as an improved implementation of plume properties, such as currents. These results demonstrate the importance of correctly incorporating bubble hydrate processes in efforts to predict the impact of deepsea seepage as well as to understand the fate of bubble-transported oil and methane from deepsea pipeline leaks and well blowouts. Application to the DWH spill demonstrated the importance of deepsea processes to the fate of spilled subsurface oil. Because several of these parameters vary temporally (bubble flux, currents, temperature), sensitivity studies indicate the importance of real-time monitoring data.

CD and MCD studies of the effects of component B variant binding on the biferrous active site of methane monooxygenase.

PubMed

Mitić, Natasa; Schwartz, Jennifer K; Brazeau, Brian J; Lipscomb, John D; Solomon, Edward I

2008-08-12

The multicomponent soluble form of methane monooxygenase (sMMO) catalyzes the oxidation of methane through the activation of O 2 at a nonheme biferrous center in the hydroxylase component, MMOH. Reactivity is limited without binding of the sMMO effector protein, MMOB. Past studies show that mutations of specific MMOB surface residues cause large changes in the rates of individual steps in the MMOH reaction cycle. To define the structural and mechanistic bases for these observations, CD, MCD, and VTVH MCD spectroscopies coupled with ligand-field (LF) calculations are used to elucidate changes occurring near and at the MMOH biferrous cluster upon binding of MMOB and the MMOB variants. Perturbations to both the CD and MCD are observed upon binding wild-type MMOB and the MMOB variant that similarly increases O 2 reactivity. MMOB variants that do not greatly increase O 2 reactivity fail to cause one or both of these changes. LF calculations indicate that reorientation of the terminal glutamate on Fe2 reproduces the spectral perturbations in MCD. Although this structural change allows O 2 to bridge the diiron site and shifts the redox active orbitals for good overlap, it is not sufficient for enhanced O 2 reactivity of the enzyme. Binding of the T111Y-MMOB variant to MMOH induces the MCD, but not CD changes, and causes only a small increase in reactivity. Thus, both the geometric rearrangement at Fe2 (observed in MCD) coupled with a more global conformational change that may control O 2 access (probed by CD), induced by MMOB binding, are critical factors in the reactivity of sMMO.

The effect of heat treatment on the performance of the Ni/(Zr-Sm oxide) catalysts for carbon dioxide methanation

NASA Astrophysics Data System (ADS)

Takano, Hiroyuki; Izumiya, Koichi; Kumagai, Naokazu; Hashimoto, Koji

2011-07-01

The active catalysts for methane formation from the gas mixture of CO 2 + 4H 2 with almost 100% methane selectivity were prepared by reduction of the oxide mixture of NiO and ZrO 2 prepared by calcination of aqueous ZrO 2 sol with Sm(NO 3) 3 and Ni(NO 3) 2. The 50 at%Ni-50 at%(Zr-Sm oxide) catalyst consisting of 50 at%Ni-50 at%(Zr + Sm) with Zr/Sm = 5 calcined at 650 or 800 °C showed the highest activity for methanation. The active catalysts were Ni supported on tetragonal ZrO 2, and the activity for methanation increased by an increase in inclusion of Sm 3+ ions substituting Zr 4+ ions in the tetragonal ZrO 2 lattice as a result of an increase in calcination temperature. However, the increase in calcination temperature decreased BET surface area, metal dispersion and hydrogen uptake due to grain growth. Thus, the optimum calcination temperature existed.

Catalytic conversion of methane to methanol using Cu-zeolites.

PubMed

Alayon, Evalyn Mae C; Nachtegaal, Maarten; Ranocchiari, Marco; van Bokhoven, Jeroen A

2012-01-01

The conversion of methane to value-added liquid chemicals is a promising answer to the imminent demand for fuels and chemical synthesis materials in the advent of a dwindling petroleum supply. Current technology requires high energy input for the synthesis gas production, and is characterized by low overall selectivity, which calls for alternative reaction routes. The limitation to achieve high selectivity is the high C-H bond strength of methane. High-temperature reaction systems favor gas-phase radical reactions and total oxidation. This suggests that the catalysts for methane activation should be active at low temperatures. The enzymatic-inspired metal-exchanged zeolite systems apparently fulfill this need, however, methanol yield is low and a catalytic process cannot yet be established. Homogeneous and heterogeneous catalytic systems have been described which stabilize the intermediate formed after the first C-H activation. The understanding of the reaction mechanism and the determination of the active metal sites are important for formulating strategies for the upgrade of methane conversion catalytic technologies.

Polyhydroxyalkanoates in waste activated sludge enhances anaerobic methane production through improving biochemical methane potential instead of hydrolysis rate.

PubMed

Wang, Qilin; Sun, Jing; Zhang, Chang; Xie, Guo-Jun; Zhou, Xu; Qian, Jin; Yang, Guojing; Zeng, Guangming; Liu, Yiqi; Wang, Dongbo

2016-01-21

Anaerobic sludge digestion is the main technology for sludge reduction and stabilization prior to sludge disposal. Nevertheless, methane production from anaerobic digestion of waste activated sludge (WAS) is often restricted by the poor biochemical methane potential and slow hydrolysis rate of WAS. This work systematically investigated the effect of PHA levels of WAS on anaerobic methane production, using both experimental and mathematical modeling approaches. Biochemical methane potential tests showed that methane production increased with increased PHA levels in WAS. Model-based analysis suggested that the PHA-based method enhanced methane production by improving biochemical methane potential of WAS, with the highest enhancement being around 40% (from 192 to 274 L CH4/kg VS added; VS: volatile solid) when the PHA levels increased from 21 to 143 mg/g VS. In contrast, the hydrolysis rate (approximately 0.10 d(-1)) was not significantly affected by the PHA levels. Economic analysis suggested that the PHA-based method could save $1.2/PE/y (PE: population equivalent) in a typical wastewater treatment plant (WWTP). The PHA-based method can be easily integrated into the current WWTP to enhance methane production, thereby providing a strong support to the on-going paradigm shift in wastewater management from pollutant removal to resource recovery.

Zero valent iron significantly enhances methane production from waste activated sludge by improving biochemical methane potential rather than hydrolysis rate.

PubMed

Liu, Yiwen; Wang, Qilin; Zhang, Yaobin; Ni, Bing-Jie

2015-02-05

Anaerobic digestion has been widely applied for waste activated sludge (WAS) treatment. However, methane production from anaerobic digestion of WAS is usually limited by the slow hydrolysis rate and/or poor biochemical methane potential of WAS. This work systematically studied the effects of three different types of zero valent iron (i.e., iron powder, clean scrap and rusty scrap) on methane production from WAS in anaerobic digestion, by using both experimental and mathematical approaches. The results demonstrated that both the clean and the rusty iron scrap were more effective than the iron powder for improving methane production from WAS. Model-based analysis showed that ZVI addition significantly enhanced methane production from WAS through improving the biochemical methane potential of WAS rather than its hydrolysis rate. Economic analysis indicated that the ZVI-based technology for enhancing methane production from WAS is economically attractive, particularly considering that iron scrap can be freely acquired from industrial waste. Based on these results, the ZVI-based anaerobic digestion process of this work could be easily integrated with the conventional chemical phosphorus removal process in wastewater treatment plant to form a cost-effective and environment-friendly approach, enabling maximum resource recovery/reuse while achieving enhanced methane production in wastewater treatment system.

Zero Valent Iron Significantly Enhances Methane Production from Waste Activated Sludge by Improving Biochemical Methane Potential Rather Than Hydrolysis Rate

PubMed Central

Liu, Yiwen; Wang, Qilin; Zhang, Yaobin; Ni, Bing-Jie

2015-01-01

Anaerobic digestion has been widely applied for waste activated sludge (WAS) treatment. However, methane production from anaerobic digestion of WAS is usually limited by the slow hydrolysis rate and/or poor biochemical methane potential of WAS. This work systematically studied the effects of three different types of zero valent iron (i.e., iron powder, clean scrap and rusty scrap) on methane production from WAS in anaerobic digestion, by using both experimental and mathematical approaches. The results demonstrated that both the clean and the rusty iron scrap were more effective than the iron powder for improving methane production from WAS. Model-based analysis showed that ZVI addition significantly enhanced methane production from WAS through improving the biochemical methane potential of WAS rather than its hydrolysis rate. Economic analysis indicated that the ZVI-based technology for enhancing methane production from WAS is economically attractive, particularly considering that iron scrap can be freely acquired from industrial waste. Based on these results, the ZVI-based anaerobic digestion process of this work could be easily integrated with the conventional chemical phosphorus removal process in wastewater treatment plant to form a cost-effective and environment-friendly approach, enabling maximum resource recovery/reuse while achieving enhanced methane production in wastewater treatment system. PMID:25652244

Polyhydroxyalkanoates in waste activated sludge enhances anaerobic methane production through improving biochemical methane potential instead of hydrolysis rate

PubMed Central

Wang, Qilin; Sun, Jing; Zhang, Chang; Xie, Guo-Jun; Zhou, Xu; Qian, Jin; Yang, Guojing; Zeng, Guangming; Liu, Yiqi; Wang, Dongbo

2016-01-01

Anaerobic sludge digestion is the main technology for sludge reduction and stabilization prior to sludge disposal. Nevertheless, methane production from anaerobic digestion of waste activated sludge (WAS) is often restricted by the poor biochemical methane potential and slow hydrolysis rate of WAS. This work systematically investigated the effect of PHA levels of WAS on anaerobic methane production, using both experimental and mathematical modeling approaches. Biochemical methane potential tests showed that methane production increased with increased PHA levels in WAS. Model-based analysis suggested that the PHA-based method enhanced methane production by improving biochemical methane potential of WAS, with the highest enhancement being around 40% (from 192 to 274 L CH4/kg VS added; VS: volatile solid) when the PHA levels increased from 21 to 143 mg/g VS. In contrast, the hydrolysis rate (approximately 0.10 d−1) was not significantly affected by the PHA levels. Economic analysis suggested that the PHA-based method could save $1.2/PE/y (PE: population equivalent) in a typical wastewater treatment plant (WWTP). The PHA-based method can be easily integrated into the current WWTP to enhance methane production, thereby providing a strong support to the on-going paradigm shift in wastewater management from pollutant removal to resource recovery. PMID:26791952

Zero Valent Iron Significantly Enhances Methane Production from Waste Activated Sludge by Improving Biochemical Methane Potential Rather Than Hydrolysis Rate

NASA Astrophysics Data System (ADS)

Liu, Yiwen; Wang, Qilin; Zhang, Yaobin; Ni, Bing-Jie

2015-02-01

Anaerobic digestion has been widely applied for waste activated sludge (WAS) treatment. However, methane production from anaerobic digestion of WAS is usually limited by the slow hydrolysis rate and/or poor biochemical methane potential of WAS. This work systematically studied the effects of three different types of zero valent iron (i.e., iron powder, clean scrap and rusty scrap) on methane production from WAS in anaerobic digestion, by using both experimental and mathematical approaches. The results demonstrated that both the clean and the rusty iron scrap were more effective than the iron powder for improving methane production from WAS. Model-based analysis showed that ZVI addition significantly enhanced methane production from WAS through improving the biochemical methane potential of WAS rather than its hydrolysis rate. Economic analysis indicated that the ZVI-based technology for enhancing methane production from WAS is economically attractive, particularly considering that iron scrap can be freely acquired from industrial waste. Based on these results, the ZVI-based anaerobic digestion process of this work could be easily integrated with the conventional chemical phosphorus removal process in wastewater treatment plant to form a cost-effective and environment-friendly approach, enabling maximum resource recovery/reuse while achieving enhanced methane production in wastewater treatment system.

Polyhydroxyalkanoates in waste activated sludge enhances anaerobic methane production through improving biochemical methane potential instead of hydrolysis rate

NASA Astrophysics Data System (ADS)

Wang, Qilin; Sun, Jing; Zhang, Chang; Xie, Guo-Jun; Zhou, Xu; Qian, Jin; Yang, Guojing; Zeng, Guangming; Liu, Yiqi; Wang, Dongbo

2016-01-01

Anaerobic sludge digestion is the main technology for sludge reduction and stabilization prior to sludge disposal. Nevertheless, methane production from anaerobic digestion of waste activated sludge (WAS) is often restricted by the poor biochemical methane potential and slow hydrolysis rate of WAS. This work systematically investigated the effect of PHA levels of WAS on anaerobic methane production, using both experimental and mathematical modeling approaches. Biochemical methane potential tests showed that methane production increased with increased PHA levels in WAS. Model-based analysis suggested that the PHA-based method enhanced methane production by improving biochemical methane potential of WAS, with the highest enhancement being around 40% (from 192 to 274 L CH4/kg VS added; VS: volatile solid) when the PHA levels increased from 21 to 143 mg/g VS. In contrast, the hydrolysis rate (approximately 0.10 d-1) was not significantly affected by the PHA levels. Economic analysis suggested that the PHA-based method could save $1.2/PE/y (PE: population equivalent) in a typical wastewater treatment plant (WWTP). The PHA-based method can be easily integrated into the current WWTP to enhance methane production, thereby providing a strong support to the on-going paradigm shift in wastewater management from pollutant removal to resource recovery.

A quantitative assessment of methane cycling in Hikurangi Margin sediments (New Zealand) using geophysical imaging and biogeochemical modeling

NASA Astrophysics Data System (ADS)

Luo, Min; Dale, Andrew W.; Haffert, Laura; Haeckel, Matthias; Koch, Stephanie; Crutchley, Gareth; De Stigter, Henko; Chen, Duofu; Greinert, Jens

2016-12-01

Takahe seep, located on the Opouawe Bank, Hikurangi Margin, is characterized by a well-defined subsurface seismic chimney structure ˜80,500 m2 in area. Subseafloor geophysical data based on acoustic anomaly layers indicated the presence of gas hydrate and free gas layers within the chimney structure. Reaction-transport modeling was applied to porewater data from 11 gravity cores to constrain methane turnover rates and benthic methane fluxes in the upper 10 m. Model results show that methane dynamics were highly variable due to transport and dissolution of ascending gas. The dissolution of gas (up to 3761 mmol m-2 yr-1) dwarfed the rate of methanogenesis within the simulated sediment column (2.6 mmol m-2 yr-1). Dissolved methane is mainly consumed by anaerobic oxidation of methane (AOM) at the base of the sulfate reduction zone and trapped by methane hydrate formation below it, with maximum rates in the central part of the chimney (946 and 2420 mmol m-2 yr-1, respectively). A seep-wide methane budget was constrained by combining the biogeochemical model results with geophysical data and led to estimates of AOM rates, gas hydrate formation, and benthic dissolved methane fluxes of 3.68 × 104 mol yr-1, 73.85 × 104 mol yr-1, and 1.19 × 104 mol yr-1, respectively. A much larger flux of methane probably escapes in gaseous form through focused bubble vents. The approach of linking geochemical model results with spatial geophysical data put forward here can be applied elsewhere to improve benthic methane turnover rates from limited single spot measurements to larger spatial scales.

Influence of trace substances on methanation catalysts used in dynamic biogas upgrading.

PubMed

Jürgensen, Lars; Ehimen, Ehiaze Augustine; Born, Jens; Holm-Nielsen, Jens Bo; Rooney, David

2015-02-01

The aim of this work was to study the possible deactivation effects of biogas trace ammonia concentrations on methanation catalysts. It was found that small amounts of ammonia led to a slight decrease in the catalyst activity. A decrease in the catalyst deactivation by carbon formation was also observed, with ammonia absorbed on the active catalyst sites. This was via a suppression of the carbon formation and deposition on the catalyst, since it requires a higher number of active sites than for the methanation of carbon oxides. From the paper findings, no special pretreatment for ammonia removal from the biogas fed to a methanation process is required. Copyright © 2014 Elsevier Ltd. All rights reserved.

The radical mechanism of biological methane synthesis by methyl-coenzyme M reductase

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

Wongnate, T.; Sliwa, D.; Ginovska, B.

2016-05-19

Methyl-coenzyme M reductase (MCR), the rate-limiting enzyme in methanogenesis and anaerobic methane oxidation, is responsible for the production of over one billion tons of methane per year. The mechanism of methane synthesis is unknown, with the two leading proposals involving either a methyl-nickel(III) (Mechanism I) or methyl radical/Ni(II)-thiolate (Mechanism II) intermediate(s). When the reaction between the active Ni(I) enzyme with substrates was studied by transient kinetic, spectroscopic and computational methods, formation of an EPR-silent Ni(II)-thiolate intermediate was positively identified by magnetic circular dichroism spectroscopy. There was no evidence for an EPR-active methyl-Ni(III) species. Temperature-dependent transient kinetic studies revealed that themore » activation energy for the initial catalytic step closely matched the value computed by density functional theory for Mechanism II. Thus, our results demonstrate that biological methane synthesis occurs by generation of a methyl radical.« less

Selective anaerobic oxidation of methane enables direct synthesis of methanol.

PubMed

Sushkevich, Vitaly L; Palagin, Dennis; Ranocchiari, Marco; van Bokhoven, Jeroen A

2017-05-05

Direct functionalization of methane in natural gas remains a key challenge. We present a direct stepwise method for converting methane into methanol with high selectivity (~97%) over a copper-containing zeolite, based on partial oxidation with water. The activation in helium at 673 kelvin (K), followed by consecutive catalyst exposures to 7 bars of methane and then water at 473 K, consistently produced 0.204 mole of CH 3 OH per mole of copper in zeolite. Isotopic labeling confirmed water as the source of oxygen to regenerate the zeolite active centers and renders methanol desorption energetically favorable. On the basis of in situ x-ray absorption spectroscopy, infrared spectroscopy, and density functional theory calculations, we propose a mechanism involving methane oxidation at Cu II oxide active centers, followed by Cu I reoxidation by water with concurrent formation of hydrogen. Copyright © 2017, American Association for the Advancement of Science.

Comparative biochemical methane potential of paragrass using an unacclimated and an acclimated microbial consortium.

PubMed

Nuchdang, Sasikarn; Khemkhao, Maneerat; Techkarnjanaruk, Somkiet; Phalakornkule, Chantaraporn

2015-05-01

The effect of inoculum sources on the anaerobic digestion of paragrass was investigated. Two types of sludge were used as the inoculums: an anaerobic sludge obtained from a domestic wastewater treatment plant (OS) and a sludge acclimated to fibrous substrates in raw palm oil mill effluent (AMC). Microbial activity assays showed that the AMC had hydrolytic and acetogenic activities two times greater than the activities of the OS. In addition, the production of methane from acetate by the AMC occurred without a lag phase, while it took 8 days for the OS to start producing methane from the same substrate. The biochemical methane potential after 80 days digestion was 316 ml STP/g VS(added) using the AMC, and 277 ml STP/g VS(added) using the OS. The methane potential of the paragrass was estimated to be 3337 Nm(3) CH4/ha a. Copyright © 2015 Elsevier Ltd. All rights reserved.

Cordierite-supported metal oxide for non-methane hydrocarbon oxidation in cooking oil fumes.

PubMed

Huang, Yonghai; Yi, Honghong; Tang, Xiaolong; Zhao, Shunzheng; Gao, Fengyu; Wang, Jiangen; Yang, Zhongyu

2018-05-21

Cooking emission is an important reason for the air quality deterioration in the metropolitan area in China. Transition metal oxide and different loading of manganese oxide supported on cordierite were prepared by incipient wetness impregnation method and were used for non-methane hydrocarbon (NMHC) oxidation in cooking oil fumes (COFs). The effects of different calcination temperature and different Mn content were also studied. The SEM photographs and CO 2 temperature-programmed desorption revealed 5 wt% Mn/cordierite had the best pore structure and the largest number of the weak and moderate basic sites so it showed the best performance for NMHC oxidation. XRD analysis exhibited 5 wt% Mn/cordierite had the best dispersion of active phase and the active phase was MnO 2 when the calcination temperature was 400℃ which were good for the catalytic oxidation of NMHC.

Vertical structure and horizontal variations in the cycling of methane in the sediment of Lake Onego, Russia

NASA Astrophysics Data System (ADS)

Thomas, Camille; Perga, Marie-Elodie; Frossard, Victor; Pasche, Natacha; Hofmann, Hilmar; Ariztegui, Daniel; Dubois, Nathalie; Belkina, Natalya; Lyautey, Emilie

2017-04-01

Lake Onego, the second largest lake in Europe, is a dystrophic, seasonally ice-covered lake in Karelia, Russia. Like most winter-covered lakes, its study has largely been limited to the summer period. However, it is well known that methane production is still ongoing in lake sediments during winter, potentially resulting in accumulation and major release upon thawing. Within the "Life Under The Ice" research project, our objectives were to assess winter contribution to the annual methane flux in Lake Onego, and to understand conditions and factors influencing methane cycling. During two on-ice field campaigns in March 2015 and 2016, sediment cores were retrieved at different sites of Petrozavodsk Bay, located in the north-western part of the lake. DNA and RNA were extracted from these cores to investigate the functional structure of microbial communities. Genes involved in methanogenesis, anaerobic and aerobic methane oxidations were quantified along with the concentrations and isotopic ratio of methane in the sediment pore water. Incubations, fingerprinting and sequencing of mcrA genes were also realized. Vertically, the sediment is structured in a deep anoxic zone (below 10 cm) where mcrA gene and transcript copies increased implying methanogenesis, a transitional zone (5-8 cm) hosting methanotrophic organisms (Cand. Methanoperedens) able to oxidize the diffusing methane anaerobically by coupling nitrate reduction (Haroon et al., 2013), and a shallower oxic zone where methanotrophs were detected (pmoA gene and transcripts) and where methane concentrations drop below detection limit. Sediment cores were also collected at three sites along a transect from the mouth of the river Shuya (the major inflow to the bay) to the open lake. Functional assemblage close to the river mouth had higher diversity and higher potential production rates and consumption of methane than further in the lake. However, the methane produced was almost completely consumed regardless of the sites, suggesting that this heterogeneity does not convey significant methane inputs to Lake Onego's water column during ice cover in winter. Haroon, M. F., Hu, S., Shi, Y., Imelfort, M., Keller, J., Hugenholtz, P., … Tyson, G. W. (2013). Anaerobic oxidation of methane coupled to nitrate reduction in a novel archaeal lineage. Nature, 500(7464), 567-70.

Spatial and temporal distribution of nitrite-dependent anaerobic methane-oxidizing bacteria in an intertidal zone of the East China Sea.

PubMed

Wang, Jiaqi; Shen, Lidong; He, Zhanfei; Hu, Jiajie; Cai, Zhaoyang; Zheng, Ping; Hu, Baolan

2017-11-01

Nitrite-dependent anaerobic methane oxidation (N-DAMO), which couples anaerobic methane oxidation and nitrite reduction, is a recently discovered bioprocess coupling microbial nitrogen and carbon cycles. The discovery of this microbial process challenges the traditional knowledge of global methane sinks and nitrogen losses. In this study, the abundance and activity of N-DAMO bacteria were investigated and their contributions to methane sink and nitrogen loss were estimated in different seasons and different partitions of an intertidal zone of the East China Sea. The results showed that N-DAMO bacteria were extensively and continuously present in the intertidal zone, with the number of cells ranging from 5.5 × 10 4 to 2.8 × 10 5 copy g -1 soil and the potential activity ranging from 0.52 to 5.7 nmol CO 2  g -1 soil day -1 , contributing 5.0-36.6% of nitrite- and sulfate-dependent anaerobic methane oxidation in the intertidal zone. The N-DAMO activity and its contribution to the methane consumption were highest in the spring and in the low intertidal zone. These findings showed that the N-DAMO process is an important methane and nitrogen sink in the intertidal zone and varies with the seasons and the partitions of the intertidal zone.

Comparison of authigenic carbonates formation at mud volcanoes and pockmarks in the Portuguese Margin vs. at the Yinazao serpentinite mud volcano in the Marianas forearc

NASA Astrophysics Data System (ADS)

Magalhaes, V. H.; Freitas, M.; Azevedo, M. R.; Pinheiro, L. M.; Salgueiro, E.; Abrantes, F. F. G.

2017-12-01

On the Portuguese passive continental margin, active and past seepage processes form mud volcanoes and pockmarks at the seafloor. Often associated with these structures are extensive methane-derived authigenic carbonates that form from deep-sourced methane-rich fluids that ascend from deep to the upper sedimentary column and often discharge at the seafloor. These carbonates form within the sediments and are either dominated by dolomite and high-Mg calcites, when formed under a restricted seawater circulation environment, anoxic and low sulphate conditions; or by aragonite and calcite when formed close to or at the seafloor in a high sulphate system. The δ13C values (-56.2‰ VPDB) found on the carbonate-cemented material clearly indicates methane as the major carbon source. On the Yinazao serpentinite mud volcano at an active, non-accretionary, convergent margin, sediment samples from IODP Sites U1491 and U1492 (Exp. 366) contain authigenic minerals such as aragonite, calcite, brucite, gypsum among others. Authigenic aragonite occurs predominantly within the top meters of the cores where both oxidation and seawater circulation in the sedimentary column are higher. In this system, initial results indicate that the major carbon source is most probably not methane but seawater related. This work discusses and compares the major carbon sources in both systems: sedimentary mud volcanoes and pockmarks of a passive margin vs. a serpentinite mud volcano of an active, non-accretionary, convergent margin. We acknowledge the support from the PES project - Pockmarks and fluid seepage in the Estremadura Spur: implications for regional geology, biology, and petroleum systems (PTDC/GEOFIQ/5162/2014) financed by the Portuguese Foundation for Science and Technology (FCT).

Microbial community structure and methane-cycling activity of subsurface sediments at Mississippi Canyon 118 before the Deepwater Horizon disaster

NASA Astrophysics Data System (ADS)

Underwood, Sarah; Lapham, Laura; Teske, Andreas; Lloyd, Karen G.

2016-07-01

The Deepwater Horizon disaster caused a shift in microbial communities in Gulf of Mexico seawater, but less is known about the baseline for microbial communities in the underlying sediments. We compared 16S rRNA and functional gene sequences deriving from DNA and RNA with geochemical profiles (sulfate and methane concentrations, δ13C of methane and carbon dioxide, and chloride concentrations) of a sediment gravity core from the upper continental slope of the northwestern Gulf of Mexico (MC118) in 2008, 15 km from the spill site. The highest number of archaeal sequences were ANME-1 and ANME-2 archaea in the sulfate-reducing upper core segments (12 and 42 cmbsf), ANME-1 and Methanomicrobiales in the middle methanogenic depths (200 and 235 cmbsf), and ANME-1 at the deepest depths (309, 400, and 424 cmbsf). The presence of mcrA gene transcripts showed that members of the ANME-1 group are active throughout the core and transcribe the mcrA gene, a key gene of methanogenesis and anaerobic methane oxidation. The bacterial community consists mostly of members of the Deltaproteobacteria, Chloroflexi, Cytophaga, Epsilonproteobacteria, and the Japan Sea Group 1 throughout the core. The commonly detected genera of gammaproteobacterial hydrocarbon-degrading bacteria in the water column are not found in this sediment survey, indicating that the benthic sediment is an unlikely reservoir for these aerobes. However, the sediments contain members of the sulfate-reducing families Desulfobulbaceae and Desulfobacteraceae, some members of which degrade and completely oxidize aromatic hydrocarbons and alkanes, and the Desulfobacterium anilini lineage of obligately aromatics-degrading sulfate reducers. Thus, the benthic sediments are the most likely reservoir for the active deltaproteobacterial populations that were observed repeatedly after the Deepwater Horizon spill in the fall of 2010.

Methane emission from flooded soils - from microorganisms to the atmosphere

NASA Astrophysics Data System (ADS)

Conrad, Ralf

2016-04-01

Methane is an important greenhouse gas that is affected by anthropogenic activity. The annual budget of atmospheric methane, which is about 600 million tons, is by more than 75% produced by methanogenic archaea. These archaea are the end-members of a microbial community that degrades organic matter under anaerobic conditions. Flooded rice fields constitute a major source (about 10%) of atmospheric methane. After flooding of soil, anaerobic processes are initiated, finally resulting in the disproportionation of organic matter to carbon dioxide and methane. This process occurs in the bulk soil, on decaying organic debris and in the rhizosphere. The produced methane is mostly ventilated through the plant vascular system into the atmosphere. This system also allows the diffusion of oxygen into the rizosphere, where part of the produced methane is oxidized by aerobic methanotrophic bacteria. More than 50% of the methane production is derived from plant photosynthetic products and is formed on the root surface. Methanocellales are an important group of methanogenic archaea colonizing rice roots. Soils lacking this group seem to result in reduced root colonization and methane production. In rice soil methane is produced by two major paths of methanogenesis, the hydrogenotrophic one reducing carbon dioxide to methane, and the aceticlastic one disproportionating acetate to methane and carbon dioxide. Theoretically, at least two third of the methane should be produced by aceticlastic and the rest by hydrogenotrophic methanogenesis. In nature, however, the exact contribution of the two paths can vary from zero to 100%. Several environmental factors, such as temperature and quality of organic matter affect the path of methane production. The impact of these factors on the composition and activity of the environmental methanogenic microbial community will be discussed.

Samaria-doped Ceria Modified Ni/YSZ Anode for Direct Methane Fuel in Tubular Solid Oxide Fuel Cells by Impregnation Method

NASA Astrophysics Data System (ADS)

Zhang, Long-shan; Gao, Jian-feng; Tian, Rui-fen; Xia, Chang-rong

2009-08-01

A porous NiO/yttria-stabilized zirconia anode substrate for tubular solid oxide fuel cells was prepared by gel casting technique. Nano-scale samaria-doped ceria (SDC) particles were formed onto the anode substrate to modify the anode microstructure by the impregnation of solution of Sm(NO3)3 and Ce(NO3)3. Electrochemical impedance spectroscopy, current-voltage and current-powder curves of the cells were measured using an electrochemical workstation. Scanning electron microcopy was used to observe the microstructure. The results indicate that the stability of the performance of the cell operated on humidified methane can be significantly improved by incorporating the nano-structured SDC particles, compared with the unmodified cell. This verifies that the coated SDC electrodes are very effective in suppressing catalytic carbon formation by blocking methane from approaching the Ni, which is catalytically active towards methane pyrolysis. In addition, it was found that a small amount of deposited carbon is beneficial to the performance of the anode. The cell showed a peak power density of 225 mW/cm2 when it was fed with H2 fuel at 700 °C, but the power density increased to 400 mW/cm2 when the fuel was switched from hydrogen to methane at the same flow rate. Methane conversion achieved about 90%, measured by gas chromatogram with a 10.0 mL/min flow rate of fuel at 700 °C. Although the carbon deposition was not suppressed absolutely, some deposited carbon was beneficial for performance improvement.

Lambs Fed Fresh Winter Forage Rape (Brassica napus L.) Emit Less Methane than Those Fed Perennial Ryegrass (Lolium perenne L.), and Possible Mechanisms behind the Difference

PubMed Central

Sun, Xuezhao; Henderson, Gemma; Cox, Faith; Molano, German; Harrison, Scott J.; Luo, Dongwen; Janssen, Peter H.; Pacheco, David

2015-01-01

The objectives of this study were to examine long-term effects of feeding forage rape (Brassica napus L.) on methane yields (g methane per kg of feed dry matter intake), and to propose mechanisms that may be responsible for lower emissions from lambs fed forage rape compared to perennial ryegrass (Lolium perenne L.). The lambs were fed fresh winter forage rape or ryegrass as their sole diet for 15 weeks. Methane yields were measured using open circuit respiration chambers, and were 22-30% smaller from forage rape than from ryegrass (averages of 13.6 g versus 19.5 g after 7 weeks, and 17.8 g versus 22.9 g after 15 weeks). The difference therefore persisted consistently for at least 3 months. The smaller methane yields from forage rape were not related to nitrate or sulfate in the feed, which might act as alternative electron acceptors, or to the levels of the potential inhibitors glucosinolates and S-methyl L-cysteine sulfoxide. Ruminal microbial communities in forage rape-fed lambs were different from those in ryegrass-fed lambs, with greater proportions of potentially propionate-forming bacteria, and were consistent with less hydrogen and hence less methane being produced during fermentation. The molar proportions of ruminal acetate were smaller and those of propionate were greater in forage rape-fed lambs, consistent with the larger propionate-forming populations and less hydrogen production. Forage rape contained more readily fermentable carbohydrates and less structural carbohydrates than ryegrass, and was more rapidly degraded in the rumen, which might favour this fermentation profile. The ruminal pH was lower in forage rape-fed lambs, which might inhibit methanogenic activity, shifting the rumen fermentation to more propionate and less hydrogen and methane. The significance of these two mechanisms remains to be investigated. The results suggest that forage rape is a potential methane mitigation tool in pastoral-based sheep production systems. PMID:25803688

Dissolved methane in the residual basins of the Aral Sea

NASA Astrophysics Data System (ADS)

Izhitskaya, Elena; Zavialov, Peter; Egorov, Alexander

2017-04-01

The state of the Aral Sea has changed significantly since the second half of the 20th century. Due to the level decline the present-day sea consists of the several water bodies: the Large Aral Sea, the Small Aral Sea and Lake Tshchebas. Water balance peculiarities of each basin caused the differences in physical, chemical and biological structure of the ecosystem. Severe salinization of the Large Aral resulted in the increase of water stratification and formation of the anoxic conditions in the bottom layer. According to the field survey of 2002 [Zavialov et al., 2003; Friedrich, Oberhansli, 2004], hydrogen sulfide was detected in the bottom layer of the Large Aral Sea for the first time. Methane formation is the next reaction after sulfate reduction within process of sequential oxidation of organic matter [Break, 1974]. Thus, methane is an important indicator of biogeochemical processes in natural water environments. Besides due to high greenhouse activity of methane study of its emission to the atmosphere is essential for solution of climatological problems [Bazhin, 2000]. The presented study aims to the evaluation of methane dissolved in waters of the Aral region. Measurements of the gas concentration were carried out on surface and vertical profiles, as well as on point stations in 2012, 2013, 2015 and 2016 years in different parts of the sea. Water samples were analyzed by the head-space method with further gas chromatographic determination of methane concentration [Bolshakov, Egorov, 1987]. According to the obtained data, dissolved methane content in the surface waters of the residual basins of the Aral Sea ranges from 12 to 234 nM/l. One of the main results of the research is detection of intensive methane increase in the lower water layer of the Large Aral to 17014 nM/l in central part and to 147316 nM/l in the Chernyshev Bay.

Types and Evolution of Gas Hydrate System along the Tectonically Active Zones of the Western Pacific: Nankai Trough vs. Eastern Margin of Japan Sea

NASA Astrophysics Data System (ADS)

Matsumoto, R.; Tomaru, H.; Takeuchi, L.; Hiruta, A.; Ishizaki, O.; Aoyama, C.; Machiyama, H.; Goto, T.

2007-12-01

A series of sea-going surveys of marine gas hydrates around Japan Islands for more than a decade has revealed characteristic and contrasting features and evolution of gas hydrate system between the Nankai subduction zone and the Joetsu Basin of Japan Sea. Gas hydrate of the Nankai trough largely occurs as pore-filling type, laterally extending in turbidites. Methane is depleted in C-13, mostly derived from microbial brake-down of organic matters. Strong and continuous BSRs occur at around 270 mbsf, corresponding to the base of gas hydrate stability (BGHS). Furthermore, double BSRs with weak reflector (BSR-2) 20-30 m below BSR appear in uplifting knolls. BSR-2 is explained as a relic BSR, which coincides with BGHS. Combination effects of uplifting of gas hydrate bearing sediments and sea-level fall are likely to have caused shoaling of BGHS and BSRs, dissociation of gas hydrate between old and new BRSs, and further accumulation of gas hydrates above BSR. Thus the recycling of methane at BGHS triggered by glacial sea level fall contributed for the development of subsurface gas hydrate deposits. Joetsu basin is located on a newly formed convergent boundary between Eurasia and Philippine Sea Plates. Well-defined circular pockmarks with ca.500 m in diameter develop on the folded and faulted Umitaka spur and Joetsu knoll in the basin. A number of circular swells and mounds, 200-500 m in diameter, have been also recognized nearby the pockmarks. Thus the Umitaka spur and perhaps Joetsu knoll are characterized by rough topography of pockmarks and mounds. Methane of plumes and gas hydrate originates in deep-seated thermogenic gases with relatively heavy carbon. 3D seismic profiles clearly depict gas chimney structures below pockmark-mound zones, and gigantic methane plumes stand on the mounds not in the pockmarks. Pockmarks are often considered as vent holes, however, those of the Joestu Basin are quite. BSRs occur at about 150 mbsr, corresponding to very high heat flow, and are widely distributed throughout the area, while no double BSRs are observed. BSRs within gas chimneys are very strong and often exhibit pull-up structure. A number of piston corers have recovered chunks of massive gas hydrate from the mounds. ROV dives observed gas hydrates exposed atop the mounds. Furthermore, electric ocean floor survey has revealed that sediments below the pockmark-mound zones were not conductive. These lines of evidence suggest that the mounds are more-or-less composed of or at least contain significant amounts of methane. Sea-level fall during the last glacial, 120 m in Japan Sea, should have caused instability of gas hydrate, in particular, those within pockmarks. Pull-up structures within the chimney seem to support the model that the mounds are gas hydrate dome and the pockmark, probably a relic hydrate mound. Glacial sea level fall should have caused massive dissociation of subsurface methane hydrate as in case of the Nankai trough. However the methane from the dissociation of massive hydrate in the chimney should escape to seawater to form a crater-like depression pockmarks. Considering active venting, gigantic plumes, inferred violent venting and perhaps floating of massive gas hydrates, gas hydrate deposits are to be formed during warmer, high-sea level periods, and episodic dissociation and massive emission of methane to ocean/atmosphere system.

Binding of methane to activated mineral surfaces - a methane sink on Mars?

NASA Astrophysics Data System (ADS)

Nørnberg, P.; Knak Jensen, S. J.; Skibsted, J.; Jakobsen, H. J.; ten Kate, I. L.; Gunnlaugsson, H. P.; Merrison, J. P.; Finster, K.; Bak, Ebbe; Iversen, J. J.; Kondrup, J. C.

2015-10-01

Tumbling experiments that simulate the wind erosion of quartz grains in an atmosphere of 13 C-enriched methane are reported. The eroded grains are analyzed by 13C and 29 Si solid-state NMR techniques after several months of tumbling. The analysis shows that methane has reacted with the eroded surface to form covalent Si-CH3 bonds, which stay intact for temperatures up to at least 250oC. These findings offer a model for a methane sink that might explain the fast disappearance of methane on Mars.

A microbial biogeochemistry network for soil carbon and nitrogen cycling and methane flux: model structure and application to Asia

NASA Astrophysics Data System (ADS)

Xu, X.; Song, C.; Wang, Y.; Ricciuto, D. M.; Lipson, D.; Shi, X.; Zona, D.; Song, X.; Yuan, F.; Oechel, W. C.; Thornton, P. E.

2017-12-01

A microbial model is introduced for simulating microbial mechanisms controlling soil carbon and nitrogen biogeochemical cycling and methane fluxes. The model is built within the CN (carbon-nitrogen) framework of Community Land Model 4.5, named as CLM-Microbe to emphasize its explicit representation of microbial mechanisms to biogeochemistry. Based on the CLM4.5, three new pools were added: bacteria, fungi, and dissolved organic matter. It has 11 pools and 34 transitional processes, compared with 8 pools and 9 transitional flow in the CLM4.5. The dissolve organic carbon was linked with a new microbial functional group based methane module to explicitly simulate methane production, oxidation, transport and their microbial controls. Comparing with CLM4.5-CN, the CLM-Microbe model has a number of new features, (1) microbial control on carbon and nitrogen flows between soil carbon/nitrogen pools; (2) an implicit representation of microbial community structure as bacteria and fungi; (3) a microbial functional-group based methane module. The model sensitivity analysis suggests the importance of microbial carbon allocation parameters on soil biogeochemistry and microbial controls on methane dynamics. Preliminary simulations validate the model's capability for simulating carbon and nitrogen dynamics and methane at a number of sites across the globe. The regional application to Asia has verified the model in simulating microbial mechanisms in controlling methane dynamics at multiple scales.

Metabolic activity of subterranean microbial communities in deep granitic groundwater supplemented with methane and H2

PubMed Central

Pedersen, Karsten

2013-01-01

It was previously concluded that opposing gradients of sulphate and methane, observations of 16S ribosomal DNA sequences displaying great similarity to those of anaerobic methane-oxidizing Archaea and a peak in sulphide concentration in groundwater from a depth of 250–350 m in Olkiluoto, Finland, indicated proper conditions for methane oxidation with sulphate. In the present research, pressure-resistant, gas-tight circulating systems were constructed to enable the investigation of attached and unattached anaerobic microbial populations from a depth of 327 m in Olkiluoto under in situ pressure (2.4 MPa), diversity, dissolved gas and chemistry conditions. Three parallel flow cell cabinets were configured to allow observation of the influence on microbial metabolic activity of 11 mℳ methane, 11 mℳ methane plus 10 mℳ H2 or 2.1 mℳ O2 plus 7.9 mℳ N2 (that is, air). The concentrations of these gases and of organic acids and carbon, sulphur chemistry, pH and Eh, ATP, numbers of cultivable micro-organisms, and total numbers of cells and bacteriophages were subsequently recorded under batch conditions for 105 days. The system containing H2 and methane displayed microbial reduction of 0.7 mℳ sulphate to sulphide, whereas the system containing only methane resulted in 0.2 mℳ reduced sulphate. The system containing added air became inhibited and displayed no signs of microbial activity. Added H2 and methane induced increasing numbers of lysogenic bacteriophages per cell. It appears likely that a microbial anaerobic methane-oxidizing process coupled to acetate formation and sulphate reduction may be ongoing in aquifers at a depth of 250–350 m in Olkiluoto. PMID:23235288

A Possible Sink for Methane on Mars

NASA Astrophysics Data System (ADS)

Nørnberg, P.; Jensen, S. J. K.; Skibsted, J.; Jakobsen, H. J.; ten Kate, I. L.; Gunnlaugsson, H. P.; Merrison, J. P.; Finster, K.; Bak, E.; Iversen, J. J.; Kondrup, J. C.

2014-07-01

Mechanical simulated wind activation of mineral surfaces act as a trap for Methane through formation of covalent Si-C bonds stable up to temperatures above 250 C. This mechanism is proposed as a Methane sink on Mars.

Studying methane migration mechanisms at Walker Ridge, Gulf of Mexico, via 3D methane hydrate reservoir modeling

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

Nole, Michael; Daigle, Hugh; Mohanty, Kishore

We have developed a 3D methane hydrate reservoir simulator to model marine methane hydrate systems. Our simulator couples highly nonlinear heat and mass transport equations and includes heterogeneous sedimentation, in-situ microbial methanogenesis, the influence of pore size contrast on solubility gradients, and the impact of salt exclusion from the hydrate phase on dissolved methane equilibrium in pore water. Using environmental parameters from Walker Ridge in the Gulf of Mexico, we first simulate hydrate formation in and around a thin, dipping, planar sand stratum surrounded by clay lithology as it is buried to 295mbsf. We find that with sufficient methane beingmore » supplied by organic methanogenesis in the clays, a 200x pore size contrast between clays and sands allows for a strong enough concentration gradient to significantly drop the concentration of methane hydrate in clays immediately surrounding a thin sand layer, a phenomenon that is observed in well log data. Building upon previous work, our simulations account for the increase in sand-clay solubility contrast with depth from about 1.6% near the top of the sediment column to 8.6% at depth, which leads to a progressive strengthening of the diffusive flux of methane with time. By including an exponentially decaying organic methanogenesis input to the clay lithology with depth, we see a decrease in the aqueous methane supplied to the clays surrounding the sand layer with time, which works to further enhance the contrast in hydrate saturation between the sand and surrounding clays. Significant diffusive methane transport is observed in a clay interval of about 11m above the sand layer and about 4m below it, which matches well log observations. The clay-sand pore size contrast alone is not enough to completely eliminate hydrate (as observed in logs), because the diffusive flux of aqueous methane due to a contrast in pore size occurs slower than the rate at which methane is supplied via organic methanogenesis. Therefore, it is likely that additional mechanisms are at play, notably bound water activity reduction in clays. Three-dimensionality allows for inclusion of lithologic heterogeneities, which focus fluid flow and subsequently allow for heterogeneity in the methane migration mechanisms that dominate in marine sediments at a local scale. Incorporating recently acquired 3D seismic data from Walker Ridge to inform the lithologic structure of our modeled reservoir, we show that even with deep adjective sourcing of methane along highly permeable pathways, local hydrate accumulations can be sourced either by diffusive or advective methane flux; advectively-sourced hydrates accumulate evenly in highly permeable strata, while diffusively-sourced hydrates are characterized by thin strata-bound intervals with high clay-sand pore size contrasts.« less

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

NASA Astrophysics Data System (ADS)

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

2012-04-01

Within subduction zones of active continental margins, large amounts of methane can be mobilized by dewatering processes and transported to the seafloor along migration pathways. A recently discovered seep area located off Concepción (Chile) at water depth between 600 to 1100 mbsl is characterized by active methane vent sites as well as massive carbonates boulders and plates which probably are related to methane seepage in the past. During the SO210 research expedition "Chiflux" (Sept-Oct 2010), sediment from the Concepción Methane Seep Area (CSMA) at the fore arc of the Chilean margin was sampled to study microbial activity related to methane seepage. We sampled surface sediments (0-30cm) from sulfur bacteria mats, as well as clam, pogonophoran, and tubeworm fields with push cores and a TV-guided multicorer system. Anaerobic oxidation of methane (AOM) and sulfate reduction rates were determined using ex-situ radioisotope tracer techniques. Additionally, porewater chemistry of retrieved cores as well as isotopic composition and age record of surrounding authigenic carbonates were analyzed. The shallowest sulfate-methane-transition zone (SMTZ) was identified at 4 cm sediment depth hinting to locally strong fluid fluxes. However, a lack of Cl- anomalies in porewater profiles indicates a shallow source of these fluids, which is supported by the biogenic origin of the methane (δ13C -70‰ PDB). Sulfide and alkalinity was relatively high (up to 20 mM and 40 mEq, respectively). Rates of AOM and sulfate reduction within this area reached magnitudes typical for seeps with variation between different habitat types, indicating a diverse methane supply, which is affecting the depths of the SMTZ. Rates were highest at sulfur a bacteria mats (20 mmol m-2 d-1) followed by a large field of dead clams, a pogonophoran field, a black sediment spot, and a carbonate rich clam field. Lowest rates (0.2 mmol m-2 d-1) were measured in close vicinity to these hot spots. Abundant massive carbonate blocks and plates hint to a very old seep system with a probably much higher activity in the past. The U-Th age record of these authigenic carbonates reach back to periods of venting activity with more than 150 ka ago. Carbon isotopic signatures of authigenic carbonates (δ13C -50 to -40‰ PDB) suggest a biogenic carbon source (i.e. methane), also in the past. We found several indications for the impact of recent earthquakes within the seep area (cracks, shifted seafloor), which could be an important mechanism for the triggering of new seepage activity, change in fluid expulsion rates and colonization patterns of the cold seep fauna.

Oxygen storage properties and catalytic activity of layer-ordered perovskites BaY 1-xGd xMn 2O 5+δ

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

Klimkowicz, A.; Świerczek, K.; Rząsa, T.

2016-05-01

Crystal structure, oxygen storage-related and preliminary anaerobic methane combustion studies were conducted for BaY 1-xGd xMn 2O 5+δ (0, 0.25, 0.5, 0.75 and 1) series of oxides prepared by a sol–gel method. All samples were found to possess layered-type A-site cation ordering, with the unit cell volume linearly dependent on the average radius of Y 1-xGd x for both the reduced and the oxidized materials. The oxygen content in the temperature range of 400 °C–600 °C indicates change on the order of 1 atomic mole, occurring when the sample's surrounding atmosphere was changed from air to 5 vol.% H 2more » in Ar. The time dependence of the reduction shows activated character on temperature, with an activation energy, which seems to be related to the oxygen diffusion in the bulk of the materials. Initial data concerning methane combustion in oxygen-free conditions show promising catalytic activity of BaYMn 2O 6 at elevated temperatures.« less

Carbon Dioxide Methanation for Human Exploration of Mars: A Look at Catalyst Longevity and Activity Using Supported Ruthenium

NASA Technical Reports Server (NTRS)

Petersen, Elspeth M.; Meier, Anne J.; Tessonnier, Jean-Philippe

2018-01-01

Overarching Purpose: To design a carbon dioxide methanation/Sabatier reaction catalyst able to withstand variable conditions including fluctuations in bed temperature and feed flow rates for 480 days of remote operation to produce seven tons of methane. Current Study Purpose: Examine supported Ruthenium as a carbon dioxide methanation catalyst to determine the effects support properties have on the active phase by studying activity and selectivity. Objective: The remote operation of the Mars ISRU (In Situ Resources Utilization) lander to produce rocket fuel prior to crew arrival on the planet to power an ascent vehicle. Constraints: Long-term operation (480 days); Variable conditions: Feed gas flow rates, Feed gas flow ratios, Reactor bed temperature.

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

USGS Publications Warehouse

Malinverno, A.; Pohlman, J.W.

2011-01-01

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

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

Holdridge, D. J.

Global Warming and Methane--Global warming, an increase in Earth's near-surface temperature, is believed to result from the buildup of what scientists refer to as ''greenhouse gases.'' These gases include water vapor, carbon dioxide, methane, nitrous oxide, ozone, perfluorocarbons, hydrofluoro-carbons, and sulfur hexafluoride. Greenhouse gases can absorb outgoing infrared (heat) radiation and re-emit it back to Earth, warming the surface. Thus, these gases act like the glass of a greenhouse enclosure, trapping infrared radiation inside and warming the space. One of the more important greenhouse gases is the naturally occurring hydrocarbon methane. Methane, a primary component of natural gas, is themore » second most important contributor to the greenhouse effect (after carbon dioxide). Natural sources of methane include wetlands, fossil sources, termites, oceans, fresh-waters, and non-wetland soils. Methane is also produced by human-related (or anthropogenic) activities such as fossil fuel production, coal mining, rice cultivation, biomass burning, water treatment facilities, waste management operations and landfills, and domesticated livestock operations (Figure 1). These anthropogenic activities account for approximately 70% of the methane emissions to the atmosphere. Methane is removed naturally from the atmosphere in three ways. These methods, commonly referred to as sinks, are oxidation by chemical reaction with tropospheric hydroxyl ion, oxidation within the stratosphere, and microbial uptake by soils. In spite of their important role in removing excess methane from the atmosphere, the sinks cannot keep up with global methane production. Methane concentrations in the atmosphere have increased by 145% since 1800. Increases in atmospheric methane roughly parallel world population growth, pointing to anthropogenic sources as the cause (Figure 2). Increases in the methane concentration reduce Earth's natural cooling efficiency by trapping more of the outgoing terrestrial infrared radiation, increasing the near-surface temperature.« less

Global tropospheric methane: An indication of atmosphere-biosphere-climate interactions?

NASA Technical Reports Server (NTRS)

Harriss, Robert C.; Sebacher, Daniel I.; Bartlett, Karen B.

1985-01-01

Methane is an important atmospheric gas with potentially critical roles in both photochemical and radiation transfer processes. A major natural source of atmospheric methane involves anaerobic fermentation of organic materials in wetland soils and sediments. A data base of field measurements of atmospheric methane was used in the development of a global methane emissions inventory. Calculations support the following hypotheses: (1) Human activities currently produce methane at a rate approximately equal to natural resources (these rapidly increasing anthropogenic sources can explain most of the recent increase observed in tropospheric methane); and (2) Prior to 200 B.P. (before the present), the influence of climate on wetland extent and distribution was probably a dominant factor controlling global biogenic methane emissions to the atmosphere.

Role of microorganisms for cycling of atmospheric constituents, emphasizing the greenhouse gas methane (Invited)

NASA Astrophysics Data System (ADS)

Conrad, R.

2013-12-01

Microorganisms have contributed significantly to the formation of the atmosphere and the habitability of Earth. Microbial methanogenesis probably helped overcoming the faint sun problem on young Earth. Later on, cyanobacterial photosynthesis produced oxygen and thus restricted the life zone of methanogenic microbial communities, which nowadays contribute only about 1% to total carbon cycle. Nevertheless, methanogenesis still dominates the budget of atmospheric methane and contributes significantly to the greenhouse effect. There are numerous habitats, which exchange methane with the atmosphere, and even more in which methane is intensively cycled albeit little emitted. Methane can be a byproduct of chemical reactions in plant leaves, or of aerobic methyl phosphonate consumption in ocean water. Most commonly, however, methane is a stoichiometric catabolic product in the degradation of organic matter by anaerobic microorganisms. The degradation is achieved by a complex microbial community consisting of various species of hydrolytic and fermentative Bacteria that produce hydrogen, carbon dioxide and acetate as major end products, and of methanogenic Archaea that eventually convert these compounds to methane and carbon dioxide. The composition of such methanogenic microbial communities, the rates and paths of methane formation, and the isotopic composition of the produced methane all exhibit quite some variability across the different habitats in which methane is produced from organic matter decomposition, such as flooded soils, lake sediments, peatlands, animal gut systems. The structure of the microbial communities often strongly affects their function. It is a challenging task to understand the environmental and biochemical basis of the interactions of abiotic factors and microorganisms shaping the structure and function of the microbial communities in the different methanogenic habitats.

Room-temperature activation of methane and dry re-forming with CO 2 on Ni-CeO 2 (111) surfaces: Effect of Ce 3+ sites and metal–support interactions on C–H bond cleavage

DOE PAGES

Lustemberg, Pablo G.; Ramírez, Pedro J.; Liu, Zongyuan; ...

2016-10-27

The results of core-level photoemission indicate that Ni-CeO 2(111) surfaces with small or medium coverages of nickel are able to activate methane at 300 K, producing adsorbed CH x and CO x (x = 2, 3) groups. Calculations based on density functional theory predict a relatively low activation energy of 0.6–0.7 eV for the cleavage of the first C–H bond in the adsorbed methane molecule. Ni and O centers of ceria work in a cooperative way in the dissociation of the C–H bond at room temperature, where a low Ni loading is crucial for the catalyst activity and stability. Themore » strong electronic perturbations in the Ni nanoparticles produced by the ceria supports of varying natures, such as stoichiometric and reduced, result in a drastic change in their chemical properties toward methane adsorption and dissociation as well as the dry reforming of methane reaction. Lastly, the coverage of Ni has a drastic effect on the ability of the system to dissociate methane and catalyze the dry re-forming process.« less

Room-temperature activation of methane and dry re-forming with CO 2 on Ni-CeO 2 (111) surfaces: Effect of Ce 3+ sites and metal–support interactions on C–H bond cleavage

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

Lustemberg, Pablo G.; Ramírez, Pedro J.; Liu, Zongyuan

The results of core-level photoemission indicate that Ni-CeO 2(111) surfaces with small or medium coverages of nickel are able to activate methane at 300 K, producing adsorbed CH x and CO x (x = 2, 3) groups. Calculations based on density functional theory predict a relatively low activation energy of 0.6–0.7 eV for the cleavage of the first C–H bond in the adsorbed methane molecule. Ni and O centers of ceria work in a cooperative way in the dissociation of the C–H bond at room temperature, where a low Ni loading is crucial for the catalyst activity and stability. Themore » strong electronic perturbations in the Ni nanoparticles produced by the ceria supports of varying natures, such as stoichiometric and reduced, result in a drastic change in their chemical properties toward methane adsorption and dissociation as well as the dry reforming of methane reaction. Lastly, the coverage of Ni has a drastic effect on the ability of the system to dissociate methane and catalyze the dry re-forming process.« less

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

NASA Astrophysics Data System (ADS)

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

2014-06-01

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

Anaerobic methanotrophic communities thrive in deep submarine permafrost.

PubMed

Winkel, Matthias; Mitzscherling, Julia; Overduin, Pier P; Horn, Fabian; Winterfeld, Maria; Rijkers, Ruud; Grigoriev, Mikhail N; Knoblauch, Christian; Mangelsdorf, Kai; Wagner, Dirk; Liebner, Susanne

2018-01-22

Thawing submarine permafrost is a source of methane to the subsurface biosphere. Methane oxidation in submarine permafrost sediments has been proposed, but the responsible microorganisms remain uncharacterized. We analyzed archaeal communities and identified distinct anaerobic methanotrophic assemblages of marine and terrestrial origin (ANME-2a/b, ANME-2d) both in frozen and completely thawed submarine permafrost sediments. Besides archaea potentially involved in anaerobic oxidation of methane (AOM) we found a large diversity of archaea mainly belonging to Bathyarchaeota, Thaumarchaeota, and Euryarchaeota. Methane concentrations and δ 13 C-methane signatures distinguish horizons of potential AOM coupled either to sulfate reduction in a sulfate-methane transition zone (SMTZ) or to the reduction of other electron acceptors, such as iron, manganese or nitrate. Analysis of functional marker genes (mcrA) and fluorescence in situ hybridization (FISH) corroborate potential activity of AOM communities in submarine permafrost sediments at low temperatures. Modeled potential AOM consumes 72-100% of submarine permafrost methane and up to 1.2 Tg of carbon per year for the total expected area of submarine permafrost. This is comparable with AOM habitats such as cold seeps. We thus propose that AOM is active where submarine permafrost thaws, which should be included in global methane budgets.

A Long-Term Cultivation of an Anaerobic Methane-Oxidizing Microbial Community from Deep-Sea Methane-Seep Sediment Using a Continuous-Flow Bioreactor

PubMed Central

Aoki, Masataka; Ehara, Masayuki; Saito, Yumi; Yoshioka, Hideyoshi; Miyazaki, Masayuki; Saito, Yayoi; Miyashita, Ai; Kawakami, Shuji; Yamaguchi, Takashi; Ohashi, Akiyoshi; Nunoura, Takuro; Takai, Ken; Imachi, Hiroyuki

2014-01-01

Anaerobic oxidation of methane (AOM) in marine sediments is an important global methane sink, but the physiological characteristics of AOM-associated microorganisms remain poorly understood. Here we report the cultivation of an AOM microbial community from deep-sea methane-seep sediment using a continuous-flow bioreactor with polyurethane sponges, called the down-flow hanging sponge (DHS) bioreactor. We anaerobically incubated deep-sea methane-seep sediment collected from the Nankai Trough, Japan, for 2,013 days in the bioreactor at 10°C. Following incubation, an active AOM activity was confirmed by a tracer experiment using 13C-labeled methane. Phylogenetic analyses demonstrated that phylogenetically diverse Archaea and Bacteria grew in the bioreactor. After 2,013 days of incubation, the predominant archaeal components were anaerobic methanotroph (ANME)-2a, Deep-Sea Archaeal Group, and Marine Benthic Group-D, and Gammaproteobacteria was the dominant bacterial lineage. Fluorescence in situ hybridization analysis showed that ANME-1 and -2a, and most ANME-2c cells occurred without close physical interaction with potential bacterial partners. Our data demonstrate that the DHS bioreactor system is a useful system for cultivating fastidious methane-seep-associated sedimentary microorganisms. PMID:25141130

Transcontinental Surface Validation of Satellite Observations of Enhanced Methane Anomalies Associated with Fossil Fuel Industrial Methane Emissions

NASA Astrophysics Data System (ADS)

Leifer, I.; Culling, D.; Schneising, O.; Bovensmann, H.; Buchwitz, M.; Burrows, J. P.

2012-12-01

A ground-based, transcontinental (Florida to California - i.e., satellite-scale) survey was conducted to understand better the role of fossil fuel industrial (FFI) fugitive emissions of the potent greenhouse gas, methane. Data were collected by flame ion detection gas chromatography (Fall 2010) and by a cavity ring-down sensor (Winter 2012) from a nearly continuously moving recreational vehicle, allowing 24/7 data collection. Nocturnal methane measurements for similar sources tended to be higher compared to daytime values, sometime significantly, due to day/night meteorological differences. Data revealed strong and persistent FFI methane sources associated with refining, a presumed major pipeline leak, and several minor pipeline leaks, a coal loading plant, and areas of active petroleum production. Data showed FFI source emissions were highly transient and heterogeneous; however, integrated over these large-scale facilities, methane signatures overwhelmed that of other sources, creating clearly identifiable plumes that were well elevated above ambient. The highest methane concentration recorded was 39 ppm at an active central valley California production field, while desert values were as low as 1.80 ppm. Surface methane data show similar trends with strong emissions correlated with FFI on large (4° bin) scales and positive methane anomalies centered on the Gulf Coast area of Houston, home to most of US refining capacity. Comparison with SCIAMACHY and GOSAT satellite data show agreement with surface data in the large-scale methane spatial patterns. Positive satellite methane anomalies in the southeast and Mexico largely correlated with methane anthropogenic and wetland inventory models suggests most strong ground methane anomalies in the Gulf of Mexico region were related to dominant FFI input for most seasons. Wind advection played a role, in some cases confounding a clear relationship. Results are consistent with a non-negligible underestimation of the FFI contribution to global methane budgets.; In situ methane concentrations during transcontinental survey Fall 2010.

Observed variations of methane on Mars unexplained by known atmospheric chemistry and physics.

PubMed

Lefèvre, Franck; Forget, François

2009-08-06

The detection of methane on Mars has revived the possibility of past or extant life on this planet, despite the fact that an abiogenic origin is thought to be equally plausible. An intriguing aspect of the recent observations of methane on Mars is that methane concentrations appear to be locally enhanced and change with the seasons. However, methane has a photochemical lifetime of several centuries, and is therefore expected to have a spatially uniform distribution on the planet. Here we use a global climate model of Mars with coupled chemistry to examine the implications of the recently observed variations of Martian methane for our understanding of the chemistry of methane. We find that photochemistry as currently understood does not produce measurable variations in methane concentrations, even in the case of a current, local and episodic methane release. In contrast, we find that the condensation-sublimation cycle of Mars' carbon dioxide atmosphere can generate large-scale methane variations differing from those observed. In order to reproduce local methane enhancements similar to those recently reported, we show that an atmospheric lifetime of less than 200 days is necessary, even if a local source of methane is only active around the time of the observation itself. This implies an unidentified methane loss process that is 600 times faster than predicted by standard photochemistry. The existence of such a fast loss in the Martian atmosphere is difficult to reconcile with the observed distribution of other trace gas species. In the case of a destruction mechanism only active at the surface of Mars, destruction of methane must occur with an even shorter timescale of the order of approximately 1 hour to explain the observations. If recent observations of spatial and temporal variations of methane are confirmed, this would suggest an extraordinarily harsh environment for the survival of organics on the planet.

A modeling study of methane hydrate decomposition in contact with the external surface of zeolites.

PubMed

Smirnov, Konstantin S

2017-08-30

The behavior of methane hydrate (MH) enclosed between the (010) surfaces of the silicalite-1 zeolite was studied by means of molecular dynamics simulations at temperatures of 150 and 250 K. Calculations reveal that the interaction with the hydrophilic surface OH groups destabilizes the clathrate structure of hydrate. While MH mostly conserves the structure in the simulation at the low temperature, thermal motion at the high temperature breaks the fragilized cages of H-bonded water molecules, thus leading to the release of methane. The dissociation proceeds in a layer-by-layer manner starting from the outer parts of the MH slab until complete hydrate decomposition. The released CH 4 molecules are absorbed by the microporous solid, whereas water is retained at the surfaces of hydrophobic silicalite and forms a meniscus in the interlayer space. Methane uptake reaches 70% of the silicalite sorption capacity. The energy necessary for the endothermic MH dissociation is supplied by the exothermic methane absorption by the zeolite.

Temperature- and pressure-dependent structural transformation of methane hydrates in salt environments

NASA Astrophysics Data System (ADS)

Shin, Donghoon; Cha, Minjun; Yang, Youjeong; Choi, Seunghyun; Woo, Yesol; Lee, Jong-Won; Ahn, Docheon; Im, Junhyuck; Lee, Yongjae; Han, Oc Hee; Yoon, Ji-Ho

2017-03-01

Understanding the stability of volatile species and their compounds under various surface and subsurface conditions is of great importance in gaining insights into the formation and evolution of planetary and satellite bodies. We report the experimental results of the temperature- and pressure-dependent structural transformation of methane hydrates in salt environments using in situ synchrotron X-ray powder diffraction, solid-state nuclear magnetic resonance, and Raman spectroscopy. We find that under pressurized and concentrated brine solutions methane hydrate forms a mixture of type I clathrate hydrate, ice, and hydrated salts. Under a low-pressure condition, however, the methane hydrates are decomposed through a rapid sublimation of water molecules from the surface of hydrate crystals, while NaCl · 2H2O undergoes a phase transition into a crystal growth of NaCl via the migration of salt ions. In ambient pressure conditions, the methane hydrate is fully decomposed in brine solutions at temperatures above 252 K, the eutectic point of NaCl · 2H2O.

A Novel Study of Methane-Rich Gas Reforming to Syngas and Its Kinetics over Semicoke Catalyst

PubMed Central

Zhang, Guojie; Su, Aiting; Qu, Jiangwen; Du, Yannian

2014-01-01

A small-size gasification unit is improved through process optimization to simulate industrial United Gas Improvement Company gasification. It finds that the reaction temperature has important impacts on semicoke catalyzed methane gas mixture. The addition of water vapor can enhance the catalytic activity of reforming, which is due to the fact that addition of water vapor not only removes carbon deposit produced in the reforming and gasification reaction processes, but also participates in gasification reaction with semicoke to generate some active oxygen-containing functional groups. The active oxygen-containing functional groups provide active sites for carbon dioxide reforming of methane, promoting the reforming reaction. It also finds that the addition of different proportions of methane-rich gas can yield synthesis gas with different H2/CO ratio. The kinetics study shows that the semicoke can reduce the activation energy of the reforming reaction and promote the occurrence of the reforming reaction. The kinetics model of methane reforming under the conditions of steam gasification over semicoke is as follows: k-=5.02×103·pCH40.71·pH20.26·exp(−74200/RT). PMID:24959620

Low upper limit to methane abundance on Mars.

PubMed

Webster, Christopher R; Mahaffy, Paul R; Atreya, Sushil K; Flesch, Gregory J; Farley, Kenneth A

2013-10-18

By analogy with Earth, methane in the Martian atmosphere is a potential signature of ongoing or past biological activity. During the past decade, Earth-based telescopic observations reported "plumes" of methane of tens of parts per billion by volume (ppbv), and those from Mars orbit showed localized patches, prompting speculation of sources from subsurface bacteria or nonbiological sources. From in situ measurements made with the Tunable Laser Spectrometer (TLS) on Curiosity using a distinctive spectral pattern specific to methane, we report no detection of atmospheric methane with a measured value of 0.18 ± 0.67 ppbv corresponding to an upper limit of only 1.3 ppbv (95% confidence level), which reduces the probability of current methanogenic microbial activity on Mars and limits the recent contribution from extraplanetary and geologic sources.

Electroreduction of carbon monoxide over a copper nanocube catalyst: Surface structure and pH dependence on selectivity

DOE PAGES

Roberts, F. Sloan; Kuhl, Kendra P.; Nilsson, Anders

2016-02-16

The activity and selectivity for CO 2/CO reduction over copper electrodes is strongly dependent on the local surface structure of the catalyst and the pH of the electrolyte. Here we investigate a unique, copper nanocube surface (CuCube) as a CO reduction electrode under neutral and basic pH, using online electrochemical mass spectroscopy (OLEMS) to determine the onset potentials and relative intensities of methane and ethylene production. To relate the unique selectivity to the surface structure, the CuCube surface reactivity is compared to polycrystalline copper and three single crystals under the same reaction conditions. Here, we find that the high selectivitymore » for ethylene over the CuCube surface is most comparable to the Cu(100) surface, which has the cubic unit cell. However, the suppression of methane production over CuCube is unique to that particular surface. Basic pH is also shown to enhance ethylene selectivity on all surfaces, again with the CuCube surface being unique.« less

[Sources of Methane in the Boreal Region

NASA Technical Reports Server (NTRS)

1998-01-01

In determining the global methane budget the sources of methane must be balanced with the sinks and atmospheric inventory. The approximate contribution of the different methane sources to the budget has been establish showing the major terrestrial inputs as rice, wetlands, bogs, fens, and tundra. Measurements and modeling of production in these sources suggest that temperature, water table height and saturation along with substratum composition are important in controlling methane production and emission. The isotopic budget of 13 C and D/H in methane can be used as a tool to clarify the global budget. This approach has achieved success at constraining the inputs. Studies using the isotopic approach place constraints on global methane production from different sources. Also, the relation between the two biogenic production pathways, acetate fermentation and CO2 reduction, and the effect of substratum composition can be made using isotope measurements shows the relation between the different biogenic, thermogenic and anthropogenic sources of methane as a function of the carbon and hydrogen isotope values for each source and the atmosphere, tropospheric composition. Methane emissions from ponds and fens are a significant source in the methane budget of the boreal region. An initial study in 1993 and 1994 on the isotopic composition of this methane source and the isotopic composition in relation to oxidation of methane at the sediment surface of the ponds or fen was conducted as part of our BOREAS project. The isotopic composition of methane emitted by saturated anoxic sediment is dependent on the sediment composition and geochemistry, but will be influenced by in situ oxidation, in part, a function of rooted plant activity. The influence of oxidation mediated by rooted plant activities on the isotopic composition of methane is not well known and will depend on the plant type, sediment temperature, and numerous other variables. Information on this isotopic composition is important in both understanding the bio-geochemistry of the system and also in determining the regional and global inputs for the methane isotope budget. In determining the destruction of methane for balancing the atmospheric methane budget soil oxidation must be considered.

Dry/Wet Cycles Change the Activity and Population Dynamics of Methanotrophs in Rice Field Soil

PubMed Central

Ma, Ke; Conrad, Ralf

2013-01-01

The methanotrophs in rice field soil are crucial in regulating the emission of methane. Drainage substantially reduces methane emission from rice fields. However, it is poorly understood how drainage affects microbial methane oxidation. Therefore, we analyzed the dynamics of methane oxidation rates, composition (using terminal restriction fragment length polymorphism [T-RFLP]), and abundance (using quantitative PCR [qPCR]) of methanotroph pmoA genes (encoding a subunit of particulate methane monooxygenase) and their transcripts over the season and in response to alternate dry/wet cycles in planted paddy field microcosms. In situ methane oxidation accounted for less than 15% of total methane production but was enhanced by intermittent drainage. The dry/wet alternations resulted in distinct effects on the methanotrophic communities in different soil compartments (bulk soil, rhizosphere soil, surface soil). The methanotrophic communities of the different soil compartments also showed distinct seasonal dynamics. In bulk soil, potential methanotrophic activity and transcription of pmoA were relatively low but were significantly stimulated by drainage. In contrast, however, in the rhizosphere and surface soils, potential methanotrophic activity and pmoA transcription were relatively high but decreased after drainage events and resumed after reflooding. While type II methanotrophs dominated the communities in the bulk soil and rhizosphere soil compartments (and to a lesser extent also in the surface soil), it was the pmoA of type I methanotrophs that was mainly transcribed under flooded conditions. Drainage affected the composition of the methanotrophic community only minimally but strongly affected metabolically active methanotrophs. Our study revealed dramatic dynamics in the abundance, composition, and activity of the various type I and type II methanotrophs on both a seasonal and a spatial scale and showed strong effects of dry/wet alternation cycles, which enhanced the attenuation of methane flux into the atmosphere. PMID:23770899

Critical Factors Driving the High Volumetric Uptake of Methane in Cu₃(btc)₂.

PubMed

Hulvey, Zeric; Vlaisavljevich, Bess; Mason, Jarad A; Tsivion, Ehud; Dougherty, Timothy P; Bloch, Eric D; Head-Gordon, Martin; Smit, Berend; Long, Jeffrey R; Brown, Craig M

2015-08-26

A thorough experimental and computational study has been carried out to elucidate the mechanistic reasons for the high volumetric uptake of methane in the metal-organic framework Cu3(btc)2 (btc(3-) = 1,3,5-benzenetricarboxylate; HKUST-1). Methane adsorption data measured at several temperatures for Cu3(btc)2, and its isostructural analogue Cr3(btc)2, show that there is little difference in volumetric adsorption capacity when the metal center is changed. In situ neutron powder diffraction data obtained for both materials were used to locate four CD4 adsorption sites that fill sequentially. This data unequivocally shows that primary adsorption sites around, and within, the small octahedral cage in the structure are favored over the exposed Cu(2+) or Cr(2+) cations. These results are supported by an exhaustive parallel computational study, and contradict results recently reported using a time-resolved diffraction structure envelope (TRDSE) method. Moreover, the computational study reveals that strong methane binding at the open metal sites is largely due to methane-methane interactions with adjacent molecules adsorbed at the primary sites instead of an electronic interaction with the metal center. Simulated methane adsorption isotherms for Cu3(btc)2 are shown to exhibit excellent agreement with experimental isotherms, allowing for additional simulations that show that modifications to the metal center, ligand, or even tuning the overall binding enthalpy would not improve the working capacity for methane storage over that measured for Cu3(btc)2 itself.

Low-temperature conversion of methane to methanol on CeO x/Cu 2O catalysts: Water controlled activation of the C–H Bond

DOE PAGES

Zuo, Zhijun; Ramírez, Pedro J.; Senanayake, Sanjaya D.; ...

2016-10-10

Here, an inverse CeO 2/Cu 2O/Cu(111) catalyst is able to activate methane at room temperature producing C, CH x fragments and CO x species on the oxide surface. The addition of water to the system leads to a drastic change in the selectivity of methane activation yielding only adsorbed CH x fragments. At a temperature of 450 K, in the presence of water, a CH 4 → CH 3OH catalytic transformation occurs with a high selectivity. OH groups formed by the dissociation of water saturate the catalyst surface, removing sites that could decompose CH x fragments, and generating centers onmore » which methane can directly interact to yield methanol.« less

The effects and mechanism of action of methane on ileal motor function.

PubMed

Park, Y M; Lee, Y J; Hussain, Z; Lee, Y H; Park, H

2017-09-01

Methane has been associated with constipation-predominant irritable bowel syndrome, slowing intestinal transit time by augmenting contractile activity. However, the precise mechanism underlying this effect remains unclear. Therefore, we investigated the mechanisms underlying the effect of methane on contractile activity, and whether such effects are mediated by nerve impulses or muscular contraction. We connected guinea pig ileal muscle strips to a force/tension transducer and measured amplitudes of contraction in response to electrical field stimulation (EFS; 1, 2, 8, 16 Hz) following methane infusion in the presence of tetradotoxin (TTX), atropine, guanethidine, or GR 113808. We then performed calcium imaging using Oregon Green 488 BAPTA-1 AM in order to visualize changes in calcium fluorescence in response to EFS following methane infusion in the presence of TTX, atropine, or a high K + solution. Methane significantly increased amplitudes of contraction (P<.05), while treatment with TTX abolished such contraction. Methane-induced increases in amplitude were inhibited when lower-frequency (1, 2 Hz) EFS was applied following atropine infusion (P<.05). Neither guanethidine nor GR 113808 significantly altered contraction amplitudes. Methane significantly increased calcium fluorescence, while this increase was attenuated following atropine infusion (P<.05). Although calcium fluorescence was increased by the high K + solution under pretreatment with TTX, the intensity of fluorescence remained unchanged after methane infusion. The actions of methane on the intestine are influenced by the cholinergic pathway of the enteric nervous system. Our findings support the classification of methane as a gasotransmitter. © 2017 John Wiley & Sons Ltd.

First-principles investigation of the dissociation and coupling of methane on small copper clusters: Interplay of collision dynamics and geometric and electronic effects

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

Varghese, Jithin J.; Mushrif, Samir H., E-mail: shmushrif@ntu.edu.sg

Small metal clusters exhibit unique size and morphology dependent catalytic activity. The search for alternate minimum energy pathways and catalysts to transform methane to more useful chemicals and carbon nanomaterials led us to investigate collision induced dissociation of methane on small Cu clusters. We report here for the first time, the free energy barriers for the collision induced activation, dissociation, and coupling of methane on small Cu clusters (Cu{sub n} where n = 2–12) using ab initio molecular dynamics and metadynamics simulations. The collision induced activation of the stretching and bending vibrations of methane significantly reduces the free energy barriermore » for its dissociation. Increase in the cluster size reduces the barrier for dissociation of methane due to the corresponding increase in delocalisation of electron density within the cluster, as demonstrated using the electron localisation function topology analysis. This enables higher probability of favourable alignment of the C–H stretching vibration of methane towards regions of high electron density within the cluster and makes higher number of sites available for the chemisorption of CH{sub 3} and H upon dissociation. These characteristics contribute in lowering the barrier for dissociation of methane. Distortion and reorganisation of cluster geometry due to high temperature collision dynamics disturb electron delocalisation within them and increase the barrier for dissociation. Coupling reactions of CH{sub x} (x = 1–3) species and recombination of H with CH{sub x} have free energy barriers significantly lower than complete dehydrogenation of methane to carbon. Thus, competition favours the former reactions at high hydrogen saturation on the clusters.« less

Investigation of shallow gas hydrate occurrence and gas seep activity on the Sakhalin continental slope, Russia

NASA Astrophysics Data System (ADS)

Jin, Young Keun; Baranov, Boris; Obzhirov, Anatoly; Salomatin, Alexander; Derkachev, Alexander; Hachikubo, Akihiro; Minami, Hrotsugu; Kuk Hong, Jong

2016-04-01

The Sakhalin continental slope has been a well-known gas hydrate area since the first finding of gas hydrate in 1980's. This area belongs to the southernmost glacial sea in the northern hemisphere where most of the area sea is covered by sea ice the winter season. Very high organic carbon content in the sediment, cold sea environment, and active tectonic regime in the Sakhalin slope provide a very favorable condition for occurring shallow gas hydrate accumulation and gas emission phenomena. Research expeditions under the framework of a Korean-Russian-Japanese long-term international collaboration projects (CHAOS, SSGH-I, SSGH-II projects) have been conducted to investigate gas hydrate occurrence and gas seepage activities on the Sakhalin continental slope, Russia from 2003 to 2015. During the expeditions, near-surface gas hydrate samples at more than 30 sites have been retrieved and hundreds of active gas seepage structures on the seafloor were newly registered by multidisciplinary surveys. The gas hydrates occurrence at the various water depths from about 300 m to 1000 m in the study area were accompanied by active gas seepage-related phenomena in the sub-bottom, on the seafloor, and in the water column: well-defined upward gas migration structures (gas chimney) imaged by high-resolution seismic, hydroacoustic anomalies of gas emissions (gas flares) detected by echosounders, seafloor high backscatter intensities (seepage structures) imaged by side-scan sonar and bathymetric structures (pockmarks and mounds) mapped by single/multi-beam surveys, and very shallow SMTZ (sulphate-methane transition zone) depths, strong microbial activities and high methane concentrations measured in sediment/seawater samples. The highlights of the expeditions are shallow gas hydrate occurrences around 300 m in the water depth which is nearly closed to the upper boundary of gas hydrate stability zone in the area and a 2,000 m-high gas flare emitted from the deep seafloor.

Stepped Single Crystals as Improved Model for Supported Catalysts: Ethylene, Methanol and Assorted Molecules on PLATINUM(511) and PLATINUM(331)

NASA Astrophysics Data System (ADS)

Spaendonk, Vincent Van

Past research has shown unusual activity of the (1 x 1)Pt(110) surface to break carbon-carbon and carbon -oxygen bonds. Methane formation from ethylene or ethane has been reported for supported platinum catalysts. A model for the methane formation on (1 x 1)Pt(110), was proposed by Yagasaki. In this study, the mechanism of methane formation has been further investigated, and Yagasaki's model tested, by studying the decomposition of ethylene and methanol on the stepped surfaces Pt(511) and Pt(331) with Temperature Programmed Desorption. The experiments have been carried out in a Ultra High Vacuum system, equipped with a mass spectrometer, LEED and AES. Hydrogen and carbon monoxide desorption show that on Pt(511) different adsorption sites are available than on Pt(331). Ethylene decomposition on Pt(511) leads to small amounts of methane formation compared to (1 x 1)Pt(110). The metastable (1 x 1) phase of Pt(511) is 2-3 times more active than the stable (hex) phase. When ^{13}C_2H _4 is used, ^{13 }CH_4 is not detected. Methane formation is not seen on the Pt(331) surface. Arguments are given why Pt(511) is a superior model for supported catalysts compared to (1 x 1)Pt(110). The carbon-oxygen bond of methanol is not broken on either Pt(511) or Pt(331), whether the surface is clean or covered with oxygen. Hydrogen saturating the surface, prevents the chemisorption of ethylene and the formation of methane. Postadsorption of hydrogen does not lead to an increase in methane formation. Coadsorption of ethylene with carbon monoxide shows a maximum methane formation at 0.3 L carbon monoxide exposure. Poison experiments with 'oxide' and carbon indicate that the active site for methane formation is located at the step. The amount of carbon deposited during ethylene decomposition, increases in the order (1 x 1)Pt(511) to (hex)Pt(511) to Pt(331). This is also the order for decreasing methane activity. In a new model, it is proposed that in order to be active for methane formation, a surface has to prevent the polymerization of single carbon species to inactive graphite. The model predicts that surfaces with large enough (111) terraces have higher diffusion rates and allow the single carbon species to convert to graphite before the species can be hydrogenated.

Microbial oxidation as a methane sink beneath the West Antarctic Ice Sheet

NASA Astrophysics Data System (ADS)

Michaud, Alexander B.; Dore, John E.; Achberger, Amanda M.; Christner, Brent C.; Mitchell, Andrew C.; Skidmore, Mark L.; Vick-Majors, Trista J.; Priscu, John C.

2017-08-01

Aquatic habitats beneath ice masses contain active microbial ecosystems capable of cycling important greenhouse gases, such as methane (CH4). A large methane reservoir is thought to exist beneath the West Antarctic Ice Sheet, but its quantity, source and ultimate fate are poorly understood. For instance, O2 supplied by basal melting should result in conditions favourable for aerobic methane oxidation. Here we use measurements of methane concentrations and stable isotope compositions along with genomic analyses to assess the sources and cycling of methane in Subglacial Lake Whillans (SLW) in West Antarctica. We show that sub-ice-sheet methane is produced through the biological reduction of CO2 using H2. This methane pool is subsequently consumed by aerobic, bacterial methane oxidation at the SLW sediment-water interface. Bacterial oxidation consumes >99% of the methane and represents a significant methane sink, and source of biomass carbon and metabolic energy to the surficial SLW sediments. We conclude that aerobic methanotrophy may mitigate the release of methane to the atmosphere upon subglacial water drainage to ice sheet margins and during periods of deglaciation.

The lipid response of aerobic marine methanotroph communities under changing environmental conditions.

NASA Astrophysics Data System (ADS)

Rush, D.; Villanueva, L.; van der Meer, M.; S Sinninghe Damsté, J.

2017-12-01

Methane (CH4) originating from marine environments accounts for a significant amount of atmospheric greenhouse gas. Aerobic methanotrophs, which convert CH4 to CO­2, are responsible for quenching a part of this methane before its release. Modern-day climate projections show a rapid shift towards a warmer, more acidic ocean. How do these important methanotrophic communities respond to such changes to their environment? Here, we present the results of microcosm experiments from three marine regions influenced by CH4. Particulate organic matter and sediment were collected from the Black Sea, the Baltic Sea, and the North Sea, at depths ideal for aerobic methanotroph communities at the time of sampling (e.g. oxic, in area of active CH4 release). These were incubated under different temperatures, pHs, and labelled 13CH4 concentrations. We monitored methane concentration in these microcosms as an indication of 13CH4 consumption by methanotrophs. Once the methane concentration was <0.1%, incubations were terminated. We will trace isotopically heavy 13C in the DNA and lipids of the organisms oxidising methane in order to elucidate which organisms are performing methane oxidation and whether they synthesize specific biomarker lipids. Particular attention will be paid to the abundances and diversity of bacteriohopanepolyol lipids, known methanotroph biomarkers. The ultimate goal of our investigation is to determine the effect changes in these environmental parameters have on aerobic methanotroph community structures and their lipid fingerprints. By establishing reliable biomarker lipids for aerobic methanotrophy at certain conditions, we will then be able to investigate the contribution of aerobic methanotrophy throughout Earth's history, especially at times when CH4 concentrations were higher than they are at present.

Thermodynamic properties and diffusion of water + methane binary mixtures

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

Shvab, I.; Sadus, Richard J., E-mail: rsadus@swin.edu.au

2014-03-14

Thermodynamic and diffusion properties of water + methane mixtures in a single liquid phase are studied using NVT molecular dynamics. An extensive comparison is reported for the thermal pressure coefficient, compressibilities, expansion coefficients, heat capacities, Joule-Thomson coefficient, zero frequency speed of sound, and diffusion coefficient at methane concentrations up to 15% in the temperature range of 298–650 K. The simulations reveal a complex concentration dependence of the thermodynamic properties of water + methane mixtures. The compressibilities, heat capacities, and diffusion coefficients decrease with increasing methane concentration, whereas values of the thermal expansion coefficients and speed of sound increase. Increasing methanemore » concentration considerably retards the self-diffusion of both water and methane in the mixture. These effects are caused by changes in hydrogen bond network, solvation shell structure, and dynamics of water molecules induced by the solvation of methane at constant volume conditions.« less

The effect of moisture on the methane adsorption capacity of shales: A study case in the eastern Qaidam Basin in China

NASA Astrophysics Data System (ADS)

Wang, Lu; Yu, Qingchun

2016-11-01

This study investigated the effects of moisture on high-pressure methane adsorption in carboniferous shales from the Qaidam Basin, China. The shale characteristics, including the organic/inorganic compositions and pore structure (volume and surface) distribution, were obtained using various techniques. Gibbs adsorption measurements were performed over a pressure range up to 6 MPa and temperatures of 308.15 K on dry samples and moisture-equilibrated samples to analyze the correlations between organic/inorganic matter, pore structure, and moisture content on the methane sorption capacity. Compared to dry samples, the sorption capacity of wet samples (0.44-2.52% of water content) is reduced from 19.7 ± 5.3% to 36.1% ± 6.1%. Langmuir fitting is conducted to investigate moisture-dependent variations of adsorbed methane density, Langmuir pressure, and volume. By combining the pore volume and surface distribution analyses, our observations suggested that the main competition sites for CH4-H2O covered pores of approximately 2-7 nm, whereas the effective sites for methane and water were predominantly distributed within smaller (<4 nm) and larger pores (>10 nm), respectively. Regarding the compositional correlations, the impact of moisture on the amount of adsorbed methane shows a roughly linearly decreasing trend with increasing TOC content ranging from 0.62 to 2.88%, whereas the correlation between the moisture effect and various inorganic components is more complicated. Further fitting results indicate that illite/smectite mixed formations are closely related to the methane capacity, whereas the illite content show an evident connection to the pore structural (volume and surface) variations in the presence of moisture.

Thermodynamic and structural signatures of water-driven methane-methane attraction in coarse-grained mW water.

PubMed

Song, Bin; Molinero, Valeria

2013-08-07

Hydrophobic interactions are responsible for water-driven processes such as protein folding and self-assembly of biomolecules. Microscopic theories and molecular simulations have been used to study association of a pair of methanes in water, the paradigmatic example of hydrophobic attraction, and determined that entropy is the driving force for the association of the methane pair, while the enthalpy disfavors it. An open question is to which extent coarse-grained water models can still produce correct thermodynamic and structural signatures of hydrophobic interaction. In this work, we investigate the hydrophobic interaction between a methane pair in water at temperatures from 260 to 340 K through molecular dynamics simulations with the coarse-grained monatomic water model mW. We find that the coarse-grained model correctly represents the free energy of association of the methane pair, the temperature dependence of free energy, and the positive change in entropy and enthalpy upon association. We investigate the relationship between thermodynamic signatures and structural order of water through the analysis of the spatial distribution of the density, energy, and tetrahedral order parameter Qt of water. The simulations reveal an enhancement of tetrahedral order in the region between the first and second hydration shells of the methane molecules. The increase in tetrahedral order, however, is far from what would be expected for a clathrate-like or ice-like shell around the solutes. This work shows that the mW water model reproduces the key signatures of hydrophobic interaction without long ranged electrostatics or the need to be re-parameterized for different thermodynamic states. These characteristics, and its hundred-fold increase in efficiency with respect to atomistic models, make mW a promising water model for studying water-driven hydrophobic processes in more complex systems.

Methane hydrate formation in confined nanospace can surpass nature

DOE PAGES

Casco, Mirian E.; Silvestre-Albero, Joaquín; Ramírez-Cuesta, Anibal J.; ...

2015-03-02

Natural methane hydrates are believed to be the largest source of hydrocarbons on Earth. These structures are formed in specific locations such as deep-sea sediments and the permafrost based on demanding conditions of high pressure and low temperature. We report that, by taking advantage of the confinement effects on nanopore space, synthetic methane hydrates grow under mild conditions (3.5 MPa and 2 degrees C), with faster kinetics (within minutes) than nature, fully reversibly and with a nominal stoichiometry that mimics nature. Furthermore, the formation of the hydrate structures in nanospace and their similarity to natural hydrates is confirmed using inelasticmore » neutron scattering experiments and synchrotron X-ray powder diffraction. Our findings may be a step towards the application of a smart synthesis of methane hydrates in energy-demanding applications (for example, transportation).« less

Application of meta-omics techniques to understand greenhouse gas emissions originating from ruminal metabolism.

PubMed

Wallace, Robert J; Snelling, Timothy J; McCartney, Christine A; Tapio, Ilma; Strozzi, Francesco

2017-01-16

Methane emissions from ruminal fermentation contribute significantly to total anthropological greenhouse gas (GHG) emissions. New meta-omics technologies are beginning to revolutionise our understanding of the rumen microbial community structure, metabolic potential and metabolic activity. Here we explore these developments in relation to GHG emissions. Microbial rumen community analyses based on small subunit ribosomal RNA sequence analysis are not yet predictive of methane emissions from individual animals or treatments. Few metagenomics studies have been directly related to GHG emissions. In these studies, the main genes that differed in abundance between high and low methane emitters included archaeal genes involved in methanogenesis, with others that were not apparently related to methane metabolism. Unlike the taxonomic analysis up to now, the gene sets from metagenomes may have predictive value. Furthermore, metagenomic analysis predicts metabolic function better than only a taxonomic description, because different taxa share genes with the same function. Metatranscriptomics, the study of mRNA transcript abundance, should help to understand the dynamic of microbial activity rather than the gene abundance; to date, only one study has related the expression levels of methanogenic genes to methane emissions, where gene abundance failed to do so. Metaproteomics describes the proteins present in the ecosystem, and is therefore arguably a better indication of microbial metabolism. Both two-dimensional polyacrylamide gel electrophoresis and shotgun peptide sequencing methods have been used for ruminal analysis. In our unpublished studies, both methods showed an abundance of archaeal methanogenic enzymes, but neither was able to discriminate high and low emitters. Metabolomics can take several forms that appear to have predictive value for methane emissions; ruminal metabolites, milk fatty acid profiles, faecal long-chain alcohols and urinary metabolites have all shown promising results. Rumen microbial amino acid metabolism lies at the root of excessive nitrogen emissions from ruminants, yet only indirect inferences for nitrogen emissions can be drawn from meta-omics studies published so far. Annotation of meta-omics data depends on databases that are generally weak in rumen microbial entries. The Hungate 1000 project and Global Rumen Census initiatives are therefore essential to improve the interpretation of sequence/metabolic information.

Long-term effect of the antibiotic cefalexin on methane production during waste activated sludge anaerobic digestion.

PubMed

Lu, Xueqin; Zhen, Guangyin; Liu, Yuan; Hojo, Toshimasa; Estrada, Adriana Ledezma; Li, Yu-You

2014-10-01

Long-term experiments herein were conducted to investigate the effect of cefalexin (CLX) on methane production during waste activated sludge (WAS) anaerobic digestion. CLX exhibited a considerable inhibition in methane production during the initial 25 days while the negative effect attenuated subsequently and methane production recovered depending on CLX doses used (600 and 1000 mg/L). The highest methane yield reached 450 mL at 1000 mg-CLX/L after 157 days of digestion, 63.8% higher than CLX-free one. Stimulated excretion of extracellular polymeric substances (EPS) by CLX served as microbial protecting layers, creating a suitable environment for microbes' growth and fermentation. Further examination via ultraviolet visible (UV-Vis) spectra also verified the elevated slime EPS, LB-EPS and TB-EPS indicated by UV-254 in the presence of CLX. Unlike the commonly accepted adverse effect, this study demonstrated the beneficial role of CLX in methane production, providing new insights into its true environmental impacts. Copyright © 2014 Elsevier Ltd. All rights reserved.

Systems level insights into alternate methane cycling modes in a freshwater lake via community transcriptomics, metabolomics and nano-SIMS analysis

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

Lidstrom, Mary E.; Chistoserdova, Ludmila; Kalyuzhnaya, Marina G.

2014-08-07

The research conducted as part of this project contributes significantly to the understanding of the microbes and their activities involved in methane metabolism in freshwater lake sediments and in the environment in a more global sense. Significant new insights have been gained into the identity of the species that are most active in methane oxidation. New concepts have been developed based on the new data on how these organisms metabolize methane, impacting not only environmental microbiology but also biotechnology, including biotechnology of next generation biofuels. Novel approaches have been developed for studying functional microbial communities, via holistic approaches, such asmore » metagenomics, metatrancriptomics and metabolite analysis. As a result, a novel outlook has been obtained at how such communities operate in nature. Understanding methane-oxidizing communities in lakes and other environments is of significant benefit to the public, in terms of methane emission mitigation and in terms of potential biotechnological applications.« less

Distribution and geochemical characterization of coalbed gases at excavation fields at natural analogue site area Velenje Basin, Slovenia

NASA Astrophysics Data System (ADS)

Kanduč, Tjaša; Žigon, Stojan; Grassa, Fausto; Sedlar, Jerneja; Zadnik, Ivo; Zavšek, Simon

2016-04-01

Unconventional gas resources, including coal bed methane and shale gas, are a growing part of the global energy mix, which has changed the economic and strategic picture for gas consuming and producing countries, including the USA, China and Australia that, together are responsible for around half the currently recoverable unconventional gas resources. However, CBM production was often hindered by low permeability and mineralization in cleats and fractures, necessitating the development of cost effective horizontal drilling and completion techniques. Geochemical and isotopic monitoring of coalbed gases at excavation fields in Velenje Basin started in year 2000, with the aim to obtain better insights into the origin of coalbed gases. Results from active excavation fields in the mining areas Pesje and Preloge in the year period 2014-2015 are presented in this study. Composition and isotopic composition of coalbed gases were determined with mass - spectrometric methods. The chemical (methane, carbon dioxide, nitrogen) and isotopic composition of carbon in methane and carbon dioxide in the Velenje Basin vary and depend on the composition of the source of coalbed gas before excavation, advancement of the working face, depth of the longwall face, pre-mining activity and newly mined activity. The basic gas components determined in excavation fields are carbon dioxide and methane. Knowledge of the stable isotope geochemistry of coal bed and shale gas and the related production water is essential to determine not only gas origins but also the dominant methanogenic pathway in the case of microbial gas. Concentrations of methane at active excavation fields are changing from 1.8 to 63.9 %, concentrations of carbon dioxide are changing from 36.1 to 98.2% and CDMI (Carbon Dioxide Methane Index) index from 0.2 to 100 %. Isotopic composition of carbon dioxide is changing from -11.0 to -1.9‰ , isotopic composition of methane from -71.8 to -43.3‰ , isotopic composition of deuterium in methane from -343.9 to -223.1‰ , respectively. Further, these characteristics of methane have been compared with those observed in other coal sedimentary basins worldwide. The isotopic compositions of carbon and hydrogen in methane in the excavation fields show its biogenic origin, while a high Carbon Dioxide Methane Index (CDMI index) indicates the bacterial and endogenic origin of carbon dioxide.

Methane Seep Carbonates Host Distinct, Diverse, and Dynamic Microbial Assemblages

PubMed Central

Pasulka, Alexis L.; Marlow, Jeffrey J.; Grupe, Benjamin M.; Levin, Lisa A.

2015-01-01

ABSTRACT Marine methane seeps are globally distributed geologic features in which reduced fluids, including methane, are advected upward from the subsurface. As a result of alkalinity generation during sulfate-coupled methane oxidation, authigenic carbonates form slabs, nodules, and extensive pavements. These carbonates shape the landscape within methane seeps, persist long after methane flux is diminished, and in some cases are incorporated into the geologic record. In this study, microbial assemblages from 134 native and experimental samples across 5,500 km, representing a range of habitat substrates (carbonate nodules and slabs, sediment, bottom water, and wood) and seepage conditions (active and low activity), were analyzed to address two fundamental questions of seep microbial ecology: (i) whether carbonates host distinct microbial assemblages and (ii) how sensitive microbial assemblages are to habitat substrate type and temporal shifts in methane seepage flux. Through massively parallel 16S rRNA gene sequencing and statistical analysis, native carbonates are shown to be reservoirs of distinct and highly diverse seep microbial assemblages. Unique coupled transplantation and colonization experiments on the seafloor demonstrated that carbonate-associated microbial assemblages are resilient to seep quiescence and reactive to seep activation over 13 months. Various rates of response to simulated seep quiescence and activation are observed among similar phylogenies (e.g., Chloroflexi operational taxonomic units) and similar metabolisms (e.g., putative S oxidizers), demonstrating the wide range of microbial sensitivity to changes in seepage flux. These results imply that carbonates do not passively record a time-integrated history of seep microorganisms but rather host distinct, diverse, and dynamic microbial assemblages. PMID:26695630

Freshwater bacteria release methane as a byproduct of phosphorus acquisition.

PubMed

Yao, Mengyin; Henny, Cynthia; Maresca, Julia A

2016-09-30

Freshwater lakes emit large amounts of methane, some of which is produced in oxic surface waters. Two potential pathways for aerobic methane production exist: methanogenesis in oxygenated water, which has been observed in some lakes, or demethylation of small organic molecules. Although methane is produced via demethylation in oxic marine environments, this mechanism of methane release has not yet been demonstrated in freshwater systems. Genes related to the C-P lyase pathway, which cleaves C-P bonds in phosphonate compounds, were found in a metagenomic survey of the surface water of Lake Matano, which is chronically P-starved and methane-rich. We demonstrate that four bacterial isolates from Lake Matano obtain P from methylphosphonate and release methane, and that this activity is repressed by phosphate. We further demonstrate that expression of phnJ, which encodes the enzyme that releases methane, is higher in the presence of methylphosphonate and lower when both methylphosphonate and phosphate are added. This gene is also found in most of the metagenomic data sets from freshwater environments. These experiments link methylphosphonate degradation and methane production with gene expression and phosphate availability in freshwater organisms, and suggest that some of the excess methane in the Lake Matano surface water, and in other methane-rich lakes, may be produced by P-starved bacteria. Methane is an important greenhouse gas, and contributes substantially to global warming. Although freshwater environments are known to release methane into the atmosphere, estimates of the amount of methane emitted by freshwater lakes vary from 8 to 73 Tg per year. Methane emissions are difficult to predict in part because the source of the methane can vary: it is the end product of the energy-conserving pathway in methanogenic archaea, which predominantly live in anoxic sediments or waters, but have also been identified in some oxic freshwater environments. More recently, methane release from small organic molecules has been observed in oxic marine environments. Here we show that demethylation of methylphosphonate may also contribute to methane release from lakes, and that phosphate can repress this activity. Since lakes are typically phosphorus-limited, some methane release in these environments may be a byproduct of phosphorus metabolism, rather than carbon or energy metabolism. Methane emissions from lakes are currently predicted using primary production, eutrophication status, extent of anoxia, and the shape and size of the lake; to improve prediction of methane emissions, phosphorus availability and sources may also need to be included in these models. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

Big Soda Lake (Nevada). 3. Pelagic methanogenesis and anaerobic methane oxidation

USGS Publications Warehouse

Iversen, Niels; Oremland, Ronald S.; Klug, Michael J.

1987-01-01

In situ rates of methanogenesis and methane oxidation were measured in meromictic Big Soda Lake. Methane production was measured by the accumulation of methane in the headspaces of anaerobically sealed water samples; radiotracer was used to follow methane oxidation. Nearly all the methane oxidation occurred in the anoxic zones of the lake. Rates of anaerobic oxidation exceeded production at all depths studied in both the mixolimnion (2–6 vs. 0.1–1 nmol liter−1 d−1) and monimolimnion (49–85 vs. 1.6–12 nmol liter−1 d−1) of the lake. Thus, a net consumption of methane equivalent to 1.36 mmol m−2 d−1 occurred in the anoxic water column. Anaerobic methane oxidation had a first-order rate constant of 8.1±0.5 × 10−4 d−1, and activity was eliminated by filter sterilization. However, in situ methane oxidation was of insufficient magnitude to cause a noticeable decrease of ambient dissolved methane levels over an incubation period of 97 h.

The effects of acid deposition on sulfate reduction and methane production in peatlands

NASA Technical Reports Server (NTRS)

Murray, Georgia L.; Hines, Mark E.; Bayley, Suzanne E.

1992-01-01

Peatlands, as fens and bods, make up a large percentage of northern latitude terrestrial environments. They are organic rich and support an active community of anaerobic bacteria, such as methanogenic and sulfate-reducing bacteria. The end products of these microbial activities, methane and hydrogen sulfide, are important components in the global biogeochemical cycles of carbon and sulfur. Since these two bacterial groups compete for nutritional substrates, increases in sulfate deposition due to acid rain potentially can disrupt the balance between these processes leading to a decrease in methane production and emission. This is significant because methane is a potent greenhouse gas that effects the global heat balance. A section of Mire 239 in the Experimental Lakes Area, in Northwestern Ontario, was artificially acidified and rates of sulfate reduction and methane production were measured with depth. Preliminary results suggested that methane production was not affected immediately after acidification. However, concentrations of dissolved methane decreased and dissolved sulfide increased greatly after acidification and both took several days to recover. The exact mechanism for the decrease in methane was not determined. Analyses are under way which will be used to determine rates of sulfate reduction. These results will be available by Spring and will be discussed.

Quantifying the Presence and Activity of Aerobic, Vinyl Chloride-Degrading Microorganisms in Dilute Groundwater Plumes by Using Real-Time PCR

DTIC Science & Technology

2013-07-01

throughout the observation period. A 0.25-ml Pressure-Lok gas -tight syringe with a side-ported needle was used to take 0.1 ml headspace samples during...33. Biodegradation of methane, VC and a methane+VC mixture by methane enrichment cultures derived from Carver well RB63I. These results indicate that...VC and a methane+VC mixture by methane enrichment cultures derived from Carver well RB63I. These results are a repeat of the experiment depicted in

Variations in archaeal and bacterial diversity associated with the anaerobic oxidation of methane in the active mud volcanoes of the Canadian Beaufort Sea

NASA Astrophysics Data System (ADS)

Lee, Y. M.; Lee, D. H.; Hwang, K.; Hong, S. G.; Jin, Y. K.

2016-12-01

The prokaryotic microorganisms inhabiting Mud Volcanoes (MVs) play an important role for mitigation of methane (CH4) emission. Despite the identification of active MVs in the continental slope of the Canadian Beaufort Sea, little is known about the distribution and functions of prokaryotic community in this region. Hence, we investigated the prokaryotic diversity of four sediment cores (three from the active MVs and one from a non-methane influenced reference site) of the Canadian Beaufort Sea using 454-pyrosequencing of 16S rRNA genes as the first step to understand the prokaryotic roles in controlling outgassing methane. Bacterial and archaeal communities of MVs were distinctive from those of the reference site, and the communities of MVs were similar to each other at deeper depth levels. Chloroflexi, Actinobacteria, unclassified bacterial groups, and MCG_c of Crenarchaeota were predominant in the MVs, while Firmicutes, Deltaproteobacteria, and unclassified class of Thaumarchaeota were dominant in reference site. The relative abundance of dominant bacterial groups varied at sulfate-methane transition zone (SMTZ) of individual MVs. However, certain microbial taxa such as members of SAGMEG_o or Methanosarcinales of Euryarcheaota and Dehalococcoidales of Chloroflexi were predominant at SMTZs. Since they are not the classical representative taxa known to be involved in anaerobic oxidation of methane, their dominance implicates that they could be playing important roles in methane cycling using unrevealed mechanisms. We will further perform the phylogenetic and network analyses to infer mechanisms and interactions of dominant operational taxonomic units in controlling methane flux.

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

PubMed

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

2007-05-01

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

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

PubMed Central

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

2007-01-01

Submarine mud volcanoes are formed by expulsions of mud, fluids, and gases from deeply buried subsurface sources. They are highly reduced benthic habitats and often associated with intensive methane seepage. In this study, the microbial diversity and community structure in methane-rich sediments of the Haakon Mosby Mud Volcano (HMMV) were investigated by comparative sequence analysis of 16S rRNA genes and fluorescence in situ hybridization. In the active volcano center, which has a diameter of about 500 m, the main methane-consuming process was bacterial aerobic oxidation. In this zone, aerobic methanotrophs belonging to three bacterial clades closely affiliated with Methylobacter and Methylophaga species accounted for 56% ± 8% of total cells. In sediments below Beggiatoa mats encircling the center of the HMMV, methanotrophic archaea of the ANME-3 clade dominated the zone of anaerobic methane oxidation. ANME-3 archaea form cell aggregates mostly associated with sulfate-reducing bacteria of the Desulfobulbus (DBB) branch. These ANME-3/DBB aggregates were highly abundant and accounted for up to 94% ± 2% of total microbial biomass at 2 to 3 cm below the surface. ANME-3/DBB aggregates could be further enriched by flow cytometry to identify their phylogenetic relationships. At the outer rim of the mud volcano, the seafloor was colonized by tubeworms (Siboglinidae, formerly known as Pogonophora). Here, both aerobic and anaerobic methane oxidizers were found, however, in lower abundances. The level of microbial diversity at this site was higher than that at the central and Beggiatoa species-covered part of the HMMV. Analysis of methyl-coenzyme M-reductase alpha subunit (mcrA) genes showed a strong dominance of a novel lineage, mcrA group f, which could be assigned to ANME-3 archaea. Our results further support the hypothesis of Niemann et al. (54), that high methane availability and different fluid flow regimens at the HMMV provide distinct niches for aerobic and anaerobic methanotrophs. PMID:17369343

Changes in pore structure of coal caused by coal-to-gas bioconversion

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

Zhang, Rui; Liu, Shimin; Bahadur, Jitendra

Microbial enhanced coalbed methane (ME-CBM) recovery is critically examined as a viable technology for natural gas recovery from coalbed methane (CBM) reservoirs. Since the majority of gas-in-place (GIP) is stored as an adsorbed phase in fine pores of coal matrix, the nano-pore structure directly influences gas storage and transport properties. Only limited studies have quantified the alteration of the nano-pore structure due to ME-CBM treatment. This study examines the evolution of the pore structure using a combination of small angle X-ray scattering (SAXS), low-pressure N 2 and CO 2 adsorption (LPGA) and high-pressure methane adsorption methods. The results show thatmore » the surface fractal dimension decreases for the two bioconverted coals compared to the untreated coal. After bio-treatment, the mesopore surface area and pore volume decrease with the average pore diameter increases, while the micropore surface area increases with pore volume decreases. Both inaccessible meso-/micropore size distributions decrease after bioconversion, while the accessible micropore size distribution increases, making a portion of closed micropore network accessible. In addition, the methane adsorption capacities increase after bio-treatment, which is confirmed by the increase of micropore surface area. A conceptual physical model of methanogenesis is proposed based on the evolution of the pore structure.« less

Changes in pore structure of coal caused by coal-to-gas bioconversion

DOE PAGES

Zhang, Rui; Liu, Shimin; Bahadur, Jitendra; ...

2017-06-19

Microbial enhanced coalbed methane (ME-CBM) recovery is critically examined as a viable technology for natural gas recovery from coalbed methane (CBM) reservoirs. Since the majority of gas-in-place (GIP) is stored as an adsorbed phase in fine pores of coal matrix, the nano-pore structure directly influences gas storage and transport properties. Only limited studies have quantified the alteration of the nano-pore structure due to ME-CBM treatment. This study examines the evolution of the pore structure using a combination of small angle X-ray scattering (SAXS), low-pressure N 2 and CO 2 adsorption (LPGA) and high-pressure methane adsorption methods. The results show thatmore » the surface fractal dimension decreases for the two bioconverted coals compared to the untreated coal. After bio-treatment, the mesopore surface area and pore volume decrease with the average pore diameter increases, while the micropore surface area increases with pore volume decreases. Both inaccessible meso-/micropore size distributions decrease after bioconversion, while the accessible micropore size distribution increases, making a portion of closed micropore network accessible. In addition, the methane adsorption capacities increase after bio-treatment, which is confirmed by the increase of micropore surface area. A conceptual physical model of methanogenesis is proposed based on the evolution of the pore structure.« less

Methane Hydrate Field Program: Development of a Scientific Plan for a Methane Hydrate-Focused Marine Drilling, Logging and Coring Program

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

Myers, Greg

This final report document summarizes the activities undertaken and the output from three primary deliverables generated during this project. This fifteen month effort comprised numerous key steps including the creation of an international methane hydrate science team, determining and reporting the current state of marine methane hydrate research, convening an international workshop to collect the ideas needed to write a comprehensive Marine Methane Hydrate Field Research Plan and the development and publication of that plan. The following documents represent the primary deliverables of this project and are discussed in summary level detail in this final report: Historical Methane Hydrate Projectmore » Review Report; Methane Hydrate Workshop Report; Topical Report: Marine Methane Hydrate Field Research Plan; and Final Scientific/Technical Report.« less

Martian methane plume models for defining Mars rover methane source search strategies

NASA Astrophysics Data System (ADS)

Nicol, Christopher; Ellery, Alex; Lynch, Brian; Cloutis, Ed

2018-07-01

The detection of atmospheric methane on Mars implies an active methane source. This introduces the possibility of a biotic source with the implied need to determine whether the methane is indeed biotic in nature or geologically generated. There is a clear need for robotic algorithms which are capable of manoeuvring a rover through a methane plume on Mars to locate its source. We explore aspects of Mars methane plume modelling to reveal complex dynamics characterized by advection and diffusion. A statistical analysis of the plume model has been performed and compared to analyses of terrestrial plume models. Finally, we consider a robotic search strategy to find a methane plume source. We find that gradient-based techniques are ineffective, but that more sophisticated model-based search strategies are unlikely to be available in near-term rover missions.

Microbial Methane Oxidation Rates in Guandu Wetland of northern Taiwan

NASA Astrophysics Data System (ADS)

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

2016-04-01

Wetland is one of the major sources of atmospheric methane. The exact magnitude of methane emission is essentially controlled by microbial processes. Besides of methanogenesis, methanotrophy oxidizes methane with the reduction of various electron acceptors under oxic or anoxic conditions. The interplay of these microbial activities determines the final methane flux under different circumstances. In a tidal wetland, the cyclic flooding and recession of tide render oxygen and sulfate the dominant electron acceptors for methane oxidation. However, the details have not been fully examined, especially for the linkage between potential methane oxidation rates and in situ condition. In this study, a sub-tropical wetland in northern Taiwan, Guandu, was chosen to examine the tidal effect on microbial methane regulation. Several sediment cores were retrieved during high tide and low tide period and their geochemical profiles were characterized to demonstrate in situ microbial activities. Incubation experiments were conducted to estimate potential aerobic and anaerobic methane oxidation rates in surface and core sediments. Sediment cores collected in high tide and low tide period showed different geochemical characteristics, owning to tidal inundation. Chloride and sulfate concentration were lower during low tide period. A spike of enhanced sulfate at middle depth intervals was sandwiched by two sulfate depleted zones above and underneath. Methane was accumulated significantly with two methane depletion zones nearly mirroring the sulfate spike zone identified. During the high tide period, sulfate decreased slightly with depth with methane production inhibited at shallow depths. However, a methane consumption zone still occurred near the surface. Potential aerobic methane oxidation rates were estimated between 0.7 to 1.1 μmole/g/d, showing no difference between the samples collected at high tide or low tide period. However, a lag phase was widely observed and the lag phase lasted over a longer period of time for the samples collected in high tide period. It seems that aerobic methanotrophs needed a longer period of time to recovery and/or had low activities, since they had been suppressed by low oxygen concentration during high tide period. The rates of anaerobic methane oxidation ranged between 1.5 and 4.0 nmole/g/d for samples collected at high tide period, whereas lower rates ranging from 0.2 to 2.0 nmole/g/d were observed for samples at low tide period. The addition of basal salt solution apparently stimulated methane consumption significantly. Based on the field observation and laboratory incubations, our results indicated a dynamic shift of metabolic zonation in tidally influenced wetlands. Aerobic methanotrophy appears to outpace anaerobic methanotrophy by orders of magnitude regardless of tidal inundation. This together with methanogenesis regulated by the availability of sulfate and organic degradation plays a major role in controlling methane emission. While anaerobic methanotrophy is relatively minor in methane cycling, its linkage with the sulfate availability modulates the coupling of carbon and sulfur turnover under anoxic conditions.

Improved methane production from waste activated sludge with low organic content by alkaline pretreatment at pH 10.

PubMed

Feng, L Y; Yang, L Q; Zhang, L X; Chen, H L; Chen, J

2013-01-01

Sludge with low organic content always results in an unsatisfactory performance, even failure of anaerobic digestion. The alkaline pretreatment effect on anaerobic digestion of sludge with low organic content has seldom been studied although it gives many benefits for sludge with high organic content. In this study the influence of alkaline pretreatment (pH 10, an effective alkaline pH) on the solubilization and methane production from waste activated sludge (WAS) with low organic content was investigated. Results from biochemical methane potential (BMP) experiments showed that anaerobic biodegradability of WAS was greatly improved by alkaline pretreatment at pH 10. Methane production from the current WAS under conditions of pretreatment time 4 h and digestion time 15 d was 139.6 mL/g VS (volatile solids), much higher than that from the unpretreated WAS with digestion time of 20 d (75.2 mL/g VS). Also, the solubilization of WAS was significantly accelerated by alkaline pretreatment. Mechanism exploration indicated that the general activities of anaerobic microorganisms, specific activities of key enzymes and the amounts of methanogens were enhanced by alkaline pretreatment at pH 10, showing good agreement with methane production.

A novel method for estimating methane emissions from underground coal mines: The Yanma coal mine, China

NASA Astrophysics Data System (ADS)

Ji, Zhong-Min; Chen, Zhi-Jian; Pan, Jie-Nan; Niu, Qing-He

2017-12-01

As the world's largest coal producer and consumer, China accounts for a relatively high proportion of methane emissions from coal mines. Several estimation methods had been established for the coal mine methane (CMM) emission. However, with large regional differences, various reservoir formation types of coalbed methane (CBM) and due to the complicated geological conditions in China, these methods may be deficient or unsuitable for all the mining areas (e.g. Jiaozuo mining area). By combing the CMM emission characteristics and considering the actual situation of methane emissions from underground coal mine, we found that the methane pre-drainage is a crucial reason creating inaccurate evaluating results for most estimation methods. What makes it so essential is the extensive pre-drainage quantity and its irrelevance with annual coal production. Accordingly, the methane releases were divided into two categories: methane pre-drainage and methane release during mining. On this basis, a pioneering method for estimating CMM emissions was proposed. Taking the Yanma coal mine in the Jiaozuo mining area as a study case, the evaluation method of the pre-drainage methane quantity was established after the correlation analysis between the pre-drainage rate and time. Thereafter, the mining activity influence factor (MAIF) was first introduced to reflect the methane release from the coal and rock seams around where affected by mining activity, and the buried depth was adopted as the predictor of the estimation for future methane emissions. It was verified in the six coal mines of Jiaozuo coalfield (2011) that the new estimation method has the minimum errors of 12.11%, 9.23%, 5.77%, -5.20%, -8.75% and 4.92% respectively comparing with other methods. This paper gives a further insight and proposes a more accurate evaluation method for the CMM emissions, especially for the coal seams with low permeability and strong tectonic deformation in methane outburst coal mines.

Diversity and biogeochemical structuring of bacterial communities across the Porangahau ridge accretionary prism, New Zealand

USGS Publications Warehouse

Hamdan, L.J.; Gillevet, P.M.; Pohlman, J.W.; Sikaroodi, M.; Greinert, J.; Coffin, R.B.

2011-01-01

Sediments from the Porangahau ridge, located off the northeastern coast of New Zealand, were studied to describe bacterial community structure in conjunction with differing biogeochemical regimes across the ridge. Low diversity was observed in sediments from an eroded basin seaward of the ridge and the community was dominated by uncultured members of the Burkholderiales. Chloroflexi/GNS and Deltaproteobacteria were abundant in sediments from a methane seep located landward of the ridge. Gas-charged and organic-rich sediments further landward had the highest overall diversity. Surface sediments, with the exception of those from the basin, were dominated by Rhodobacterales sequences associated with organic matter deposition. Taxa related to the Desulfosarcina/Desulfococcus and the JS1 candidates were highly abundant at the sulfate-methane transition zone (SMTZ) at three sites. To determine how community structure was influenced by terrestrial, pelagic and in situ substrates, sequence data were statistically analyzed against geochemical data (e.g. sulfate, chloride, nitrogen, phosphorous, methane, bulk inorganic and organic carbon pools) using the Biota-Environmental matching procedure. Landward of the ridge, sulfate was among the most significant structuring factors. Seaward of the ridge, silica and ammonium were important structuring factors. Regardless of the transect location, methane was the principal structuring factor on SMTZ communities. FEMS Microbiology Ecology ?? 2011 Federation of European Microbiological Societies. Published by Blackwell Publishing Ltd. No claim to original US government works.

Heterogeneous Nucleation of Methane Hydrate in a Water-Decane-Methane Emulsion

NASA Astrophysics Data System (ADS)

Shestakov, V. A.; Kosyakov, V. I.; Manakov, A. Yu.; Stoporev, A. S.; Grachev, E. V.

2018-07-01

Heterogeneous nucleation in disperse systems with metastable disperse phases plays an important role in the mechanisms of environmental and technological processes. The effect the concentration and activity of particles that initiate the formation of a new phase have on nucleation processes in such systems is considered. An approach is proposed that allows construction of a spectrum of particle activity characterizing the features of nucleation in a sample, based on the fraction of crystallized droplets depending on the level of supercooling and the use of Weibull's distribution. The proposed method is used to describe experimental data on the heterogeneous nucleation of methane hydrate in an emulsion in a water-decane-methane system.

Methanation of gas streams containing carbon monoxide and hydrogen

DOEpatents

Frost, Albert C.

1983-01-01

Carbon monoxide-containing gas streams having a relatively high concentration of hydrogen are pretreated so as to remove the hydrogen in a recoverable form for use in the second step of a cyclic, essentially two-step process for the production of methane. The thus-treated streams are then passed over a catalyst to deposit a surface layer of active surface carbon thereon essentially without the formation of inactive coke. This active carbon is reacted with said hydrogen removed from the feed gas stream to form methane. The utilization of the CO in the feed gas stream is appreciably increased, enhancing the overall process for the production of relatively pure, low-cost methane from CO-containing waste gas streams.

Evaluating the biogas potential of the dry fraction from pretreatment of food waste from households.

PubMed

Murto, Marika; Björnsson, Lovisa; Rosqvist, Håkan; Bohn, Irene

2013-05-01

At the waste handling company NSR, Helsingborg, Sweden, the food waste fraction of source separated municipal solid waste is pretreated to obtain a liquid fraction, which is used for biogas production, and a dry fraction, which is at present incinerated. This pretreatment and separation is performed to remove impurities, however also some of the organic material is removed. The possibility of realising the methane potential of the dry fraction through batch-wise dry anaerobic digestion was investigated. The anaerobic digestion technique used was a two-stage process consisting of a static leach bed reactor and a methane reactor. Treatment of the dry fraction alone and in a mixture with structural material was tested to investigate the effect on the porosity of the leach bed. A tracer experiment was carried out to investigate the liquid flow through the leach beds, and this method proved useful in demonstrating a more homogenous flow through the leach bed when structural material was added. Addition of structural material to the dry fraction was needed to achieve a functional digestion process. A methane yield of 98 m3/ton was obtained from the dry fraction mixed with structural material after 76 days of digestion. This was in the same range as obtained in the laboratory scale biochemical methane potential test, showing that it was possible to extract the organic content in the dry fraction in this type of dry digestion system for the production of methane. Copyright © 2013 Elsevier Ltd. All rights reserved.

First principles investigation of heterogeneous catalysis on metal oxide surfaces

NASA Astrophysics Data System (ADS)

Ghoussoub, Mireille

Metal oxides possess unique electronic and structural properties that render them highly favourable for applications in heterogeneous catalysis. In this study, computational atomistic modelling based on Density Functional Theory was used to investigate the reduction of carbon dioxide over hydroxylated indium oxide nanoparticles, as well at the activation of methane over oxygen-covered bimetallic surfaces. The first study employed metadynamics-biased ab initio molecular dynamics to obtain the free energy surface of the various reaction steps at finite temperature. In the second study, the nudged elastic band method was used to probe the C-H activation mechanisms for different surface configurations. In both cases, activation energies, reaction energies, transition state structures, and charge analysis results are used to explain the underlying mechanistic pathways.

Theoretical Insights into Direct Methane to Methanol Conversion over Supported Dicopper Oxo Nanoclusters

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

Doan, Hieu A.; Li, Zhanyong; Farha, Omar K.

In this study, the prospect of using copper oxide nanoclusters grown by atomic layer deposition on a porphyrin support for selective oxidation of methane to methanol was examined by means of density functional theory (DFT) calculations. Ab initio thermodynamic analysis indicates that an active site in the form of Cu(μ-O)Cu can be stabilized by activation in O2 at 465K. Furthermore, a moderate methane activation energy barrier (Ea=54kJ/mol) is predicted, and the hydrogen abstraction activity of the active site could be attributed to the radical character of the bridging oxygen. Methanol extraction in this system is limited by a thermodynamic barriermore » to desorption of ΔG=57kJ/mol at 473K; however, desorption can be facilitated by the addition of water in a “stepped conversion” process. Overall, our results indicate similar activity between porphyrin-supported copper oxide nanoclusters and existing Cu-exchanged zeolites and provide a computational proof-of-concept for utilizing functionalized organic linkers in metal-organic frameworks (MOFs) for selective oxidation of methane to methanol.« less

Theoretical Insights into Direct Methane to Methanol Conversion over Supported Dicopper Oxo Nanoclusters

DOE PAGES

Doan, Hieu A.; Li, Zhanyong; Farha, Omar K.; ...

2018-04-08

In this study, the prospect of using copper oxide nanoclusters grown by atomic layer deposition on a porphyrin support for selective oxidation of methane to methanol was examined by means of density functional theory (DFT) calculations. Ab initio thermodynamic analysis indicates that an active site in the form of Cu(μ-O)Cu can be stabilized by activation in O2 at 465K. Furthermore, a moderate methane activation energy barrier (Ea=54kJ/mol) is predicted, and the hydrogen abstraction activity of the active site could be attributed to the radical character of the bridging oxygen. Methanol extraction in this system is limited by a thermodynamic barriermore » to desorption of ΔG=57kJ/mol at 473K; however, desorption can be facilitated by the addition of water in a “stepped conversion” process. Overall, our results indicate similar activity between porphyrin-supported copper oxide nanoclusters and existing Cu-exchanged zeolites and provide a computational proof-of-concept for utilizing functionalized organic linkers in metal-organic frameworks (MOFs) for selective oxidation of methane to methanol.« less

Root biomass as a major means of affecting methane emissions

USDA-ARS?s Scientific Manuscript database

Human activities are contributing to greenhouse gas emissions. Methane, the second most abundant greenhouse gas, is ~25 times more potent in global warming potential than carbon dioxide, and 7-17% of atmospheric methane comes from paddy rice fields. The purpose of the study was to investigate gene...

75 FR 12796 - Petitions for Modification

Federal Register 2010, 2011, 2012, 2013, 2014

2010-03-17

... to continuously monitor methane, oxygen and carbon monoxide concentrations at the specified... activated for the following initial levels: (1) Oxygen: 19.4%; (2) Methane: 1.5%; (3) Carbon Monoxide: 8 ppm...: 19.0%: (2) Methane: 2.0%; and (3) Carbon Monoxide: 13 ppm; (d) if an AMS sensor indicates an alert...

78 FR 11643 - Agency Information Collection Activities; Submission to OMB for Review and Approval; Comment...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-02-19

... monitoring, accumulated refuse, surface methane monitoring, and collection and control system exceedances... included a burden item for Agency review of surface methane monitoring reports. Respondents, however, are... adjusted the calculations to exclude any Agency burden associated with surface methane monitoring. We have...

The key nickel enzyme of methanogenesis catalyses the anaerobic oxidation of methane.

PubMed

Scheller, Silvan; Goenrich, Meike; Boecher, Reinhard; Thauer, Rudolf K; Jaun, Bernhard

2010-06-03

Large amounts (estimates range from 70 Tg per year to 300 Tg per year) of the potent greenhouse gas methane are oxidized to carbon dioxide in marine sediments by communities of methanotrophic archaea and sulphate-reducing bacteria, and thus are prevented from escaping into the atmosphere. Indirect evidence indicates that the anaerobic oxidation of methane might proceed as the reverse of archaeal methanogenesis from carbon dioxide with the nickel-containing methyl-coenzyme M reductase (MCR) as the methane-activating enzyme. However, experiments showing that MCR can catalyse the endergonic back reaction have been lacking. Here we report that purified MCR from Methanothermobacter marburgensis converts methane into methyl-coenzyme M under equilibrium conditions with apparent V(max) (maximum rate) and K(m) (Michaelis constant) values consistent with the observed in vivo kinetics of the anaerobic oxidation of methane with sulphate. This result supports the hypothesis of 'reverse methanogenesis' and is paramount to understanding the still-unknown mechanism of the last step of methanogenesis. The ability of MCR to cleave the particularly strong C-H bond of methane without the involvement of highly reactive oxygen-derived intermediates is directly relevant to catalytic C-H activation, currently an area of great interest in chemistry.

Structures of microbial communities found in anaerobic batch runs that produce methane from propionic acid--Seeded from full-scale anaerobic digesters above a certain threshold.

PubMed

Kim, Woong; Shin, Seung Gu; Han, Gyuseong; Cho, Kyungjin; Hwang, Seokhwan

2015-11-20

The volatile fatty acid propionate inhibits anaerobic digestion during organic waste treatments. To examine potential microbial interactions that accelerate propionate oxidation, anaerobic digestion systems seeded with various types of anaerobic sludge were analyzed. Seed samples were collected from 10 different full-scale anaerobic reactors in South Korea. Propionate oxidation was estimated as the methane production rate per gram of propionate used per day. Two domestic sewage sludge showed the highest methane production rate values, 109.1 ± 4.2 and 74.5 ± 8.6 mL CH4/(g propionate ∙ d). A food waste recycling wastewater source exhibited the lowest methane production rate, 33.2 ± 2.6 mL CH4/(g propionate ∙ d). To investigate how the microbial community structure affected propionate oxidation, qualitative molecular analyses were carried out using denaturing gradient gel electrophoresis. Methanosaeta concilii, an aceticlastic methanogen, was detected in most batch runs. Smithella propionica, a unique propionate oxidizer and simultaneous producer of acetate, was found in domestic sewage sludge sources showing the highest methane production rate; in contrast, Desulfobulbus rhabdoformis, a sulfate reducer coupled with the consumption of acetate to be used as a precursor of methane, was observed in food waste recycling wastewater sludge source showing the lowest methane production rate. Thus, we propose that S. propionica, a syntrophic acetate producer using propionate, might cooperate with aceticlastic methanogens for high methane production during anaerobic digestion that included propionate. Copyright © 2015 Elsevier B.V. All rights reserved.

Voyager 1 imaging and IRIS observations of Jovian methane absorption and thermal emission: Implications for cloud structure

NASA Technical Reports Server (NTRS)

West, R. A.; Kupferman, P. N.; Hart, H.

1984-01-01

Images from three filters of the Voyager 1 wide angle camera are used to measure the continuum reflectivity and spectral gradient near 6000 A and the 6190 A band methane/continuum ratio for a variety of cloud features in Jupiter's atmosphere. The dark barge features in the North Equatorial Belt have anomalously strong positive continuum spectral gradients suggesting unique composition. Methane absorption is shown at unprecedented spatial scales for the Great Red Spot and its immediate environment, for a dark barge feature in the North Equatorial Belt, and for two hot spot and plume regions in the North Equatorial Belt. Methane absorption and five micrometer emission are correlated in the vicinity of the Great Red Spot but are anticorrelated in one of the plume hot spot regions. Methane absorption and simultaneous maps of five micrometer brightness temperature is quantitatively compared to realistic cloud structure models which include multiple scattering at five micrometer as well as in the visible. Variability in H2 quadrupole lines are also investigated.

Effects of co-digestion of cucumber residues to corn stover and pig manure ratio on methane production in solid state anaerobic digestion.

PubMed

Wang, Yaya; Li, Guoxue; Chi, Menghao; Sun, Yanbo; Zhang, Jiaxing; Jiang, Shixu; Cui, Zongjun

2018-02-01

This study investigated the performance of co-digesting cucumber residues, corn stover, and pig manure at different ratios. Microbial community structure was analyzed to elucidate functional microorganism contributing to methane production during co-digestion. Results show that mixing cucumber residues with pig manure and corn stover could significantly improved methane yields 1.27-3.46 times higher than mono-feedstock. The methane yields decreased with the cucumber residues increasing when the pig manure ratio was fixed at 4 and 3, and was opposite at ratio 5. The optimal mixture ratio was T2 with the highest methane yield (305.4 mL/g VS) and co-digestion performance index (1.97). The main microbiological community in T2 was bacteria of Firmicutes (44.6%), Bacteroidetes (32.5%), Synergistetes (3.8%) and archaea of Methanosaeta (37.1%), Methanospirillum (18.2%). The mixture ratios changed the microbial community structures. The adding proportion of cucumber residues changed the community composition of the archaea, especially the proportion of Methanosaeta. Copyright © 2017 Elsevier Ltd. All rights reserved.

Comparison of seven types of thermo-chemical pretreatments on the structural features and anaerobic digestion of sunflower stalks.

PubMed

Monlau, F; Barakat, A; Steyer, J P; Carrere, H

2012-09-01

Sunflower stalks can be used for the production of methane, but their recalcitrant structure requires the use of thermo-chemical pretreatments. Two thermal (55 and 170°C) and five thermo-chemical pretreatments (NaOH, H(2)O(2), Ca(OH)(2), HCl and FeCl(3)) were carried out, followed by anaerobic digestion. The highest methane production (259 ± 6 mL CH(4)g(-1) VS) was achieved after pretreatment at 55°C with 4% NaOH for 24h. Acidic pretreatments at 170°C removed more than 90% of hemicelluloses and uronic acids whereas alkaline and oxidative pretreatments were more effective in dissolving lignin. However, no pretreatment was effective in reducing the crystallinity of cellulose. Methane production rate was positively correlated with the amount of solubilized matter whereas methane potential was negatively correlated with the amount of lignin. Considering that the major challenge is obtaining increased methane potential, alkaline pretreatments can be recommended in order to optimize the anaerobic digestion of lignocellulosic substrates. Copyright © 2012 Elsevier Ltd. All rights reserved.

Voyager 1 imaging and IRIS observations of Jovian methane absorption and thermal emission - Implications for cloud structure

NASA Technical Reports Server (NTRS)

West, R. A.; Kupferman, P. N.; Hart, H.

1985-01-01

Images from three filters of the Voyager 1 wide angle camera are used to measure the continuum reflectivity and spectral gradient near 6000 A and the 6190 A band methane/continuum ratio for a variety of cloud features in Jupiter's atmosphere. The dark barge features in the North Equatorial Belt have anomalously strong positive continuum spectral gradients suggesting unique composition. Methane absorption is shown at unprecedented spatial scales for the Great Red Spot and its immediate environment, for a dark barge feature in the North Equatorial Belt, and for two hot spot and plume regions in the North Equatorial Belt. Methane absorption and five micrometer emission are correlated in the vicinity of the Great Red Spot but are anticorrelated in one of the plume hot spot regions. Methane absorption and simultaneous maps of five micrometer brightness temperature are quantitatively compared to realistic cloud structure models which include multiple scattering at five micrometer as well as in the visible. Variability in H2 quadrupole lines are also investigated.

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

USGS Publications Warehouse

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

2013-01-01

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

Similar PAH Fate in Anaerobic Digesters Inoculated with Three Microbial Communities Accumulating Either Volatile Fatty Acids or Methane

PubMed Central

Braun, Florence; Hamelin, Jérôme; Bonnafous, Anaïs; Delgenès, Nadine; Steyer, Jean-Philippe; Patureau, Dominique

2015-01-01

Urban sludge produced on wastewater treatment plants are often contaminated by organic pollutants such as polycyclic aromatic hydrocarbons (PAH). Their removal under methanogenic conditions was already reported, but the factors influencing this removal remain unclear. Here, we determined the influence of microbial communities on PAH removal under controlled physico-chemical conditions. Twelve mesophilic anaerobic digesters were inoculated with three microbial communities extracted from ecosystems with contrasting pollution histories: a PAH contaminated soil, a PCB contaminated sediment and a low contaminated anaerobic sludge. These anaerobic digesters were operated during 100 days in continuous mode. A sterilised activated sludge, spiked with 13 PAH at concentrations usually encountered in full-scale wastewater treatment plants, was used as substrate. The dry matter and volatile solid degradation, the biogas production rate and composition, the volatile fatty acids (VFA) production and the PAH removals were monitored. Bacterial and archaeal communities were compared in abundance (qPCR), in community structure (SSCP fingerprinting) and in dominant microbial species (454-pyrosequencing). The bioreactors inoculated with the community extracted from low contaminated anaerobic sludge showed the greater methane production. The PAH removals ranged from 10 % to 30 %, respectively, for high and low molecular weight PAH, whatever the inoculums tested, and were highly correlated with the dry matter and volatile solid removals. The microbial community structure and diversity differed with the inoculum source; this difference was maintained after the 100 days of digestion. However, the PAH removal was not correlated to these diverse structures and diversities. We hence obtained three functional stable consortia with two contrasted metabolic activities, and three different pictures of microbial diversity, but similar PAH and matter removals. These results confirm that PAH removal depends on the molecule type and on the solid matter removal. But, as PAH elimination is similar whether the solid substrate is degraded into VFA or into methane, it seems that the fermentative communities are responsible for their elimination. PMID:25874750

Similar PAH fate in anaerobic digesters inoculated with three microbial communities accumulating either volatile fatty acids or methane.

PubMed

Braun, Florence; Hamelin, Jérôme; Bonnafous, Anaïs; Delgenès, Nadine; Steyer, Jean-Philippe; Patureau, Dominique

2015-01-01

Urban sludge produced on wastewater treatment plants are often contaminated by organic pollutants such as polycyclic aromatic hydrocarbons (PAH). Their removal under methanogenic conditions was already reported, but the factors influencing this removal remain unclear. Here, we determined the influence of microbial communities on PAH removal under controlled physico-chemical conditions. Twelve mesophilic anaerobic digesters were inoculated with three microbial communities extracted from ecosystems with contrasting pollution histories: a PAH contaminated soil, a PCB contaminated sediment and a low contaminated anaerobic sludge. These anaerobic digesters were operated during 100 days in continuous mode. A sterilised activated sludge, spiked with 13 PAH at concentrations usually encountered in full-scale wastewater treatment plants, was used as substrate. The dry matter and volatile solid degradation, the biogas production rate and composition, the volatile fatty acids (VFA) production and the PAH removals were monitored. Bacterial and archaeal communities were compared in abundance (qPCR), in community structure (SSCP fingerprinting) and in dominant microbial species (454-pyrosequencing). The bioreactors inoculated with the community extracted from low contaminated anaerobic sludge showed the greater methane production. The PAH removals ranged from 10% to 30%, respectively, for high and low molecular weight PAH, whatever the inoculums tested, and were highly correlated with the dry matter and volatile solid removals. The microbial community structure and diversity differed with the inoculum source; this difference was maintained after the 100 days of digestion. However, the PAH removal was not correlated to these diverse structures and diversities. We hence obtained three functional stable consortia with two contrasted metabolic activities, and three different pictures of microbial diversity, but similar PAH and matter removals. These results confirm that PAH removal depends on the molecule type and on the solid matter removal. But, as PAH elimination is similar whether the solid substrate is degraded into VFA or into methane, it seems that the fermentative communities are responsible for their elimination.

Unmanned aerial system laser based measurements of ammonia and methane emissions from animal feeding operations

NASA Astrophysics Data System (ADS)

Shadman, S.; McHale, L.; Miller, T.; Yalin, A.

2017-12-01

In the US, 40 Tg of ammonia is emitted every year into the atmosphere via agricultural activities. Ammonia is the third most abundant nitrogen containing species in the atmosphere and it has important impacts on atmospheric chemistry, health, and the environment. Since the atmospheric lifetime of ammonia is a few days, it typically deposits to the ground close to its source. In this study we are developing two laser-based sensors to measure ammonia and methane emissions from concentrated animal feeding operations (CAFOs) with the specific goal of quantifying the dry deposition of ammonia in the first few kilometers downwind of the CAFOs. Since methane is nonreactive and does not undergo dry deposition, its change in concentration with downwind distance is due to dispersion alone. We therefore plan to use methane as a conservative tracer, and will infer the ammonia deposition from the changing (deceasing) ratio of ammonia to methane as a function of downwind position. The laser sensors (ammonia and methane) developed in this study are relatively lightweight (<3.5 kg), low power (<40 W) and achieve part-per-billion level concentration sensitivity via sensitive open-path absorption spectroscopy methods. The sensors are designed for simultaneous airborne measurements of both species on a 12 foot Telemaster unmanned aerial system (UAS). The methane sensor employs cavity ring-down spectroscopy (CRDS) at 1.65 um with a distributed feedback laser and has effective cavity length of 20 km. The ammonia sensor employs wavelength modulation spectroscopy (WMS) with a quantum cascade laser at 10.33 um with a Herriot multipass cell (19 m effective length). In order to minimize the thermal expansion effects, most mounts and physical structures are made from carbon-fiber. For each sensor, a custom electronics module has been designed to control and power the electro-optic components, as well as to acquire, analyze, and save data (including concentration, temperature, pressure, and GPS time and position). The sensors have been characterized in the lab (Allan variance) and show sensitivities of 1.5 ppb (at 1 Hz) and 20 ppb (at 1 Hz), for ammonia and methane respectively.

Diffusion of gas mixtures in the sI hydrate structure

NASA Astrophysics Data System (ADS)

Waage, Magnus H.; Trinh, Thuat T.; van Erp, Titus S.

2018-06-01

Replacing methane with carbon dioxide in gas hydrates has been suggested as a way of harvesting methane, while at the same time storing carbon dioxide. Experimental evidence suggests that this process is facilitated if gas mixtures are used instead of pure carbon dioxide. We studied the free energy barriers for diffusion of methane, carbon dioxide, nitrogen, and hydrogen in the sI hydrate structure using molecular simulation techniques. Cage hops between neighboring cages were considered with and without a water vacancy and with a potential inclusion of an additional gas molecule in either the initial or final cage. Our results give little evidence for enhanced methane and carbon dioxide diffusion if nitrogen is present as well. However, the inclusion of hydrogen seems to have a substantial effect as it diffuses rapidly and can easily enter occupied cages, which reduces the barriers of diffusion for the gas molecules that co-occupy a cage with hydrogen.

Martian Methane From a Cometary Source: A Hypothesis

NASA Technical Reports Server (NTRS)

Fries, M.; Christou, A.; Archer, D.; Conrad, P.; Cooke, W.; Eigenbrode, J.; ten Kate, I. L.; Matney, M.; Niles, P.; Sykes, M.;

A QSAR-like analysis of the adsorption of endocrine disrupting compounds, pharmaceuticals, and personal care products on modified activated carbons.

PubMed

Redding, Adam M; Cannon, Fred S; Snyder, Shane A; Vanderford, Brett J

2009-08-01

Rapid small-scale column tests (RSSCTs) examined the removal of 29 endocrine disrupting compounds (EDCs) and pharmaceutical/personal care products (PPCPs). The RSSCTs employed three lignite variants: HYDRODARCO 4000 (HD4000), steam-modified HD4000, and methane/steam-modified HD4000. RSSCTs used native Lake Mead, NV water spiked with 100-200 ppt each of 29 EDCs/PPCPs. For the steam and methane/steam variants, breakthrough occurred at 14,000-92,000 bed volumes (BV); and this was 3-4 times more bed volumes than for HD4000. Most EDC/PPCP bed life data were describable by a normalized quantitative structure-activity relationship (i.e. QSAR-like model) of the form: where TPV is the pore volume, rho(mc) is the apparent density, CV is the molecular volume, C(o) is the concentration, (8)chi(p) depicts the molecule's compactness, and FOSA is the molecule's hydrophobic surface area.

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

Yu, Ning; Rahman, Muhammad Mahfuzur; Chen, Jixiang

Steam reforming of simulated bio-oil (ethanol, acetone, phenol, and acetic acid) and phenol has been studied on K-Ni-Cu-Mg-Ce-O/Al 2O 3 composite catalysts. Complementary characterization techniques, such as nitrogen sorption, XRD, H 2-TPR, H 2-TPD, CO-TPD, CO-DRIFTS, and in situ XPS, were used to correlate surface structure and functionality to catalytic performance of potassium (K) doped catalysts. K doping of the Ni-Cu-Mg-Ce-O/Al 2O 3 catalyst created a Ni°/Ni 2+ mixed active phase, which not only enhanced steam reforming activity, but also suppressed the methanation reaction. In addition, K doping changed the surface acid-basic properties of the catalyst, which instead favor themore » gasifcation and water-gas shift reactions. In conclusion, with the combination of these effects, K doping of Ni-Cu-Mg-Ce-O/Al 2O 3 catalysts led to higher C1 yield and much lower methane formation, favoring hydrogen production in steam reforming of both phenol and simulated bio-oil.« less

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

DOE PAGES

Tao, Franklin Feng; Shan, Jun-jun; Nguyen, Luan; ...

2015-08-04

It is crucial to develop a catalyst made of earth-abundant elements highly active for a complete oxidation of methane at a relatively low temperature. NiCo 2O 4 consisting of earth-abundant elements which can completely oxidize methane in the temperature range of 350-550 °C. Being a cost-effective catalyst, NiCo 2O 4 exhibits activity higher than precious-metal-based catalysts. Here we report that the higher catalytic activity at the relatively low temperature results from the integration of nickel cations, cobalt cations and surface lattice oxygen atoms/oxygen vacancies at the atomic scale. Finally, in situ studies of complete oxidation of methane on NiCo 2Omore » 4 and theoretical simulations show that methane dissociates to methyl on nickel cations and then couple with surface lattice oxygen atoms to form -CH 3O with a following dehydrogenation to -CH 2O; a following oxidative dehydrogenation forms CHO; CHO is transformed to product molecules through two different sub-pathways including dehydrogenation of OCHO and CO oxidation.« less

Effect of packing material on methane activation in a dielectric barrier discharge reactor

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

Jo, Sungkwon; Hoon Lee, Dae; Seok Kang, Woo

2013-12-15

The conversion of methane is measured in a planar-type dielectric barrier discharge reactor using γ-Al{sub 2}O{sub 3} (sphere), α-Al{sub 2}O{sub 3} (sphere), and γ-Al{sub 2}O{sub 3} (16–20 mesh). Investigations on the surface properties and shape of the three packing materials clearly indicate that methane activation is considerably affected by the material used. Capacitances inside the discharge gap are estimated from charge–voltage plots, and a comparison of the generated and transferred charges for different packing conditions show that the difference in surface properties between γ- and α-phase Al{sub 2}O{sub 3} affects the discharge characteristics. Moreover, all packing conditions show different chargemore » characteristics that are related to the electron density. Finally, the packing material's shape affects the local electron temperature, which is strongly related to methane conversion. The combined results indicate that both microscale and macroscale variations in a packing material affect the discharge characteristics, and a packing material should be considered carefully for effective methane activation.« less

Enrichment of specific electro-active microorganisms and enhancement of methane production by adding granular activated carbon in anaerobic reactors.

PubMed

Lee, Jung-Yeol; Lee, Sang-Hoon; Park, Hee-Deung

2016-04-01

Direct interspecies electron transfer (DIET) via conductive materials can provide significant benefits to anaerobic methane formation in terms of production amount and rate. Although granular activated carbon (GAC) demonstrated its applicability in facilitating DIET in methanogenesis, DIET in continuous flow anaerobic reactors has not been verified. Here, evidences of DIET via GAC were explored. The reactor supplemented with GAC showed 1.8-fold higher methane production rate than that without GAC (35.7 versus 20.1±7.1mL-CH4/d). Around 34% of methane formation was attributed to the biomass attached to GAC. Pyrosequencing of 16S rRNA gene demonstrated the enrichment of exoelectrogens (e.g. Geobacter) and hydrogenotrophic methanogens (e.g. Methanospirillum and Methanolinea) from the biomass attached to GAC. Furthermore, anodic and cathodic currents generation was observed in an electrochemical cell containing GAC biomass. Taken together, GAC supplementation created an environment for enriching the microorganisms involved in DIET, which increased the methane production rate. Copyright © 2016 Elsevier Ltd. All rights reserved.

Natural gas hydrates; vast resource, uncertain future

USGS Publications Warehouse

Collett, T.S.

2001-01-01

Gas hydrates are naturally occurring icelike solids in which water molecules trap gas molecules in a cagelike structure known as a clathrate. Although many gases form hydrates in nature, methane hydrate is by far the most common; methane is the most abundant natural gas. The volume of carbon contained in methane hydrates worldwide is estimated to be twice the amount contained in all fossil fuels on Earth, including coal.

Trees as methane sources: A case study of West Siberian South taiga

NASA Astrophysics Data System (ADS)

Churkina, A. I.; Mochenov, S. Yu; Sabrekov, S. F.; Glagolev, M. V.; Il’yasov, D. V.; Terentieva, I. E.; Maksyutov, S. S.

2018-03-01

Within this study, we were measuring methane emission from the tree trunks, leaves and branches in the seasonally flooded forest and in the forested bogs (pine-shrub-sphagnum ecosystems or “ryams”) in south taiga zone of Western Siberia. Our results suggest that the tree trunks may act as a methane conductor from the soil to the atmosphere bypassing the methanotrophically active zones of soil. The tree methane flux depends on a trunk diameter and an ecosystem type. The average methane emission from tree trunks was 0.0061±0.0003 mg CH4·m-2·h-1 per unit of ground area. The methane emission from branches and leaves was zero.

Linking Microbial and Biogeochemical Studies: Biological Controls of Methane Release from an Acidic Natural Wetland in Central Pennsylvania

NASA Astrophysics Data System (ADS)

Biddle, J. F.; Turich, C.; Brantley, S.; Bruns, M.

2002-12-01

Wetlands produce between 55 and 150 Tg of methane per year, or ~70% of all natural methane, and 20% of total methane (natural and anthropogenic). Understanding inputs to the global methane cycle depends on integrated in situ study of the sources and sinks of methane, as well as the rate and magnitude of methane production and consumption. Bear Meadows Natural Area in central Pennsylvania (N 40° 43.796' W 077° 45.310; 554 m elevation) contains an acidic, methane-producing, peaty bog with vegetation that is typical of wetlands at higher latitudes. In this four year study conducted within a cross-disciplinary training course offered by the NSF-IGERT Biogeochemical Research Initiative in Education (BRIE) program at Penn State University, graduate students applied a combination of geochemical and microbiological techniques to explore microbial diversity and activity in Bear Meadows sediments. The methane flux at the peat:water interface was highly variable, from 0.01 to over 3000 umol/m2/min in both sphagnum and sedge vegetation. The methane released from the bog had a carbon isotopic composition of -60 %o, typical of biogenic methane. Analysis of peat pore waters showed that the most methane was produced 30 cm below the peat:water interface, with a broad peak of methane in pore waters from 20-40 cm. At 21 cm below the peat:water interface, profiles of Archaeal 16S-23S ribosomal RNA spacer regions revealed the presence of populations having 92% similarity to 16S rRNA sequences of Methanoculleus marisnigri. Phospholipid fatty acids (PLFA) and compound specific isotope analysis revealed other biological controls on the methane cycle. PLFAs typical of methanotrophic bacteria were also present within peat cores from 20-30 cm below the water interface. The depleted carbon isotopic composition of these biomarkers (C16:1 and C18:1 fatty acids) was - 31.4 %o and - 33.8%o, indicative of methane oxidation. The presence of biomarkers of methane oxidizing bacteria within the zone of methane production may indicate that there is temporal or spatial heterogeneity in oxygen concentration within the peat. This interdisciplinary approach helped define specific ecological niches where novel methanogens and methane oxidizers may be active in a typical northern wetland. Through BRIE, on-going studies of the Bear Meadows wetland will focus on detecting other potentially novel aerobic and anaerobic microbes, and determining the biological influence on methane release to the atmosphere.

Bio-methane from an-aerobic digestion using activated carbon adsorption.

PubMed

Farooq, Muhammad; Bell, Alexandra H; Almustapha, M N; Andresen, John M

2017-08-01

There is an increasing global demand for carbon-neutral bio-methane from an-aerobic digestion (AD) to be injected into national gas grids. Bio-gas, a methane -rich energy gas, is produced by microbial decomposition of organic matter through an-aerobic conditions where the presence of carbon dioxide and hydrogen sulphide affects its performance. Although the microbiological process in the AD can be tailored to enhance the bio-gas composition, physical treatment is needed to convert the bio-gas into bio-methane. Water washing is the most common method for upgrading bio-gas for bio-methane production, but its large use of water is challenging towards industrial scale-up. Hence, the present study focuses on scale-up comparison of water washing with activated-carbon adsorption using HYSYS and Aspen Process Economic Analyzer. The models show that for plants processing less than 500 m 3 /h water scrubbing was cost effective compared with activated carbon. However, against current fossil natural-gas cost of about 1 p/kWh in the UK both relied heavily on governmental subsidies to become economically feasible. For plants operating at 1000 m 3 /hr, the treatment costs were reduced to below 1.5 p/kWh for water scrubbing and 0.9 p/kWh for activated carbon where the main benefits of activated carbon were lower capital and operating costs and virtually no water losses. It is envisioned that this method can significantly aid the production of sustainable bio-methane. Copyright © 2017 Elsevier Ltd. All rights reserved.

Surface modification processes during methane decomposition on Cu-promoted Ni–ZrO2 catalysts

PubMed Central

Wolfbeisser, Astrid; Klötzer, Bernhard; Mayr, Lukas; Rameshan, Raffael; Zemlyanov, Dmitry; Bernardi, Johannes; Rupprechter, Günther

2015-01-01

The surface chemistry of methane on Ni–ZrO2 and bimetallic CuNi–ZrO2 catalysts and the stability of the CuNi alloy under reaction conditions of methane decomposition were investigated by combining reactivity measurements and in situ synchrotron-based near-ambient pressure XPS. Cu was selected as an exemplary promoter for modifying the reactivity of Ni and enhancing the resistance against coke formation. We observed an activation process occurring in methane between 650 and 735 K with the exact temperature depending on the composition which resulted in an irreversible modification of the catalytic performance of the bimetallic catalysts towards a Ni-like behaviour. The sudden increase in catalytic activity could be explained by an increase in the concentration of reduced Ni atoms at the catalyst surface in the active state, likely as a consequence of the interaction with methane. Cu addition to Ni improved the desired resistance against carbon deposition by lowering the amount of coke formed. As a key conclusion, the CuNi alloy shows limited stability under relevant reaction conditions. This system is stable only in a limited range of temperature up to ~700 K in methane. Beyond this temperature, segregation of Ni species causes a fast increase in methane decomposition rate. In view of the applicability of this system, a detailed understanding of the stability and surface composition of the bimetallic phases present and the influence of the Cu promoter on the surface chemistry under relevant reaction conditions are essential. PMID:25815163

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

PubMed Central

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

2015-01-01

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

Martian Atmospheric Methane Plumes from Meteor Shower Infall: A Hypothesis

NASA Technical Reports Server (NTRS)

Fries, M.; Christou, A.; Archer, D.; Conrad, P.; Cooke, W.; Eigenbrode, J.; ten Kate, I. L.; Matney, M.; Niles, P.; Sykes, M.

2016-01-01

Methane plumes in the martian atmosphere have been detected using Earth-based spectroscopy, the Planetary Fourier Spectrometer on the ESA Mars Express mission, and the NASA Mars Science Laboratory. The methane's origin remains a mystery, with proposed sources including volcanism, exogenous sources like impacts and interplanetary dust, aqueous alteration of olivine in the presence of carbonaceous material, release from ancient deposits of methane clathrates, and/or biological activity. To date, none of these phenomena have been found to reliably correlate with the detection of methane plumes. An additional source exists, however: meteor showers could generate martian methane via UV pyrolysis of carbon-rich infall material. We find a correlation between the dates of Mars/cometary orbit encounters and detections of methane on Mars. We hypothesize that cometary debris falls onto Mars during these interactions, depositing freshly disaggregated meteor shower material in a regional concentration. The material generates methane via UV photolysis, resulting in a localized "plume" of short-lived methane.

Direct catalytic conversion of methane and light hydrocarbon gases. Quarterly report No. 9, October 1--December 31, 1988

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

Wilson, R.B. Jr.; Posin, B.M.; Chan, Yee Wai

The goal of this research is to develop catalysts that directly convert methane and light hydrocarbons to intermediates that later can be converted to either liquid fuels or value-added chemicals, as economics dictate. During this reporting period, we completed our IR spectroscopic examination of the Ru{sub 4}/MgO and FeRu{sub 3}/MgO systems under nitrogen and methane by examining FeRu{sub 3}/MgO under methane. This system behaved quite differently than the same system under nitrogen. Under methane, only one very broad peak is observed at room temperature. Upon heating, the catalyst transformed so that by 300{degrees}C, the spectrum of FeRu{sub 3}/MgO under methanemore » was the same as that of Ru{sub 4}/MgO. This suggests that methane promotes the segregation of the metals in the mixed metal system. The differences in catalytic activity between the FeRu{sub 3}/MgO and Ru{sub 4}/MgO systems may then be due to the presence of IR transparent species such as iron ions which cause different nucleation in the ruthenium clusters. We examined several systems for activity in the methane dehydrogenation reaction. Focusing on systems which produce C{sub 6} hydrocarbons since this is the most useful product. These systems all displayed low activity so that the amount of hydrocarbon product is very low. Some C{sub 6} hydrocarbon is observed over zeolite supports, but its production ceases after the first few hours of reaction. We prepared a new system, Ru{sub 4} supported on carbon, and examined its reactivity. Its activity was very low and in fact the carbon support had the same level of activity. We synthesized four new systems for examination as catalysts in the partial oxidation of methane. Three of these (PtTSPC/MgO, PtTSPC and PdTSPC on carbon) are analogs of PdTSPC/MgO. This system is of interest because we have observed the production of ethane from methane oxidation over PdTSPC/MgO at relatively low temperatures and we wished to explore its generality among close analogs.« less

Methane contamination of drinking water accompanying gas-well drilling and hydraulic fracturing

PubMed Central

Osborn, Stephen G.; Vengosh, Avner; Warner, Nathaniel R.; Jackson, Robert B.

2011-01-01

Directional drilling and hydraulic-fracturing technologies are dramatically increasing natural-gas extraction. In aquifers overlying the Marcellus and Utica shale formations of northeastern Pennsylvania and upstate New York, we document systematic evidence for methane contamination of drinking water associated with shale-gas extraction. In active gas-extraction areas (one or more gas wells within 1 km), average and maximum methane concentrations in drinking-water wells increased with proximity to the nearest gas well and were 19.2 and 64 mg CH4 L-1 (n = 26), a potential explosion hazard; in contrast, dissolved methane samples in neighboring nonextraction sites (no gas wells within 1 km) within similar geologic formations and hydrogeologic regimes averaged only 1.1 mg L-1 (P < 0.05; n = 34). Average δ13C-CH4 values of dissolved methane in shallow groundwater were significantly less negative for active than for nonactive sites (-37 ± 7‰ and -54 ± 11‰, respectively; P < 0.0001). These δ13C-CH4 data, coupled with the ratios of methane-to-higher-chain hydrocarbons, and δ2H-CH4 values, are consistent with deeper thermogenic methane sources such as the Marcellus and Utica shales at the active sites and matched gas geochemistry from gas wells nearby. In contrast, lower-concentration samples from shallow groundwater at nonactive sites had isotopic signatures reflecting a more biogenic or mixed biogenic/thermogenic methane source. We found no evidence for contamination of drinking-water samples with deep saline brines or fracturing fluids. We conclude that greater stewardship, data, and—possibly—regulation are needed to ensure the sustainable future of shale-gas extraction and to improve public confidence in its use. PMID:21555547

[Acclimatization and characteristics of microbial community in sulphate-dependent anaerobic methane oxidation].

PubMed

Xi, Jing-Ru; Liu, Su-Qin; Li, Lin; Liu, Jun-Xin

2014-12-01

The greenhouse effect of methane is 26 times worse than that of carbon dioxide, and wastewater containing high concentrations of sulfate is harmful to water, soil and plants. Therefore, anaerobic oxidation of methane driven by sulfate is one of the effective ways for methane reduction. In this paper, with sulfate as the electron accepter, a microbial consortium capable of oxidating methane under anaerobic condition was cultured. The diversity and characteristics of bacterial and archaeal community were investigated by PCR-DGGE, and phylogenetic analysis of the dominant microorganisms was also carried out. The DGGE fingerprints showed that microbial community structure changed distinctly, and the abundance of methane-oxidizing archea and sulfate-reducing bacteria increased in the acclimatization system added sulfate. After acclimatization, the bacterial diversity increased, while archaea diversity decreased slightly. The representative bands in the DGGE profiles were excised and sequenced. Results indicated that the dominant species in the acclimatization system were Spirochaetes, Desulfuromonadales, Methanosarcinales, Methanosaeta. Methane converted into carbon dioxide while sulfate transformed into hydrogen sulfide and sulfur in the process of anaerobic methane oxidation accompanied by sulphate reduction.

Synthesis of single-site copper catalysts for methane partial oxidation

DOE PAGES

Grundner, S.; Luo, W.; Sanchez-Sanchez, M.; ...

2015-12-24

Cu-Exchanged zeolites are known as active materials for methane oxidation to methanol. However, understanding of the formation of Cu active species during synthesis, dehydration and activation is fragmented and rudimentary. We show here how a synthesis protocol guided by insight in the ion exchange elementary steps leads to highly uniform Cu species in mordenite (MOR).

77 FR 47438 - Agency Information Collection Activities; Submission for OMB Review; Comment Request...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-08-08

... for OMB Review; Comment Request; Notification of Methane Detected in Underground Metal and Nonmetal... of Methane Detected in Underground Metal and Nonmetal Mine Atmospheres,'' to the Office of Management... following events occur: There is an outburst that results in 0.25 percent or more methane in the mine...

Freshwater wetland sediments support substantial rates of anaerobic oxidation of methane (AOM)

NASA Astrophysics Data System (ADS)

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

2012-12-01

Freshwater wetlands are characterized by high rates of methanogenesis and are the single largest source of atmospheric methane. Anaerobic oxidation of methane (AOM), a previously underappreciated process in these systems, may be an important component in freshwater methane budgets. Here we report some of the first direct measurements of AOM in wetland sediments. We examined seasonal methane cycling within three freshwater wetlands (two peat wetlands and one tidal, freshwater creekbank) along the eastern coast of the US. Rates of AOM were high (up to 286 nmol per cubic cm per day) and varied on a seasonal basis. Despite low sulfate concentrations, rates of sulfate reduction were sufficient to support all the observed AOM activity, though rates of these two processes were not correlated. This study highlights the importance of AOM in freshwater sediments, where this process, in conjunction with sulfate reduction, may control emissions of methane to the atmosphere through competitive interactions with methanogens and the consumption of large fractions of the methane produced from acetate and hydrogen. The zone of maximum AOM activity was marked by enriched stable carbon isotopic signatures (δ13C) of methane and depleted signatures of DIC. However, the δ13C of archaeal and bacterial lipids were not indicative of methanotrophy. Studies that evaluate the role of AOM in wetlands using lipid and isotope-based approaches may therefore underestimate its importance.

[Effect of fertilization on cucumber growth and soil biological characteristics in sunlight greenhouse].

PubMed

Xu, Fuli; Liang, Yinli; Zhang, Chenge; Du, Sheni; Chen, Zhijie

2004-07-01

This paper studied the effect of fertilization on cucumber growth and yield, soil microbial biomass and soil enzyme activities in sunlight greenhouse in Loess Plateau. The results indicated that the growth and yield of cucumber were increased with application of manure and methane. Foliage application reduced the application rate of NP and manure. Fertilization had an obvious effect on the biological characteristics of soil in sunlight greenhouse. The number of bacteria was increased by manure and foliage fertilization, and that of fungi was increased by NP and methane fertilization but decreased by manure fertilization. Fertilization with manure, NP and methane also remarkably increased the number of actinomyces and the activities of urease, phosphatase and sucrase in soil. The activities of soil urease and phosphatase were increased by fertilization of manure, but little effect was found with fertilization of NP and methane.

Enhanced methane production via repeated batch bioaugmentation pattern of enriched microbial consortia.

PubMed

Yang, Zhiman; Guo, Rongbo; Xu, Xiaohui; Wang, Lin; Dai, Meng

2016-09-01

Using batch and repeated batch cultivations, this study investigated the effects of bioaugmentation with enriched microbial consortia (named as EMC) on methane production from effluents of hydrogen-producing stage of potato slurry, as well as on the indigenous bacterial community. The results demonstrated that the improved methane production and shift of the indigenous bacterial community structure were dependent on the EMC/sludge ratio and bioaugmentation patterns. The methane yield and production rate in repeated batch bioaugmentation pattern of EMC were, respectively, average 15% and 10% higher than in one-time bioaugmentation pattern of EMC. DNA-sequencing approach showed that the enhanced methane production in the repeated batch bioaugmentation pattern of EMC mainly resulted from the enriched iron-reducing bacteria and the persistence of the introduced Syntrophomonas, which led to a rapid degradation of individual VFAs to methane. The findings contributed to understanding the correlation between the bioaugmentation of microbial consortia, community shift, and methane production. Copyright © 2016 Elsevier Ltd. All rights reserved.

Quantifying the relative contribution of natural gas fugitive emissions to total methane emissions in Colorado, Utah, and Texas using mobile isotopic methane analysis based on Cavity Ringdown Spectroscopy

NASA Astrophysics Data System (ADS)

Rella, Chris; Winkler, Renato; Sweeney, Colm; Karion, Anna; Petron, Gabrielle; Crosson, Eric

2014-05-01

Fugitive emissions of methane into the atmosphere are a major concern facing the natural gas production industry. Because methane is more energy-rich than coal per kg of carbon dioxide emitted into the atmosphere, it represents an attractive alternative to coal for electricity generation, provided that the fugitive emissions of methane are kept under control. A key step in assessing these emissions in a given region is partitioning the observed methane emissions between natural gas fugitive emissions and other sources of methane, such as from landfills or agricultural activities. One effective method for assessing the contribution of these different sources is stable isotope analysis, using the isotopic carbon signature to distinguish between natural gas and landfills or ruminants. We present measurements of methane using a mobile spectroscopic stable isotope analyzer based on cavity ringdown spectroscopy, in three intense natural gas producing regions of the United States: the Denver-Julesburg basin in Colorado, the Uintah basin in Utah, and the Barnett Shale in Texas. Performance of the CRDS isotope analyzer is presented, including precision, calibration, stability, and the potential for measurement bias due to other atmospheric constituents. Mobile isotope measurements of individual sources and in the nocturnal boundary layer have been combined to establish the fraction of the observed methane emissions that can be attributed to natural gas activities. The fraction of total methane emissions in the Denver-Julesburg basin attributed to natural gas emissions is 78 +/- 13%. In the Uinta basin, which has no other significant sources of methane, the fraction is 96% +/- 15%. In addition, results from the Barnett shale are presented, which includes a major urban center (Dallas / Ft. Worth). Methane emissions in this region are spatially highly heterogeneous. Spatially-resolved isotope and concentration measurements are interpreted using a simple emissions model to arrive at an overall isotope ratio for the region.

Methane-Stimulated Benthic Marine Nitrogen Fixation at Deep-Sea Methane Seeps

NASA Astrophysics Data System (ADS)

Dekas, A. E.; Orphan, V.

2011-12-01

Biological nitrogen fixation (the conversion of N2 to NH3) is a critical process in the oceans, counteracting the production of N2 gas by dissimilatory bacterial metabolisms and providing a source of bioavailable nitrogen to many nitrogen-limited ecosystems. Although current measurements of N2 production and consumption in the oceans indicate that the nitrogen cycle is not balanced, recent findings on the limits of nitrogen fixation suggest that the perceived imbalance is an artifact of an incomplete assessment of marine diazotrophy. One currently poorly studied and potentially underappreciated habitat for diazotrophic organisms is the sediments of the deep-sea. In the present study we investigate the distribution and magnitude of benthic marine diazotrophy at several active deep-sea methane seeps (Mound 12, Costa Rica; Eel River Basin, CA, USA; Hydrate Ridge, OR, USA; and Monterey Canyon, CA, USA). Using 15N2 and 15NH4 sediment incubation experiments followed by single-cell (FISH-NanoSIMS) and bulk isotopic analysis (EA-IRMS), we observed total protein synthesis (15N uptake from 15NH4) and nitrogen fixation (15N update from 15N2). The highest rates of nitrogen fixation observed in the methane seep sediment incubation experiments were over an order of magnitude greater than those previously published from non-seep deep-sea sediments (Hartwig and Stanley, Deep-Sea Research, 1978, 25:411-417). However, methane seep diazotrophy appears to be highly spatially variable, with sediments exhibiting no nitrogen fixation originating only centimeters away from sediments actively incorporating 15N from 15N2. The greatest spatial variability in diazotrophy was observed with depth in the sediment, and corresponded to steep gradients in sulfate and methane. The maximum rates of nitrogen fixation were observed within the methane-sulfate transition zone, where organisms mediating the anaerobic oxidation of methane are typically in high abundance. Additionally, incubation experiments without added methane were observed to have little to no nitrogen fixation activity. In previous work, we demonstrated the capability of uncultured methanotrophic archaea (ANME-2) to fix nitrogen when associated with sulfate reducing bacterial symbionts. These new results suggest that these microbes may be the dominant nitrogen-fixing organisms in methane seep sediment. Intriguingly, characterization of the diversity of nifH genes from our sediment incubations as well as published nifH sequences reported from other seep habitats suggest the potential for other diazotrophic microorganisms in addition to the ANME-2 archaea. To further explore this possibility, FISH-NanoSIMS analyses were conducted on two dominant free-living sulfate-reducing lineages from seep incubations demonstrating nitrogen fixation activity. Preliminary results from this analysis suggest that single cells belonging to the Desulfobulbaceae may also be involved in nitrogen fixation in methane seeps. Despite this demonstrated potential, the extent of methane-independent diazotrophy by non-ANME diazotrophs appears to be low within the methane seep environment. Further studies are necessary to assess the greater diversity and activity of diazotrophs in other deep-sea sedimentary habitats.

Methane distribution and oxidation around the Lena Delta in summer 2013

NASA Astrophysics Data System (ADS)

Bussmann, Ingeborg; Hackbusch, Steffen; Schaal, Patrick; Wichels, Antje

2017-11-01

The Lena River is one of the largest Russian rivers draining into the Laptev Sea. The predicted increases in global temperatures are expected to cause the permafrost areas surrounding the Lena Delta to melt at increasing rates. This melting will result in high amounts of methane reaching the waters of the Lena and the adjacent Laptev Sea. The only biological sink that can lower methane concentrations within this system is methane oxidation by methanotrophic bacteria. However, the polar estuary of the Lena River, due to its strong fluctuations in salinity and temperature, is a challenging environment for bacteria. We determined the activity and abundance of aerobic methanotrophic bacteria by a tracer method and by the quantitative polymerase chain reaction. We described the methanotrophic population with a molecular fingerprinting method (monooxygenase intergenic spacer analysis), as well as the methane distribution (via a headspace method) and other abiotic parameters, in the Lena Delta in September 2013. The median methane concentrations were 22 nmol L-1 for riverine water (salinity (S) < 5), 19 nmol L-1 for mixed water (5 < S < 20) and 28 nmol L-1 for polar water (S > 20). The Lena River was not the source of methane in surface water, and the methane concentrations of the bottom water were mainly influenced by the methane concentration in surface sediments. However, the bacterial populations of the riverine and polar waters showed similar methane oxidation rates (0.419 and 0.400 nmol L-1 d-1), despite a higher relative abundance of methanotrophs and a higher estimated diversity in the riverine water than in the polar water. The methane turnover times ranged from 167 days in mixed water and 91 days in riverine water to only 36 days in polar water. The environmental parameters influencing the methane oxidation rate and the methanotrophic population also differed between the water masses. We postulate the presence of a riverine methanotrophic population that is limited by sub-optimal temperatures and substrate concentrations and a polar methanotrophic population that is well adapted to the cold and methane-poor polar environment but limited by a lack of nitrogen. The diffusive methane flux into the atmosphere ranged from 4 to 163 µmol m2 d-1 (median 24). The diffusive methane flux accounted for a loss of 8 % of the total methane inventory of the investigated area, whereas the methanotrophic bacteria consumed only 1 % of this methane inventory. Our results underscore the importance of measuring the methane oxidation activities in polar estuaries, and they indicate a population-level differentiation between riverine and polar water methanotrophs.

Synthesis, crystal structure, catalytic and anti-Trypanosoma cruzi activity of a new chromium(III) complex containing bis(3,5-dimethylpyrazol-1-yl)methane

NASA Astrophysics Data System (ADS)

Hurtado, John; Ibarra, Laura; Yepes, David; García-Huertas, Paola; Macías, Mario A.; Triana-Chavez, Omar; Nagles, Edgar; Suescun, Leopoldo; Muñoz-Castro, Alvaro

2017-10-01

The reaction of CrCl36H2O with the ligand bis(3,5-dimethylpyrazol-1-yl)methane (L) yielded the cationic complex [(Cr(L)(H2O)2Cl2]+, which crystallized as the chloride trihydrate [(Cr(L)(H2O)2Cl2]Cl·3H2O. The chromium complex was characterized by elemental analysis, electrical conductivity, Infrared and Ultraviolet/Visible spectroscopy. The crystal structure determination using single-crystal X-ray diffraction showed a chromium center in a distorted octahedral coordination sphere. In the crystal, the packing was directed by Osbnd H⋯(O,Cl) hydrogen bonds and weak Csbnd H⋯O interactions to build a monoclinic P21/c supramolecular structure. The complex showed excellent properties as an initiator for the ring opening polymerization of є-caprolactone (CL) under solvent-free conditions. The obtained polymer showed high crystallinity (89.9%) and a decomposition temperature above 475 °C. In addition, the new complex was evaluated against epimastigotes from Trypanosoma cruzi (T. cruzi) strains. The results indicated that this complex has a high activity against this parasite with a minimum inhibitory concentration 50 (MIC50) of 1.08 μg/mL. Interestingly, this compound showed little effect on erythrocytes, indicating that it is not cytotoxic. These results provide interesting contributions to the design of metal complexes by using simple and accessible ligands with activity against T. cruzi and with potential applications in the polymerization of CL.

Activity and diversity of aerobic methanotrophs in a coastal marine oxygen minimum zone

NASA Astrophysics Data System (ADS)

Padilla, C. C.; Bristow, L. A.; Sarode, N. D.; Garcia-Robledo, E.; Girguis, P. R.; Thamdrup, B.; Stewart, F. J.

2016-02-01

The pelagic ocean is a sink for the potent greenhouse gas methane, with methane consumption regulated primarily by aerobic methane-oxidizing bacteria (MOB). Marine oxygen minimum zones (OMZs) contain the largest pool of pelagic methane in the oceans but remain largely unexplored for their potential to harbor MOB communities and contribute to methane cycling. Here, we present meta-omic and geochemical evidence that aerobic MOB are present and active in a coastal OMZ, in Golfo Dulce, Costa Rica. Oxygen concentrations were < 50 nM below 85 m, and sulfide accumulated below 140 m, with methane concentrations ranging from trace levels above the oxycline to 78 nM at 180 m. The upper OMZ (90 m) was characterized by an abundant MOB and methylotroph community representing diverse lineages of the Methylophilaceae, Methylophaga, and Methylococcales. Of these, Type I methanotrophs of the Order Methylococcales dominated , representing >5% of total 16S rRNA genes and >19% of 16S rRNA transcripts. This peak in ribosomal abundance and activity was affiliated with methane oxidation rates of 2.6 ± 0.7 nM d-1, measured in seawater incubations with estimated O2 concentrations of 50 nM. Rates fell to zero with the addition of acetylene, an inhibitor of aerobic methanotrophy. In contrast, methane oxidation was below detection at lower depths in the OMZ (100 m and 120 m). Metatranscriptome sequencing indicated a peak at 90 m in the expression of pathways essential to Methylococcales, including aerobic methanotrophy and the RuMP pathway of carbon assimilation, as well as the serine pathway of Type II methanotrophs. Preliminary analysis of single-cell genomes suggests distinct adaptations by Methylococcales from the Golfo Dulce, helping explain the persistence of putative aerobic methanotrophs under very low oxygen in this OMZ. Taken together, these data suggest the boundary layers of OMZs, despite extreme oxygen depletion, are a niche for aerobic MOBs and therefore potentially important zones of pelagic methane loss.

Methane emission from sewers.

PubMed

Liu, Yiwen; Ni, Bing-Jie; Sharma, Keshab R; Yuan, Zhiguo

2015-08-15

Recent studies have shown that sewer systems produce and emit a significant amount of methane. Methanogens produce methane under anaerobic conditions in sewer biofilms and sediments, and the stratification of methanogens and sulfate-reducing bacteria may explain the simultaneous production of methane and sulfide in sewers. No significant methane sinks or methanotrophic activities have been identified in sewers to date. Therefore, most of the methane would be emitted at the interface between sewage and atmosphere in gravity sewers, pumping stations, and inlets of wastewater treatment plants, although oxidation of methane in the aeration basin of a wastewater treatment plant has been reported recently. Online measurements have also revealed highly dynamic temporal and spatial variations in methane production caused by factors such as hydraulic retention time, area-to-volume ratio, temperature, and concentration of organic matter in sewage. Both mechanistic and empirical models have been proposed to predict methane production in sewers. Due to the sensitivity of methanogens to environmental conditions, most of the chemicals effective in controlling sulfide in sewers also suppress or diminish methane production. In this paper, we review the recent studies on methane emission from sewers, including the production mechanisms, quantification, modeling, and mitigation. Copyright © 2015 Elsevier B.V. All rights reserved.

Methane Hydrate in Confined Spaces: An Alternative Storage System.

PubMed

Borchardt, Lars; Casco, Mirian Elizabeth; Silvestre-Albero, Joaquin

2018-06-05

Methane hydrate inheres the great potential to be a nature-inspired alternative for chemical energy storage, as it allows to store large amounts of methane in a dense solid phase. The embedment of methane hydrate in the confined environment of porous materials can be capitalized for potential applications as its physicochemical properties, such as the formation kinetics or pressure and temperature stability, are significantly changed compared to the bulk system. We review this topic from a materials scientific perspective by considering porous carbons, silica, clays, zeolites, and polymers as host structures for methane hydrate formation. We discuss the contribution of advanced characterization techniques and theoretical simulations towards the elucidation of the methane hydrate formation and dissociation process within the confined space. We outline the scientific challenges this system is currently facing and look on possible future applications for this technology. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Contributions of available substrates and activities of trophic microbial community to methanogenesis in vegetative and reproductive rice rhizospheric soil.

PubMed

Chawanakul, Sansanee; Chaiprasert, Pawinee; Towprayoon, Sirintornthep; Tanticharoen, Morakot

2009-01-01

Potential of methane production and trophic microbial activities at rhizospheric soil during rice cv. Supanbunri 1 cultivation were determined by laboratory anaerobic diluents vials. The methane production was higher from rhizospheric than non-rhizospheric soil, with the noticeable peaks during reproductive phase (RP) than vegetative phase (VP). Glucose, ethanol and acetate were the dominant available substrates found in rhizospheric soil during methane production at both phases. The predominance activities of trophic microbial consortium in methanogenesis, namely fermentative bacteria (FB), acetogenic bacteria (AGB), acetate utilizing bacteria (AB) and acetoclastic methanogens (AM) were also determined. At RP, these microbial groups were enhanced in the higher of methane production than VP. This correlates with our finding that methane production was greater at the rhizospheric soil with the noticeable peaks during RP (1,150 +/- 60 nmol g dw(-1) d(-1)) compared with VP (510 +/- 30 nmol g dw(-1) d(-1)). The high number of AM showed the abundant (1.1x10(4) cell g dw(-1)) with its high activity at RP, compared to the less activity with AM number at VP (9.8x10(2) cell g dw(-1)). Levels of AM are low in the total microbial population, being less than 1% of AB. These evidences revealed that the microbial consortium of these two phases were different.

Active Microbial Communities Inhabit Sulphate-Methane Interphase in Deep Bedrock Fracture Fluids in Olkiluoto, Finland

PubMed Central

Bomberg, Malin; Nyyssönen, Mari; Pitkänen, Petteri; Lehtinen, Anne; Itävaara, Merja

2015-01-01

Active microbial communities of deep crystalline bedrock fracture water were investigated from seven different boreholes in Olkiluoto (Western Finland) using bacterial and archaeal 16S rRNA, dsrB, and mcrA gene transcript targeted 454 pyrosequencing. Over a depth range of 296–798 m below ground surface the microbial communities changed according to depth, salinity gradient, and sulphate and methane concentrations. The highest bacterial diversity was observed in the sulphate-methane mixing zone (SMMZ) at 250–350 m depth, whereas archaeal diversity was highest in the lowest boundaries of the SMMZ. Sulphide-oxidizing ε-proteobacteria (Sulfurimonas sp.) dominated in the SMMZ and γ-proteobacteria (Pseudomonas spp.) below the SMMZ. The active archaeal communities consisted mostly of ANME-2D and Thermoplasmatales groups, although Methermicoccaceae, Methanobacteriaceae, and Thermoplasmatales (SAGMEG, TMG) were more common at 415–559 m depth. Typical indicator microorganisms for sulphate-methane transition zones in marine sediments, such as ANME-1 archaea, α-, β- and δ-proteobacteria, JS1, Actinomycetes, Planctomycetes, Chloroflexi, and MBGB Crenarchaeota were detected at specific depths. DsrB genes were most numerous and most actively transcribed in the SMMZ while the mcrA gene concentration was highest in the deep methane rich groundwater. Our results demonstrate that active and highly diverse but sparse and stratified microbial communities inhabit the Fennoscandian deep bedrock ecosystems. PMID:26425566

Metaproteomics analysis of the functional insights into microbial communities of combined hydrogen and methane production by anaerobic fermentation from reed straw.

PubMed

Jia, Xuan; Xi, Bei-Dou; Li, Ming-Xiao; Yang, Yang; Wang, Yong

2017-01-01

A metaproteomic approach was used to analyse the proteins expressed and provide functional evidence of key metabolic pathways in the combined production of hydrogen and methane by anaerobic fermentation (CHMP-AF) for reed straw utilisation. The functions and structures of bacteria and archaea populations show significant succession in the CHMP-AF process. There are many kinds of bacterial functional proteins, mainly belonging to phyla Firmicutes, Proteobacteria, Actinobacteria and Bacteroidetes, that are involved in carbohydrate metabolism, energy metabolism, lipid metabolism, and amino acid metabolism. Ferredoxin-NADP reductase, present in bacteria in genus Azotobacter, is an important enzyme for NADH/NAD+ equilibrium regulation in hydrogen production. The archaeal functional proteins are mainly involved in methane metabolism in energy metabolism, such as acetyl-CoA decarboxylase, and methyl-coenzyme M reductase, and the acetic acid pathway exhibited the highest proportion of the total. The archaea of genus Methanosarcina in phylum Euryarchaeota can produce methane under the effect of multi-functional proteins through acetic acid, CO2 reduction, and methyl nutrient pathways. The study demonstrates metaproteomics as a new way of uncovering community functional and metabolic activity. The combined information was used to identify the metabolic pathways and organisms crucial for lignocellulosic biomass degradation and biogas production. This also regulates the process from its protein levels and improves the efficiency of biogas production using reed straw biomass.

Metaproteomics analysis of the functional insights into microbial communities of combined hydrogen and methane production by anaerobic fermentation from reed straw

PubMed Central

Yang, Yang; Wang, Yong

2017-01-01

A metaproteomic approach was used to analyse the proteins expressed and provide functional evidence of key metabolic pathways in the combined production of hydrogen and methane by anaerobic fermentation (CHMP-AF) for reed straw utilisation. The functions and structures of bacteria and archaea populations show significant succession in the CHMP-AF process. There are many kinds of bacterial functional proteins, mainly belonging to phyla Firmicutes, Proteobacteria, Actinobacteria and Bacteroidetes, that are involved in carbohydrate metabolism, energy metabolism, lipid metabolism, and amino acid metabolism. Ferredoxin-NADP reductase, present in bacteria in genus Azotobacter, is an important enzyme for NADH/NAD+ equilibrium regulation in hydrogen production. The archaeal functional proteins are mainly involved in methane metabolism in energy metabolism, such as acetyl-CoA decarboxylase, and methyl-coenzyme M reductase, and the acetic acid pathway exhibited the highest proportion of the total. The archaea of genus Methanosarcina in phylum Euryarchaeota can produce methane under the effect of multi-functional proteins through acetic acid, CO2 reduction, and methyl nutrient pathways. The study demonstrates metaproteomics as a new way of uncovering community functional and metabolic activity. The combined information was used to identify the metabolic pathways and organisms crucial for lignocellulosic biomass degradation and biogas production. This also regulates the process from its protein levels and improves the efficiency of biogas production using reed straw biomass. PMID:28817657

Saga of coal bed methane, Ignacio Blanco gas field, Colorado

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

Boyce, B.C.; Harr, C.L.; Burch, L.C.

1989-09-01

Prior to the 1977 discovery of the Cedar Hill Basal Fruitland pool (the first officially designated coal-bed methane field in the western US) 28.5 bcf of gas had been produced from Fruitland Formation coal seams in the Ignacio Blanco Fruitland-Pictured Cliffs field, Northern San Juan basin, Colorado. The discovery well for the field, Southern Ute D-1, was drilled and completed in 1951 on the Ignacio anticline, La Plata County, Colorado. Initial completion was attempted in the Pictured Cliffs Sandstone. The well was plugged back after making water from the Pictured Cliffs and was completed in the lower coal-bearing section ofmore » the Fruitland Formation. The well produced 487,333 mcf of gas in nine years and was abandoned in 1959 due to water encroachment. Additionally, 52 similarly completed Ignacio anticline Fruitland wells were abandoned by the early 1970s due to the nemesis of If it's starting to kick water, you're through. Under today's coal-bed methane technology and economics, Amoco has twinned 12 of the abandoned wells, drilled five additional wells, and is successfully dewatering and producing adsorbed methane from previously depleted coal sections of the Ignacio structure. Field-wide drilling activity in 1988 exceeded all previous annual levels, with coal-seam degasification projects leading the resurgence. Drilling and completion forecasts for 1989 surpass 1988 levels by 50%.« less

Characterization of Metabolically Active Bacterial Populations in Subseafloor Nankai Trough Sediments above, within, and below the Sulfate–Methane Transition Zone

PubMed Central

Mills, Heath J.; Reese, Brandi Kiel; Shepard, Alicia K.; Riedinger, Natascha; Dowd, Scot E.; Morono, Yuki; Inagaki, Fumio

2012-01-01

A remarkable number of microbial cells have been enumerated within subseafloor sediments, suggesting a biological impact on geochemical processes in the subseafloor habitat. However, the metabolically active fraction of these populations is largely uncharacterized. In this study, an RNA-based molecular approach was used to determine the diversity and community structure of metabolically active bacterial populations in the upper sedimentary formation of the Nankai Trough seismogenic zone. Samples used in this study were collected from the slope apron sediment overlying the accretionary prism at Site C0004 during the Integrated Ocean Drilling Program Expedition 316. The sediments represented microbial habitats above, within, and below the sulfate–methane transition zone (SMTZ), which was observed approximately 20 m below the seafloor (mbsf). Small subunit ribosomal RNA were extracted, quantified, amplified, and sequenced using high-throughput 454 pyrosequencing, indicating the occurrence of metabolically active bacterial populations to a depth of 57 mbsf. Transcript abundance and bacterial diversity decreased with increasing depth. The two communities below the SMTZ were similar at the phylum level, however only a 24% overlap was observed at the genus level. Active bacterial community composition was not confined to geochemically predicted redox stratification despite the deepest sample being more than 50 m below the oxic/anoxic interface. Genus-level classification suggested that the metabolically active subseafloor bacterial populations had similarities to previously cultured organisms. This allowed predictions of physiological potential, expanding understanding of the subseafloor microbial ecosystem. Unique community structures suggest very diverse active populations compared to previous DNA-based diversity estimates, providing more support for enhancing community characterizations using more advanced sequencing techniques. PMID:22485111

Impact of different antibiotics on methane production using waste-activated sludge: mechanisms and microbial community dynamics.

PubMed

Mustapha, Nurul Asyifah; Sakai, Kenji; Shirai, Yoshihito; Maeda, Toshinari

2016-11-01

Anaerobic digestion is an effective method for reducing the by-product of waste-activated sludge (WAS) from wastewater treatment plants and for producing bioenergy from WAS. However, only a limited number of studies have attempted to improve anaerobic digestion by targeting the microbial interactions in WAS. In this study, we examined whether different antibiotics positively, negatively, or neutrally influence methane fermentation by evaluating changes in the microbial community and functions in WAS. Addition of azithromycin promoted the microbial communities related to the acidogenic and acetogenic stages, and a high concentration of soluble proteins and a high activity of methanogens were detected. Chloramphenicol inhibited methane production but did not affect the bacteria that contribute to the hydrolysis, acidogenesis, and acetogenesis digestion stages. The addition of kanamycin, which exhibits the same methane productivity as a control (antibiotic-free WAS), did not affect all of the microbial communities during anaerobic digestion. This study demonstrates the simultaneous functions and interactions of diverse bacteria and methanogenic Archaea in different stages of the anaerobic digestion of WAS. The ratio of Caldilinea, Methanosarcina, and Clostridium may correspond closely to the trend of methane production in each antibiotic. The changes in microbial activities and function by antibiotics facilitate a better understanding of bioenergy production.

Forest strata drive spatial structure of bacterial and archaeal communities and microbial methane cycling in neotropical bromeliad wetlands

NASA Astrophysics Data System (ADS)

Martinson, Guntars; Brandt, Franziska; Conrad, Ralf

2016-04-01

Several thousands of tank bromeliads per hectare of neotropical forest create a unique wetland ecosystem that harbors diverse communities of archaea and bacteria and emit substantial amounts of methane. We studied spatial distribution of archaeal and bacterial communities, microbial methane cycling and their environmental drivers in tank bromeliad wetlands. We selected tank bromeliads of different species and functional types (terrestrial and canopy bromeliads) in a neotropical montane forest of Southern Ecuador and sampled the organic tank slurry. Archaeal and bacterial communities were characterized using terminal-restriction fragment length polymorphism (T-RFLP) and Illumina MiSeq sequencing, respectively, and linked with physico-chemical tank-slurry properties. Additionally, we performed tank-slurry incubations to measure methane production potential, stable carbon isotope fractionation and pathway of methane formation. Archaeal and bacterial community composition in bromeliad wetlands was dominated by methanogens and by Alphaproteobacteria, respectively, and did not differ between species but between functional types. Hydrogenotrophic Methanomicrobiales were the dominant methanogens among all bromeliads but the relative abundance of aceticlastic Methanosaetaceae increased in terrestrial bromeliads. Complementary, hydrogenotrophic methanogenesis was the dominant pathway of methane formation but the relative contribution of aceticlastic methanogenesis increased in terrestrial bromeliads and led to a concomitant increase in total methane production. Rhodospirillales were characteristic for canopy bromeliads, Planctomycetales and Actinomycetalis for terrestrial bromeliads. While nitrogen concentration and pH explained 32% of the archaeal community variability, 29% of the bacterial community variability was explained by nitrogen, acetate and propionate concentrations. Our study demonstrates that bromeliad functional types, associated with different forest strata, and their constrained environmental characteristics shape the spatial structure of archaeal and bacterial communities and microbial methane cycling in neotropical bromeliad wetlands.

Effect of Elevated CO2 Concentration, Elevated Temperature and No Nitrogen Fertilization on Methanogenic Archaeal and Methane-Oxidizing Bacterial Community Structures in Paddy Soil

PubMed Central

Liu, Dongyan; Tago, Kanako; Hayatsu, Masahito; Tokida, Takeshi; Sakai, Hidemitsu; Nakamura, Hirofumi; Usui, Yasuhiro; Hasegawa, Toshihiro; Asakawa, Susumu

2016-01-01

Elevated concentrations of atmospheric CO2 ([CO2]) enhance the production and emission of methane in paddy fields. In the present study, the effects of elevated [CO2], elevated temperature (ET), and no nitrogen fertilization (LN) on methanogenic archaeal and methane-oxidizing bacterial community structures in a free-air CO2 enrichment (FACE) experimental paddy field were investigated by PCR-DGGE and real-time quantitative PCR. Soil samples were collected from the upper and lower soil layers at the rice panicle initiation (PI) and mid-ripening (MR) stages. The composition of the methanogenic archaeal community in the upper and lower soil layers was not markedly affected by the elevated [CO2], ET, or LN condition. The abundance of the methanogenic archaeal community in the upper and lower soil layers was also not affected by elevated [CO2] or ET, but was significantly increased at the rice PI stage and significantly decreased by LN in the lower soil layer. In contrast, the composition of the methane-oxidizing bacterial community was affected by rice-growing stages in the upper soil layer. The abundance of methane-oxidizing bacteria was significantly decreased by elevated [CO2] and LN in both soil layers at the rice MR stage and by ET in the upper soil layer. The ratio of mcrA/pmoA genes correlated with methane emission from ambient and FACE paddy plots at the PI stage. These results indicate that the decrease observed in the abundance of methane-oxidizing bacteria was related to increased methane emission from the paddy field under the elevated [CO2], ET, and LN conditions. PMID:27600710

Effect of Elevated CO2 Concentration, Elevated Temperature and No Nitrogen Fertilization on Methanogenic Archaeal and Methane-Oxidizing Bacterial Community Structures in Paddy Soil.

PubMed

Liu, Dongyan; Tago, Kanako; Hayatsu, Masahito; Tokida, Takeshi; Sakai, Hidemitsu; Nakamura, Hirofumi; Usui, Yasuhiro; Hasegawa, Toshihiro; Asakawa, Susumu

2016-09-29

Elevated concentrations of atmospheric CO2 ([CO2]) enhance the production and emission of methane in paddy fields. In the present study, the effects of elevated [CO2], elevated temperature (ET), and no nitrogen fertilization (LN) on methanogenic archaeal and methane-oxidizing bacterial community structures in a free-air CO2 enrichment (FACE) experimental paddy field were investigated by PCR-DGGE and real-time quantitative PCR. Soil samples were collected from the upper and lower soil layers at the rice panicle initiation (PI) and mid-ripening (MR) stages. The composition of the methanogenic archaeal community in the upper and lower soil layers was not markedly affected by the elevated [CO2], ET, or LN condition. The abundance of the methanogenic archaeal community in the upper and lower soil layers was also not affected by elevated [CO2] or ET, but was significantly increased at the rice PI stage and significantly decreased by LN in the lower soil layer. In contrast, the composition of the methane-oxidizing bacterial community was affected by rice-growing stages in the upper soil layer. The abundance of methane-oxidizing bacteria was significantly decreased by elevated [CO2] and LN in both soil layers at the rice MR stage and by ET in the upper soil layer. The ratio of mcrA/pmoA genes correlated with methane emission from ambient and FACE paddy plots at the PI stage. These results indicate that the decrease observed in the abundance of methane-oxidizing bacteria was related to increased methane emission from the paddy field under the elevated [CO2], ET, and LN conditions.

Room temperature continuous wave mid-infrared VCSEL operating at 3.35 μm

NASA Astrophysics Data System (ADS)

Jayaraman, V.; Segal, S.; Lascola, K.; Burgner, C.; Towner, F.; Cazabat, A.; Cole, G. D.; Follman, D.; Heu, P.; Deutsch, C.

2018-02-01

Tunable vertical cavity surface emitting lasers (VCSELs) offer a potentially low cost tunable optical source in the 3-5 μm range that will enable commercial spectroscopic sensing of numerous environmentally and industrially important gases including methane, ethane, nitrous oxide, and carbon monoxide. Thus far, achieving room temperature continuous wave (RTCW) VCSEL operation at wavelengths beyond 3 μm has remained an elusive goal. In this paper, we introduce a new device structure that has enabled RTCW VCSEL operation near the methane absorption lines at 3.35 μm. This device structure employs two GaAs/AlGaAs mirrors wafer-bonded to an optically pumped active region comprising compressively strained type-I InGaAsSb quantum wells grown on a GaSb substrate. This substrate is removed in processing, as is one of the GaAs mirror substrates. The VCSEL structure is optically pumped at room temperature with a CW 1550 nm laser through the GaAs substrate, while the emitted 3.3 μm light is captured out of the top of the device. Power and spectrum shape measured as a function of pump power exhibit clear threshold behavior and robust singlemode spectra.

Oxygen-Promoted Methane Activation on Copper

DOE PAGES

Niu, Tianchao; Jiang, Zhao; Zhu, Yaguang; ...

2017-11-01

The role of oxygen in the activation of C–H bonds in methane on clean and oxygen-precovered Cu(111) and Cu 2O(111) surfaces was studied with combined in situ near-ambient-pressure scanning tunneling microscopy and X-ray photoelectron spectroscopy. Activation of methane at 300 K and “moderate pressures” was only observed on oxygen-precovered Cu(111) surfaces. Density functional theory calculations reveal that the lowest activation energy barrier of C–H on Cu(111) in the presence of chemisorbed oxygen is related to a two-active-site, four-centered mechanism, which stabilizes the required transition-state intermediate by dipole–dipole attraction of O–H and Cu–CH 3 species. Furthermore, the C–H bond activation barriersmore » on Cu 2O(111) surfaces are large due to the weak stabilization of H and CH 3 fragments.« less

Oxygen-Promoted Methane Activation on Copper

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

Niu, Tianchao; Jiang, Zhao; Zhu, Yaguang

The role of oxygen in the activation of C–H bonds in methane on clean and oxygen-precovered Cu(111) and Cu 2O(111) surfaces was studied with combined in situ near-ambient-pressure scanning tunneling microscopy and X-ray photoelectron spectroscopy. Activation of methane at 300 K and “moderate pressures” was only observed on oxygen-precovered Cu(111) surfaces. Density functional theory calculations reveal that the lowest activation energy barrier of C–H on Cu(111) in the presence of chemisorbed oxygen is related to a two-active-site, four-centered mechanism, which stabilizes the required transition-state intermediate by dipole–dipole attraction of O–H and Cu–CH 3 species. Furthermore, the C–H bond activation barriersmore » on Cu 2O(111) surfaces are large due to the weak stabilization of H and CH 3 fragments.« less

Catalytic combustion of methane over commercial catalysts in presence of ammonia and hydrogen sulphide.

PubMed

Hurtado, Paloma; Ordóñez, Salvador; Vega, Aurelio; Díez, Fernando V

2004-05-01

The performance of different commercially available catalysts (supported Pd, Pt, Rh, bimetallic Pd-Pt, and Cr-Cu-Ti oxide catalyst) for the oxidation of methane, alone and in presence of ammonia and hydrogen sulphide is studied in this work. Catalysts performance was evaluated both in terms of activity and resistance to poisoning. The main conclusions are that supported Pd and Rh, present the highest activities for methane oxidation, both alone and in presence of ammonia, whereas they are severely poisoned in presence of H2S. Pt and Cr-Cu-Ti are less active but more sulphur resistant, but their activity is lower than the residual activity of sulphur-deactivated Pd and Rh catalysts. The Pd-Pt catalyst exhibits low activity and it is quickly deactivated in presence of hydrogen sulphide.

Equilibrium structures and flows of polar and nonpolar liquids in different carbon nanotubes

NASA Astrophysics Data System (ADS)

Abramyan, Andrey K.; Bessonov, Nick M.; Mirantsev, Leonid V.; Chevrychkina, Anastasiia A.

2018-03-01

Molecular dynamics (MD) simulations of equilibrium structures and flows of polar water and nonpolar methane confined by single-walled carbon nanotubes (SWCNTs) with circular and square cross sections and bounding walls with regular graphene structure and random (amorphous) distribution of carbon atoms have been performed. The results of these simulations show that equilibrium structures of both confined liquids depend strongly on the shape of the cross section of SWCNTs, whereas the structure of their bounding walls has a minor influence on these structures. On contrary, the external pressure driven water and methane flows through above mentioned SWCNTs depend significantly on both the shape of their cross sections and the structure of their bounding walls.

Methane sources in gas hydrate-bearing cold seeps: Evidence from radiocarbon and stable isotopes

USGS Publications Warehouse

Pohlman, J.W.; Bauer, J.E.; Canuel, E.A.; Grabowski, K.S.; Knies, D.L.; Mitchell, C.S.; Whiticar, Michael J.; Coffin, R.B.

2009-01-01

Fossil methane from the large and dynamic marine gas hydrate reservoir has the potential to influence oceanic and atmospheric carbon pools. However, natural radiocarbon (14C) measurements of gas hydrate methane have been extremely limited, and their use as a source and process indicator has not yet been systematically established. In this study, gas hydrate-bound and dissolved methane recovered from six geologically and geographically distinct high-gas-flux cold seeps was found to be 98 to 100% fossil based on its 14C content. Given this prevalence of fossil methane and the small contribution of gas hydrate (??? 1%) to the present-day atmospheric methane flux, non-fossil contributions of gas hydrate methane to the atmosphere are not likely to be quantitatively significant. This conclusion is consistent with contemporary atmospheric methane budget calculations. In combination with ??13C- and ??D-methane measurements, we also determine the extent to which the low, but detectable, amounts of 14C (~ 1-2% modern carbon, pMC) in methane from two cold seeps might reflect in situ production from near-seafloor sediment organic carbon (SOC). A 14C mass balance approach using fossil methane and 14C-enriched SOC suggests that as much as 8 to 29% of hydrate-associated methane carbon may originate from SOC contained within the upper 6??m of sediment. These findings validate the assumption of a predominantly fossil carbon source for marine gas hydrate, but also indicate that structural gas hydrate from at least certain cold seeps contains a component of methane produced during decomposition of non-fossil organic matter in near-surface sediment.

Microbial minorities modulate methane consumption through niche partitioning

PubMed Central

Bodelier, Paul LE; Meima-Franke, Marion; Hordijk, Cornelis A; Steenbergh, Anne K; Hefting, Mariet M; Bodrossy, Levente; von Bergen, Martin; Seifert, Jana

2013-01-01

Microbes catalyze all major geochemical cycles on earth. However, the role of microbial traits and community composition in biogeochemical cycles is still poorly understood mainly due to the inability to assess the community members that are actually performing biogeochemical conversions in complex environmental samples. Here we applied a polyphasic approach to assess the role of microbial community composition in modulating methane emission from a riparian floodplain. We show that the dynamics and intensity of methane consumption in riparian wetlands coincide with relative abundance and activity of specific subgroups of methane-oxidizing bacteria (MOB), which can be considered as a minor component of the microbial community in this ecosystem. Microarray-based community composition analyses demonstrated linear relationships of MOB diversity parameters and in vitro methane consumption. Incubations using intact cores in combination with stable isotope labeling of lipids and proteins corroborated the correlative evidence from in vitro incubations demonstrating γ-proteobacterial MOB subgroups to be responsible for methane oxidation. The results obtained within the riparian flooding gradient collectively demonstrate that niche partitioning of MOB within a community comprised of a very limited amount of active species modulates methane consumption and emission from this wetland. The implications of the results obtained for biodiversity–ecosystem functioning are discussed with special reference to the role of spatial and temporal heterogeneity and functional redundancy. PMID:23788331

Microbial minorities modulate methane consumption through niche partitioning.

PubMed

Bodelier, Paul L E; Meima-Franke, Marion; Hordijk, Cornelis A; Steenbergh, Anne K; Hefting, Mariet M; Bodrossy, Levente; von Bergen, Martin; Seifert, Jana

2013-11-01

Microbes catalyze all major geochemical cycles on earth. However, the role of microbial traits and community composition in biogeochemical cycles is still poorly understood mainly due to the inability to assess the community members that are actually performing biogeochemical conversions in complex environmental samples. Here we applied a polyphasic approach to assess the role of microbial community composition in modulating methane emission from a riparian floodplain. We show that the dynamics and intensity of methane consumption in riparian wetlands coincide with relative abundance and activity of specific subgroups of methane-oxidizing bacteria (MOB), which can be considered as a minor component of the microbial community in this ecosystem. Microarray-based community composition analyses demonstrated linear relationships of MOB diversity parameters and in vitro methane consumption. Incubations using intact cores in combination with stable isotope labeling of lipids and proteins corroborated the correlative evidence from in vitro incubations demonstrating γ-proteobacterial MOB subgroups to be responsible for methane oxidation. The results obtained within the riparian flooding gradient collectively demonstrate that niche partitioning of MOB within a community comprised of a very limited amount of active species modulates methane consumption and emission from this wetland. The implications of the results obtained for biodiversity-ecosystem functioning are discussed with special reference to the role of spatial and temporal heterogeneity and functional redundancy.

Upward revision of global fossil fuel methane emissions based on isotope database.

PubMed

Schwietzke, Stefan; Sherwood, Owen A; Bruhwiler, Lori M P; Miller, John B; Etiope, Giuseppe; Dlugokencky, Edward J; Michel, Sylvia Englund; Arling, Victoria A; Vaughn, Bruce H; White, James W C; Tans, Pieter P

2016-10-06

Methane has the second-largest global radiative forcing impact of anthropogenic greenhouse gases after carbon dioxide, but our understanding of the global atmospheric methane budget is incomplete. The global fossil fuel industry (production and usage of natural gas, oil and coal) is thought to contribute 15 to 22 per cent of methane emissions to the total atmospheric methane budget. However, questions remain regarding methane emission trends as a result of fossil fuel industrial activity and the contribution to total methane emissions of sources from the fossil fuel industry and from natural geological seepage, which are often co-located. Here we re-evaluate the global methane budget and the contribution of the fossil fuel industry to methane emissions based on long-term global methane and methane carbon isotope records. We compile the largest isotopic methane source signature database so far, including fossil fuel, microbial and biomass-burning methane emission sources. We find that total fossil fuel methane emissions (fossil fuel industry plus natural geological seepage) are not increasing over time, but are 60 to 110 per cent greater than current estimates owing to large revisions in isotope source signatures. We show that this is consistent with the observed global latitudinal methane gradient. After accounting for natural geological methane seepage, we find that methane emissions from natural gas, oil and coal production and their usage are 20 to 60 per cent greater than inventories. Our findings imply a greater potential for the fossil fuel industry to mitigate anthropogenic climate forcing, but we also find that methane emissions from natural gas as a fraction of production have declined from approximately 8 per cent to approximately 2 per cent over the past three decades.

Transition metal sulfide loaded catalyst

DOEpatents

Maroni, Victor A.; Iton, Lennox E.; Pasterczyk, James W.; Winterer, Markus; Krause, Theodore R.

1994-01-01

A zeolite based catalyst for activation and conversion of methane. A zeolite support includes a transition metal (Mo, Cr or W) sulfide disposed within the micropores of the zeolite. The catalyst allows activation and conversion of methane to C.sub.2 + hydrocarbons in a reducing atmosphere, thereby avoiding formation of oxides of carbon.

30 CFR 57.22206 - Main ventilation failure (I-A, II-A, III, and V-A mines).

Code of Federal Regulations, 2010 CFR

2010-07-01

... AND NONMETAL MINES Safety Standards for Methane in Metal and Nonmetal Mines Ventilation § 57.22206..., tests for methane shall be conducted in affected active workings until normal air flow has resumed. (b... less than 1.0 percent methane. Persons other than examiners shall not reenter a Subcategory II-A mine...

Methane-oxidizing seawater microbial communities from an Arctic shelf

NASA Astrophysics Data System (ADS)

Uhlig, Christiane; Kirkpatrick, John B.; D'Hondt, Steven; Loose, Brice

2018-06-01

Marine microbial communities can consume dissolved methane before it can escape to the atmosphere and contribute to global warming. Seawater over the shallow Arctic shelf is characterized by excess methane compared to atmospheric equilibrium. This methane originates in sediment, permafrost, and hydrate. Particularly high concentrations are found beneath sea ice. We studied the structure and methane oxidation potential of the microbial communities from seawater collected close to Utqiagvik, Alaska, in April 2016. The in situ methane concentrations were 16.3 ± 7.2 nmol L-1, approximately 4.8 times oversaturated relative to atmospheric equilibrium. The group of methane-oxidizing bacteria (MOB) in the natural seawater and incubated seawater was > 97 % dominated by Methylococcales (γ-Proteobacteria). Incubations of seawater under a range of methane concentrations led to loss of diversity in the bacterial community. The abundance of MOB was low with maximal fractions of 2.5 % at 200 times elevated methane concentration, while sequence reads of non-MOB methylotrophs were 4 times more abundant than MOB in most incubations. The abundances of MOB as well as non-MOB methylotroph sequences correlated tightly with the rate constant (kox) for methane oxidation, indicating that non-MOB methylotrophs might be coupled to MOB and involved in community methane oxidation. In sea ice, where methane concentrations of 82 ± 35.8 nmol kg-1 were found, Methylobacterium (α-Proteobacteria) was the dominant MOB with a relative abundance of 80 %. Total MOB abundances were very low in sea ice, with maximal fractions found at the ice-snow interface (0.1 %), while non-MOB methylotrophs were present in abundances similar to natural seawater communities. The dissimilarities in MOB taxa, methane concentrations, and stable isotope ratios between the sea ice and water column point toward different methane dynamics in the two environments.

A complete active space valence bond method with nonorthogonal orbitals

NASA Astrophysics Data System (ADS)

Hirao, Kimihiko; Nakano, Haruyuki; Nakayama, Kenichi

1997-12-01

A complete active space self-consistent field (SCF) wave function is transformed into a valence bond type representation built from nonorthogonal orbitals, each strongly localized on a single atom. Nonorthogonal complete active space SCF orbitals are constructed by Ruedenberg's projected localization procedure so that they have maximal overlaps with the corresponding minimum basis set of atomic orbitals of the free-atoms. The valence bond structures which are composed of such nonorthogonal quasiatomic orbitals constitute the wave function closest to the concept of the oldest and most simple valence bond method. The method is applied to benzene, butadiene, hydrogen, and methane molecules and compared to the previously proposed complete active space valence bond approach with orthogonal orbitals. The results demonstrate the validity of the method as a powerful tool for describing the electronic structure of various molecules.

Clumped isotopologue constraints on the origin of methane at seafloor hot springs

NASA Astrophysics Data System (ADS)

Wang, David T.; Reeves, Eoghan P.; McDermott, Jill M.; Seewald, Jeffrey S.; Ono, Shuhei

2018-02-01

Hot-spring fluids emanating from deep-sea vents hosted in unsedimented ultramafic and mafic rock commonly contain high concentrations of methane. Multiple hypotheses have been proposed for the origin(s) of this methane, ranging from synthesis via reduction of aqueous inorganic carbon (∑CO2) during active fluid circulation to leaching of methane-rich fluid inclusions from plutonic rocks of the oceanic crust. To further resolve the process(es) responsible for methane generation in these systems, we determined the relative abundances of several methane isotopologues (including 13CH3D, a "clumped" isotopologue containing two rare isotope substitutions) in hot-spring source fluids sampled from four geochemically-distinct hydrothermal vent fields (Rainbow, Von Damm, Lost City, and Lucky Strike). Apparent equilibrium temperatures retrieved from methane clumped isotopologue analyses average 310-42+53 °C, with no apparent relation to the wide range of fluid temperatures (96-370 °C) and chemical compositions (pH, [H2], [∑CO2], [CH4]) represented. Combined with very similar bulk stable isotope ratios (13C/12C and D/H) of methane across the suite of hydrothermal fluids, all available geochemical and isotopic data suggest a common mechanism of methane generation at depth that is disconnected from active fluid circulation. Attainment of equilibrium amongst methane isotopologues at temperatures of ca. 270-360 °C is compatible with the thermodynamically-favorable reduction of CO2 to CH4 at temperatures at or below ca. 400 °C under redox conditions characterizing intrusive rocks derived from sub-ridge melts. Collectively, the observations support a model where methane-rich aqueous fluids, known to be trapped in rocks of the oceanic lithosphere, are liberated from host rocks during hydrothermal circulation and perhaps represent the major source of methane venting with thermal waters at unsedimented hydrothermal fields. The results also provide further evidence that water-rock reactions occurring at temperatures lower than 200 °C do not contribute significantly to the quantities of methane venting at mid-ocean ridge hot springs.

Rainfall, Plant Communities and Methane Fluxes in the Ka`au Crater Wetland, Oahu, Hawaii

NASA Astrophysics Data System (ADS)

Grand, M.; Gaidos, E.

2003-12-01

Tropical wetlands constitute a major source of methane, an atmospheric greenhouse gas. Net methane emission in freshwater settings is the result of organic matter decomposition under anaerobic conditions modulated by aerobic methane oxidation and is thus also an indicator of wetland ecosystem processes. This study is monitoring the methane flux from the Ka`au crater wetland on the island of Oahu (Hawaii) and correlating it with environmental parameters such as precipitation and sunlight. We are obtaining precipitation, Photosynthetic Active Radiation (PAR), and water table level data with data loggers and are correlating these data with static chamber methane flux measurements and measurements of soil methane production potential. Additionally, our research is studying the effects of changes in vegetation type, i.e., of the invasive strawberry guava tree (Psidium Cattleianum) on the wetland methane emissions. Changes in soil chemistry and in the transport of gases by roots that accompany such vegetation change are a potential driver of methane flux modifications that have not been previously examined. Strawberry guava forms dense mats of surface roots that may change soil gas exchange and prolific fruiting may raise the soil organic content. We collected soil samples along a 30 meter transect that extends through two vegetation patterns; the strawberry guava canopy and the sedge meadow (Cladium Leptostachyum). Samples were incubated for 24 hours to estimate their methane generation potential. Our preliminary results show that methane generation potential is greater under the strawberry guava canopy. However, 2 of the 15 samples collected in the sedge meadow section of the transect did not match this pattern. Soil organic carbon content is slightly higher in the strawberry guava than in the sedge. We recorded a 90% decrease in methane generation potential in sedge meadow soils during a dry period relative to a wet period 2 months earlier. We propose that this change reflects a difference in the relative activity of microorganisms in the oxic and anoxic parts of the soil column. We will use environmental molecular technique to compare the microbial community component responsible for the production of methane in the different wetland soils.

Field measures show methanotroph sensitivity to soil moisture follows precipitation regime of the grassland sites across the US Great Plains

NASA Astrophysics Data System (ADS)

Koyama, A.; Webb, C. T.; Johnson, N. G.; Brewer, P. E.; von Fischer, J. C.

2015-12-01

Methane uptake rates are known to have temporal variation in response to changing soil moisture levels. However, the relative importance of soil diffusivity vs. methanotroph physiology has not been disentangled to date. Testing methanotroph physiology in the laboratory can lead to misleading results due to changes in the fine-scale habitat where methanotrophs reside. To assay the soil moisture sensitivity of methanotrophs under field conditions, we studied 22 field plots scattered across eight Great Plains grassland sites that differed in precipitation regime and soil moisture, making ca. bi-weekly measures during the growing seasons over three years. Quantification of methanotroph activity was achieved from chamber-based measures of methane uptake coincident with SF6-derived soil diffusivity, and interpretation in a reaction-diffusion model. At each plot, we also measured soil water content (SWC), soil temperature and inorganic nitrogen (N) contents. We also assessed methanotroph community composition via 454 sequencing of the pmoA gene. Statistical analyses showed that methanotroph activity had a parabolic response with SWC (concave down), and significant differences in the shape of this response among sites. Moreover, we found that the SWC at peak methanotroph activity was strongly correlated with mean annual precipitation (MAP) of the site. The sequence data revealed distinct composition patterns, with structure that was associated with variation in MAP and soil texture. These results suggest that local precipitation regime shapes methanotroph community composition, which in turn lead to unique sensitivity of methane uptake rates with soil moisture. Our findings suggest that methanotroph activity may be more accurately modeled when the biological and environmental responses are explicitly described.

Dense ceramic membranes for converting methane to syngas

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

Balachandran, U.; Dusek, J.T.; Picciolo, J.J.

1995-07-01

Dense mixed-oxide ceramics capable of conducting both electrons and oxygen ions are promising materials for partial oxygenation of methane to syngas. We are particularly interested in an oxide based on the Sr-Fe-Co-O system. Dense ceramic membrane tubes have been fabricated by a plastic extrusion technique. The sintered tubes were then used to selectively transport oxygen from air through the membrane to make syngas without the use of external electrodes. The sintered tubes have operated for >1000 h, and methane conversion efficiencies of >98% have been observed. Mechanical properties, structural integrity of the tubes during reactor operation, results of methane conversion,more » selectivity of methane conversion products, oxygen permeation, and fabrication of multichannel configurations for large-scale production of syngas will be presented.« less

Quantifying the relative contribution of natural gas fugitive emissions to total methane emissions in Weld County Colorado using δ13CH4 analysis

NASA Astrophysics Data System (ADS)

Rella, C.; Jacobson, G. A.; Crosson, E.; Sweeney, C.; Karion, A.; Petron, G.

2012-12-01

Fugitive emissions of methane into the atmosphere are a major concern facing the natural gas production industry. Given that the global warming potential of methane is many times greater than that of carbon dioxide (Forster et al. 2007), the importance of quantifying methane emissions becomes clear. Companion presentations at this meeting describe efforts to quantify the overall methane emissions in two separate gas producing areas in Colorado and Utah during intensive field campaigns undertaken in 2012. A key step in the process of assessing the emissions arising from natural gas production activities is partitioning the observed methane emissions between natural gas fugitive emissions and other sources of methane, such as from landfills or agricultural activities. One method for assessing the contribution of these different sources is stable isotope analysis. In particular, the δ13CH4 signature of natural gas (-37 permil) is significantly different that the signature of other significant sources of methane, such as landfills or ruminants (-50 to -70 permil). In this paper we present measurements of δ13CH4 in Colorado in Weld County, a region of intense natural gas production, using a mobile δ13CH4¬ analyzer capable of high-precision measurements of the stable isotope ratio of methane at ambient levels. This analyzer was used to make stable isotope measurements at a fixed location near the center of the gas producing region, from which an overall isotope ratio for the regional emissions is determined. In addition, mobile measurements in the nocturnal boundary layer have been made, over a total distance of 150 km throughout Weld County, allowing spatially resolved measurements of this isotope signature. Finally, this analyzer was used to quantify the isotopic signature of those individual sources (natural gas fugitive emissions, concentrated animal feeding operations, and landfills) that constitute the majority of methane emissions in this region, by making measurements of the isotope ratio directly in the downwind plume from each source. These data are combined to establish the fraction of the observed methane emissions that can be attributed to natural gas activities in the region. The results are compared to inventories as well as other measurement techniques, and the uncertainty of the measurement is estimated.

An experimental study of the structure of laminar premixed flames of ethanol/methane/oxygen/argon

PubMed Central

Tran, L.S.; Glaude, P.A.; Battin-Leclerc, F.

2013-01-01

The structures of three laminar premixed stoichiometric flames at low pressure (6.7 kPa): a pure methane flame, a pure ethanol flame and a methane flame doped by 30% of ethanol, have been investigated and compared. The results consist of concentration profiles of methane, ethanol, O2, Ar, CO, CO2, H2O, H2, C2H6, C2H4, C2H2, C3H8, C3H6, p-C3H4, a-C3H4, CH2O, CH3HCO, measured as a function of the height above the burner by probe sampling followed by on-line gas chromatography analyses. Flame temperature profiles have been also obtained using a PtRh (6%)-PtRh (30%) type B thermocouple. The similarities and differences between the three flames were analyzed. The results show that, in these three flames, the concentration of the C2 intermediates is much larger than that of the C3 species. In general, mole fraction of all intermediate species in the pure ethanol flame is the largest, followed by the doped flame, and finally the pure methane flame. PMID:24092946

Greenhouse Gas Fluxes at the Tablelands, NL, Canada: A Site of Active Serpentinization

NASA Astrophysics Data System (ADS)

Morrill, P. L.; Morrissey, L. S.; Cumming, E.

2016-12-01

Active sites of serpentinization have been proposed as sites for carbon capture and storage (CCS) projects. However, in addition to their ability to convert carbon dioxide to carbonate rock, sites of serpentinization also have the potential release methane, which is a more power greenhouse gas than carbon dioxide. Very little is known about the natural flux of carbon dioxide sequestered and methane released into the atmosphere from active sites of serpentinization. In this study we measured carbon dioxide, methane, and nitrous oxide gas fluxes at a pool of ultra-basic water discharging from serpentinized rock in Winterhouse Canyon, Gros Morne, Newfoundland. We found that the flux of methane released was 4.6 x 10-7 mol/m2/min and the carbon dioxide sequestered was 1.9 x 10-5 mol/m2/min, while the concentrations of nitrous oxide showed little change. Based on these fluxes we calculated predictive climate change parameters such as net radiative forcing and global warming potential which predicted that despite the methane being released the site still had an overall long-term atmospheric cooling effect based on the natural rate of carbon dioxide sequestration.

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.

Study of Methanogenesis while Bioutilisation of Plant Residuals

NASA Astrophysics Data System (ADS)

Ilyin, V. K.; Korniushenkova, I. N.; Starkova, L. V.; Lauriniavichius, K. S.

respect principals of planet ecology, and compatibility with other habitability systems. For these purpose the waste management technologies, relevant to application of the biodegradation properties of bacteria are of great value. Biological treatment method is based upon the biodegradation of organic substances by various microorganisms. vegetable non-edible residual, using artificial inoculum; to study peculiarities of biogas, possibilities to optimize or to reduce the share of methane. fermentation. The biogas production achieved 46 l per 1 kg of substrate. The microbial studies of biodegradation process revealed following peculiarities: (i)gradual quantitative increasing of Lactobacillus sp. (from 103 to 105 colony forming units (CFU) per ml); (ii)activation of Clostridia sp. (from 102 to 104 CFU/ml); (iii) elimination of aerobic conventional pathogens (Enterobacteriaceae sp., Protea sp., staphylococci). methane content measures revealed traces 0.1-0.4%. granules, the amount of methane in biogas reached 80-90%. biodegradation of vegetable wastes. This inoculum consists of active sludge adapted to wastes mixed with excretes of insects which consume plant wastes. Using this inoculum the biodegradation process takes less time, then that using active sludge. Regulation of methane concentration from traces to 90% may be achieved by adding of methane reactor to the plant digester.

Methane Leak Rates from Natural Gas Wells in Norther California

NASA Astrophysics Data System (ADS)

Cui, Y.; Yoon, S.; Chen, Y.; Falk, M.; Kuwayama, T.; Croes, B. E.; Herner, J.; Vijayan, A.

2017-12-01

Methane is a potent greenhouse gas (GHG) and is the second most prevalent GHG emitted in California from human activities. As part of a comprehensive effort to reduce GHG emissions and meet the statewide climate goals, California has proposed a Short Lived Climate Pollutant (SLCP) Strategy that includes a 40% reduction of methane emissions from 2013 levels by 2030, with goals to reduce oil and gas related emissions and capture methane emissions from dairy operations and organic waste. There is growing evidence in the recent scientific literature suggesting that methane emissions can come from every stage of the oil and gas supply chain. During oil and gas production operations, studies reported that a small number of oil and gas wells made up a large fraction of total methane emissions from the wells. In such a fat-tail distribution, the mean methane leak rate from wells is orders of magnitude larger than the median, which indicates the presence of super emitter sources. However, since the super emitters are often positioned as outliers in a fat-tail distribution and do not always behave consistently, measuring their leak rates is challenging, but critical to quantify their impacts and identify potential mitigation opportunities. This presentation will discuss of methane leak rates measured from natural gas wells in Northern California for different well operations: active, idle, and plugged. The leak rates demonstrated fat-tail distributions, and the mean leak rates for each well operation status were an order of magnitude higher than the median leak rates. It was also observed that roughly 20% of wells contributed more than 80% of methane emissions. Further data collection is needed with a larger number of samples to better understand the relationship between the leak rates and well operation status. Such measurements could help improve the estimate of methane emissions from natural gas wells and inform methane reduction policies and programs in California.

Methane Ebullition in Temperate Hydropower Reservoirs and Implications for US Policy on Greenhouse Gas Emissions

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

Miller, Benjamin L.; Arntzen, Evan V.; Goldman, Amy E.

The United States is home to more than 87,000 dams, 2,198 of which are actively used for hydropower production. With the December 2015 consensus adoption of the United Nations Framework Convention on Climate Change’s Paris Agreement, it is imperative for the U.S. to accurately quantify greenhouse gas fluxes from its hydropower reservoirs. Methane ebullition, or methane bubbles originating from river or lake sediments, can account for nearly all of a reservoir’s methane emissions to the atmosphere. However, methane ebullition in hydropower reservoirs has been studied in only three temperate locations, none of which are in the United States. This studymore » measures high ebullitive methane fluxes from two hydropower reservoirs in eastern Washington, synthesizes the known information about methane ebullition from tropical, boreal, and temperate hydropower reservoirs, and investigates the implications for U.S. hydropower management and growth.« less

Three-Dimensional Model Synthesis of the Global Methane Cycle

NASA Technical Reports Server (NTRS)

Fung, I.; Prather, M.; John, J.; Lerner, J.; Matthews, E.

1991-01-01

A synthesis of the global methane cycle is presented to attempt to generate an accurate global methane budget. Methane-flux measurements, energy data, and agricultural statistics are merged with databases of land-surface characteristics and anthropogenic activities. The sources and sinks of methane are estimated based on atmospheric methane composition and variations, and a global 3D transport model simulates the corresponding atmospheric responses. The geographic and seasonal variations of candidate budgets are compared with observational data, and the available observations are used to constrain the plausible methane budgets. The preferred budget includes annual destruction rates and annual emissions for various sources. The lack of direct flux measurements in the regions of many of these fluxes makes the unique determination of each term impossible. OH oxidation is found to be the largest single term, although more measurements of this and other terms are recommended.

Effect of Trichloroethylene on Minimum Energy Requirement and Gene Expression in a Nutrient Limited Methanotroph

NASA Astrophysics Data System (ADS)

Colwell, F. S.; Delwiche, M.; Newby, D.; Wood, A.; Bingham, M.; Crawford, R. L.; Strap, J. L.

2005-12-01

Monitored natural attenuation (MNA) of contaminant plumes requires data for predictive modeling of plume destruction including the rates of microbial contaminant degradation. Methanotrophs are implicated in co-metabolism of trichloroethylene (TCE) in the Snake River Plain aquifer (SRPA) where MNA is the selected method of treatment. Our research aims to: 1) determine realistic activities of these cells when starved, a condition typical of subsurface microbes, and 2) detect the genes that are transcribed when methanotrophs experience stress or starvation related to TCE exposure and conditions in the subsurface. Methylosinus trichosporium OB3b (OB3b), a model methanotroph, was starved in a biomass recycle reactor and soluble methane monooxygenase (sMMO) activities determined, with and without TCE exposure (ca. 100 μg TCE/L). Starved methanotrophs, present at 3 x 109 cells/mL in the reactor, consumed methane at 0.001 fmoles of methane/cell/day and gradually increased sMMO activities when exposed to higher methane concentrations. sMMO activities of starved OB3b cells exposed to TCE were indistinguishable from cells that were not exposed over brief (one day) periods. The sequences of eight genes, known to code for starvation/stress proteins, were retrieved from phylogenetic relatives (α-proteobacteria) of OB3b. Primers (18-22 bp) were designed from conserved regions in the consensus sequences to obtain OB3b-specific sequences for the eight genes. Primers for the starvation/stress genes successfully amplified all eight genes in OB3b using PCR. Our plan is to clone and sequence these OB3b genes then synthesize oligonucleotides that can be added to a microarray that includes targets for OB3b structural and regulatory gene sequences as a prelude to evaluating gene expression under different nutrient availability conditions and in the presence and absence of TCE. Incorporation of starvation-based rate estimates into natural attenuation models of contaminant plumes will permit estimates of the fraction of TCE natural attenuation that can be attributed to methanotrophic co-metabolism in a given aquifer system.

Biomethanation potential of macroalgae Ulva spp. and Gracilaria spp. and in co-digestion with waste activated sludge.

PubMed

Costa, J C; Gonçalves, P R; Nobre, A; Alves, M M

2012-06-01

Biochemical methane potential of four species of Ulva and Gracilaria genus was assessed in batch assays at mesophilic temperature. The results indicate a higher specific methane production (per volatile solids) for one of the Ulva sp. compared with other macroalgae and for tests running with 2.5% of total solids (196±9 L CH(4) kg(-1)VS). Considering that macroalgae can potentially be a post treatment of municipal wastewater for nutrients removal, co-digestion of macroalgae with waste activated sludge (WAS) was assessed. The co-digestion of macroalgae (15%) with WAS (85%) is feasible at a rate of methane production 26% higher than WAS alone without decreasing the overall biodegradability of the substrate (42-45% methane yield). The use of anoxic marine sediment as inoculum had no positive effect on the methane production in batch assays. The limiting step of the overall anaerobic digestion process was the hydrolysis. Copyright © 2012 Elsevier Ltd. All rights reserved.

Interactions of Methylotrophs with Plants and Other Heterotrophic Bacteria

PubMed Central

Iguchi, Hiroyuki; Yurimoto, Hiroya; Sakai, Yasuyoshi

2015-01-01

Methylotrophs, which can utilize methane and/or methanol as sole carbon and energy sources, are key players in the carbon cycle between methane and CO2, the two most important greenhouse gases. This review describes the relationships between methylotrophs and plants, and between methanotrophs (methane-utilizers, a subset of methylotrophs) and heterotrophic bacteria. Some plants emit methane and methanol from their leaves, and provide methylotrophs with habitats. Methanol-utilizing methylotrophs in the genus Methylobacterium are abundant in the phyllosphere and have the ability to promote the growth of some plants. Methanotrophs also inhabit the phyllosphere, and methanotrophs with high methane oxidation activities have been found on aquatic plants. Both plant and environmental factors are involved in shaping the methylotroph community on plants. Methanotrophic activity can be enhanced by heterotrophic bacteria that provide growth factors (e.g., cobalamin). Information regarding the biological interaction of methylotrophs with other organisms will facilitate a better understanding of the carbon cycle that is driven by methylotrophs. PMID:27682083

Anaerobic co-digestion of spent coffee grounds with different waste feedstocks for biogas production.

PubMed

Kim, Jaai; Kim, Hakchan; Baek, Gahyun; Lee, Changsoo

2017-02-01

Proper management of spent coffee grounds has become a challenging problem as the production of this waste residue has increased rapidly worldwide. This study investigated the feasibility of the anaerobic co-digestion of spent coffee ground with various organic wastes, i.e., food waste, Ulva, waste activated sludge, and whey, for biomethanation. The effect of co-digestion was evaluated for each tested co-substrate in batch biochemical methane potential tests by varying the substrate mixing ratio. Co-digestion with waste activated sludge had an apparent negative effect on both the yield and production rate of methane. Meanwhile, the other co-substrates enhanced the reaction rate while maintaining methane production at a comparable or higher level to that of the mono-digestion of spent coffee ground. The reaction rate increased with the proportion of co-substrates without a significant loss in methanation potential. These results suggest the potential to reduce the reaction time and thus the reactor capacity without compromising methane production. Copyright © 2016 Elsevier Ltd. All rights reserved.

Measurements and modeling to quantify emissions of methane and VOCs from shale gas operations: Final Report

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

Presto, Albert A

The objectives of the project were to determine the leakage rates of methane and ozone-forming Volatile Organic Compounds (VOCs) and the emission rates of air toxics from Marcellus shale gas activities. Methane emissions in the Marcellus Shale region were differentiated between “newer” sources associated with shale gas development and “older” sources associated with coal or conventional natural gas exploration. This project conducted measurements of methane and VOC emissions from both shale and non-shale natural gas resources. The initial scope of the project was the Marcellus Shale basin, and measurements were conducted in both the western wet gas regions (southwest PAmore » and WV) and eastern dry gas region (northeast PA) of the basin. During this project, we obtained additional funding from other agencies to expand the scope of measurements to include additional basins. The data from both the Marcellus and other basins were combined to construct a national analysis of methane emissions from oil & gas production activities.« less

Toxic effects of butyl elastomers on aerobic methane oxidation

NASA Astrophysics Data System (ADS)

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

2013-04-01

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

Methanotrophic bacteria.

PubMed Central

Hanson, R S; Hanson, T E

1996-01-01

Methane-utilizing bacteria (methanotrophs) are a diverse group of gram-negative bacteria that are related to other members of the Proteobacteria. These bacteria are classified into three groups based on the pathways used for assimilation of formaldehyde, the major source of cell carbon, and other physiological and morphological features. The type I and type X methanotrophs are found within the gamma subdivision of the Proteobacteria and employ the ribulose monophosphate pathway for formaldehyde assimilation, whereas type II methanotrophs, which employ the serine pathway for formaldehyde assimilation, form a coherent cluster within the beta subdivision of the Proteobacteria. Methanotrophic bacteria are ubiquitous. The growth of type II bacteria appears to be favored in environments that contain relatively high levels of methane, low levels of dissolved oxygen, and limiting concentrations of combined nitrogen and/or copper. Type I methanotrophs appear to be dominant in environments in which methane is limiting and combined nitrogen and copper levels are relatively high. These bacteria serve as biofilters for the oxidation of methane produced in anaerobic environments, and when oxygen is present in soils, atmospheric methane is oxidized. Their activities in nature are greatly influenced by agricultural practices and other human activities. Recent evidence indicates that naturally occurring, uncultured methanotrophs represent new genera. Methanotrophs that are capable of oxidizing methane at atmospheric levels exhibit methane oxidation kinetics different from those of methanotrophs available in pure cultures. A limited number of methanotrophs have the genetic capacity to synthesize a soluble methane monooxygenase which catalyzes the rapid oxidation of environmental pollutants including trichloroethylene. PMID:8801441

The Structural and Functional Capacity of Ruminal and Cecal Microbiota in Growing Cattle Was Unaffected by Dietary Supplementation of Linseed Oil and Nitrate

PubMed Central

Popova, Milka; McGovern, Emily; McCabe, Matthew S.; Martin, Cécile; Doreau, Michel; Arbre, Marie; Meale, Sarah J.; Morgavi, Diego P.; Waters, Sinéad M.

2017-01-01

Microorganisms in the digestive tract of ruminants differ in their functionality and ability to use feed constituents. While cecal microbiota play an important role in post-rumen fermentation of residual substrates undigested in the rumen, limited knowledge exists regarding its structure and function. In this trial we investigated the effect of dietary supplementation with linseed oil and nitrate on methane emissions and on the structure of ruminal and cecal microbiota of growing bulls. Animals were allocated to either a CTL (control) or LINNIT (CTL supplemented with 1.9% linseed and 1.0% nitrates) diet. Methane emissions were measured using the GreenFeed system. Microbial diversity was assessed using amplicon sequencing of microbial genomic DNA. Additionally, total RNA was extracted from ruminal contents and functional mcrA and mtt genes were targeted in amplicon sequencing approach to explore the diversity of functional gene expression in methanogens. LINNIT had no effect on methane yield (g/kg DMI) even though it decreased methane production by 9% (g/day; P < 0.05). Methanobrevibacter- and Methanomassiliicoccaceae-related OTUs were more abundant in cecum (72 and 24%) compared to rumen (60 and 11%) irrespective of the diet (P < 0.05). Feeding LINNIT reduced the relative abundance of Methanomassiliicoccaceae mcrA cDNA reads in the rumen. Principal component analysis revealed significant differences in taxonomic composition and abundance of bacterial communities between rumen and cecum. Treatment decreased the relative abundance of a few Ruminococcaceae genera, without affecting global bacterial community structure. Our research confirms a high level of heterogeneity in species composition of microbial consortia in the main gastrointestinal compartments where feed is fermented in ruminants. There was a parallel between the lack of effect of LINNIT on ruminal and cecal microbial community structure and functions on one side and methane emission changes on the other. These results suggest that the sequencing strategy used here to study microbial diversity and function accurately reflected the absence of effect on methane phenotypes in bulls treated with linseed plus nitrate. PMID:28596764

Type and amount of organic amendments affect enhanced biogenic methane production from coal and microbial community structure

USGS Publications Warehouse

Davis, Katherine J.; Lu, Shipeng; Barnhart, Elliott P.; Parker, Albert E.; Fields, Matthew W.; Gerlach, Robin

2018-01-01

Slow rates of coal-to-methane conversion limit biogenic methane production from coalbeds. This study demonstrates that rates of coal-to-methane conversion can be increased by the addition of small amounts of organic amendments. Algae, cyanobacteria, yeast cells, and granulated yeast extract were tested at two concentrations (0.1 and 0.5 g/L), and similar increases in total methane produced and methane production rates were observed for all amendments at a given concentration. In 0.1 g/L amended systems, the amount of carbon converted to methane minus the amount produced in coal only systems exceeded the amount of carbon added in the form of amendment, suggesting enhanced coal-to-methane conversion through amendment addition. The amount of methane produced in the 0.5 g/L amended systems did not exceed the amount of carbon added. While the archaeal communities did not vary significantly, the bacterial populations appeared to be strongly influenced by the presence of coal when 0.1 g/L of amendment was added; at an amendment concentration of 0.5 g/L the bacterial community composition appeared to be affected most strongly by the amendment type. Overall, the results suggest that small amounts of amendment are not only sufficient but possibly advantageous if faster in situcoal-to-methane production is to be promoted.

Methane emission during municipal wastewater treatment.

PubMed

Daelman, Matthijs R J; van Voorthuizen, Ellen M; van Dongen, Udo G J M; Volcke, Eveline I P; van Loosdrecht, Mark C M

2012-07-01

Municipal wastewater treatment plants emit methane. Since methane is a potent greenhouse gas that contributes to climate change, the abatement of the emission is necessary to achieve a more sustainable urban water management. This requires thorough knowledge of the amount of methane that is emitted from a plant, but also of the possible sources and sinks of methane on the plant. In this study, the methane emission from a full-scale municipal wastewater facility with sludge digestion was evaluated during one year. At this plant the contribution of methane emissions to the greenhouse gas footprint were slightly higher than the CO₂ emissions related to direct and indirect fossil fuel consumption for energy requirements. By setting up mass balances over the different unit processes, it could be established that three quarters of the total methane emission originated from the anaerobic digestion of primary and secondary sludge. This amount exceeded the carbon dioxide emission that was avoided by utilizing the biogas. About 80% of the methane entering the activated sludge reactor was biologically oxidized. This knowledge led to the identification of possible measures for the abatement of the methane emission. Copyright © 2012 Elsevier Ltd. All rights reserved.

Methane Distribution In Plumes Of The South Mariana Back-arc Spreading Center

NASA Astrophysics Data System (ADS)

Toki, T.; Hirota, A.; Tsunogai, U.; Gamo, T.; Nakamura, K.; Noguchi, T.; Taira, N.; Oomori, T.; Ishibashi, J.; Utsumi, M.

2004-12-01

In the South Mariana Back-arc Spreading Center, two methane plumes were observed in water column based on analysis of methane in seawater samples collected during the R/V Thompson expeditions in 2003 around water depth of 2,700 m over the Fryer site on the ridge-axis seamount (12\\deg57.22N, 143\\deg37.16E, depth: 2,850 m). The estimated end-member isotopic compositions of methane in the two plumes are \\delta13C_{CH4} = -5‰ PDB and -50‰ PDB. These values indicated that the two plumes were originated from the different sources. During YK03-09 cruise using the submersible Shinkai 6500 from October to November in 2003, detailed seafloor observation discovered sulfide chimneys emitting black and clear hydrothermal fluid on the off-axis seamount at Pika site (12°55.15N, 143°36.96E, depth: 2,773 m). The result of analysis of isotopic composition of methane in the hydrothermal fluids recovered from the off-axis hydrothermal vents using WHATS (Water and Hydrothermal Atsuryoku Tight Sampler) was averaged value of -4‰ PDB (standard deviation = 1‰ PDB, n = 3). Hydrothermal fluids from the Fryer site were also sampled and were measured: average value = -6.7‰ PDB, standard deviation = 0.3‰ PDB, n = 3. During the R/V Thompson expeditions in March 2004 using ROV ROPOS, 11 ROPOS dives and CTD-RMS plume surveys were conducted, and newly discovered a huge hydrothermal structure with active fluid venting at Achaean site on the ridge skirt (12°56.37N, 143°37.92E, depth: 2,990 m). The δ ^{13}C_{CH4} value of the fluid sample from the site using ROCS (Rotary Clean Seawater sampler) was -14.7‰ PDB. Analysis of isotopic composition of methane in the plume samples collected using the CTD-hydrocast at water depth of 2,500 m over the Archaean site showed -45‰ PDB. Source of methane (δ ^{13}C_{CH4} = -50‰ PDB), however, in the two plumes of the South Mariana Back-arc Spreading Center has been missing. The δ ^{13}C of methane cannot be considered in sediment-starved seafloor hydrothermal fluids as the results from an abiogenic reaction in magma. Alternative explanation would be the secondary stimulated plume of methane that is formed in invertebrate guts of zooplankton swarmed about microbes in the plume, as proposed about a subsurface CH_{4} maximum in the upper oceanic water column. The secondary methane plume may be associated with methane plume without a corresponding enrichment in ^{3}He, observed in the Mariana Trough Back-arc basin at 14° N.

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

NASA Technical Reports Server (NTRS)

King, G. M.

1997-01-01

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

Nonequilibrium adiabatic molecular dynamics simulations of methane clathrate hydrate decomposition

NASA Astrophysics Data System (ADS)

Alavi, Saman; Ripmeester, J. A.

2010-04-01

Nonequilibrium, constant energy, constant volume (NVE) molecular dynamics simulations are used to study the decomposition of methane clathrate hydrate in contact with water. Under adiabatic conditions, the rate of methane clathrate decomposition is affected by heat and mass transfer arising from the breakup of the clathrate hydrate framework and release of the methane gas at the solid-liquid interface and diffusion of methane through water. We observe that temperature gradients are established between the clathrate and solution phases as a result of the endothermic clathrate decomposition process and this factor must be considered when modeling the decomposition process. Additionally we observe that clathrate decomposition does not occur gradually with breakup of individual cages, but rather in a concerted fashion with rows of structure I cages parallel to the interface decomposing simultaneously. Due to the concerted breakup of layers of the hydrate, large amounts of methane gas are released near the surface which can form bubbles that will greatly affect the rate of mass transfer near the surface of the clathrate phase. The effects of these phenomena on the rate of methane hydrate decomposition are determined and implications on hydrate dissociation in natural methane hydrate reservoirs are discussed.

Nonequilibrium adiabatic molecular dynamics simulations of methane clathrate hydrate decomposition.

PubMed

Alavi, Saman; Ripmeester, J A

2010-04-14

Nonequilibrium, constant energy, constant volume (NVE) molecular dynamics simulations are used to study the decomposition of methane clathrate hydrate in contact with water. Under adiabatic conditions, the rate of methane clathrate decomposition is affected by heat and mass transfer arising from the breakup of the clathrate hydrate framework and release of the methane gas at the solid-liquid interface and diffusion of methane through water. We observe that temperature gradients are established between the clathrate and solution phases as a result of the endothermic clathrate decomposition process and this factor must be considered when modeling the decomposition process. Additionally we observe that clathrate decomposition does not occur gradually with breakup of individual cages, but rather in a concerted fashion with rows of structure I cages parallel to the interface decomposing simultaneously. Due to the concerted breakup of layers of the hydrate, large amounts of methane gas are released near the surface which can form bubbles that will greatly affect the rate of mass transfer near the surface of the clathrate phase. The effects of these phenomena on the rate of methane hydrate decomposition are determined and implications on hydrate dissociation in natural methane hydrate reservoirs are discussed.

Prospecting for Methane in Arabia Terra, Mars - First Results

NASA Technical Reports Server (NTRS)

Allen, Carlton C.; Oehler, Dotoyhy Z.; Venechuk, Elizabeth M.

2006-01-01

Methane has been measured in the Martian atmosphere at concentrations of approx. 10 ppb. Since the photochemical lifetime of this gas is approx. 300 years, it is likely that methane is currently being released from the surface. Possible sources for the methane include 1) hydrothermal activity, 2) serpentinization of basalts and other water-rock interactions, 3) thermal maturation of sedimentary organic matter, and 4) metabolism of living bacteria. Any such discovery would revolutionize our understanding of Mars. Longitudinal variations in methane concentration, as measured by the Planetary Fourier Spectrometer (PFS) on Mars Express, show the highest values over Arabia Terra, Elysium Planum, and Arcadia-Memnonia, suggesting localized areas of methane release. We are using orbital data and methodologies derived from petroleum exploration in an attempt to locate these release points.

Unusual Entropy of Adsorbed Methane on Zeolite-Templated Carbon

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

Stadie, Nicholas P.; Murialdo, Maxwell; Ahn, Channing C.

2015-11-25

Methane adsorption at high pressures and across a wide range of temperatures was investigated on the surface of three porous carbon adsorbents with complementary structural properties. The measured adsorption equilibria were analyzed using a method that can accurately account for nonideal fluid properties and distinguish between absolute and excess quantities of adsorption, and that also allows the direct calculation of the thermodynamic potentials relevant to adsorption. On zeolite-templated carbon (ZTC), a material that exhibits extremely high surface area with optimal pore size and homogeneous structure, methane adsorption occurs with unusual thermodynamic properties that are greatly beneficial for deliverable gas storage:more » an enthalpy of adsorption that increases with site occupancy, and an unusually low entropy of the adsorbed phase. The origin of these properties is elucidated by comparison of the experimental results with a statistical mechanical model. The results indicate that temperature-dependent clustering (i.e., reduced configurations) of the adsorbed phase due to enhanced lateral interactions can account for the peculiarities of methane adsorbed on ZTC.« less

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.

Transition metal sulfide loaded catalyst

DOEpatents

Maroni, V.A.; Iton, L.E.; Pasterczyk, J.W.; Winterer, M.; Krause, T.R.

1994-04-26

A zeolite-based catalyst is described for activation and conversion of methane. A zeolite support includes a transition metal (Mo, Cr or W) sulfide disposed within the micropores of the zeolite. The catalyst allows activation and conversion of methane to C[sub 2]+ hydrocarbons in a reducing atmosphere, thereby avoiding formation of oxides of carbon.

Lipid Biomarkers for Methanogens in Hypersaline Cyanobacterial Mats for Guerrero Negro, Baja California Sur

NASA Technical Reports Server (NTRS)

Jahnke, Linda L.; Embaye, Tsegereda; Summons, Roger E.; Fonda, Mark (Technical Monitor)

2002-01-01

Analyses of sediments from the vicinity of active methane seeps have uncovered a particular suite of lipid biomarker patterns that characterize methane consuming archaea and their syntrophic, sulfate reducing partners. These isoprenoid biomarkers, largely identified by their anomalously light carbon isotopic signatures, have been a topic of intense research activity and are recorded in numerous methane-rich environments from Holocene to Cenozoic. This phenomenon has implications for depleted kerogens at 2.7 Ga on early Earth (Hinrichs 2002). In contrast, the lipid biosignatures of methane producing archaea are not readily identified through distinct isotopic labels and have received comparably little attention in analyses of archaea in environmental samples. Indeed, environmental analyses generally detect only free archaeal lipids, not the intact, polar molecules found in the membrane of living organisms. As part of the Ames NAI, the 'Early Microbial Ecosystem Research Group' (EMERG) is working to understand microbial processes in the hypersaline cyanobacterial mats growing in the salt evaporation ponds of the Exportadora de Sal at Guerrero Negro, Baja California Sur, Mexico. The aim of this study was to develop methods by which we could identify the organisms responsible for methane generation in this environment. While the ester-bound fatty acids, hopanoids and wax esters provide a means to identify most of the bacterial components of these mats, the archaea which Ere evidently present through genomic assays and the fact of intense methane production (Hoehler et al. 200l), have not been identified through their corresponding lipid signatures. Archaeal core lipids present a number of analytical challenges. The core lipids of methanogens comprise C20, C40 and sometimes C25 isoprenoid chains, linked through ether bonds to glycerol. As well as archaeal (C20), sn-2- and sn-3-hydroxyarchaeol are associated particularly with methylotrophic methanogens. Recently, we have also identified a dihydroxyarchaeol in a hyperthermophilic methanogen (Summons et al. 2002). Additional structural diversity is encoded into the polar head groups that are attached to the glycerol ether cores. The C20 core lipids are readily analyzed by GC-MS as their volatile trimethylsilyl derivatives while compounds with intact polar head groups can only be detected using LC-MS approaches. Our approach was to utilize the alternative of an ether cleavage reagent (BBr3 vs. HI) and a hydride reducing agent to convert all ether lipids to hydrocarbon in order to provide a vertical profile of quantitative information that might be matched to methane fluxes. We have found that while conventional acid hydrolysis and HI treatment will destroy hydroxyarchaeols, molecular information remains intact through use of BBr3 for ether cleavage. This method revealed the presence of traces of biphytane and various ether alkyls associated with some sulfate reducing bacteria within the mat structure. An interesting, and potentially valuable, byproduct of the method utilizing HI was the identification of abundant homohopanoids after superhydride reduction. Evidently present as sulfur-bound diagenetic products these hopanoids are likely cyanobacterial biomarkers in the early stages of diagenetic preservation.

Methane hydrate - A major reservoir of carbon in the shallow geosphere?

USGS Publications Warehouse

Kvenvolden, K.A.

1988-01-01

Methane hydrates are solids composed of rigid cages of water molecules that enclose methane. Sediment containing methane hydrates is found within specific pressure-temperature conditions that occur in regions of permafrost and beneath the sea in outer continental margins. Because methane hydrates are globally widespread and concentrate methane within the gas-hydrate structure, the potential amount of methane present in the shallow geosphere at subsurface depths of < ???2000 m is very large. However, estimates of the amount are speculative and range over about three orders of magnitude, from 2 ?? 103 to 4 ?? 106 Gt (gigatons = 1015 g) of carbon, depending on the assumptions made. The estimate I favor is ??? 1 ?? 104 Gt of carbon. The estimated amount of organic carbon in the methane-hydrate reservoir greatly exceeds that in many other reservoirs of the global carbon cycle - for example, the atmosphere (3.6 Gt); terrestrial biota (830 Gt); terrestrial soil, detritus and peat (1960 Gt); marine biota (3 Gt); and marine dissolved materials (980 Gt). In fact, the amount of carbon may exceed that in all fossil fuel deposits (5 ?? 103 Gt). Because methane hydrates contain so much methane and occur in the shallow geosphere, they are of interest as a potential resource of natural gas and as a possible source of atmospheric methane released by global warming. As a potential resource, methane hydrates pose both engineering and production problems. As a contributor to a changing global climate, destabilized methane hydrates, particularly those in shallow, nearshore regions of the Arctic Ocean, may have some effect, but this effect will probably be minimal, at least during the next 100 years. ?? 1988.

Controls on tree species stem transport and emission of methane from tropical peatlands

NASA Astrophysics Data System (ADS)

Van Haren, J. L. M.; Cadillo-Quiroz, H.

2016-12-01

Methane emissions from wetlands dominate the global budget and are most likely responsible for the annual variability in emissions. Methane is produced and consumed by microbial activity and then transported to the atmosphere. Plants have been shown to facilitate the transport of methane to significant amounts, but broad surveys across multiple sites have been lacking. We present data collected from multiple peatland and wetland sites south of Iquitos Peru and varzea sites from Santarem Brazil and compare our results to the limited literature of tree stem fluxes. The survey suggests that methane stem emissions might be conserved at the genera level, but not the family level. Large emitters exist in the Aracaceae, Euphorbiaceae, and Sapotaceae, however, other genera within the same families do not emit any methane. Certain genera are consistent pan-tropical methane emitters. The methane emission from the stems decreases generally with height, suggesting a diffusion constrained stem flux. Further constraints on the methane emissions from tree stems involve soil methane concentration and wood density, which is likely an indicator for stem conductivity. Diurnal cycles, flooding level and tree leaves appear to have less of an influence on the tree methane emissions though flooding can lead to a translocation of emissions up the stem to above the flooding level. Methane emissions and the plant transport pathways appear to be constrained at the genera level within wetlands.

Harnessing a methane-fueled, sediment-free mixed microbial community for utilization of distributed sources of natural gas.

PubMed

Marlow, Jeffrey J; Kumar, Amit; Enalls, Brandon C; Reynard, Linda M; Tuross, Noreen; Stephanopoulos, Gregory; Girguis, Peter

2018-06-01

Harnessing the metabolic potential of uncultured microbial communities is a compelling opportunity for the biotechnology industry, an approach that would vastly expand the portfolio of usable feedstocks. Methane is particularly promising because it is abundant and energy-rich, yet the most efficient methane-activating metabolic pathways involve mixed communities of anaerobic methanotrophic archaea and sulfate reducing bacteria. These communities oxidize methane at high catabolic efficiency and produce chemically reduced by-products at a comparable rate and in near-stoichiometric proportion to methane consumption. These reduced compounds can be used for feedstock and downstream chemical production, and at the production rates observed in situ they are an appealing, cost-effective prospect. Notably, the microbial constituents responsible for this bioconversion are most prominent in select deep-sea sediments, and while they can be kept active at surface pressures, they have not yet been cultured in the lab. In an industrial capacity, deep-sea sediments could be periodically recovered and replenished, but the associated technical challenges and substantial costs make this an untenable approach for full-scale operations. In this study, we present a novel method for incorporating methanotrophic communities into bioindustrial processes through abstraction onto low mass, easily transportable carbon cloth artificial substrates. Using Gulf of Mexico methane seep sediment as inoculum, optimal physicochemical parameters were established for methane-oxidizing, sulfide-generating mesocosm incubations. Metabolic activity required >∼40% seawater salinity, peaking at 100% salinity and 35 °C. Microbial communities were successfully transferred to a carbon cloth substrate, and rates of methane-dependent sulfide production increased more than threefold per unit volume. Phylogenetic analyses indicated that carbon cloth-based communities were substantially streamlined and were dominated by Desulfotomaculum geothermicum. Fluorescence in situ hybridization microscopy with carbon cloth fibers revealed a novel spatial arrangement of anaerobic methanotrophs and sulfate reducing bacteria suggestive of an electronic coupling enabled by the artificial substrate. This system: 1) enables a more targeted manipulation of methane-activating microbial communities using a low-mass and sediment-free substrate; 2) holds promise for the simultaneous consumption of a strong greenhouse gas and the generation of usable downstream products; and 3) furthers the broader adoption of uncultured, mixed microbial communities for biotechnological use. © 2018 The Authors. Biotechnology and Bioengineering Published by Wiley Periodicals Inc.

Methane from shallow seep areas of the NW Svalbard Arctic margin does not reach the sea surface

NASA Astrophysics Data System (ADS)

Silyakova, Anna; Greinert, Jens; Jansson, Pär; Ferré, Bénédicte

2015-04-01

Methane, an important greenhouse gas, leaks from large areas of the Arctic Ocean floor. One overall question is how much methane passes from the seabed through the water column, potentially reaching the atmosphere. Transport of methane from the ocean floor into and through the water column depends on many factors such as distribution of gas seeps, microbial methane oxidation, and ambient oceanographic conditions, which may trigger a change in seep activity. From June-July 2014 we investigated dissolved methane in the water column emanating from the "Prins Karls Forland seeps" area offshore the NW Svalbard Arctic margin. Measurements of the spatial variability of dissolved methane in the water column included 65 CTD stations located in a grid covering an area of 30 by 15 km. We repeated an oceanographic transect twice in a week for time lapse studies, thus documenting significant temporal variability in dissolved methane above one shallow seep site (~100 m water depth). Analysis of both nutrient concentrations and dissolved methane in water samples from the same transect, reveal striking similarities in spatial patterns of both dissolved methane and nutrients indicating that microbial community is involved in methane cycling above the gas seepage. Our preliminary results suggest that although methane release can increase in a week's time, providing twice as much dissolved gas to the water column, no methane from a seep reaches the sea surface. Instead it spreads horizontally under the pycnocline. Yet microbial communities react rapidly to the methane supply above gas seepage areas and may also have an important role as an effective filter, hindering methane release from the ocean to the atmosphere during rapid methane ebullition. This study is funded by CAGE (Centre for Arctic Gas Hydrate, Environment and Climate), Norwegian Research Council grant no. 223259.

30 CFR 22.4 - Application procedures and requirements.

Code of Federal Regulations, 2010 CFR

2010-07-01

..., EVALUATION, AND APPROVAL OF MINING PRODUCTS PORTABLE METHANE DETECTORS § 22.4 Application procedures and requirements. (a) Before MSHA will undertake an active investigation leading to approval of any methane...

Origin and migration of hydrocarbon gases and carbon dioxide, Bekes Basin, southeastern Hungary

USGS Publications Warehouse

Clayton, J.L.; Spencer, C.W.; Koncz, I.; Szalay, A.

1990-01-01

The Bekes Basin is a sub-basin within the Pannonian Basin, containing about 7000 m of post-Cretaceous sedimentary rocks. Natural gases are produced from reservoirs (Precambrian to Tertiary in age) located on structural highs around the margins of the basin. Gas composition and stable carbon isotopic data indicate that most of the flammable gases were derived from humic kerogen contained in source rocks located in the deep basin. The depth of gas generation and vertical migration distances were estimated using quantitative source rock maturity-carbon isotope relationships for methane compared to known Neogene source rock maturity-depth relationships in the basin. These calculations indicate that as much as 3500 m of vertical migration has occured in some cases. Isotopically heavy (> - 7 > 0) CO2 is the predominant species present in some shallow reservoirs located on basin-margin structural highs and has probably been derived via long-distance vertical and lateral migration from thermal decompositon of carbonate minerals in Mesozoic and older rocks in the deepest parts of the basin. A few shallow reservoirs (< 2000m) contain isotopically light (-50 to -60%0) methane with only minor amounts of C2+ homologs (< 3% v/v). This methane is probably mostly microbial in origin. Above-normal pressures, occuring at depths greater than 1800 m, are believed to be the principal driving force for lateral and vertical gas migration. These pressures are caused in part by active hydrocarbon generation, undercompaction, and thermal decomposition of carbonates. 

Oceanic methane hydrate: The character of the Blake Ridge hydrate stability zone, and the potential for methane extraction

USGS Publications Warehouse

Max, M.D.; Dillon, William P.

1998-01-01

Oceanic methane hydrates are mineral deposits formed from a crystalline 'ice' of methane and water in sea-floor sediments (buried to less than about 1 km) in water depths greater than about 500 m; economic hydrate deposits are probably restricted to water depths of between 1.5 km and 4 km. Gas hydrates increase a sediment's strength both by 'freezing' the sediment and by filling the pore spaces in a manner similar to water-ice in permafrost. Concentrated hydrate deposits may be underlain by significant volumes of methane gas, and these localities are the most favourable sites for methane gas extraction operations. Seismic reflection records indicate that trapped gas may blow-out naturally, causing large-scale seafloor collapse. In this paper, we consider both the physical properties and the structural integrity of the hydrate stability zone and the associated free gas deposits, with special reference to the Blake Ridge area, SE US offshore, in order to help establish a suitable framework for the safe, efficient, and economic recovery of methane from oceanic gas hydrates. We also consider the potential effects of the extraction of methane from hydrate (such as induced sea-floor faulting, gas venting, and gas-pocket collapse). We assess the ambient pressure effect on the production of methane by hydrate dissociation, and attempt to predict the likelihood of spontaneous gas flow in a production situation.Oceanic methane hydrates are mineral sits formed from a crystalline `ice' of methane and water in sea-floor sediments (buried to less than about 1 km) in water depths greater than about 500 m; economic hydrate deposits are probably restricted to water depths of between 1.5 km and 4 km. Gas hydrates increase a sediment's strength both by `freezing' the sediment and by filling the pore spaces in a manner similar to water-ice in permafrost. Concentrated hydrate deposits may be underlain by significant volumes of methane gas, and these localities are the most favourable sites for methane gas extraction operations. Seismic reflection records indicate that trapped gas may blow-out naturally, causing large-scale seafloor collapse. In this paper, we consider both the physical properties and the structural integrity of the hydrate stability zone and the associated free gas deposits, with special reference to the Blake Ridge area, SE US offshore, in order to help establish a suitable framework for the safe, efficient, and economic recovery of methane from oceanic gas hydrates. We also consider the potential effects of the extraction of methane from hydrate (such as induced sea-floor faulting, gas venting, and gas-pocket collapse). We assess the ambient pressure effect on the production of methane by hydrate dissociation, and attempt to predict the likelihood of spontaneous gas flow in a production situation.

Seismic-reflection surveys of the Blake Ridge, R/V Cape Hatteras, 1992 and 1995; data acquisition, navigation and processing

USGS Publications Warehouse

Taylor, Michael H.; Dillon, William P.; Anton, Christopher H.; Danforth, William W.

1999-01-01

As part of an ongoing study, seismic-reflection profiles were collected over the Blake Ridge in 1992 and 1995, in order to map the volume and distribution of methane hydrate. Faulting and seafloor instabilities appear to be related to methane hydrate processes at the Blake Ridge. Seismic profiles display a prominent collapse structure at the crest, which is inferred to have resulted from the mobilization of sediment that was associated with methane hydrate dissociation.

Tectono-thermal History of the Southern Nenana Basin, Interior Alaska: Implications for Conventional and Unconventional Hydrocarbon Exploration

NASA Astrophysics Data System (ADS)

Dixit, N. C.; Hanks, C. L.

2014-12-01

The Tertiary Nenana basin of Interior Alaska is currently the focus of both new oil exploration and coalbed methane exploitation and is being evaluated as a potential CO2sequestration site. The basin first formed as a Late Paleocene extensional rift with the deposition of oil and gas-prone, coal-bearing non-marine sediments with excellent source potential. Basin inversion during the Early Eocene-Early Oligocene times resulted in folding and erosion of higher stratigraphic levels, forming excellent structural and stratigraphic traps. Initiation of active faulting on its eastern margin in the middle Oligocene caused slow tectonic subsidence that resulted in the deposition of reservoir and seal rocks of the Usibelli Group. Onset of rapid tectonic subsidence in Pliocene that continues to the present-day has provided significant pressure and temperature gradient for the source rocks. Apatite fission-track and vitrinite reflectance data reveals two major paleo-thermal episodes: Late Paleocene to Early Eocene (60 Ma to 54.8 Ma) and Late Miocene to present-day (7 Ma to present). These episodes of maximum paleotemperatures have implications for the evolution of source rock maturity within the basin. In this study, we are also investigating the potential for coalbed methane production from the Late Paleocene coals via injection of CO2. Our preliminary analyses demonstrate that 150 MMSCF of methane could be produced while 33000 tonnes of CO2 per injection well (base case of ~9 years) can be sequestered in the vicinity of existing infrastructure. However, these volumes of sequestered CO2and coal bed methane recovery are estimates and are sensitive to the reservoir's geomechanical and flow properties. Keywords: extensional rift, seismic, subsidence, thermal history, fission track, vitrinite reflectance, coal bed methane, Nenana basin, CO2 sequestration

Association of Ocean Energy Exploitation of Resources Promotion Sea of Japan

NASA Astrophysics Data System (ADS)

Aoyama, C.; Aoyama, S.

2014-12-01

Nine prefectures of 1 local government prefecture of the Sea of Japan side established "Association of Ocean Energy Exploitation of Resources Promotion Sea of Japan" (the following, Association of Sea of Japan) in September, 2012. They support methane hydrate exploitation of resources of the government and aim at the local activation and job creation. Niigata and Hyogo that were members of the association of Sea of Japan carried out a prefecture original methane hydrate investigation. They appeal to the government for development promotion of the government by showing the result. On the other hand, Wakayama located on the Pacific side wants to appeal to the government for the reexamination of the development sea area by showing that outer layer type methane hydrate exists to the sea area that is nearer the landside than the sea area that the government develops. The Independent Institute carried out collaborative investigation each with Niigata, Hyogo and Wakayama in 2013. I show the results of research. In the joint investigation with Niigata, plural plumes　were observed in Mogami trough east slope (from depth of the water 200m 600m) . In the joint investigation with Hyogo, I carried out observation of a methane plume and the structure and the seafloor topography under the sea bottom in Oki east sea area. Furthermore, I performed a piston core ring and gathered five samples and confirmed plural traces of the methane hydrate. In the joint investigation with Wakayama, plural plumes were observed in Shionomisaki canyon (from depth of the water 1,700m 2,200m). There is hardly the report of the plume on the Pacific side so far. Therefore I want to continue observing it in future.

Generation of methane from paddy fields and cattle in India, and its reduction at source

NASA Astrophysics Data System (ADS)

Bandyopadhyay, T. K.; Goyal, P.; Singh, M. P.

Methane (CH4) is a saturated organic gas. About 500 Tg yr -1 methane is generated globally. It is evident that 70% of the total emission have anthropogenic sources. The paddy fields contribute a significant portion of the total methane generated. About 20% of the total methane is generated from the paddy fields. In India, methane efflux rate is negative to 49 mg m -2 hr -1. The mean CH4 flux from Indian paddy fields is calculated to be 4.0 Tgyr -1. Livestock, and in particular ruminants are one of the important sources of methane emission on a global scale. There are two sources of methane emission from live stock: (1) from digestive process of ruminants, (2) from animal wastes. The estimated value of methane emission from digestive process of ruminants in India accounts for 6.47 Tgyr -1, and animal wastes accounts for 1.60 Tgyr -1. Total generation of methane from animals in India is about 8.0 Tg yr -1 . In paddy fields the key of controlling methane emission lies in the control of irrigation water. The methane emission can be decreased drastically if the field is under dry conditions for a few days at the end of tillering. In the case of livestock, reduction of methane emission can be done by (1) increasing the intake of the animal, (2) modifying the composition of the diet, (3) eliminating protozoa in rumen, (4) improving fibre digestion efficiency and (5) inhibiting activity of methanogenic bacteria.

Deep-biosphere methane production stimulated by geofluids in the Nankai accretionary complex

PubMed Central

Kubo, Yusuke; Hoshino, Tatsuhiko; Sakai, Sanae; Arnold, Gail L.; Case, David H.; Lever, Mark A.; Morita, Sumito; Nakamura, Ko-ichi

2018-01-01

Microbial life inhabiting subseafloor sediments plays an important role in Earth’s carbon cycle. However, the impact of geodynamic processes on the distributions and carbon-cycling activities of subseafloor life remains poorly constrained. We explore a submarine mud volcano of the Nankai accretionary complex by drilling down to 200 m below the summit. Stable isotopic compositions of water and carbon compounds, including clumped methane isotopologues, suggest that ~90% of methane is microbially produced at 16° to 30°C and 300 to 900 m below seafloor, corresponding to the basin bottom, where fluids in the accretionary prism are supplied via megasplay faults. Radiotracer experiments showed that relatively small microbial populations in deep mud volcano sediments (102 to 103 cells cm−3) include highly active hydrogenotrophic methanogens and acetogens. Our findings indicate that subduction-associated fluid migration has stimulated microbial activity in the mud reservoir and that mud volcanoes may contribute more substantially to the methane budget than previously estimated. PMID:29928689

Catalytic Oxidation of Methane into Methanol over Copper-Exchanged Zeolites with Oxygen at Low Temperature

PubMed Central

2016-01-01

The direct catalytic conversion of methane to liquid oxygenated compounds, such as methanol or dimethyl ether, at low temperature using molecular oxygen is a grand challenge in C–H activation that has never been met with synthetic, heterogeneous catalysts. We report the first demonstration of direct, catalytic oxidation of methane into methanol with molecular oxygen over copper-exchanged zeolites at low reaction temperatures (483–498 K). Reaction kinetics studies show sustained catalytic activity and high selectivity for a variety of commercially available zeolite topologies under mild conditions (e.g., 483 K and atmospheric pressure). Transient and steady state measurements with isotopically labeled molecules confirm catalytic turnover. The catalytic rates and apparent activation energies are affected by the zeolite topology, with caged-based zeolites (e.g., Cu-SSZ-13) showing the highest rates. Although the reaction rates are low, the discovery of catalytic sites in copper-exchanged zeolites will accelerate the development of strategies to directly oxidize methane into methanol under mild conditions. PMID:27413787

Enhancement of sludge reduction and methane production by removing extracellular polymeric substances from waste activated sludge.

PubMed

Nguyen, Minh Tuan; Mohd Yasin, Nazlina Haiza; Miyazaki, Toshiki; Maeda, Toshinari

2014-12-01

The management of waste activated sludge (WAS) recycling is a concern that affects the development of the future low-carbon society, particularly sludge reduction and biomass utilization. In this study, we investigated the effect of removing extracellular polymeric substances (EPS), which play important roles in the adhesion and flocculation of WAS, on increased sludge disintegration, thereby enhancing sludge reduction and methane production by anaerobic digestion. EPS removal from WAS by ethylenediaminetetraacetic acid (EDTA) significantly enhanced sludge reduction, i.e., 49 ± 5% compared with 27 ± 1% of the control at the end the digestion process. Methane production was also improved in WAS without EPS by 8881 ± 109 CH4 μmol g(-1) dry-weight of sludge. Microbial activity was determined by denaturing gradient gel electrophoresis and real-time polymerase chain reaction, which showed that the hydrolysis and acetogenesis stages were enhanced by pretreatment with 2% EDTA, with a larger methanogenic community and better methane production. Copyright © 2014 Elsevier Ltd. All rights reserved.

Environment-Dependent Distribution of the Sediment nifH-Harboring Microbiota in the Northern South China Sea

PubMed Central

Yang, Jinying; Li, Jing; Luan, Xiwu; Zhang, Yunbo; Gu, Guizhou; Xue, Rongrong; Zong, Mingyue; Klotz, Martin G.

2013-01-01

The South China Sea (SCS), the largest marginal sea in the Western Pacific Ocean, is a huge oligotrophic water body with very limited influx of nitrogenous nutrients. This suggests that sediment microbial N2 fixation plays an important role in the production of bioavailable nitrogen. To test the molecular underpinning of this hypothesis, the diversity, abundance, biogeographical distribution, and community structure of the sediment diazotrophic microbiota were investigated at 12 sampling sites, including estuarine, coastal, offshore, deep-sea, and methane hydrate reservoirs or their prospective areas by targeting nifH and some other functional biomarker genes. Diverse and novel nifH sequences were obtained, significantly extending the evolutionary complexity of extant nifH genes. Statistical analyses indicate that sediment in situ temperature is the most significant environmental factor influencing the abundance, community structure, and spatial distribution of the sediment nifH-harboring microbial assemblages in the northern SCS (nSCS). The significantly positive correlation of the sediment pore water NH4+ concentration with the nifH gene abundance suggests that the nSCS sediment nifH-harboring microbiota is active in N2 fixation and NH4+ production. Several other environmental factors, including sediment pore water PO43− concentration, sediment organic carbon, nitrogen and phosphorus levels, etc., are also important in influencing the community structure, spatial distribution, or abundance of the nifH-harboring microbial assemblages. We also confirmed that the nifH genes encoded by archaeal diazotrophs in the ANME-2c subgroup occur exclusively in the deep-sea methane seep areas, providing for the possibility to develop ANME-2c nifH genes as a diagnostic tool for deep-sea methane hydrate reservoir discovery. PMID:23064334

Tracking Dissolved Methane Concentrations near Active Seeps and Gas Hydrates: Sea of Japan.

NASA Astrophysics Data System (ADS)

Snyder, G. T.; Aoki, S.; Matsumoto, R.; Tomaru, H.; Owari, S.; Nakajima, R.; Doolittle, D. F.; Brant, B.

2015-12-01

A number of regions in the Sea of Japan are known for active gas venting and for gas hydrate exposures on the sea floor. In this investigation we employed several gas sensors mounted on a ROV in order to determine the concentrations of dissolved methane in the water near these sites. Methane concentrations were determined during two-second intervals throughout each ROV deployment during the cruise. The methane sensor deployments were coupled with seawater sampling using Niskin bottles. Dissolved gas concentrations were later measured using gas chromatography in order to compare with the sensor results taken at the same time. The observed maximum dissolved methane concentrations were much lower than saturation values, even when the ROV manipulators were in contact with gas hydrate. Nonetheless, dissolved concentrations did reach several thousands of nmol/L near gas hydrate exposures and gas bubbles, more than two orders of magnitude over the instrumental detection limits. Most of the sensors tested were able to detect dissolved methane concentrations as low as 10 nmol/L which permitted detection when the ROV approached methane plume sites, even from several tens of meters above the sea floor. Despite the low detection limits, the methane sensors showed variable response times when returning to low-background seawater (~5nM). For some of the sensors, the response time necessary to return to background values occurred in a matter of minutes, while for others it took several hours. Response time, as well as detection limit, should be an important consideration when selecting methane sensors for ROV or AUV investigations. This research was made possible, in part, through funding provided by the Japanese Ministry of Economy, Trade and Industry (METI).

In situ Investigation of Methane Dry Reforming on M-CeO 2(111) {M= Co, Ni, Cu} Surfaces: Metal-Support Interactions and the activation of C-H bonds at Low Temperature

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

Rodriguez, Jose A.; Liu, Zongyuan; Lustemberg, Pablo

Studies with a series of M-CeO 2(111) {M= Co, Ni, Cu} surfaces indicate that metal-oxide interactions can play a very important role for the activation of methane and its reforming with CO 2 at relatively low temperatures (600-700 K). Among the systems examined, Co-CeO 2(111) exhibits the best performance and Cu-CeO 2(111) has negligible activity. Experiments using ambient pressure XPS indicate that methane dissociates on Co-CeO2(111), at temperatures as low as 300 K, generating CH x and CO x species on the catalyst surface. The results of density-functional calculations show a reduction in the methane activation barrier from 1.07 eVmore » on Co(0001) to 0.87 eV on Co 2+/CeO 2(111), and to only 0.05 eV on Co 0/CeO 2-x(111). At 700 K, under methane dry reforming conditions, CO 2 dissociates on the oxide surface and a catalytic cycle is established without coke deposition. In conclusion, a significant part of the CH x formed on the Co 0/CeO 2-x (111) catalyst recombines to yield ethane or ethylene.« less

In situ Investigation of Methane Dry Reforming on M-CeO 2(111) {M= Co, Ni, Cu} Surfaces: Metal-Support Interactions and the activation of C-H bonds at Low Temperature

DOE PAGES

Rodriguez, Jose A.; Liu, Zongyuan; Lustemberg, Pablo; ...

2017-08-16

Studies with a series of M-CeO 2(111) {M= Co, Ni, Cu} surfaces indicate that metal-oxide interactions can play a very important role for the activation of methane and its reforming with CO 2 at relatively low temperatures (600-700 K). Among the systems examined, Co-CeO 2(111) exhibits the best performance and Cu-CeO 2(111) has negligible activity. Experiments using ambient pressure XPS indicate that methane dissociates on Co-CeO2(111), at temperatures as low as 300 K, generating CH x and CO x species on the catalyst surface. The results of density-functional calculations show a reduction in the methane activation barrier from 1.07 eVmore » on Co(0001) to 0.87 eV on Co 2+/CeO 2(111), and to only 0.05 eV on Co 0/CeO 2-x(111). At 700 K, under methane dry reforming conditions, CO 2 dissociates on the oxide surface and a catalytic cycle is established without coke deposition. In conclusion, a significant part of the CH x formed on the Co 0/CeO 2-x (111) catalyst recombines to yield ethane or ethylene.« less

Infrared spectroscopy of water clusters isolated in methane matrices: Effects of isotope substitution and annealing

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

Yamakawa, Koichiro, E-mail: koichiro.yamakawa@gakushuin.ac.jp; Ehara, Namika; Ozawa, Nozomi

2016-07-15

Using infrared-active solvents of CH{sub 4} and CD{sub 4} for matrix isolation, we measured infrared spectra of H{sub 2}O and D{sub 2}O clusters at 7 K. The solute-concentration dependence of the spectrum of H{sub 2}O clusters in a CH{sub 4} matrix was investigated and was used for the peak assignment. Annealing procedures were found to promote the size growth of water clusters in methane matrices for all the combinations of (H{sub 2}O, CH{sub 4}), (H{sub 2}O, CD{sub 4}), (D{sub 2}O, CH{sub 4}), and (D{sub 2}O, CD{sub 4}). We also monitored the ν{sub 3} absorption due to methane to find themore » annealing-induced structural change only of solid CH{sub 4}. The matrix effects on the vibrations of the clusters are discussed on the basis of “T{sub c} plots”, where their frequencies are plotted as a function of the square root of the matrix critical temperature, T{sub c}. The obtained plots assure the validity of the assignment of the cluster peaks.« less

Asymmetric hydrogenation of α,β-unsaturated phosphonates with Rh-BisP* and Rh-MiniPHOS catalysts: Scope and mechanism of the reaction

PubMed Central

Gridnev, Ilya D.; Yasutake, Masaya; Imamoto, Tsuneo; Beletskaya, Irina P.

2004-01-01

Optically active 1,2-bis(alkylmethylphosphino)ethanes and bis(alkylmethylphosphino)methanes are unique diphosphine ligands combining the simple molecular structure and P-stereogenic asymmetric environment. This work shows that these ligands exhibit excellent enantioselectivity in rhodium-catalyzed asymmetric hydrogenation of α,β-unsaturated phosphonic acid derivatives. The enantioselective hydrogenation mechanism elucidated by NMR study is also described. PMID:15024119

Inorganic and methane clathrates: Versatility of guest–host compounds for energy harvesting

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

Krishna, Lakshmi; Koh, Carolyn A.

ABSTRACT This review article evaluates the structure–property relations of inorganic clathrates and clathrate hydrates and their potential role in energy harvesting. There is potential cross-fertilization between the two research areas. Guest–host clathrate compounds exhibit unique structural and physical properties, which lead to their versatile roles in energy applications. Prominent classes of clathrate compounds are gas hydrates and inorganic clathrates. That said, there is limited cross-fertilization between the clathrate hydrate and inorganic clathrate communities, with researchers in the respective fields being less informed on the other field. Yet the structures and unique guest–host interactions in both these compounds are common importantmore » features of these clathrates. Common features and procedures can inspire and inform development between the compound classes, which may be important to the technological advancements for the different clathrate materials, e.g., structure characterization techniques and guest–host dynamics in which the “guest” tends to be imprisoned in the host structure, until external forces are applied. Conversely, the diversity in chemical compositions of these two classes of materials leads to the different applications from methane capture and storage to converting waste heat to electricity (thermoelectrics). This article highlights the structural and physical similarities and differences of inorganic and methane clathrates. The most promising state-of-the-art applications of the clathrates are highlighted for harvesting energy from methane (clathrate) hydrate deposits under the ocean and for inorganic clathrates as promising thermoelectric materials.« less

Inorganic and methane clathrates: Versatility of guest–host compounds for energy harvesting

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

Krishna, Lakshmi; Koh, Carolyn A.

2015-01-01

ABSTRACT This review article evaluates the structure–property relations of inorganic clathrates and clathrate hydrates and their potential role in energy harvesting. There is potential cross-fertilization between the two research areas. Guest–host clathrate compounds exhibit unique structural and physical properties, which lead to their versatile roles in energy applications. Prominent classes of clathrate compounds are gas hydrates and inorganic clathrates. That said, there is limited cross-fertilization between the clathrate hydrate and inorganic clathrate communities, with researchers in the respective fields being less informed on the other field. Yet the structures and unique guest–host interactions in both these compounds are common importantmore » features of these clathrates. Common features and procedures can inspire and inform development between the compound classes, which may be important to the technological advancements for the different clathrate materials, e.g., structure characterization techniques and guest–host dynamics in which the “guest” tends to be imprisoned in the host structure, until external forces are applied. Conversely, the diversity in chemical compositions of these two classes of materials leads to the different applications from methane capture and storage to converting waste heat to electricity (thermoelectrics). This article highlights the structural and physical similarities and differences of inorganic and methane clathrates. The most promising state-of-the-art applications of the clathrates are highlighted for harvesting energy from methane (clathrate) hydrate deposits under the ocean and for inorganic clathrates as promising thermoelectric materials.« less

Microscopic Origin of Strain Hardening in Methane Hydrate

PubMed Central

Jia, Jihui; Liang, Yunfeng; Tsuji, Takeshi; Murata, Sumihiko; Matsuoka, Toshifumi

2016-01-01

It has been reported for a long time that methane hydrate presents strain hardening, whereas the strength of normal ice weakens with increasing strain after an ultimate strength. However, the microscopic origin of these differences is not known. Here, we investigated the mechanical characteristics of methane hydrate and normal ice by compressive deformation test using molecular dynamics simulations. It is shown that methane hydrate exhibits strain hardening only if the hydrate is confined to a certain finite cross-sectional area that is normal to the compression direction. For normal ice, it does not present strain hardening under the same conditions. We show that hydrate guest methane molecules exhibit no long-distance diffusion when confined to a finite-size area. They appear to serve as non-deformable units that prevent hydrate structure failure, and thus are responsible for the strain-hardening phenomenon. PMID:27009239

Light-induced diurnal pattern of methane exchange in a boreal forest

NASA Astrophysics Data System (ADS)

Sundqvist, Elin; Crill, Patrick; Mölder, Meelis; Vestin, Patrik; Lindroth, Anders

2013-04-01

Boreal forests represents one third of the Earth's forested land surface area and is a net sink of methane and an important component of the atmospheric methane budget. Methane is oxidized in well-aerated forest soils whereas ponds and bog soils are sources of methane. Besides the microbial processes in the soil also forest vegetation might contribute to methane exchange. Due to a recent finding of methane consumption by boreal plants that correlated with photosynthetic active radiation (PAR), we investigate the impact of PAR on soil methane exchange at vegetated plots on the forest floor. The study site, Norunda in central Sweden, is a 120 years old boreal forest stand, dominated by Scots pine and Norway spruce. We used continuous chamber measurements in combination with a high precision laser gas analyzer (Los Gatos Research), to measure the methane exchange at four different plots in July-November 2009, and April-June 2010. The ground vegetation consisted almost entirely of mosses and blueberry-shrubs. Two of the plots acted as stable sinks of methane whereas the other two plots shifted from sinks to sources during very wet periods. The preliminary results show a clear diurnal pattern of the methane exchange during the growing season, which cannot be explained by temperature. The highest consumption occurs at high PAR levels. The amplitude of the diurnal methane exchange during the growing season is in the order of 10 μmol m-2 h-1. This indicates that besides methane oxidation by methanotrophs in the soil there is an additional removal of methane at soil level by a process related to ground vegetation.

Assessment of Methane Emissions – Impact of Using Natural Gas Engines in Unconventional Resource Development

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

Nix, Andrew; Johnson, Derek; Heltzel, Robert

Researchers at the Center for Alternative Fuels, Engines, and Emissions (CAFEE) completed a multi-year program under DE-FE0013689 entitled, “Assessing Fugitive Methane Emissions Impact Using Natural Gas Engines in Unconventional Resource Development.” When drilling activity was high and industry sought to lower operating costs and reduce emissions they began investing in dual fuel and dedicated natural gas engines to power unconventional well equipment. From a review of literature we determined that the prime-movers (or major fuel consumers) of unconventional well development were the service trucks (trucking), horizontal drilling rig (drilling) engines, and hydraulic stimulation pump (fracturing) engines. Based on early findingsmore » from on-road studies we assessed that conversion of prime movers to operate on natural gas could contribute to methane emissions associated with unconventional wells. As such, we collected significant in-use activity data from service trucks and in-use activity, fuel consumption, and gaseous emissions data from drilling and fracturing engines. Our findings confirmed that conversion of the prime movers to operate as dual fuel or dedicated natural gas – created an additional source of methane emissions. While some gaseous emissions were decreased from implementation of these technologies – methane and CO 2 equivalent emissions tended to increase, especially for non-road engines. The increases were highest for dual fuel engines due to methane slip from the exhaust and engine crankcase. Dedicated natural gas engines tended to have lower exhaust methane emissions but higher CO 2 emissions due to lower efficiency. Therefore, investing in currently available natural gas technologies for prime movers will increase the greenhouse gas footprint of the unconventional well development industry.« less

Methane oxidation in anoxic lake waters

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

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

PubMed

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

2017-11-01

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

Effects of household detergent on anaerobic fermentation of kitchen wastewater from food waste disposer.

PubMed

Lee, K H; Park, K Y; Khanal, S K; Lee, J W

2013-01-15

This study examines the effects of household detergent on anaerobic methane fermentation of wastewater from food waste disposers (FWDs). Anaerobic toxicity assay (ATA) demonstrated that methane production substantially decreased at a higher detergent concentration. The Gompertz three-parameter model fitted well with the ATA results, and both the extent of methane production (M) and methane production rate (R(m)) obtained from the model were strongly affected by the concentration of the detergent. The 50% inhibitory concentration (IC(50)) of the detergent was 603 mg/L based on R(m). Results from fatty acid methyl esters (FAMEs) analysis of microbial culture revealed that deterioration of methane fermentation was attributed to impaired structure of anaerobic microbial membrane due to detergent. This study suggests that wastewater from FWD could be used for methane production, but it is necessary to reduce the concentration of detergent prior to anaerobic fermentation. Copyright © 2012 Elsevier B.V. All rights reserved.

Methane and hydrogen sulfide emissions in UASB reactors treating domestic wastewater.

PubMed

Souza, C L; Chernicharo, C A L; Melo, G C B

2012-01-01

The release of CH(4) and H(2)S in UASB reactors was evaluated with the aim to quantify the emissions from the liquid surfaces (three-phase separator and settler compartment) and also from the reactor's discharge hydraulic structures. The studies were carried out in two pilot- (360 L) and one demo-scale (14 m(3)) UASB reactors treating domestic wastewater. As expected, the release rates were much higher across the gas/liquid interfaces of the three-phase separators (5.4-9.7 kg CH(4) m(-2) d(-1) and 23.0-35.8 g S m(-2) d(-1)) as compared with the quiescent settler surfaces (11.0-17.8 g CH(4) m(-2) d(-1) and 0.21 to 0.37 g S m(-2) d(-1)). The decrease of dissolved methane and dissolved hydrogen sulfide was very large in the discharging hydraulic structures very close to the reactor (>60 and >80%, respectively), largely due to the loss to the atmosphere, indicating that the concentration of these compounds will probably fall to values close to zero in the near downstream structures. The emission factors due to the release of dissolved methane in the discharge structure amounted to around 0.040 g CH(4) g COD(infl)(-1) and 0.060 g CH(4) g COD(rem)(-1), representing around 60% of the methane collected in the three-phase separator.

Structural design of liquid oxygen/liquid methane robotic lander JANUS

NASA Astrophysics Data System (ADS)

Chaidez, Mariana

As the attempt to send humans to Mars has gained momentum in the last decade, the need to find alternative propellants that are safer, less toxic, and yields a better performance has become apparent [1]. Liquid methane and oxygen have emerged as a suitable alternative. In addition, the incorporation of liquid methane/liquid oxygen into the propulsion system has demonstrated an increase in engine performance, as well as a reduction in the volume, size and complexity of the propulsion system. In an attempt to further understand the technologies that are possible to develop using liquid oxygen (LO 2) and liquid methane (LCH4), a preliminary design of a robotic lander JANUS is being completed by the Center for Space Exploration and Technology Research (cSTER). The structural design of the vehicle is important because it acts as the skeleton of the vehicle and dictates the maneuverability of the robotic lander. To develop the structure of the robotic lander, six different design vehicle concepts with varying tank configurations were considered. Finite Element Analysis (FEA) was completed on each model to optimize each vehicle. Trade studies were completed to choose the best design for JANUS. Upon completion of the trade studies the design for the first prototype of JANUS was initiated in which the tank and thrust modules were designed. This thesis will describe the design process for the structural design of the JANUS.

From Black Hole to Hydrate Hole: Gas hydrates, authigenic carbonates and vent biota as indicators of fluid migration at pockmark sites of the Northern Congo Fan

NASA Astrophysics Data System (ADS)

Kasten, S.; Schneider, R.; Spiess, V.; Cruise Participants Of M56b

2003-04-01

A recent high-resolution seismic, echosounder and video survey combined with detailed geological and geochemical sampling of pockmark sites on the Northern Congo Fan was carried out with RV Meteor in November/December 2002 in the frame of the project "CONGO" (BMBF/BEO "Geotechnologien"). These investigations revealed the extensive occurrence of surface and sub-surface gas hydrates as well as characteristic features of fluid venting such as clams (Calyptogena), tube worms (Pogonophera) and huge amounts of authigenic carbonates. In a first approach the patchyness in the occurrence of these features was mapped in relation to pockmark structure and seismic reflectors. Detailed sampling of three pockmarks by gravity corer showed that gas hydrates are present at and close to the sediment surface and often occur as several distinct layers and/or veins intercalated with hemipelagic muds. The depth of the upper boundary of these hydrate-bearing sediments increases from the center towards the edge of the pockmark structures. Pore water concentration profiles of sulfate and methane document the process of anaerobic methane oxidation above the hydrate-bearing layers. For those cores which contained several gas hydrate layers preliminary pore water profiles suggest the occurrence of more than one zone of anaerobic methane oxidation. Authigenic carbonates are found in high abundance, irregularly distributed within the pockmarks close to the sediment surface. These carbonates occur in a wide variety with respect to size, shape, structure and mineralogy. Their formation is associated with high amounts of bicarbonate released by the process of anaerobic methane oxidation. In the gravity cores authigenic carbonates are always present above hydrate-bearing sections. However, the quantities and characteristics of these authigenic minerals in relation to venting and microbial activity as well as to gas hydrate dissociation are not clear yet. Unraveling this relationship will be a major target of further investigation. By means of detailed studies of the sedimentary solid-phase, authigenic carbonates, clam layers and molecular biomarkers we will also try to reconstruct the history of venting and the dynamics of gas hydrate formation and decomposition in the Northern Congo fan area.

Conversion of Methane into Methanol and Ethanol over Nickel Oxide on Ceria-Zirconia Catalysts in a Single Reactor

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

Okolie, Chukwuemeka; Belhseine, Yasmeen F.; Lyu, Yimeng

Direct conversion of methane into alcohols is a promising technology for converting stranded methane reserves into liquids that can be transported in pipelines and upgraded to value-added chemicals. We demonstrate that a catalyst consisting of small nickel oxide clusters supported on ceria-zirconia (NiO/CZ) can selectively oxidize methane to methanol and ethanol in a single, steady-state process at 723 K using O2 as an abundantly available oxidant. The presence of steam is required to obtain alcohols rather than CO2 as the product of catalytic combustion. The unusual activity of this catalyst is attributed to the synergy between the small Lewis acidicmore » NiO clusters and the redox-active CZ support, which also stabilizes the small NiO clusters.« less

Conversion of Methane to Methanol and Ethanol over Nickel Oxide on Ceria-Zirconia Catalysts in a Single Reactor

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

Okolie, Chukwuemeka; Belhseine, Yasmeen F.; Lyu, Yimeng

Here, the conversion of methane into alcohols under moderate reaction conditions is a promising technology for converting stranded methane reserves into liquids that can be transported in pipelines and upgraded to value-added chemicals. We demonstrate that a catalyst consisting of small nickel oxide clusters supported on ceria-zirconia (NiO/CZ) can convert methane to methanol and ethanol in a single, steady-state process at 723 K using O 2 as an abundantly available oxidant. The presence of steam is required to obtain alcohols rather than CO 2 as the product of catalytic combustion. The unusual activity of this catalyst is attributed to themore » synergy between the small Lewis acidic NiO clusters and the redox-active CZ support, which also stabilizes the small NiO clusters.« less

Conversion of Methane to Methanol and Ethanol over Nickel Oxide on Ceria-Zirconia Catalysts in a Single Reactor

DOE PAGES

Okolie, Chukwuemeka; Belhseine, Yasmeen F.; Lyu, Yimeng; ...

2017-08-08

Here, the conversion of methane into alcohols under moderate reaction conditions is a promising technology for converting stranded methane reserves into liquids that can be transported in pipelines and upgraded to value-added chemicals. We demonstrate that a catalyst consisting of small nickel oxide clusters supported on ceria-zirconia (NiO/CZ) can convert methane to methanol and ethanol in a single, steady-state process at 723 K using O 2 as an abundantly available oxidant. The presence of steam is required to obtain alcohols rather than CO 2 as the product of catalytic combustion. The unusual activity of this catalyst is attributed to themore » synergy between the small Lewis acidic NiO clusters and the redox-active CZ support, which also stabilizes the small NiO clusters.« less

Exploratory study on the effects of novel diamine curing agents and isocyanate precursors on the properties of new epoxy and urethane adhesives

NASA Technical Reports Server (NTRS)

Glasgow, D. G.

1976-01-01

The effects of novel aromatic diamine structures on the adhesive properties of epoxy and polyurethane adhesives were studied. Aromatic diamines based on benzophenone and diphenyl-methane isomers were evaluated as curing agents for epoxy resins and benzophenone and diphenyl-methane based diamine isomers were evaluated as curing agents for polyurethane adhesives. Polyurethane adhesives were prepared based on m, m prime-diisocyanato-diphenyl-methane and m, m prime-diisocyanato-benzophenone. The m, m prime-diisocayanato-diphenyl-methane based adhesive had properties comparable to state-of-the-art adhesives. The m, m prime-diisocyanato-benzophenone based adhesive was extremely reactive.

Methane rescues retinal ganglion cells and limits retinal mitochondrial dysfunction following optic nerve crush.

PubMed

Wang, Ruobing; Sun, Qinglei; Xia, Fangzhou; Chen, Zeli; Wu, Jiangchun; Zhang, Yuelu; Xu, Jiajun; Liu, Lin

2017-06-01

Secondary degeneration is a common event in traumatic central nervous system disorders, which involves neuronal apoptosis and mitochondrial dysfunction. Exogenous methane exerts the therapeutic effects in many organ injury. Our study aims to investigate the potential neuroprotection of methane in a rat model of optic nerve crush (ONC). Adult male Sprague-Dawley rats were subjected to ONC and administrated intraperitoneally with methane-saturated or normal saline (10 ml/kg) once per day for one week after ONC. The retinal ganglion cells (RGCs) density was assessed by hematoxylin and eosin staining and Fluoro-Gold retrogradely labeling. Visual function was evaluated by flash visual evoked potentials (FVEP). The retinal apoptosis was measured by terminal-deoxy-transferase-mediated dUTP nick end labeling (TUNEL) assay and the expression of apoptosis-related factors, such as phosphorylated Bcl-2-associated death promoter (pBAD), phosphorylated glycogen synthase kinase-3β (pGSK-3β), Bcl-2 associated X protein (Bax) and Bcl-2 extra large (Bcl-xL). Retinal mitochondrial function was assessed by the mRNA expressions of peroxisome proliferator-activated receptor gamma coactivator-1α (PGC-1α), nuclear respiratory factor 1 (NRF1) and mitochondrial transcription factor A (TFAM), the mitochondrial DNA (mtDNA) copy number, citrate synthase activity and ATP content. Methane treatment significantly improved the RGC loss and visual dysfunction following ONC. As expected, methane also remarkably inhibited the retinal neural apoptosis, such as the fewer TUNEL-positive cells in ganglion cell layer, accompanied by the up-regulations of anti-apoptotic factors (pGSK-3β, pBAD, Bcl-xL) and the down-regulation of pro-apoptotic factor (Bax). Furthermore, methane treatment suppressed up-regulations of critical mitochondrial components (PGC-1α, NRF1 and TFAM) mRNA and mtDNA copy number, as well as improved the reduction of functional mitochondria markers, including citrate synthase activity and ATP content, in retinas with ONC. Taken together, methane treatment promotes RGC survival and limits retinal mitochondrial dysfunction against ONC insult. Methane can be a potential neuroprotective agent for traumatic and glaucomatous neurodegeneration. Copyright © 2017. Published by Elsevier Ltd.

The Application of Methane Clumped Isotope Measurements to Determine the Source of Large Methane Seeps in Alaskan Lakes

NASA Astrophysics Data System (ADS)

Douglas, P. M.; Stolper, D. A.; Eiler, J. M.; Sessions, A. L.; Walter Anthony, K. M.

2014-12-01

Natural methane emissions from the Arctic present an important potential feedback to global warming. Arctic methane emissions may come from either active microbial sources or from deep fossil reservoirs released by the thawing of permafrost and melting of glaciers. It is often difficult to distinguish between and quantify contributions from these methane sources based on stable isotope data. Analyses of methane clumped isotopes (isotopologues with two or more rare isotopes such as 13CH3D) can complement traditional stable isotope-based classifications of methane sources. This is because clumped isotope abundances (for isotopically equilibrated systems) are a function of temperature and can be used to identify pathways of methane generation. Additionally, distinctive effects of mixing on clumped isotope abundances make this analysis valuable for determining the origins of mixed gasses. We find large variability in clumped isotope compositions of methane from seeps in several lakes, including thermokarst lakes, across Alaska. At Lake Sukok in northern Alaska we observe the emission of dominantly thermogenic methane, with a formation temperature of at least 100° C. At several other lakes we find evidence for mixing between thermogenic methane and biogenic methane that forms in low-temperature isotopic equilibrium. For example, at Eyak Lake in southeastern Alaska, analysis of three methane samples results in a distinctive isotopic mixing line between a high-temperature end-member that formed between 100-170° C, and a biogenic end-member that formed in isotopic equilibrium between 0-20° C. In this respect, biogenic methane in these lakes resembles observations from marine gas seeps, oil degradation, and sub-surface aquifers. Interestingly, at Goldstream Lake in interior Alaska, methane with strongly depleted clumped-isotope abundances, indicative of disequilibrium gas formation, is found, similar to observations from methanogen culture experiments.

Reducing Open Cell Landfill Methane Emissions with a Bioactive Alternative Daily

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

Helene Hilger; James Oliver; Jean Bogner

2009-03-31

Methane and carbon dioxide are formed in landfills as wastes degrade. Molecule-for-molecule, methane is about 20 times more potent than carbon dioxide at trapping heat in the earth's atmosphere, and thus, it is the methane emissions from landfills that are scrutinized. For example, if emissions composed of 60% methane and 40% carbon dioxide were changed to a mix that was 40% methane and 60% carbon dioxide, a 30% reduction in the landfill's global warming potential would result. A 10% methane, 90% carbon dioxide ratio will result in a 75% reduction in global warming potential compared to the baseline. Gas collectionmore » from a closed landfill can reduce emissions, and it is sometimes combined with a biocover, an engineered system where methane oxidizing bacteria living in a medium such as compost, convert landfill methane to carbon dioxide and water. Although methane oxidizing bacteria merely convert one greenhouse gas (methane) to another (carbon dioxide), this conversion can offer significant reductions in the overall greenhouse gas contribution, or global warming potential, associated with the landfill. What has not been addressed to date is the fact that methane can also escape from a landfill when the active cell is being filled with waste. Federal regulations require that newly deposited solid waste to be covered daily with a 6 in layer of soil or an alternative daily cover (ADC), such as a canvas tarp. The aim of this study was to assess the feasibility of immobilizing methane oxidizing bacteria into a tarp-like matrix that could be used for alternative daily cover at open landfill cells to prevent methane emissions. A unique method of isolating methanotrophs from landfill cover soil was used to create a liquid culture of mixed methanotrophs. A variety of prospective immobilization techniques were used to affix the bacteria in a tarp-like matrix. Both gel encapsulation of methanotrophs and gels with liquid cores containing methanotrophs were readily made but prone to rapid desiccation. Bacterial adsorption onto foam padding, natural sponge, and geotextile was successful. The most important factor for success appeared to be water holding capacity. Prototype biotarps made with geotextiles plus adsorbed methane oxidizing bacteria were tested for their responses to temperature, intermittent starvation, and washing (to simulate rainfall). The prototypes were mesophilic, and methane oxidation activity remained strong after one cycle of starvation but then declined with repeated cycles. Many of the cells detached with vigorous washing, but at least 30% appeared resistant to sloughing. While laboratory landfill simulations showed that four-layer composite biotarps made with two different types of geotextile could remove up to 50% of influent methane introduced at a flux rate of 22 g m{sup -2} d{sup -1}, field experiments did not yield high activity levels. Tests revealed that there were high hour-to-hour flux variations in the field, which, together with frequent rainfall events, confounded the field testing. Overall, the findings suggest that a methanotroph embedded biotarp appears to be a feasible strategy to mitigate methane emission from landfill cells, although the performance of field-tested biotarps was not robust here. Tarps will likely be best suited for spring and summer use, although the methane oxidizer population may be able to shift and adapt to lower temperatures. The starvation cycling of the tarp may require the capacity for intermittent reinoculation of the cells, although it is also possible that a subpopulation will adapt to the cycling and become dominant. Rainfall is not expected to be a major factor, because a baseline biofilm will be present to repopulate the tarp. If strong performance can be achieved and documented, the biotarp concept could be extended to include interception of other compounds beyond methane, such as volatile aromatic hydrocarbons and chlorinated solvents.« less

Applications for activated carbons from waste tires: Natural gas storage and air pollution control

USGS Publications Warehouse

Brady, T.A.; Rostam-Abadi, M.; Rood, M.J.

1996-01-01

Natural gas storage for natural gas vehicles and the separation and removal of gaseous contaminants from gas streams represent two emerging applications for carbon adsorbents. A possible precursor for such adsorbents is waste tires. In this study, activated carbon has been developed from waste tires and tested for its methane storage capacity and SO2 removal from a simulated flue-gas. Tire-derived carbons exhibit methane adsorption capacities (g/g) within 10% of a relatively expensive commercial activated carbon; however, their methane storage capacities (Vm/Vs) are almost 60% lower. The unactivated tire char exhibits SO2 adsorption kinetics similar to a commercial carbon used for flue-gas clean-up. Copyright ?? 1996 Elsevier Science Ltd.

Aragonite precipitation induced by anaerobic oxidation of methane in shallow-water seeps, Tyrrhenian Sea, Italy

NASA Astrophysics Data System (ADS)

Wiedling, Johanna; Kuhfuß, Hanna; Lott, Christian; Böttcher, Michael E.; Lichtschlag, Anna; Wegener, Gunter; Deusner, Christian; Bach, Wolfgang; Weber, Miriam

2014-05-01

In the shallow-water organic-poor silicate sands off the West coast of Elba, Italy, we found aragonite precipitates within a radius of 10 cm to methane seeps in 20 - 40 cm sediment depth. The shallow seep site was mapped by SCUBA diving and in an area of 100 m2 nine gas emission spots were observed. The gas emission, containing 73 Vol. % methane, was measured to be 0.72 L m-2 d-1. Findings of anaerobic methane oxidizing archea (ANME 1, 2, 2a, 2b) and sulphate reducing bacteria (SRB) as well as in vitro rate measurements of anaerobic oxidation of methane (AOM) with a maximum of 67 ± 7 nmol CH4 cm-3 d-1 led to the hypothesis that carbonate precipitation is coupled to these microbial processes. Porewater analysis showed elevated concentrations of dissolved inorganic carbon (DIC) (up to 15.5 mmol L-1) and hydrogen sulfide (up to 6.6 mmol L-1). The presence of bicarbonate and the ambient temperature (14 - 25 ° C) facilitate the precipitation of needle-shaped aragonite. Oxygen isotope compositions of the mineral are consistent with the ambient temperatures and may indicate a recent diagenetic formation of this mineral. Although precipitation should not be preserved in these sandy permeable sediments, influenced by seasonality, wave action, and fluid flow, we found up to 10-50 cm3 irregular pieces of cemented sand grains, very often encrusting dead seagrass rhizomes. Commonly known carbonate structures, especially from the deep sea, are chimneys, mounds, hardgrounds and nodules. These structures are well known from seep and vent sites, usually showing the same range of stable carbon isotope fractionation as the escaping methane. The permeable sediment at the Elba site possibly allows the gas to frequently change its pathway to the sediment surface and thus precipitation can occure at several spots and more irregular than in the reported sites. Preservation of precipitates, however, requires sufficient authigenic aragonite to be formed before fluid dynamics changed the flow path. The Elba aragonites, showed a carbon isotope signature of -14.9o vs. VPDB, mirroring the isotopic signature of the pore-water DIC at this sediment depth. Similar δ13C-compositions of -15.3o were obtained for the discharging methane, giving room for discussion about the origin of the gas. We suppose that AOM is the main driver for aragonite precipitation in the permeable sands at the shallow-water seeps because of (1) very low organic carbon contents (0.5 mg/g) in the sediment, (2) 13C enrichment in the methane gas, (3) elevated DIC concentrations in the pore-water, and (4) AOM in vitro activity. Thus, aragonite precipitates of the seep site near Elba may represent a unique system to study ongoing abiogenic seep carbonate formation at shallow depth as a modern analogue for seep carbonates occurring in the geological record.

Catalysis of carbon monoxide methanation by deep sea manganate minerals

NASA Technical Reports Server (NTRS)

Cabrera, A. L.; Maple, M. B.; Arrhenius, G.

1990-01-01

The catalytic activity of deep sea manganese nodule minerals for the methanation of carbon monoxide was measured with a microcatalytic technique between 200 and 460 degrees C. The manganate minerals were activated at 248 degrees C by immersion into a stream of hydrogen in which pulses of carbon monoxide were injected. Activation energies for the methanation reaction and hydrogen desorption from the manganate minerals were obtained and compared with those of pure nickel. Similar energy values indicate that the activity of the nodule materials for the reaction appears to be related to the amount of reducible transition metals present in the samples (ca. 11 wt.-%). Since the activity of the nodule minerals per gram is comparable to that of pure nickel, most of the transition metal ions located between manganese oxide layers appear to be exposed and available to catalyze the reaction.

Physical disturbance to ecological niches created by soil structure alters community composition of methanotrophs.

PubMed

Kumaresan, Deepak; Stralis-Pavese, Nancy; Abell, Guy C J; Bodrossy, Levente; Murrell, J Colin

2011-10-01

Aggregates of different sizes and stability in soil create a composite of ecological niches differing in terms of physico-chemical and structural characteristics. The aim of this study was to identify, using DNA-SIP and mRNA-based microarray analysis, whether shifts in activity and community composition of methanotrophs occur when ecological niches created by soil structure are physically perturbed. Landfill cover soil was subject to three treatments termed: 'control' (minimal structural disruption), 'sieved' (sieved soil using 2 mm mesh) and 'ground' (grinding using mortar and pestle). 'Sieved' and 'ground' soil treatments exhibited higher methane oxidation potentials compared with the 'control' soil treatment. Analysis of the active community composition revealed an effect of physical disruption on active methanotrophs. Type I methanotrophs were the most active methanotrophs in 'sieved' and 'ground' soil treatments, whereas both Type I and Type II methanotrophs were active in the 'control' soil treatment. The result emphasize that changes to a particular ecological niche may not result in an immediate change to the active bacterial composition and change in composition will depend on the ability of the bacterial communities to respond to the perturbation. © 2011 Society for Applied Microbiology and Blackwell Publishing Ltd.

Ni nanoparticles and the Kirkendall effect in dry reforming of methane

NASA Astrophysics Data System (ADS)

Pegios, N.; Bliznuk, V.; Theofanidis, S. A.; Galvita, V. V.; Marin, G. B.; Palkovits, R.; Simeonov, K.

2018-09-01

In this study we report a simple preparation technique for Ni/γ-Al2O3 catalysts for the dry reforming of methane (DRM) at 800 °C to produce CO and H2 (synthesis gas). Hard-templating with low and high surface area activated carbon was applied. The produced synthesis gas exhibited a low product ratio of H2:CO [0.04-0.12], due to reverse water-gas shift. After 75 h time on stream (TOS) minimal deactivation of the catalyst could be observed. A rather unusual activity evolution was found involving a sequence of minimum-maximum-plateau. A scheme was suggested, explaining the activity evolution based on the Ni-nanoparticle positioning from being bare or encapsulated by Al2O3. The Al2O3 shell cracks and undergoes restructuring during reaction making more active sites available for the reaction. Superior metal dispersion was achieved with average nickel nanoparticle size at 4.9 ± 1.3 nm. The sintering mechanism was also investigated. Surprisingly, hollow nickel nanoparticles were observed at 25 h TOS due to the nanoscale Kirkendall effect. This diffusion phenomenon between the core, Ni0, and the outer shell, NiO, (Ni2+) lead to pronounced structural and morphological changes of the catalyst.

Clathrate hydrates as possible source of episodic methane releases on Mars

NASA Astrophysics Data System (ADS)

Karatekin, Özgür; Gloesener, Elodie; Temel, Orkun

2017-04-01

Methane has been shown to vary with location and time in the Martian atmosphere, with abundances of up to tens of parts-per-billion by volume (ppbv). Since methane is short-lived on geological time scales, its presence implies the existence of an active, current source of methane that is yet to be understood. In this study we investigate the destabilization of subsurface reservoirs of clathrate hydrates as a possible geological source of methane. Clathrate hydrates are crystalline compounds constituted by cages of hydrogen-bonded water molecules, inside of which guest gas molecules are trapped. We show the present-day maps of methane clathrate stability zones, in particular in the vicinity of Gale Crater where the Sample Analysis at Mars (SAM) suite on the Curiosity rover has made in situ measurements of atmospheric methane, during more than 3 years. Curiosity has observed spikes of elevated methane levels of 7 ppbv on four sequential observations over a 2-month period. The possibility of episodic releases consistent with curiosity observations from a subsurface clathrate source, is investigated using a gas transport through porous Martian regolith considering different depths of reservoirs. Transport of the released methane spike into the atmosphere is simulated using the PlanetWRF model.

Mobility and persistence of methane in groundwater in a controlled-release field experiment

NASA Astrophysics Data System (ADS)

Cahill, Aaron G.; Steelman, Colby M.; Forde, Olenka; Kuloyo, Olukayode; Emil Ruff, S.; Mayer, Bernhard; Ulrich Mayer, K.; Strous, Marc; Cathryn Ryan, M.; Cherry, John A.; Parker, Beth L.

2017-03-01

Expansion of shale gas extraction has fuelled global concern about the potential impact of fugitive methane on groundwater and climate. Although methane leakage from wells is well documented, the consequences on groundwater remain sparsely studied and are thought by some to be minor. Here we present the results of a 72-day methane gas injection experiment into a shallow, flat-lying sand aquifer. In our experiment, although a significant fraction of methane vented to the atmosphere, an equal portion remained in the groundwater. We find that methane migration in the aquifer was governed by subtle grain-scale bedding that impeded buoyant free-phase gas flow and led to episodic releases of free-phase gas. The result was lateral migration of gas beyond that expected by groundwater advection alone. Methane persisted in the groundwater zone despite active growth of methanotrophic bacteria, although much of the methane that vented into the vadose zone was oxidized. Our findings demonstrate that even small-volume releases of methane gas can cause extensive and persistent free phase and solute plumes emanating from leaks that are detectable only by contaminant hydrogeology monitoring at high resolution.

Evidence of Methane Outgassing During MIS3 in the Bering Sea

NASA Astrophysics Data System (ADS)

Cook, M. S.; Keigwin, L. D.

2005-12-01

There are multiple negative excursions in planktonic and benthic foraminifer δ13C in a core from 1467m in the southeast Bering Sea. These excursions occur episodically during the last glacial period, and may coincide with Dansgaard-Oeschger (D-O) events. Measured foraminifer δ13C during the excursions is as low as -14‰ and are probably the result of overgrowths of diagenetic calcium carbonate. We estimate overgrowth δ13C is -23‰, and hypothesize that the occurrence of overgrowths is associated with anaerobic oxidation of biogenic methane. The likely pressure and temperature conditions at this site and during the last glacial period were well within the zone of methane-hydrate stability, so the source of methane is probably not from destabilization of methane hydrate at this depth. The methane may have originated from increased in-situ methanogenesis resulting from greater burial of organic carbon, or from destabilization of methane hydrate at shallower sites near the methane-hydrate stability threshold. Both these scenarios could be active, consistent with the ``Clathrate Gun Hypothesis'' (Kennett et al., 2003), in which there is widespread destabilization of marine methane hydrates during D-O events, where methane gas both is oxidized within the water column and escapes to the atmosphere.

Characterisation of methane isotope composition over the Silesian Coal Basin, Poland.

NASA Astrophysics Data System (ADS)

Necki, Jaroslaw; Zimnoch, Miroslaw; Jasek, Alina; Chmura, Lukasz; Galkowski, Michal; Wolkowicz, Wojciech

2017-04-01

Methane emissions from Silesian Coal Basin (SCB), one of European regions associated with coal excavation industry constitute an important component of the continental anthropogenic flux of this gas into the atmosphere. It is estimated by different methodology that SCB is responsible for between 450 - 1350 Gg CH4 of atmospheric methane releases annually, making it one of the most significant sources of this gas in Europe. In this region, active or restructuring coal mining methane emissions may lead to elevated concentrations of this gas in near-ground atmosphere. Observed methane mixing ratio in pbl during nighttime over the specific areas of SCB is elevated by up to 50ppm with carbon isotope source ratio -46‰ to -52‰ with occasionally lighter methane (-58) form particular coal beds. Numbers were derived from direct measurement of samples taken from ventilation shafts (concentration 1.5% to 4% of CH4, subsequently diluted to 2ppm with zero air and measured by Picarro CRDS analyzer). Measurements of CH4 mixing ratios and isotopic composition were performed along latitudinal transects (ca. 50oN), typically extending from ca. 15oE to 20oE, covering the Upper Silesia and bordering regions on the public roads in vicinity of the mine ventilation shafts. Apart from CH4 emissions associated with coal production, other sources of anthropogenic methane are also active over SCB. These include city gas networks leakages that enrich the air by up to 5ppm (in the city centers, carbon isotope ratio on average -52). Most of the numerous landfills, not yet equipped with appropriate CH4 uptake installations, also contribute to substantial anthropogenic flux of this gas to the atmosphere. Values of methane mixing ratio recorded during the in-situ measurements close to the landfill sites reached 15ppm (with carbon isotope ratio -56‰ to -60). The transects of methane concentration over Silesian area, assisted by analysis of its stable isotopic composition has been performed in all of the locations where active and closed mining shafts are positioned, and most of the landfills and cities under the different meteorological and synoptic conditions to provide a base for efficient future verification of methane inventory over SCB. Project will be continued with MEMO2 ITN H2020.

Methanotrophs and methanogens in masonry

PubMed

Kussmaul; Wilimzig; Bock

1998-11-01

Methanotrophs were present in 48 of 225 stone samples which were removed from 19 historical buildings in Germany and Italy. The average cell number of methanotrophs was 20 CFU per g of stone, and their activities ranged between 11 and 42 pmol of CH4 g of stone-1 day-1. Twelve strains of methane-oxidizing bacteria were isolated. They belonged to the type II methanotrophs of the genera Methylocystis, Methylosinus, and Methylobacterium. In masonry, growth substrates like methane or methanol are available in very low concentrations. To determine if methane could be produced by the stone at rates sufficient to support growth of methanotrophs, methane production by stone samples under nonoxic conditions was examined. Methane production of 0.07 to 215 nmol of CH4 g of stone-1 day-1 was detected in 23 of 47 stone samples examined. This indicated the presence of the so-called "mini-methane"-producing bacteria and/or methanogenic archaea. Methanotrophs occurred in nearly all samples which showed methane production. This finding indicated that methanotrophs depend on biogenic methane production in or on stone surfaces of historical buildings.

Methane on Mars: Measurements and Possible Origins

NASA Technical Reports Server (NTRS)

Mumma, Michael J.; Villanueva, Geronimo L.; Novak, Robert E.; Radeva, Yana L.; Kaufl, H. Ulrich; Tokunaga, Alan; Encrenaz, Therese; Hartogh, Paul

2011-01-01

The presence of abundant methane in Earth's atmosphere (1.6 parts per million) requires sources other than atmospheric chemistry. Living systems produce more than 90% of Earth's atmospheric methane; the balance is of geochemical origin. On Mars, methane has been sought for nearly 40 years because of its potential biological significance, but it was detected only recently [1-5]. Its distribution on the planet is found to be patchy and to vary with time [1,2,4,5], suggesting that methane is released recently from the subsurface in localized areas, and is then rapidly destroyed [1,6]. Before 2000, searchers obtained sensitive upper limits for methane by averaging over much of Mars' dayside hemisphere, using data acquired by Marsorbiting spacecraft (Mariner 9) and Earth-based observatories (Kitt Peak National Observatory, Canada- France-Hawaii Telescope, Infrared Space Observatory). These negative findings suggested that methane should be searched at higher spatial resolution since the local abundance could be significantly larger at active sites. Since 2001, searches for methane have emphasized spatial mapping from terrestrial observatories and from Mars orbit (Mars Express).

Steam reforming of simulated bio-oil on K-Ni-Cu-Mg-Ce-O/Al 2O 3: The effect of K

DOE PAGES

Yu, Ning; Rahman, Muhammad Mahfuzur; Chen, Jixiang; ...

2018-04-10

Steam reforming of simulated bio-oil (ethanol, acetone, phenol, and acetic acid) and phenol has been studied on K-Ni-Cu-Mg-Ce-O/Al 2O 3 composite catalysts. Complementary characterization techniques, such as nitrogen sorption, XRD, H 2-TPR, H 2-TPD, CO-TPD, CO-DRIFTS, and in situ XPS, were used to correlate surface structure and functionality to catalytic performance of potassium (K) doped catalysts. K doping of the Ni-Cu-Mg-Ce-O/Al 2O 3 catalyst created a Ni°/Ni 2+ mixed active phase, which not only enhanced steam reforming activity, but also suppressed the methanation reaction. In addition, K doping changed the surface acid-basic properties of the catalyst, which instead favor themore » gasifcation and water-gas shift reactions. In conclusion, with the combination of these effects, K doping of Ni-Cu-Mg-Ce-O/Al 2O 3 catalysts led to higher C1 yield and much lower methane formation, favoring hydrogen production in steam reforming of both phenol and simulated bio-oil.« less

Steam reforming of simulated bio-oil on K-Ni-Cu-Mg-Ce-O/Al 2O 3: The effect of K

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

Yu, Ning; Rahman, Muhammad Mahfuzur; Chen, Jixiang

Steam reforming of simulated bio-oil (ethanol, acetone, phenol, and acetic acid) and phenol has been studied on K-Ni-Cu-Mg-Ce-O/Al 2O 3 composite catalysts. Complementary characterization techniques, such as nitrogen sorption, XRD, H 2-TPR, H 2-TPD, CO-TPD, CO-DRIFTS, and in situ XPS, were used to correlate surface structure and functionality to catalytic performance of potassium (K) doped catalysts. K doping of the Ni-Cu-Mg-Ce-O/Al 2O 3 catalyst created a Ni°/Ni 2+ mixed active phase, which not only enhanced steam reforming activity, but also suppressed the methanation reaction. In addition, K doping changed the surface acid-basic properties of the catalyst, which instead favor themore » gasifcation and water-gas shift reactions. In conclusion, with the combination of these effects, K doping of Ni-Cu-Mg-Ce-O/Al 2O 3 catalysts led to higher C1 yield and much lower methane formation, favoring hydrogen production in steam reforming of both phenol and simulated bio-oil.« less

Low archaeal diversity linked to subseafloor geochemical processes at the Lost City Hydrothermal Field, Mid-Atlantic Ridge.

PubMed

Schrenk, Matthew O; Kelley, Deborah S; Bolton, Sheryl A; Baross, John A

2004-10-01

The recently discovered Lost City Hydrothermal Field (LCHF) represents a new type of submarine hydrothermal system driven primarily by exothermic serpentinization reactions in ultramafic oceanic crust. Highly reducing, alkaline hydrothermal environments at the LCHF produce considerable quantities of hydrogen, methane and organic molecules through chemo- and biosynthetic reactions. Here, we report the first analyses of microbial communities inhabiting carbonate chimneys awash in warm, high pH fluids at the LCHF and the predominance of a single group of methane-metabolizing Archaea. The predominant phylotype, related to the Methanosarcinales, formed tens of micrometre-thick biofilms in regions adjacent to hydrothermal flow. Exterior portions of active structures harboured a diverse microbial community composed primarily of filamentous Eubacteria that resembled sulphide-oxidizing species. Inactive samples, away from regions of hydrothermal flow, contained phylotypes related to pelagic microorganisms. The abundance of organisms linked to the volatile chemistry at the LCHF hints that similar metabolic processes may operate in the subseafloor. These results expand the range of known geological settings that support biological activity to include submarine hydrothermal systems that are not dependent upon magmatic heat sources.

Possible roles of uncultured archaea in carbon cycling in methane-seep sediments

NASA Astrophysics Data System (ADS)

Yoshinaga, Marcos Y.; Lazar, Cassandre S.; Elvert, Marcus; Lin, Yu-Shih; Zhu, Chun; Heuer, Verena B.; Teske, Andreas; Hinrichs, Kai-Uwe

2015-09-01

Studies on microbial carbon cycling uniformly confirm that anaerobic methane-oxidizing archaea (ANME) and sulfate-reducing bacteria represent the dominant and most active fraction of the sedimentary microbial community in methane-seep sediments. However, little is known about other frequently observed and abundant microbial taxa, their role in carbon cycling and association with the anaerobic oxidation of methane (AOM). Here, we provide a comprehensive characterization of stable carbon isotopes (δ13C) from several intact polar lipid (IPL) classes and metabolite pools in a downcore profile at a cold seep within the oxygen minimum zone off Pakistan. We aimed to evaluate microbial carbon metabolism using IPLs in relation to redox conditions, metabolites and 16S rRNA gene libraries. The 13C-depleted signature of carbon pools and microbial metabolites in pore waters (e.g., dissolved inorganic carbon, lactate and acetate) demonstrated high accumulation of AOM-associated biomass and subsequent turnover thereof. ANMEs accounted for a small fraction of the archaeal 16S rRNA gene survey, whereas sequences of other uncultured benthic archaea dominated the clone libraries, particularly the Marine Benthic Group D. On the basis of lipid diversity and carbon isotope information, we suggest that structurally diverse phospho- and glycolipids, including the recently identified unsaturated tetraethers that are particularly abundant in this setting, are likely derived from archaea other than ANMEs. Through the evaluation of δ13C values of individual IPL, our results indicate heterotrophy as a possible metabolic pathway of archaea in these AOM-dominated sediments.

Evaluating the biogas potential of the dry fraction from pretreatment of food waste from households

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

Murto, Marika, E-mail: marika.murto@biotek.lu.se; Björnsson, Lovisa, E-mail: lovisa.bjornsson@miljo.lth.se; Environmental and Energy Systems Studies, Lund University, P.O. Box 118, SE-221 00 Lund

2013-05-15

Highlights: ► A novel approach for biogas production from a waste fraction that today is incinerated. ► Biogas production is possible in spite of the impurities of the waste. ► Tracer studies are applied in a novel way. ► Structural material is needed to improve the flow pattern of the waste. ► We provide a solution to biological treatment for the complex waste fraction. - Abstract: At the waste handling company NSR, Helsingborg, Sweden, the food waste fraction of source separated municipal solid waste is pretreated to obtain a liquid fraction, which is used for biogas production, and a drymore » fraction, which is at present incinerated. This pretreatment and separation is performed to remove impurities, however also some of the organic material is removed. The possibility of realising the methane potential of the dry fraction through batch-wise dry anaerobic digestion was investigated. The anaerobic digestion technique used was a two-stage process consisting of a static leach bed reactor and a methane reactor. Treatment of the dry fraction alone and in a mixture with structural material was tested to investigate the effect on the porosity of the leach bed. A tracer experiment was carried out to investigate the liquid flow through the leach beds, and this method proved useful in demonstrating a more homogenous flow through the leach bed when structural material was added. Addition of structural material to the dry fraction was needed to achieve a functional digestion process. A methane yield of 98 m{sup 3}/ton was obtained from the dry fraction mixed with structural material after 76 days of digestion. This was in the same range as obtained in the laboratory scale biochemical methane potential test, showing that it was possible to extract the organic content in the dry fraction in this type of dry digestion system for the production of methane.« less

Long-term effect of ZnO nanoparticles on waste activated sludge anaerobic digestion.

PubMed

Mu, Hui; Chen, Yinguang

2011-11-01

The increasing use of zinc oxide nanoparticles (ZnO NPs) raises concerns about their environmental impacts, but the potential effect of ZnO NPs on sludge anaerobic digestion remains unknown. In this paper, long-term exposure experiments were carried out to investigate the influence of ZnO NPs on methane production during waste activated sludge (WAS) anaerobic digestion. The presence of 1 mg/g-TSS of ZnO NPs did not affect methane production, but 30 and 150 mg/g-TSS of ZnO NPs induced 18.3% and 75.1% of inhibition respectively, which showed that the impact of ZnO NPs on methane production was dosage dependant. Then, the mechanisms of ZnO NPs affecting sludge anaerobic digestion were investigated. It was found that the toxic effect of ZnO NPs on methane production was mainly due to the release of Zn(2+) from ZnO NPs, which may cause the inhibitory effects on the hydrolysis and methanation steps of sludge anaerobic digestion. Further investigations with enzyme and fluorescence in situ hybridization (FISH) assays indicated that higher concentration of ZnO NPs decreased the activities of protease and coenzyme F(420), and the abundance of methanogenesis Archaea. Copyright © 2011 Elsevier Ltd. All rights reserved.

Could Methane Oxidation in Lakes Be Enhanced by Eutrophication?

NASA Astrophysics Data System (ADS)

Van Grinsven, S.; Villanueva, L.; Harrison, J.; S Sinninghe Damsté, J.

2017-12-01

Climate change and eutrophication both affect aquatic ecosystems. Eutrophication is caused by high nutrient inputs, leading to algal blooms, oxygen depletion and disturbances of the natural balances in aquatic systems. Methane, a potent greenhouse gas produced biologically by anaerobic degradation of organic matter, is often released from the sediments of lakes and marine systems to overlying water and the atmosphere. Methane oxidation, a microbial methane consumption process, can limit methane emission from lakes and reservoirs by 50-80%. Here, we studied methane oxidation in a seasonally stratified reservoir: Lacamas Lake in Washington, USA. We found this lake has a large summer storage capacity of methane in its deep water layer, with a very active microbial community capable of oxidizing exceptionally high amounts of methane. The natural presence of terminal electron acceptors is, however, too low to support these high potential rates. Addition of eutrophication-related nutrients such as nitrate and sulfate increased the methane removal rates by 4 to 7-fold. The microbial community was studied using 16S rRNA gene amplicon sequencing and preliminary results indicate the presence of a relatively unknown facultative anaerobic methane oxidizer of the genus Methylomonas, capable of using nitrate as an electron donor. Experiments in which anoxic and oxic conditions were rapidly interchanged showed this facultative anaerobic methane oxidizer has an impressive flexibility towards large, rapid changes in environmental conditions and this feature might be key to the unexpectedly high methane removal rates in eutrophied and anoxic watersheds.

Performance of a passively vented field-scale biofilter for the microbial oxidation of landfill methane.

PubMed

Gebert, J; Gröngröft, A

2006-01-01

An upflow biofilter system was operated on a passively vented landfill for the treatment of residual landfill methane. Biofilter methane emissions as a basis for determining methane removal rates were assessed by manual and automated chamber measurements, by measuring methane concentrations in the top layer gaseous phase in combination with gas flow rates, and by evaluating the methane load in the reverse gas flow following the change of landfill gas flux direction as governed by the course of barometric pressure. Methane removal rates were very high with maximum values of 80 g h(-1) m(-3). For the observed cases, the limit of biofilter methane oxidation capacity was not reached and absolute removal rates were thus linearly correlated to the amount of methane entering the filter. The analysis of methane loads flowing back from the biofilter following phases of longer, continuous and non-oscillating landfill gas emission, however, revealed that in these situations biofilter performance is restricted by deficient oxygen supply. At the oxygen-restricted capacity limit, removal rates are influenced by temperature (positively), methane influx (negatively) and flow rate (negatively) as a measure for the displacement of oxygen. These situations, however, account for only 12% of all emission phases. The investigated biofilter capacity, as derived from laboratory analyses of methanotrophic activities, is sufficient to oxidise 62% of the methane load emitted annually. Field and laboratory data provide a stable basis for the dimensioning of filters in future applications.

Atmospheric characterization through fused mobile airborne and surface in situ surveys: methane emissions quantification from a producing oil field

NASA Astrophysics Data System (ADS)

Leifer, Ira; Melton, Christopher; Fischer, Marc L.; Fladeland, Matthew; Frash, Jason; Gore, Warren; Iraci, Laura T.; Marrero, Josette E.; Ryoo, Ju-Mee; Tanaka, Tomoaki; Yates, Emma L.

2018-03-01

Methane (CH4) inventory uncertainties are large, requiring robust emission derivation approaches. We report on a fused airborne-surface data collection approach to derive emissions from an active oil field near Bakersfield, central California. The approach characterizes the atmosphere from the surface to above the planetary boundary layer (PBL) and combines downwind trace gas concentration anomaly (plume) above background with normal winds to derive flux. This approach does not require a well-mixed PBL; allows explicit, data-based, uncertainty evaluation; and was applied to complex topography and wind flows. In situ airborne (collected by AJAX - the Alpha Jet Atmospheric eXperiment) and mobile surface (collected by AMOG - the AutoMObile trace Gas - Surveyor) data were collected on 19 August 2015 to assess source strength. Data included an AMOG and AJAX intercomparison transect profiling from the San Joaquin Valley (SJV) floor into the Sierra Nevada (0.1-2.2 km altitude), validating a novel surface approach for atmospheric profiling by leveraging topography. The profile intercomparison found good agreement in multiple parameters for the overlapping altitude range from 500 to 1500 m for the upper 5 % of surface winds, which accounts for wind-impeding structures, i.e., terrain, trees, buildings, etc. Annualized emissions from the active oil fields were 31.3 ± 16 Gg methane and 2.4 ± 1.2 Tg carbon dioxide. Data showed the PBL was not well mixed at distances of 10-20 km downwind, highlighting the importance of the experimental design.

76 FR 44581 - Agency Information Collection Activities; Submission to OMB for Review and Approval; Comment...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-07-26

... for reducing methane emissions. By joining, Natural Gas STAR partners agree to implement cost-effective technologies and practices to reduce methane emissions, which will save money, improve operational...

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

Casco, Mirian E.; Silvestre-Albero, Joaquín; Ramírez-Cuesta, Anibal J.

Natural methane hydrates are believed to be the largest source of hydrocarbons on Earth. These structures are formed in specific locations such as deep-sea sediments and the permafrost based on demanding conditions of high pressure and low temperature. We report that, by taking advantage of the confinement effects on nanopore space, synthetic methane hydrates grow under mild conditions (3.5 MPa and 2 degrees C), with faster kinetics (within minutes) than nature, fully reversibly and with a nominal stoichiometry that mimics nature. Furthermore, the formation of the hydrate structures in nanospace and their similarity to natural hydrates is confirmed using inelasticmore » neutron scattering experiments and synchrotron X-ray powder diffraction. Our findings may be a step towards the application of a smart synthesis of methane hydrates in energy-demanding applications (for example, transportation).« less

The Effects of Graphene Stacking on the Performance of Methane Sensor: A First-Principles Study on the Adsorption, Band Gap and Doping of Graphene

PubMed Central

Yang, Daoguo; Zhang, Guoqi; Chen, Liangbiao; Liu, Dongjing; Cai, Miao; Fan, Xuejun

2018-01-01

The effects of graphene stacking are investigated by comparing the results of methane adsorption energy, electronic performance, and the doping feasibility of five dopants (i.e., B, N, Al, Si, and P) via first-principles theory. Both zigzag and armchair graphenes are considered. It is found that the zigzag graphene with Bernal stacking has the largest adsorption energy on methane, while the armchair graphene with Order stacking is opposite. In addition, both the Order and Bernal stacked graphenes possess a positive linear relationship between adsorption energy and layer number. Furthermore, they always have larger adsorption energy in zigzag graphene. For electronic properties, the results show that the stacking effects on band gap are significant, but it does not cause big changes to band structure and density of states. In the comparison of distance, the average interlamellar spacing of the Order stacked graphene is the largest. Moreover, the adsorption effect is the result of the interactions between graphene and methane combined with the change of graphene’s structure. Lastly, the armchair graphene with Order stacking possesses the lowest formation energy in these five dopants. It could be the best choice for doping to improve the methane adsorption. PMID:29389860

The Effects of Graphene Stacking on the Performance of Methane Sensor: A First-Principles Study on the Adsorption, Band Gap and Doping of Graphene.

PubMed

Yang, Ning; Yang, Daoguo; Zhang, Guoqi; Chen, Liangbiao; Liu, Dongjing; Cai, Miao; Fan, Xuejun

2018-02-01

The effects of graphene stacking are investigated by comparing the results of methane adsorption energy, electronic performance, and the doping feasibility of five dopants (i.e., B, N, Al, Si, and P) via first-principles theory. Both zigzag and armchair graphenes are considered. It is found that the zigzag graphene with Bernal stacking has the largest adsorption energy on methane, while the armchair graphene with Order stacking is opposite. In addition, both the Order and Bernal stacked graphenes possess a positive linear relationship between adsorption energy and layer number. Furthermore, they always have larger adsorption energy in zigzag graphene. For electronic properties, the results show that the stacking effects on band gap are significant, but it does not cause big changes to band structure and density of states. In the comparison of distance, the average interlamellar spacing of the Order stacked graphene is the largest. Moreover, the adsorption effect is the result of the interactions between graphene and methane combined with the change of graphene's structure. Lastly, the armchair graphene with Order stacking possesses the lowest formation energy in these five dopants. It could be the best choice for doping to improve the methane adsorption.

Preparation of Ti3C2 and Ti2C MXenes by fluoride salts etching and methane adsorptive properties

NASA Astrophysics Data System (ADS)

Liu, Fanfan; Zhou, Aiguo; Chen, Jinfeng; Jia, Jin; Zhou, Weijia; Wang, Libo; Hu, Qianku

2017-09-01

Here we reported the preparation of Ti3C2 MXene and Ti2C MXene by etching Ti3AlC2 and Ti2AlC with various fluoride salts in hydrochloric acid (HCl), including lithium fluoride (LiF), sodium fluoride (NaF), potassium fluoride (KF), and ammonium fluoride (NH4F). As-prepared Ti2C was further delaminated by urea, dimethylsulfoxide or ammonium hydroxide. Based on theoretical calculation and XPS results, the type of positive ions (Li+, Na+, K+, or NH4+) in etchant solution affect the surface structure of prepared MXene, which, in turn, affects the methane adsorption properties of MXene. The highest methane adsorption capacity is 8.5 cm3/g for Ti3C2 and 11.6 cm3/g for Ti2C. MXenes made from LiF and NH4F can absorb methane under high pressure and can keep methane under normal pressure, these MXenes may have important application on capturing methane or other hazardous gas molecules. MXenes made from NaF and KF can absorb methane under high pressure and release methane under low pressure. They can have important application in the adsorb storage of nature gas.

Microbial methane production in oxygenated water column of an oligotrophic lake

PubMed Central

Grossart, Hans-Peter; Frindte, Katharina; Dziallas, Claudia; Eckert, Werner; Tang, Kam W.

2011-01-01

The prevailing paradigm in aquatic science is that microbial methanogenesis happens primarily in anoxic environments. Here, we used multiple complementary approaches to show that microbial methane production could and did occur in the well-oxygenated water column of an oligotrophic lake (Lake Stechlin, Germany). Oversaturation of methane was repeatedly recorded in the well-oxygenated upper 10 m of the water column, and the methane maxima coincided with oxygen oversaturation at 6 m. Laboratory incubations of unamended epilimnetic lake water and inoculations of photoautotrophs with a lake-enrichment culture both led to methane production even in the presence of oxygen, and the production was not affected by the addition of inorganic phosphate or methylated compounds. Methane production was also detected by in-lake incubations of lake water, and the highest production rate was 1.8–2.4 nM⋅h−1 at 6 m, which could explain 33–44% of the observed ambient methane accumulation in the same month. Temporal and spatial uncoupling between methanogenesis and methanotrophy was supported by field and laboratory measurements, which also helped explain the oversaturation of methane in the upper water column. Potentially methanogenic Archaea were detected in situ in the oxygenated, methane-rich epilimnion, and their attachment to photoautotrophs might allow for anaerobic growth and direct transfer of substrates for methane production. Specific PCR on mRNA of the methyl coenzyme M reductase A gene revealed active methanogenesis. Microbial methane production in oxygenated water represents a hitherto overlooked source of methane and can be important for carbon cycling in the aquatic environments and water to air methane flux. PMID:22089233

Microbial and Isotopic Evidence for Methane Cycling in Hydrocarbon-Containing Groundwater from the Pennsylvania Region

PubMed Central

Vigneron, Adrien; Bishop, Andrew; Alsop, Eric B.; Hull, Kellie; Rhodes, Ileana; Hendricks, Robert; Head, Ian M.; Tsesmetzis, Nicolas

2017-01-01

The Pennsylvania region hosts numerous oil and gas reservoirs and the presence of hydrocarbons in groundwater has been locally observed. However, these methane-containing freshwater ecosystems remain poorly explored despite their potential importance in the carbon cycle. Methane isotope analysis and analysis of low molecular weight hydrocarbon gases from 18 water wells indicated that active methane cycling may be occurring in methane-containing groundwater from the Pennsylvania region. Consistent with this observation, multigenic qPCR and gene sequencing (16S rRNA genes, mcrA, and pmoA genes) indicated abundant populations of methanogens, ANME-2d (average of 1.54 × 104 mcrA gene per milliliter of water) and bacteria associated with methane oxidation (NC10, aerobic methanotrophs, methylotrophs; average of 2.52 × 103 pmoA gene per milliliter of water). Methane cycling therefore likely represents an important process in these hydrocarbon-containing aquifers. The microbial taxa and functional genes identified and geochemical data suggested that (i) methane present is at least in part due to methanogens identified in situ; (ii) Potential for aerobic and anaerobic methane oxidation is important in groundwater with the presence of lineages associated with both anaerobic an aerobic methanotrophy; (iii) the dominant methane oxidation process (aerobic or anaerobic) can vary according to prevailing conditions (oxic or anoxic) in the aquifers; (iv) the methane cycle is closely associated with the nitrogen cycle in groundwater methane seeps with methane and/or methanol oxidation coupled to denitrification or nitrate and nitrite reduction. PMID:28424678

Methodology of Estimation of Methane Emissions from Coal Mines in Poland

NASA Astrophysics Data System (ADS)

Patyńska, Renata

2014-03-01

Based on a literature review concerning methane emissions in Poland, it was stated in 2009 that the National Greenhouse Inventory 2007 [13] was published. It was prepared firstly to meet Poland's obligations resulting from point 3.1 Decision no. 280/2004/WE of the European Parliament and of the Council of 11 February 2004, concerning a mechanism for monitoring community greenhouse gas emissions and for implementing the Kyoto Protocol and secondly, for the United Nations Framework Convention on Climate Change (UNFCCC) and Kyoto Protocol. The National Greenhouse Inventory states that there are no detailed data concerning methane emissions in collieries in the Polish mining industry. That is why the methane emission in the methane coal mines of Górnośląskie Zagłębie Węglowe - GZW (Upper Silesian Coal Basin - USCB) in Poland was meticulously studied and evaluated. The applied methodology for estimating methane emission from the GZW coal mining system was used for the four basic sources of its emission. Methane emission during the mining and post-mining process. Such an approach resulted from the IPCC guidelines of 2006 [10]. Updating the proposed methods (IPCC2006) of estimating the methane emissions of hard coal mines (active and abandoned ones) in Poland, assumes that the methane emission factor (EF) is calculated based on methane coal mine output and actual values of absolute methane content. The result of verifying the method of estimating methane emission during the mining process for Polish coal mines is the equation of methane emission factor EF.

DISCOVERY OF FOG AT THE SOUTH POLE OF TITAN

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

Brown, M. E.; Smith, A. L.; Chen, C.

2009-11-20

While Saturn's moon Titan appears to support an active methane hydrological cycle, no direct evidence for surface-atmosphere exchange has yet appeared. The indirect evidence, while compelling, could be misleading. It is possible, for example, that the identified lake features could be filled with ethane, an involatile long-term residue of atmospheric photolysis; the apparent stream and channel features could be ancient remnants of a previous climate; and the tropospheric methane clouds, while frequent, could cause no rain to reach the surface. We report here the detection of fog at the south pole of Titan during late summer using observations from themore » VIMS instrument on board the Cassini spacecraft. While terrestrial fog can form from a variety of causes, most of these processes are inoperable on Titan. Fog on Titan can only be caused by evaporation of nearly pure liquid methane; the detection of fog provides the first direct link between surface and atmospheric methane. Based on the detections presented here, liquid methane appears widespread at the south pole of Titan in late southern summer, and the hydrological cycle on Titan is currently active.« 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.

The Methane to Markets Coal Mine Methane Subcommittee meeting

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

NONE

2008-07-01

The presentations (overheads/viewgraphs) include: a report from the Administrative Support Group; strategy updates from Australia, India, Italy, Mexico, Nigeria, Poland and the USA; coal mine methane update and IEA's strategy and activities; the power of VAM - technology application update; the emissions trading market; the voluntary emissions reduction market - creating profitable CMM projects in the USA; an Italian perspective towards a zero emission strategies; and the wrap-up and summary.

JPRS Report. Science & Technology: Japan

DTIC Science & Technology

1987-07-16

methane. So, it has been proved that seawater containing methane and sulfur, which oozed out at this point from underground, grew bacteria, a food ...activity was measured by dispersing glass powder at the seabed and the speed of extinction due to food poisoning was also measured by leaving dead...solar light is very small due to the scarcity of food . However, a special ecosystem nourished with bacteria, which eat methane and inorganic compounds

Rice cultivation and methane emission: Documentation of distributed geographic data sets

NASA Technical Reports Server (NTRS)

Matthews, Elaine; John, Jasmin; Fung, Inez

1994-01-01

High-resolution global data bases on the geographic and seasonal distribution of rice cultivation and associated methane emission, compiled by Matthews et al., were archived for public use. In addition to the primary data sets identifying location, seasonality, and methane emission from rice cultivation, a series of supporting data sets is included, allowing users not only to replicate the work of Matthews et al. but to investigate alternative cultivation and emission scenarios. The suite of databases provided, at 1 latitude by 1 longitude resolution for the globe, includes (1) locations of rice cultivation, (2) monthly arrays of actively growing rice areas, (3) countries and political subdivisions, and (4) monthly arrays of methane emission from rice cultivation. Ancillary data include (1) a listing, by country, of harvested rice areas and seasonal distribution of crop cycles and (2) country names and codes. Summary tables of zonal/monthly distributions of actively growing rice areas and of methane emissions are presented. Users should consult original publications for complete discussion of the data bases. This short paper is designed only to document formats of the distributed information and briefly describe the contents of the data sets and their initial application to evaluating the role of rice cultivation in the methane budget.

Selection of associated heterotrophs by methane-oxidizing bacteria at different copper concentrations.

PubMed

van der Ha, David; Vanwonterghem, Inka; Hoefman, Sven; De Vos, Paul; Boon, Nico

2013-03-01

Due to the increasing atmospheric concentration of the greenhouse gas methane, more knowledge is needed on the management of methanotrophic communities. While most studies have focused on the characteristics of the methane-oxidizing bacteria (MOB), less is known about their interactions with the associated heterotrophs. Interpretative tools based on denaturing gradient gel electrophoresis allowed to evaluate the influence of copper-an important enzymatic regulator for MOB-on the activity and composition of the bacterial community. Over 30 days, enrichments with 0.1, 1.0 and 10 μM Cu(2+) respectively, showed comparable methane oxidation activities. The different copper concentrations did not create major shifts in the methanotrophic communities, as a Methylomonas sp. was able to establish dominance at all different copper concentrations by switching between both known methane monooxygenases. The associated heterotrophic communities showed continuous shifts, but over time all cultures evolved to a comparable composition, independent of the copper concentration. This indicates that the MOB selected for certain heterotrophs, possibly fulfilling vital processes such as removal of toxic compounds. The presence of a large heterotrophic food web indirectly depending on methane as sole carbon and energy source was confirmed by a clone library wherein MOB only formed a minority of the identified species.

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

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

Valentine, David

2012-09-30

In October 2008 the University of California at Santa Barbara (UCSB) initiated investigations of water column methane oxidation in methane hydrate environments, through a project funded by the National Energy Technology Laboratory (NETL) entitled: assessing the efficacy of the aerobic methanotrophic biofilter in methane hydrate environments. This Final Report describes the scientific advances and discoveries made under this award as well as the importance of these discoveries in the broader context of the research area. Benthic microbial mats inhabit the sea floor in areas where reduced chemicals such as sulfide reach the more oxidizing water that overlies the sediment. Wemore » set out to investigate the role that methanotrophs play in such mats at locations where methane reaches the sea floor along with sulfide. Mats were sampled from several seep environments and multiple sets were grown in-situ at a hydrocarbon seep in the Santa Barbara Basin. Mats grown in-situ were returned to the laboratory and used to perform stable isotope probing experiments in which they were treated with 13C-enriched methane. The microbial community was analyzed, demonstrating that three or more microbial groups became enriched in methane?s carbon: methanotrophs that presumably utilize methane directly, methylotrophs that presumably consume methanol excreted by the methanotrophs, and sulfide oxidizers that presumably consume carbon dioxide released by the methanotrophs and methylotrophs. Methanotrophs reached high relative abundance in mats grown on methane, but other bacterial processes include sulfide oxidation appeared to dominate mats, indicating that methanotrophy is not a dominant process in sustaining these benthic mats, but rather a secondary function modulated by methane availability. Methane that escapes the sediment in the deep ocean typically dissolved into the overlying water where it is available to methanotrophic bacteria. We set out to better understand the efficacy of this process as a biofilter by studying the distribution of methane oxidation and disposition of methanotrophic populations in the Pacific Ocean. We investigated several environments including the basins offshore California, the continental margin off Central America, and the shallow waters around gas seeps. We succeeded in identifying the distributions of activity in these environments, identified potential physical and chemical controls on methanotrophic activity, we further revealed details about the methanotrophic communities active in these settings, and we developed new approaches to study methanotrophic communities. These findings should improve our capacity to predict the methanotrophic response in ocean waters, and further our ability to generate specific hypotheses as to the ecology and efficacy of pelagic methanotrophic communites. The discharge of methane and other hydrocarbons to Gulf of Mexico that followed the sinking of the Deepwater Horizon provided a unique opportunity to study the methanotorphic biofilter in the deep ocean environment. We set out to understand the consumption of methane and the bloom of methanotrophs resulting from this event, as a window into the regional scale release of gas hydrate under rapid warming scenarios. We found that other hydrocarbon gases, notably propane and ethane, were preferred for consumption over methane, but that methane consumption accelerated rapidly and drove the depletion of methane within a matter of months after initial release. These results revealed the identity of the responsible community, and point to the importance of the seed population in determining the rate at which a methanotrophic community is able to respond to an input of methane. Collectively, these results provide a significant advance in our understanding of the marine methanotrohic biofilter, and further provide direction and context for future investigations of this important phenomenon. This project has resulted in fourteen publications to date, with five more circulating in draft form, and several others planned.« less

Biochemistry of methyl-coenzyme M reductase: the nickel metalloenzyme that catalyzes the final step in synthesis and the first step in anaerobic oxidation of the greenhouse gas methane.

PubMed

Ragsdale, Stephen W

2014-01-01

Methane, the major component of natural gas, has been in use in human civilization since ancient times as a source of fuel and light. Methanogens are responsible for synthesis of most of the methane found on Earth. The enzyme responsible for catalyzing the chemical step of methanogenesis is methyl-coenzyme M reductase (MCR), a nickel enzyme that contains a tetrapyrrole cofactor called coenzyme F430, which can traverse the Ni(I), (II), and (III) oxidation states. MCR and methanogens are also involved in anaerobic methane oxidation. This review describes structural, kinetic, and computational studies aimed at elucidating the mechanism of MCR. Such studies are expected to impact the many ramifications of methane in our society and environment, including energy production and greenhouse gas warming.

Ductile flow of methane hydrate

USGS Publications Warehouse

Durham, W.B.; Stern, L.A.; Kirby, S.H.

2003-01-01

Compressional creep tests (i.e., constant applied stress) conducted on pure, polycrystalline methane hydrate over the temperature range 260-287 K and confining pressures of 50-100 MPa show this material to be extraordinarily strong compared to other icy compounds. The contrast with hexagonal water ice, sometimes used as a proxy for gas hydrate properties, is impressive: over the thermal range where both are solid, methane hydrate is as much as 40 times stronger than ice at a given strain rate. The specific mechanical response of naturally occurring methane hydrate in sediments to environmental changes is expected to be dependent on the distribution of the hydrate phase within the formation - whether arranged structurally between and (or) cementing sediments grains versus passively in pore space within a sediment framework. If hydrate is in the former mode, the very high strength of methane hydrate implies a significantly greater strain-energy release upon decomposition and subsequent failure of hydrate-cemented formations than previously expected.

Quantifying the relative contribution of natural gas fugitive emissions to total methane emissions in Colorado and Utah using mobile stable isotope (13CH4) analysis

NASA Astrophysics Data System (ADS)

Rella, Chris; Jacobson, Gloria; Crosson, Eric; Karion, Anna; Petron, Gabrielle; Sweeney, Colm

2013-04-01

Fugitive emissions of methane into the atmosphere are a major concern facing the natural gas production industry. Because methane is more energy-rich than coal per kg of CO2 emitted into the atmosphere, it represents an attractive alternative to coal for electricity generation. However, given that the global warming potential of methane is many times greater than that of carbon dioxide (Solomon et al. 2007), the importance of quantifying the fugitive emissions of methane throughout the natural gas production and distribution process becomes clear (Howarth et al. 2011). A key step in the process of assessing the emissions arising from natural gas production activities is partitioning the observed methane emissions between natural gas fugitive emissions and other sources of methane, such as from landfills or agricultural activities. One effective method for assessing the contribution of these different sources is stable isotope analysis. In particular, the 13CH4 signature of natural gas (-35 to -40 permil) is significantly different that the signature of other significant sources of methane, such as landfills or ruminants (-45 to -70 permil). In this paper we present measurements of mobile field 13CH4 using a spectroscopic stable isotope analyzer based on cavity ringdown spectroscopy, in two intense natural gas producing regions of the United States: the Denver-Julesburg basin in Colorado, and the Uintah basin in Utah. Mobile isotope measurements in the nocturnal boundary layer have been made, over a total path of 100s of km throughout the regions, allowing spatially resolved measurements of the regional isotope signature. Secondly, this analyzer was used to quantify the isotopic signature of those individual sources (natural gas fugitive emissions, concentrated animal feeding operations, and landfills) that constitute the majority of methane emissions in these regions, by making measurements of the isotope ratio directly in the downwind plume from each source. These data are combined to establish the fraction of the observed methane emissions that can be attributed to natural gas activities in the regions. The fraction of total methane emissions in the Denver-Julesburg basin that can be attributed to natural gas fugitive emissions has been determined to be 71 +/- 9%. References: 1. S. Solomon, D. Qin, M. Manning, Z. Chen, M. Marquis, K.B. Averyt, M.Tignor and H.L. Miller (eds.). IPCC, 2007: Climate Change 2007: The Physical Science Basis of the Fourth Assessment Report. Cambridge University Press, Cambridge, United Kingdom and New York, NY, USA. 2. R.W. Howarth, R. Santoro, and A. Ingraffea. "Methane and the greenhouse-gas footprint of natural gas from shale formations." Climate Change, 106, 679 (2011).

Quantifying the relative contribution of natural gas fugitive emissions to total methane emissions in Colorado, Utah, and Texas using mobile δ13CH4 analysis

NASA Astrophysics Data System (ADS)

Rella, C.; Crosson, E.; Petron, G.; Sweeney, C.; Karion, A.

2013-12-01

Fugitive emissions of methane into the atmosphere are a major concern facing the natural gas production industry. Because methane is more energy-rich than coal per kg of CO2 emitted into the atmosphere, it represents an attractive alternative to coal for electricity generation, provided that the fugitive emissions of methane are kept under control. A key step in assessing these emissions in a given region is partitioning the observed methane emissions between natural gas fugitive emissions and other sources of methane, such as from landfills or agricultural activities. One effective method for assessing the contribution of these different sources is stable isotope analysis, using the δ13CH4 signature to distinguish between natural gas and landfills or ruminants. We present measurements of mobile field δ13CH4 using a spectroscopic stable isotope analyzer based on cavity ringdown spectroscopy, in three intense natural gas producing regions of the United States: the Denver-Julesburg basin in Colorado, the Uintah basin in Utah, and the Barnett Shale in Texas. Mobile isotope measurements of individual sources and in the nocturnal boundary layer have been combined to establish the fraction of the observed methane emissions that can be attributed to natural gas activities. The fraction of total methane emissions in the Denver-Julesburg basin attributed to natural gas emissions is 78 +/- 13%. In the Uinta basin, which has no other significant sources of methane, the fraction is 96% +/- 15%. In addition, results from the Barnett shale are presented, which includes a major urban center (Dallas / Ft. Worth). Methane emissions in this region are spatially highly heterogeneous. Spatially-resolved isotope and concentration measurements are interpreted using a simple emissions model to arrive at an overall isotope ratio for the region. (left panel) Distribution of oil and gas well pads (yellow) and landfills (blue) in the Dallas / Ft. Worth area. Mobile nocturnal measurements of methane are shown in red, indicating a strong degree of source heterogeneity. (right panel) Histogram of individual isotopic source signatures, showing distinct signatures for landfills (red) and oil and gas sources (green).

Community structure of planktonic methane-oxidizing bacteria in a subtropical reservoir characterized by dominance of phylotype closely related to nitrite reducer

NASA Astrophysics Data System (ADS)

Kojima, Hisaya; Tokizawa, Riho; Kogure, Kouhei; Kobayashi, Yuki; Itoh, Masayuki; Shiah, Fuh-Kwo; Okuda, Noboru; Fukui, Manabu

2014-07-01

Methane-oxidizing bacteria (MOB) gain energy from the oxidation of methane and may play important roles in freshwater ecosystems. In this study, the community structure of planktonic MOB was investigated in a subtropical reservoir. Bacterial community structure was investigated through the analysis of the 16S rRNA gene. Three groups of phylogenetically distinct MOB were detected in the clone libraries of polymerase chain reaction products obtained with universal primers. The groups belonged to the class Gammaproteobacteria, the class Alphaproteobacteria, and the candidate phylum NC10. The last group, which consists of close relatives of the nitrite reducer `Candidatus Methylomirabilis oxyfera', was frequently detected in the clone libraries of deep-water environments. The presence of 3 groups of MOB in deep water was also shown by a cloning analysis of the pmoA gene encoding particulate methane monooxygenase. The dominance of `M. oxyfera'-like organisms in deep water was confirmed by catalyzed reporter deposition-fluorescence in situ hybridization, in which cells stained with a specific probe accounted for 16% of total microbial cells. This is the first study to demonstrate that close relatives of the nitrite reducer can be major component of planktonic MOB community which may affect carbon flow in aquatic ecosystems.

Self-assembled 1D infinite inorganic [2]catenane and 2D sheet framework with calix[8]phenylazoimidazole and [4+4]metallomacrocyclic motifs based on silver and ditopic bis(imidazolyl)methane ligands

NASA Astrophysics Data System (ADS)

Jin, Tianqi; Zhou, Junqiang; Pan, Yangyang; Huang, Yu; Jin, Chuanming

2018-05-01

Three novel supramolecular complexes, [Ag4(2-mBIM)4](ClO4)4(H2O) (1), [Ag2(2-mBIM)2](PF6)2 (2) and [Ag2(PA-BIM)2](ClO4)2(CH2Cl2) (3) (2-mBIM = bis(2-methyl- imidazol-1-yl)methane; PA-BIM = 1,1-bis[(2-phenylazo)imidazol-1-yl]methane), have been prepared and structurally characterized. The reported complexes bear [4+4]metallomacrocyclic motifs comprising four silver atoms and four ditopic bis(imidazolyl)methane ligands. Complex 1 exhibits a rare 1D infinite inorganic [2]catenane structure, which was self-assembled by the interlocking action of [4+4]metallomacrocyclic units. Complex 2 is a 2D layered supramolecular motif containing [4+4]macrometallacycle units with π-π interaction between imidazole rings. Complex 3 has a 2D sheet supramolecular framework through Ag-Ag interactions in [4+4]macrometallacyclic calix [8]phenylazoimidazole with a nanocavity. The results suggest that the bisimidazolium ligands and anions play crucial roles in the formation of the different host structures. The thermal stability and photoluminescence spectra of the synthesized complexes have also been discussed.

Proteomic Stable Isotope Probing Reveals Biosynthesis Dynamics of Slow Growing Methane Based Microbial Communities

PubMed Central

Marlow, Jeffrey J.; Skennerton, Connor T.; Li, Zhou; Chourey, Karuna; Hettich, Robert L.; Pan, Chongle; Orphan, Victoria J.

2016-01-01

Marine methane seep habitats represent an important control on the global flux of methane. Nucleotide-based meta-omics studies outline community-wide metabolic potential, but expression patterns of environmentally relevant proteins are poorly characterized. Proteomic stable isotope probing (proteomic SIP) provides additional information by characterizing phylogenetically specific, functionally relevant activity in mixed microbial communities, offering enhanced detection through system-wide product integration. Here we applied proteomic SIP to 15NH4+ and CH4 amended seep sediment microcosms in an attempt to track protein synthesis of slow-growing, low-energy microbial systems. Across all samples, 3495 unique proteins were identified, 11% of which were 15N-labeled. Consistent with the dominant anaerobic oxidation of methane (AOM) activity commonly observed in anoxic seep sediments, proteins associated with sulfate reduction and reverse methanogenesis—including the ANME-2 associated methylenetetrahydromethanopterin reductase (Mer)—were all observed to be actively synthesized (15N-enriched). Conversely, proteins affiliated with putative aerobic sulfur-oxidizing epsilon- and gammaproteobacteria showed a marked decrease over time in our anoxic sediment incubations. The abundance and phylogenetic range of 15N-enriched methyl-coenzyme M reductase (Mcr) orthologs, many of which exhibited novel post-translational modifications, suggests that seep sediments provide niches for multiple organisms performing analogous metabolisms. In addition, 26 proteins of unknown function were consistently detected and actively expressed under conditions supporting AOM, suggesting that they play important roles in methane seep ecosystems. Stable isotope probing in environmental proteomics experiments provides a mechanism to determine protein durability and evaluate lineage-specific responses in complex microbial communities placed under environmentally relevant conditions. Our work here demonstrates the active synthesis of a metabolically specific minority of enzymes, revealing the surprising longevity of most proteins over the course of an extended incubation experiment in an established, slow-growing, methane-impacted environmental system. PMID:27199908

Enhanced methane emissions from oil and gas exploration areas to the atmosphere--the central Bohai Sea.

PubMed

Zhang, Yong; Zhao, Hua-de; Zhai, Wei-dong; Zang, Kun-peng; Wang, Ju-ying

2014-04-15

The distributions of dissolved methane in the central Bohai Sea were investigated in November 2011, May 2012, July 2012, and August 2012. Methane concentration in surface seawater, determined using an underway measurement system combined with wavelength-scanned cavity ring-down spectroscopy, showed marked spatiotemporal variations with saturation ratio from 107% to 1193%. The central Bohai Sea was thus a source of atmospheric methane during the survey periods. Several episodic oil and gas spill events increased surface methane concentration by up to 4.7 times and raised the local methane outgassing rate by up to 14.6 times. This study demonstrated a method to detect seafloor CH4 leakages at the sea surface, which may have applicability in many shallow sea areas with oil and gas exploration activities around the world. Copyright © 2014 Elsevier Ltd. All rights reserved.

Influence of headspace flushing on methane production in Biochemical Methane Potential (BMP) tests.

PubMed

Koch, Konrad; Bajón Fernández, Yadira; Drewes, Jörg E

2015-06-01

The influence of headspace flushing on the specific methane (CH4) production of blank samples with just inoculum in Biochemical Methane Potential (BMP) tests was studied. The three most common ways were applied: flushing with nitrogen (N2) gas, flushing with a mixture of N2 and CO2 (80/20 v/v), and no flushing. The results revealed that removing the oxygen is crucial to avoid aerobic respiration, which caused both hindered activity of methanogens and loss of methane potential. Furthermore it was demonstrated that 20% of CO2 in the flush gas increased significantly the methane production by over 20% compared to the flushing with pure N2. In order to mimic the same headspace conditions as in full-scale treatment plants, using a flush gas with a similar CO2 concentration as the expected biogas is suggested. Copyright © 2015 Elsevier Ltd. All rights reserved.

77 FR 37441 - Agency Information Collection Activities; Submission for OMB Review; Comment Request; Diesel...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-06-21

... dust and explosive methane gas are present. Diesel equipment operating in underground coal mines also..., such as cabs or canopies, methane monitors, brakes and lights. Sampling of diesel exhaust emissions is...

76 FR 80928 - Agency Information Collection Activities; Submission to OMB for Review and Approval; Comment...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-12-27

... operation and maintenance of this equipment. These standards rely on the capture and reduction of methane, carbon dioxide, and non-methane organic gas compound emissions by combustion devices (boilers, internal...

Alkane Oxidation: Methane Monooxygenases, Related Enzymes, and Their Biomimetics.

PubMed

Wang, Vincent C-C; Maji, Suman; Chen, Peter P-Y; Lee, Hung Kay; Yu, Steve S-F; Chan, Sunney I

2017-07-12

Methane monooxygenases (MMOs) mediate the facile conversion of methane into methanol in methanotrophic bacteria with high efficiency under ambient conditions. Because the selective oxidation of methane is extremely challenging, there is considerable interest in understanding how these enzymes carry out this difficult chemistry. The impetus of these efforts is to learn from the microbes to develop a biomimetic catalyst to accomplish the same chemical transformation. Here, we review the progress made over the past two to three decades toward delineating the structures and functions of the catalytic sites in two MMOs: soluble methane monooxygenase (sMMO) and particulate methane monooxygenase (pMMO). sMMO is a water-soluble three-component protein complex consisting of a hydroxylase with a nonheme diiron catalytic site; pMMO is a membrane-bound metalloenzyme with a unique tricopper cluster as the site of hydroxylation. The metal cluster in each of these MMOs harnesses O 2 to functionalize the C-H bond using different chemistry. We highlight some of the common basic principles that they share. Finally, the development of functional models of the catalytic sites of MMOs is described. These efforts have culminated in the first successful biomimetic catalyst capable of efficient methane oxidation without overoxidation at room temperature.

Investigation of flame structure and burning intensity of partially premixed methane enrichment of syngas using OH-PLIF and kinetic simulation

NASA Astrophysics Data System (ADS)

Pu, Ge; Huang, Beibei; Zhang, Xun; Du, Jiantai; Zhu, Tuanhui; Chen, Bei

2018-05-01

Various experiments were conducted to study the combustion characteristics of partially premixed methane enrichment of syngas by using the OH-PLIF technique. Experiments were conducted on a co-flow burner, and the methane concentration (XCH4 = CH4/(H2+CO+CH4)) was varied from 0 to 20%, the overall equivalence ratio was varied from 0.4 to 1.2 and the inner equivalence ratio was varied from 1.5 to 3.5. Kinetic simulation was conducted by using OPPDIF module of CHEMKIN-Pro software. Results show that an increase in XCH4 and ϕoverall weakens the OH signal intensity. Adding methane into the fuel greatly increases the height of the inner flame front, and the increase of methane concentration has a negative effect on flame propagation speed. Meanwhile, simulation results remain consistent with the experiments. The main OH radical production reaction changes from R46: H+HO2 = 2OH to R38: H+O2 = O+OH when methane concentration contained in the fuel mixture increases. Sensitivity analysis also indicates that reaction which plays a dominant effect on temperature changes with the increase of methane concentration.

Thermodynamic properties of hydrate phases immersed in ice phase

NASA Astrophysics Data System (ADS)

Belosludov, V. R.; Subbotin, O. S.; Krupskii, D. S.; Ikeshoji, T.; Belosludov, R. V.; Kawazoe, Y.; Kudoh, J.

2006-01-01

Thermodynamic properties and the pressure of hydrate phases immersed in the ice phase with the aim to understand the nature of self-preservation effect of methane hydrate in the framework of macroscopic and microscopic molecular models was studied. It was show that increasing of pressure is happen inside methane hydrate phases immersed in the ice phase under increasing temperature and if the ice structure does not destroy, the methane hydrate will have larger pressure than ice phase. This is because of the thermal expansion of methane hydrate in a few times larger than ice one. The thermal expansion of the hydrate is constrained by the thermal expansion of ice because it can remain in a region of stability within the methane hydrate phase diagram. The utter lack of preservation behavior in CS-II methane- ethane hydrate can be explain that the thermal expansion of ethane-methane hydrate coincide with than ice one it do not pent up by thermal expansion of ice. The pressure and density during the crossing of interface between ice and hydrate was found and dynamical and thermodynamic stability of this system are studied in accordance with relation between ice phase and hydrate phase.

Bacterial methane oxidation in sea-floor gas hydrate: Significance to life in extreme environments

NASA Astrophysics Data System (ADS)

Sassen, Roger; MacDonald, Ian R.; Guinasso, Norman L., Jr.; Joye, Samantha; Requejo, Adolfo G.; Sweet, Stephen T.; Alcalá-Herrera, Javier; Defreitas, Debra A.; Schink, David R.

1998-09-01

Samples of thermogenic hydrocarbon gases, from vents and gas hydrate mounds within a sea-floor chemosynthetic community on the Gulf of Mexico continental slope at about 540 m depth, were collected by research submersible. Our study area is characterized by low water temperature (mean =7 °C), high pressure (about 5400 kPa), and abundant structure II gas hydrate. Bacterial oxidation of hydrate-bound methane (CH4) is indicated by three isotopic properties of gas hydrate samples. Relative to the vent gas from which the gas hydrate formed, (1) methane-bound methane is enriched in 13C by as much as 3.8‰ PDB (Peedee belemnite), (2) hydrate-bound methane is enriched in deuterium (D) by as much as 37‰ SMOW (standard mean ocean water), and (3) hydrate-bound carbon dioxide (CO2) is depleted in 13C by as much as 22.4‰ PDB. Hydrate-associated authigenic carbonate rock is also depleted in 13C. Bacterial oxidation of methane is a driving force in chemosynthetic communities, and in the concomitant precipitation of authigenic carbonate rock that modifies sea-floor geology. Bacterial oxidation of hydrate-bound methane expands the potential boundaries of life in extreme environments.

Adsorbed Natural Gas Storage in Optimized High Surface Area Microporous Carbon

NASA Astrophysics Data System (ADS)

Romanos, Jimmy; Rash, Tyler; Nordwald, Erik; Shocklee, Joshua Shawn; Wexler, Carlos; Pfeifer, Peter

2011-03-01

Adsorbed natural gas (ANG) is an attractive alternative technology to compressed natural gas (CNG) or liquefied natural gas (LNG) for the efficient storage of natural gas, in particular for vehicular applications. In adsorbants engineered to have pores of a few molecular diameters, a strong van der Walls force allows reversible physisorption of methane at low pressures and room temperature. Activated carbons were optimized for storage by varying KOH:C ratio and activation temperature. We also consider the effect of mechanical compression of powders to further enhance the volumetric storage capacity. We will present standard porous material characterization (BET surface area and pore-size distribution from subcritical N2 adsorption) and methane isotherms up to 250 bar at 293K. At sufficiently high pressure, specific surface area, methane binding energy and film density can be extracted from supercritical methane adsorption isotherms. Research supported by the California Energy Commission (500-08-022).

Effect of bio-column composed of aged refuse on methane abatement--a novel configuration of biological oxidation in refuse landfill.

PubMed

Han, Dan; Zhao, Youcai; Xue, Binjie; Chai, Xiaoli

2010-01-01

An experimental bio-column composed of aged refuse was installed around the exhaust pipe as a new way to mitigate methane in refuse landfill. One of the objectives of this work was to assess the effect of aged refuse thickness in bio-column on reducing CH4 emissions. Over the study period, methane oxidation was observed at various thicknesses, 5 cm (small size), 10 cm (middle size) and 15 cm (large size), representing one to three times of pipeline diameters. The middle and large size both showed over 90% methane conversion, and the highest methane conversion rate of above 95% occurred in the middle-size column cell. Michaelis-Menten equation addressed the methanotrophs diffusion in different layers of the bio-columns. Maximum methanotrophic activity (Vmax) measured at the three thicknesses ranged from 6.4 x 10(-3) to 15.6 x 10(-3) units, and the half-saturation value (K(M)) ranged from 0.85% to 1.67%. Both the highest Vmax and K(M) were observed at the middle-size of the bio-column, as well as the largest methanotrophs population, suggesting a significant efficiency of methane mitigation happened in the optimum zone with greatest affinity and methanotrophic bacteria activities. Therefore, bio-column is a potential style for methane abatement in landfill, and the aged refuse both naturally formed and artificially placed in the column plays a critical role in CH4 emission.

Thermophilic and hyper-thermophilic co-digestion of waste activated sludge and fat, oil and grease: Evaluating and modeling methane production.

PubMed

Alqaralleh, Rania Mona; Kennedy, Kevin; Delatolla, Robert; Sartaj, Majid

2016-12-01

Renewable energy and clean environment are two crucial requirements for our modern world. Low cost, energy production and limited environmental impact make anaerobic digestion (AD) a promising technology for stabilizing organic waste and in particular, sewage waste. The anaerobic co-digestion of thickened waste activated sludge (TWAS) and sewage treatment plant trapped fat, oil and grease (FOG) using different FOG-TWAS mixtures (20, 40, 60 and 80% of FOG based on total volatile solids (TVS)) were investigated in this study using both thermophilic (55 ± 1 °C) and two stages hyper-thermophilic/thermophilic (70 ± 1 °C and 55 ± 1 °C) anaerobic co-digestion. The hyper-thermophilic co-digestion approach as a part of the co-digestion process has been shown to be very useful in improving the methane production. During hyper-thermophilic biochemical methane potential (BMP) assay testing the sample with 60% FOG (based on TVS) has been shown to significantly increase the maximum methane production to 673.1 ± 14.0 ml of methane as compared to 316.4 ± 14.3 ml of methane for the control sample. This represents a 112.7% increase in methane production compared to the control sample considered in this paper. These results signify the importance of hyper-thermophilic digestion to the co-digestion of TWAS-FOG field. Copyright © 2016 Elsevier Ltd. All rights reserved.

Analysis of Subsurface Clathrates in the Upper Crust of Titan

NASA Technical Reports Server (NTRS)

Elliott, John

2011-01-01

Titan has an atmosphere rich in methane, which should have long since been depleted unless a mechanism exists for storing this molecule below the surface. One hypothesis is that methane could be stored in the form of a clathrate hydrate, which is a structure with an ice lattice forming molecular cages in which gases are trapped. It is stable at low temperatures and over a wide range of pressures, suggesting that a clathrate hydrate may have stored methane on Titan from the beginning of its history.

Enhanced coal-dependent methanogenesis coupled with algal biofuels: Potential water recycle and carbon capture

USGS Publications Warehouse

Barnhart, Elliott P.; Davis, Katherine J.; Varonka, Matthew; Orem, William H.; Cunningham, Alfred B.; Ramsay, Bradley D.; Fields, Matthew W.

2017-01-01

Many coal beds contain microbial communities that can convert coal to natural gas (coalbed methane). Native microorganisms were obtained from Powder River Basin (PRB) coal seams with a diffusive microbial sampler placed downhole and used as an inoculum for enrichments with different nutrients to investigate microbially-enhanced coalbed methane production (MECoM). Coal-dependent methanogenesis more than doubled when yeast extract (YE) and several less complex components (proteins and amino acids) were added to the laboratory microcosms. Stimulated coal-dependent methanogenesis with peptone was 86% of that with YE while glutamate-stimulated activity was 65% of that with YE, and a vitamin mix had only 33% of the YE stimulated activity. For field application of MECoM, there is interest in identifying cost-effective alternatives to YE and other expensive nutrients. In laboratory studies, adding algal extract (AE) with lipids removed stimulated coal-dependent methanogenesis and the activity was 60% of that with YE at 27 d and almost 90% of YE activity at 1406 d. Analysis of British Thermal Unit (BTU) content of coal (a measure of potential energy yield) from long-term incubations indicated > 99.5% of BTU content remained after coalbed methane (CBM) stimulation with either AE or YE. Thus, the coal resource remains largely unchanged following stimulated microbial methane production. Algal CBM stimulation could lead to technologies that utilize coupled biological systems (photosynthesis and methane production) that sustainably enhance CBM production and generate algal biofuels while also sequestering carbon dioxide (CO2).

Unexpected stimulation of soil methane uptake as emergent property of agricultural soils following bio-based residue application.

PubMed

Ho, Adrian; Reim, Andreas; Kim, Sang Yoon; Meima-Franke, Marion; Termorshuizen, Aad; de Boer, Wietse; van der Putten, Wim H; Bodelier, Paul L E

2015-10-01

Intensification of agriculture to meet the global food, feed, and bioenergy demand entail increasing re-investment of carbon compounds (residues) into agro-systems to prevent decline of soil quality and fertility. However, agricultural intensification decreases soil methane uptake, reducing, and even causing the loss of the methane sink function. In contrast to wetland agricultural soils (rice paddies), the methanotrophic potential in well-aerated agricultural soils have received little attention, presumably due to the anticipated low or negligible methane uptake capacity in these soils. Consequently, a detailed study verifying or refuting this assumption is still lacking. Exemplifying a typical agricultural practice, we determined the impact of bio-based residue application on soil methane flux, and determined the methanotrophic potential, including a qualitative (diagnostic microarray) and quantitative (group-specific qPCR assays) analysis of the methanotrophic community after residue amendments over 2 months. Unexpectedly, after amendments with specific residues, we detected a significant transient stimulation of methane uptake confirmed by both the methane flux measurements and methane oxidation assay. This stimulation was apparently a result of induced cell-specific activity, rather than growth of the methanotroph population. Although transient, the heightened methane uptake offsets up to 16% of total gaseous CO2 emitted during the incubation. The methanotrophic community, predominantly comprised of Methylosinus may facilitate methane oxidation in the agricultural soils. While agricultural soils are generally regarded as a net methane source or a relatively weak methane sink, our results show that methane oxidation rate can be stimulated, leading to higher soil methane uptake. Hence, even if agriculture exerts an adverse impact on soil methane uptake, implementing carefully designed management strategies (e.g. repeated application of specific residues) may compensate for the loss of the methane sink function following land-use change. © 2015 John Wiley & Sons Ltd.

Molecular phylogenetic and chemical analyses of the microbial mats in deep-sea cold seep sediments at the northeastern Japan Sea.

PubMed

Arakawa, Shizuka; Sato, Takako; Sato, Rumi; Zhang, Jing; Gamo, Toshitaka; Tsunogai, Urumu; Hirota, Akinari; Yoshida, Yasuhiko; Usami, Ron; Inagaki, Fumio; Kato, Chiaki

2006-08-01

Microbial communities inhabiting deep-sea cold seep sediments at the northeastern Japan Sea were characterized by molecular phylogenetic and chemical analyses. White patchy microbial mats were observed along the fault offshore the Hokkaido Island and sediment samples were collected from two stations at the southern foot of the Shiribeshi seamount (M1 site at a depth of 2,961 m on the active fault) and off the Motta Cape site (M2 site at a depth of 3,064 m off the active fault). The phylogenetic and terminal-restriction fragment polymorphism analyses of PCR-amplified 16S rRNA genes revealed that microbial community structures were different between two sampling stations. The members of ANME-2 archaea and diverse bacterial components including sulfate reducers within Deltaproteobacteria were detected from M1 site, indicating the occurrence of biologically mediated anaerobic oxidation of methane, while microbial community at M2 site was predominantly composed of members of Marine Crenarchaeota group I, sulfate reducers of Deltaproteobacteria, and sulfur oxidizers of Epsilonproteobacteria. Chemical analyses of seawater above microbial mats suggested that concentrations of sulfate and methane at M1 site were largely decreased relative to those at M2 site and carbon isotopic composition of methane at M1 site shifted heavier ((13)C-enriched), the results of which are consistent with molecular analyses. These results suggest that the mat microbial communities in deep-sea cold seep sediments at the northeastern Japan Sea are significantly responsible for sulfur and carbon circulations and the geological activity associated with plate movements serves unique microbial habitats in deep-sea environments.

ACCUMULATION OF POLY-B-HYDROXYBUTYRATE IN A METHANE- ENRICHED, HALOGENATED, HYDROCARBON-DEGRADING SOIL COLUMN: IMPLICATIONS FOR MICROBIAL COMMUNITY STRUCTURE AND NUTRITIONAL STATUS

EPA Science Inventory

The prokarotic, endogenous storage polymer poly--hydroxybutyrate (PHB) accumulated in soil from a methane-enriched, halogenated hydrocarbon-degrading soil column. Based on phospholipid ester-linked fatty acid (PLFA) profiles, this mocrocosm has been previously reported to be sign...

Towards Accurate Ab Initio Predictions of the Spectrum of Methane

NASA Technical Reports Server (NTRS)

Schwenke, David W.; Kwak, Dochan (Technical Monitor)

2001-01-01

We have carried out extensive ab initio calculations of the electronic structure of methane, and these results are used to compute vibrational energy levels. We include basis set extrapolations, core-valence correlation, relativistic effects, and Born- Oppenheimer breakdown terms in our calculations. Our ab initio predictions of the lowest lying levels are superb.

Exposure to polystyrene nanoplastic leads to inhibition of anaerobic digestion system.

PubMed

Fu, Shan-Fei; Ding, Jian-Nan; Zhang, Yun; Li, Yi-Fei; Zhu, Rong; Yuan, Xian-Zheng; Zou, Hua

2018-06-01

In this study, impacts of nanoplastic on the pure and mixed anaerobic digestion systems were investigated. Results showed the growth and metabolism of Acetobacteroides hydrogenigenes were partly inhibited by nanoplastic existed in the pure anaerobic digestion system. The anaerobic digestion of sewage sludge was also obviously inhibited by nanoplastic existed in the mixed anaerobic digestion system. Both the methane yield and methane production rate of the mixed anaerobic digestion system showed negative correlation with the nanoplastic concentration. Compared with anaerobic digestion system without nanoplastic, methane yield and maximum daily methane yield at the nanoplastic concentration of 0.2g/L decreased for 14.4% and 40.7%, respectively. In addition, the start-up of mixed anaerobic digestion system was prolonged by addition of nanoplastic. Microbial community structure analysis indicated the microbial community structures were also affected by nanoplastic existed in the system. At the nanoplastic concentration of 0.2g/L, the relative abundances of family Cloacamonaceae, Porphyromonadaceae, Anaerolinaceae and Gracilibacteraceae decreased partly. Conversely, the relative abundances of family Anaerolinaceae, Clostridiaceae, Geobacteraceae, Dethiosulfovibrionaceae and Desulfobulbaceae improved partly. Copyright © 2017 Elsevier B.V. All rights reserved.

Time-resolved x-ray diffraction and Raman studies of the phase transition mechanisms of methane hydrate

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

Hirai, Hisako, E-mail: hirai@sci.ehime-u.ac.jp; Kadobayashi, Hirokazu; Hirao, Naohisa

The mechanisms by which methane hydrate transforms from an sI to sH structure and from an sH to filled-ice Ih structure were examined using time-resolved X-ray diffractometry (XRD) and Raman spectroscopy in conjunction with charge-coupled device camera observation under fixed pressure conditions. The XRD data obtained for the sI–sH transition at 0.8 GPa revealed an inverse correlation between sI and sH, suggesting that the sI structure is replaced by sH. Meanwhile, the Raman analysis demonstrated that although the 12-hedra of sI are retained, the 14-hedra are replaced sequentially by additional 12-hedra, modified 12-hedra, and 20-hedra cages of sH. With themore » sH to filled-ice Ih transition at 1.8 GPa, both the XRD and Raman data showed that this occurs through a sudden collapse of the sH structure and subsequent release of solid and fluid methane that is gradually incorporated into the filled-ice Ih to complete its structure. This therefore represents a typical reconstructive transition mechanism.« less

Conceptual design of tetraazaporphyrin- and subtetraazaporphyrin-based functional nanocarbon materials: electronic structures, topologies, optical properties, and methane storage capacities.

PubMed

Belosludov, Rodion V; Rhoda, Hannah M; Zhdanov, Ravil K; Belosludov, Vladimir R; Kawazoe, Yoshiyuki; Nemykin, Victor N

2016-05-11

A large variety of conceptual three- and fourfold tetraazaporphyrin- and subtetraazaporphyrin-based functional 3D nanocage and nanobarrel structures have been proposed on the basis of in silico design. The designed structures differ in their sizes, topology, porosity, and conjugation properties. The stability of nanocages of Oh symmetry and nanobarrels of D4h symmetry was revealed on the basis of DFT and MD calculations, whereas their optical properties were assessed using a TDDFT approach and a long-range corrected LC-wPBE exchange-correlation functional. It was shown that the electronic structures and vertical excitation energies of the functional nanocage and nanobarrel structures could be easily tuned via their size, topology, and the presence of bridging sp(3) carbon atoms. TDDFT calculations suggest significantly lower excitation energies in fully conjugated nanocages and nanobarrels compared with systems with bridging sp(3) carbon fragments. Based on DFT and TDDFT calculations, the optical properties of the new materials can rival those of known quantum dots and are superior to those of monomeric phthalocyanines and their analogues. The methane gas adsorption properties of the new nanostructures and nanotubes generated by conversion from nanobarrels were studied using an MD simulation approach. The ability to store large quantities of methane (106-216 cm(3) (STP) cm(-3)) was observed in all cases with several compounds being close to or exceeding the DOE target of 180 cm(3) (STP) cm(-3) for material-based methane storage at a pressure of 3.5 MPa and room temperature.

How Does Poly(hydroxyalkanoate) Affect Methane Production from the Anaerobic Digestion of Waste-Activated Sludge?

PubMed

Wang, Dongbo; Zhao, Jianwei; Zeng, Guangming; Chen, Yinguang; Bond, Philip L; Li, Xiaoming

2015-10-20

Recent studies demonstrate that, besides being used for production of biodegradable plastics, poly(hydroxyalkanoate) (PHA) that is accumulated in heterotrophic microorganisms during wastewater treatment has another novel application direction, i.e., being utilized for enhancing methane yield during the anaerobic digestion of waste-activated sludge (WAS). To date, however, the underlying mechanism of how PHA affects methane production remains largely unknown, and this limits optimization and application of the strategy. This study therefore aims to fill this knowledge gap. Experimental results showed that with the increase of sludge PHA levels from 21 to 184 mg/g of volatile suspended solids (VSS) the methane yield linearly increased from 168.0 to 246.1 mL/g of VSS (R(2) = 0.9834). Compared with protein and carbohydrate (the main components of a cell), PHA exhibited a higher biochemical methane potential on a unit VSS basis. It was also found that the increased PHA not only enhanced cell disruption of PHA cells but also benefited the soluble protein conversion of both PHA- and non-PHA cells. Moreover, the reactor fed with higher PHA sludge showed greater sludge hydrolysis and acidification than those fed with the lower PHA sludges. Further investigations using fluorescence in situ hybridization and enzyme analysis revealed that the increased PHA enhanced the abundance of methanogenic Archaea and increased the activities of protease, acetate kinase, and coenzyme F420, which were consistent with the observed methane yield. This work provides insights into PHA-involved WAS digestion systems and may have important implications for future operation of wastewater treatment plants.

A Non-Steady-State Condition in Sediments at the Gashydrate Stability Boundary off West Spitsbergen: Evidence for Gashydrate Dissociation or Just Dynamic Methane Transport?

NASA Astrophysics Data System (ADS)

Treude, T.; Krause, S.; Bertics, V. J.; Steinle, L.; Niemann, H.; Liebetrau, V.; Feseker, T.; Burwicz, E.; Krastel, S.; Berndt, C.

2014-12-01

In 2008, a large area with several hundred methane plumes was discovered along the West Spitsbergen continental margin at water depths between 150 and 400 m (Westbrook et al. 2009, GRL 36, doi:10.1029/2009GL039191). Many of the observed plumes were located at the boundary of gas hydrate stability (~400 m water depth). It was speculated that the methane escape at this depth was correlated with gas hydrate destabilization caused by recent increases in water temperatures recorded in this region. In a later study, geochemical analyses of authigenic carbonates and modeling of heat flow data combined with seasonal changes in water temperature demonstrated that the methane seeps were active already prior to industrial warming but that the gas hydrate system nevertheless reacts very sensitive to even seasonal temperature changes (Berndt et al. 2014, Science 343: 284-287). Here, we report about a methane seep site at the gas hydrate stability boundary (394 m water depth) that features unusual geochemical profiles indicative for non-steady state conditions. Sediment was recovered with a gravity corer (core length 210 cm) and samples were analyzed to study porewater geochemistry, methane concentration, authigenic carbonates, and microbial activity. Porewater profiles revealed two zones of sulfate-methane transition at 50 and 200 cm sediment depth. The twin zones were confirmed by a double peaking in sulfide, total alkalinity, anaerobic oxidation of methane, and sulfate reduction. δ18O values sharply increased from around -2.8 ‰ between 0 and 126 cm to -1.2 ‰ below 126 cm sediment depth. While U/Th isotope measurements of authigenic seep carbonates that were collected from different depths of the core illustrated that methane seepage must be occurring at this site since at least 3000 years, the biogeochemical profiles suggest that methane flux must have been altered recently. By applying a multi-phase reaction-transport model using known initial parameters from the study site (e.g. water depth, temperature profile, salinity, and sediment surface concentrations of CH4, SO4, DIC, and POC) were able to show that the observed twin sulfate-methane transition zones are an ephemeral phenomenon occurring during increase of methane production in the sediment, which can be introduced by, e.g., gas hydrate dissociation.

Constraining the relationships between anaerobic oxidation of methane and sulfate reduction under in situ methane concentrations

NASA Astrophysics Data System (ADS)

Zhuang, G.; Wegener, G.; Joye, S. B.

2017-12-01

The anaerobic oxidation of methane (AOM) is an important microbial metabolism in the global carbon cycle. In marine methane seeps sediment, this process is mediated by syntrophic consortium that includes anaerobic methanotrophic archaea (ANME) and sulfate-reducing bacteria (SRB). Stoichiometrically in AOM methane oxidation should be coupled to sulfate reduction (SR) in a 1:1 ratio. However, weak coupling of AOM and SR in seep sediments was frequently observed from the ex situ rate measurements, and the metabolic dynamics of AOM and SR under in situ conditions remain poorly understood. Here we investigated the metabolic activity of AOM and SR with radiotracers by restoring in situ methane concentrations under pressure to constrain the in situ relationships between AOM and SR in the cold seep sediments of Gulf of Mexico as well as the sediment-free AOM enrichments cultivated from cold seep of Italian Island Elba or hydrothermal vent of Guaymas Basin5. Surprisingly, we found that AOM rates strongly exceeded those of SR when high pressures and methane concentrations were applied at seep sites of GC600 and GC767 in Gulf of Mexico. With the addition of molybdate, SR was inhibited but AOM was not affected, suggesting the potential coupling of AOM with other terminal processes. Amendments of nitrate, iron, manganese and AQDS to the SR-inhibited slurries did not stimulate or inhibit the AOM activity, indicating either those electron acceptors were not limiting for AOM in the sediments or AOM was coupled to other process (e.g., organic matter). In the ANME enrichments, higher AOM rates were also observed with the addition of high concentrations of methane (10mM and 50 mM). The tracer transfer of CO2 to methane, i.e., the back reaction of AOM, increased with increasing methane concentrations and accounted for 1%-5% of the AOM rates. AOM rates at 10 mM and 50 mM methane concentration were much higher than the SR rates, suggesting those two processes were not tightly coupled. Collectively, our results provided evidence for the possible decoupling of AOM and SR under in situconditions. This decoupling appears to be widespread in methane-rich marine sediment, motivating a wide variety of future research endeavors.

Methane baseline concentrations and sources in shallow aquifers from the shale gas-prone region of the St. Lawrence lowlands (Quebec, Canada).

PubMed

Moritz, Anja; Hélie, Jean-Francois; Pinti, Daniele L; Larocque, Marie; Barnetche, Diogo; Retailleau, Sophie; Lefebvre, René; Gélinas, Yves

2015-04-07

Hydraulic fracturing is becoming an important technique worldwide to recover hydrocarbons from unconventional sources such as shale gas. In Quebec (Canada), the Utica Shale has been identified as having unconventional gas production potential. However, there has been a moratorium on shale gas exploration since 2010. The work reported here was aimed at defining baseline concentrations of methane in shallow aquifers of the St. Lawrence Lowlands and its sources using δ(13)C methane signatures. Since this study was performed prior to large-scale fracturing activities, it provides background data prior to the eventual exploitation of shale gas through hydraulic fracturing. Groundwater was sampled from private (n = 81), municipal (n = 34), and observation (n = 15) wells between August 2012 and May 2013. Methane was detected in 80% of the wells with an average concentration of 3.8 ± 8.8 mg/L, and a range of <0.0006 to 45.9 mg/L. Methane concentrations were linked to groundwater chemistry and distance to the major faults in the studied area. The methane δ(1)(3)C signature of 19 samples was > -50‰, indicating a potential thermogenic source. Localized areas of high methane concentrations from predominantly biogenic sources were found throughout the study area. In several samples, mixing, migration, and oxidation processes likely affected the chemical and isotopic composition of the gases, making it difficult to pinpoint their origin. Energy companies should respect a safe distance from major natural faults in the bedrock when planning the localization of hydraulic fracturation activities to minimize the risk of contaminating the surrounding groundwater since natural faults are likely to be a preferential migration pathway for methane.

Methane attenuates retinal ischemia/reperfusion injury via anti-oxidative and anti-apoptotic pathways.

PubMed

Liu, Lin; Sun, Qinglei; Wang, Ruobing; Chen, Zeli; Wu, Jiangchun; Xia, Fangzhou; Fan, Xian-Qun

2016-09-01

Retinal ischemia/reperfusion injury (IRI) may cause incurable visual impairment due to neural regeneration limits. Methane was shown to exert a protective effect against IRI in many organs. This study aims to explore the possible protective effects of methane-rich saline against retinal IRI in rat. Retinal IRI was performed on the right eyes of male Sprague-Dawley rats, which were immediately injected intraperitoneally with methane-saturated saline (25ml/kg). At one week after surgery, the number of retinal ganglion cells (RGCs), total retinal thickness, visual function were measured by hematoxylin and eosin staining, FluoroGold anterograde labeling and flash visual evoked potentials. The levels of 8-hydroxy-2-deoxyguanosine (8-OHdG), 4-Hydroxy-2-nonenal (4-HNE), malondialdehyde (MDA), superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GPx), caspase-3, caspase-9, B cell lymphoma/leukemia-2 (Bcl-2) and Bcl-2 associated X protein (Bax) in retinas were assessed by immunofluorescence staining, enzyme-linked immunosorbent assay and quantitative polymerase chain reaction. As expected, methane treatment significantly improved the retinal IRI-induced RGC loss, total retinal layer thinning and visual dysfunction. Moreover, methane treatment significantly reduced the levels of oxidative stress biomarkers (8-OHdG, 4-HNE, MDA) and increased the antioxidant enzyme activities (SOD, CAT, GPx) in the retinas with IRI. Meanwhile, methane treatment significantly increased the anti-apoptotic gene (Bcl-2) expression and decreased the pro-apoptotic gene (Bax) expression, accompanied by the suppression of caspase-3 and caspase-9 activity. Thus, these data demonstrated that methane can exert a neuroprotective role against retinal IRI through anti-oxidative and anti-apoptotic pathways. Copyright © 2016. Published by Elsevier B.V.

Non-Detection of Methane in the Mars Atmosphere by the Curiosity Rover

NASA Technical Reports Server (NTRS)

Webster, Chris R.; Mahaffy, Paul R.; Atreya, Sushil K.; Flesch, Gregory J.; Farley, Kenneth A.

2014-01-01

By analogy with Earth, methane in the atmosphere of Mars is a potential signature of ongoing or past biological activity on the planet. During the last decade, Earth-based telescopic and Mars orbit remote sensing instruments have reported significant abundances of methane in the Martian atmosphere ranging from several to tens of parts-per-billion by volume (ppbv). Observations from Earth showed plumes of methane with variations on timescales much faster than expected and inconsistent with localized patches seen from orbit, prompting speculation of sources from sub-surface methanogen bacteria, geological water-rock reactions or infall from comets, micro-meteorites or interplanetary dust. From measurements on NASAs Curiosity Rover that landed near Gale Crater on 5th August 2012, we here report no definitive detection of methane in the near-surface Martian atmosphere. Our in situ measurements were made using the Tunable Laser Spectrometer (TLS) in the Sample Analysis at Mars (SAM) instrument suite6 that made three separate searches on Martian sols 79, 81 and 106 after landing. The measured mean value of 0.39 plus or minus 1.4 ppbv corresponds to an upper limit for methane abundance of 2.7 ppbv at the 95 confidence level. This result is in disagreement with both the remote sensing spacecraft observations taken at lower sensitivity and the telescopic observations that relied on subtraction of a very large contribution from terrestrial methane in the intervening observation path. Since the expected lifetime of methane in the Martian atmosphere is hundreds of years, our results question earlier observations and set a low upper limit on the present day abundance, reducing the probability of significant current methanogenic microbial activity on Mars.

Shifts of methanogenic communities in response to permafrost thaw results in rising methane emissions and soil property changes.

PubMed

Wei, Shiping; Cui, Hongpeng; Zhu, Youhai; Lu, Zhenquan; Pang, Shouji; Zhang, Shuai; Dong, Hailiang; Su, Xin

2018-05-01

Permafrost thaw can bring negative consequences in terms of ecosystems, resulting in permafrost collapse, waterlogging, thermokarst lake development, and species composition changes. Little is known about how permafrost thaw influences microbial community shifts and their activities. Here, we show that the dominant archaeal community shifts from Methanomicrobiales to Methanosarcinales in response to the permafrost thaw, and the increase in methane emission is found to be associated with the methanogenic archaea, which rapidly bloom with nearly tenfold increase in total number. The mcrA gene clone libraries analyses indicate that Methanocellales/Rice Cluster I was predominant both in the original permafrost and in the thawed permafrost. However, only species belonging to Methanosarcinales showed higher transcriptional activities in the thawed permafrost, indicating a shift of methanogens from hydrogenotrophic to partly acetoclastic methane-generating metabolic processes. In addition, data also show the soil texture and features change as a result of microbial reproduction and activity induced by this permafrost thaw. Those data indicate that microbial ecology under warming permafrost has potential impacts on ecosystem and methane emissions.

Methane Ebullition in Temperate Hydropower Reservoirs and Implications for US Policy on Greenhouse Gas Emissions.

PubMed

Miller, Benjamin L; Arntzen, Evan V; Goldman, Amy E; Richmond, Marshall C

2017-10-01

The United States is home to 2198 dams actively used for hydropower production. With the December 2015 consensus adoption of the United Nations Framework Convention on Climate Change Paris Agreement, it is important to accurately quantify anthropogenic greenhouse gas emissions. Methane ebullition, or methane bubbles originating from river or lake sediments, has been shown to account for nearly all methane emissions from tropical hydropower reservoirs to the atmosphere. However, distinct ebullitive methane fluxes have been studied in comparatively few temperate hydropower reservoirs globally. This study measures ebullitive and diffusive methane fluxes from two eastern Washington reservoirs, and synthesizes existing studies of methane ebullition in temperate, boreal, and tropical hydropower reservoirs. Ebullition comprises nearly all methane emissions (>97%) from this study's two eastern Washington hydropower reservoirs to the atmosphere. Summer methane ebullition from these reservoirs was higher than ebullition in six southeastern U.S. hydropower reservoirs, however it was similar to temperate reservoirs in other parts of the world. Our literature synthesis suggests that methane ebullition from temperate hydropower reservoirs can be seasonally elevated compared to tropical climates, however annual emissions are likely to be higher within tropical climates, emphasizing the possible range of methane ebullition fluxes and the need for the further study of temperate reservoirs. Possible future changes to the Intergovernmental Panel on Climate Change and UNFCCC guidelines for national greenhouse gas inventories highlights the need for accurate assessment of reservoir emissions.

Methane Ebullition in Temperate Hydropower Reservoirs and Implications for US Policy on Greenhouse Gas Emissions

NASA Astrophysics Data System (ADS)

Miller, Benjamin L.; Arntzen, Evan V.; Goldman, Amy E.; Richmond, Marshall C.

2017-10-01

The United States is home to 2198 dams actively used for hydropower production. With the December 2015 consensus adoption of the United Nations Framework Convention on Climate Change Paris Agreement, it is important to accurately quantify anthropogenic greenhouse gas emissions. Methane ebullition, or methane bubbles originating from river or lake sediments, has been shown to account for nearly all methane emissions from tropical hydropower reservoirs to the atmosphere. However, distinct ebullitive methane fluxes have been studied in comparatively few temperate hydropower reservoirs globally. This study measures ebullitive and diffusive methane fluxes from two eastern Washington reservoirs, and synthesizes existing studies of methane ebullition in temperate, boreal, and tropical hydropower reservoirs. Ebullition comprises nearly all methane emissions (>97%) from this study's two eastern Washington hydropower reservoirs to the atmosphere. Summer methane ebullition from these reservoirs was higher than ebullition in six southeastern U.S. hydropower reservoirs, however it was similar to temperate reservoirs in other parts of the world. Our literature synthesis suggests that methane ebullition from temperate hydropower reservoirs can be seasonally elevated compared to tropical climates, however annual emissions are likely to be higher within tropical climates, emphasizing the possible range of methane ebullition fluxes and the need for the further study of temperate reservoirs. Possible future changes to the Intergovernmental Panel on Climate Change and UNFCCC guidelines for national greenhouse gas inventories highlights the need for accurate assessment of reservoir emissions.

Enzymes involved in the anaerobic oxidation of n-alkanes: from methane to long-chain paraffins

PubMed Central

Callaghan, Amy V.

2013-01-01

Anaerobic microorganisms play key roles in the biogeochemical cycling of methane and non-methane alkanes. To date, there appear to be at least three proposed mechanisms of anaerobic methane oxidation (AOM). The first pathway is mediated by consortia of archaeal anaerobic methane oxidizers and sulfate-reducing bacteria (SRB) via “reverse methanogenesis” and is catalyzed by a homolog of methyl-coenzyme M reductase. The second pathway is also mediated by anaerobic methane oxidizers and SRB, wherein the archaeal members catalyze both methane oxidation and sulfate reduction and zero-valent sulfur is a key intermediate. The third AOM mechanism is a nitrite-dependent, “intra-aerobic” pathway described for the denitrifying bacterium, ‘Candidatus Methylomirabilis oxyfera.’ It is hypothesized that AOM proceeds via reduction of nitrite to nitric oxide, followed by the conversion of two nitric oxide molecules to dinitrogen and molecular oxygen. The latter can be used to functionalize the methane via a particulate methane monooxygenase. With respect to non-methane alkanes, there also appear to be novel mechanisms of activation. The most well-described pathway is the addition of non-methane alkanes across the double bond of fumarate to form alkyl-substituted succinates via the putative glycyl radical enzyme, alkylsuccinate synthase (also known as methylalkylsuccinate synthase). Other proposed mechanisms include anaerobic hydroxylation via ethylbenzene dehydrogenase-like enzymes and an “intra-aerobic” denitrification pathway similar to that described for ‘Methylomirabilis oxyfera.’ PMID:23717304

Detection of Abiotic Methane in Terrestrial Continental Hydrothermal Systems: Implications for Methane on Mars

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Niles, Paul B.; Gibson, Everett K., Jr.; Romanek, Christopher S.; Zhang, Chuanlun L.; Bissada, Kadry K.

2008-01-01

The recent detection of methane in the Martian atmosphere and the possibility that its origin could be attributed to biological activity, have highlighted the importance of understanding the mechanisms of methane formation and its usefulness as a biomarker. Much debate has centered on the source of the methane in hydrothermal fluids, whether it is formed biologically by microorganisms, diagenetically through the decomposition of sedimentary organic matter, or inorganically via reduction of CO2 at high temperatures. Ongoing research has now shown that much of the methane present in sea-floor hydrothermal systems is probably formed through inorganic CO2 reduction processes at very high temperatures (greater than 400 C). Experimental results have indicated that methane might form inorganically at temperatures lower still, however these results remain controversial. Currently, methane in continental hydrothermal systems is thought to be formed mainly through the breakdown of sedimentary organic matter and carbon isotope equilibrium between CO2 and CH4 is thought to be rarely present if at all. Based on isotopic measurements of CO2 and CH4 in two continental hydrothermal systems, we suggest that carbon isotope equilibration exists at temperatures as low as 155 C. This would indicate that methane is forming through abiotic CO2 reduction at lower temperatures than previously thought and could bolster arguments for an abiotic origin of the methane detected in the martian atmosphere.

Potential sources of hydrocarbons and their microbial degradation in sediments from the deep geothermal Lusi site, Indonesia

NASA Astrophysics Data System (ADS)

Krueger, Martin; Mazzini, Adriano; Scheeder, Georg; Blumenberg, Martin

2017-04-01

The Lusi eruption represents one of the largest ongoing sedimentary hosted geothermal systems, which started in 2006 following an earthquake on Java Island. Since then it has been continuously producing hot and hydrocarbon rich mud from a central crater with peaks reaching 180.000 m3 per day. Numerous investigations focused on the study of microbial communities which thrive at offshore methane and oil seeps and mud volcanoes, however very little has been done on onshore seeping structures. Lusi represents a unique opportunity to complete a comprehensive study of onshore microbial communities fed by the seepage of CH4 as well as of liquid hydrocarbons originating from one or more km below the surface. While the source of the methane at Lusi is unambiuous, the origin of the seeping oil is still discussed. Both, source and maturity estimates from biomarkers, are in favor of a type II/III organic matter source. Likely the oils were formed from the studied black shales (deeper Ngimbang Fm.) which contained a Type III component in the Type II predominated organic matter. In all samples large numbers of active microorganisms were present. Rates for aerobic methane oxidation were high, as was the potential of the microbial communities to degrade different hydrocarbons. The data suggests a transition of microbial populations from an anaerobic, hydrocarbon-driven metabolism in fresher samples from center or from small seeps to more generalistic, aerobic microbial communities in older, more consolidated sediments. Ongoing microbial activity in crater sediment samples under high temperatures (80-95C) indicate a deep origin of the involved microorganisms. First results of molecular analyses of the microbial community compositions confirm the above findings. This study represents an initial step to better understand onshore seepage systems and provides an ideal analogue for comparison with the better investigated offshore structures.

Response of a continuous anaerobic digester to temperature transitions: A critical range for restructuring the microbial community structure and function.

PubMed

Kim, Jaai; Lee, Changsoo

2016-02-01

Temperature is a crucial factor that significantly influences the microbial activity and so the methanation performance of an anaerobic digestion (AD) process. Therefore, how to control the operating temperature for optimal activity of the microbes involved is a key to stable AD. This study examined the response of a continuous anaerobic reactor to a series of temperature shifts over a wide range of 35-65 °C using a dairy-processing byproduct as model wastewater. During the long-term experiment for approximately 16 months, the reactor was subjected to stepwise temperature increases by 5 °C at a fixed HRT of 15 days. The reactor showed stable performance within the temperature range of 35-45 °C, with the methane production rate and yield being maximum at 45 °C (18% and 26% greater, respectively, than at 35 °C). However, the subsequent increase to 50 °C induced a sudden performance deterioration with a complete cessation of methane recovery, indicating that the temperature range between 45 °C and 50 °C had a critical impact on the transition of the reactor's methanogenic activity from mesophilic to thermophilic. This serious process perturbation was associated with a severe restructuring of the reactor microbial community structure, particularly of methanogens, quantitatively as well as qualitatively. Once restored by interrupted feeding for about two months, the reactor maintained fairly stable performance under thermophilic conditions until it was upset again at 65 °C. Interestingly, in contrast to most previous reports, hydrogenotrophs largely dominated the methanogen community at mesophilic temperatures while acetotrophs emerged as a major group at thermophilic temperature. This implies that the primary methanogenesis route of the reactor shifted from hydrogen- to acetate-utilizing pathways with the temperature shifts from mesophilic to thermophilic temperatures. Our observations suggest that a mesophilic digester may not need to be cooled at up to 45 °C in case of undesired temperature rise, for example, by excessive self-heating, which offers a possibility to reduce operating costs. Copyright © 2015 Elsevier Ltd. All rights reserved.

Biogeochemical Carbon Cycling in Ultrabasic Reducing Springs in Sonoma County, CA

NASA Astrophysics Data System (ADS)

Cotton, J. M.; Morrill, P.; Johnson, O.; Nealson, K. H.; Sherwood Lollar, B.; Eigenbrode, J.; Fogel, M.

2006-12-01

Dissolved gases in the ultrabasic spring waters from The Cedars in Sonoma County, CA were analyzed for concentrations and carbon and hydrogen isotopic ratios in order to determine the geobiological processes occurring in this extreme environment of unknown biological activity. The ultrabasic, highly reducing conditions unique to these springs result from local serpentinization. Gases bubbling from the springs are mainly composed of methane, hydrogen, and nitrogen. Serpentinization is a process characteristic of early Earth, Mars and Titan that is thought to produce abiogenic hydrocarbons as well as provide geochemical energy for chemolithotrophic life. Methane, CO2, hydrogen and nitrogen were detected in the aqueous phases. Earlier work indicated that the primary source of the methane in the free gases bubbling from the springs was associated with microbial fermentation a suspected source of the dissolved methane. Here we report, a negative, linear correlation between concentrations of CO2 and methane that is an indicator of microbial anaerobic methane oxidation taking place in the ultrabasic waters. Furthermore, as the concentrations of methane decrease, the concentration of CO2 increases and both reactant and product become 13C-enriched. These observations are consistent with microbial oxidation of methane, suggesting a biogeochemical carbon cycle exists in these springs. We hypothesize that one group of microbes is breaking down organic matter by a process of fermentation to produce methane and CO2. The CO2 dissolves in the basic springs, while most of the methane escapes solution. The residual dissolved methane undergoes a conversion to CO2 by anaerobic methane oxidation.

Hypotheses for a Near-Surface Reservoir of Methane and Its Release on Mars

NASA Astrophysics Data System (ADS)

Hu, R.; Bloom, A. A.; Gao, P.; Miller, C. E.; Yung, Y. L.

2015-12-01

The Curiosity rover recently detected a background of 0.7 ppb and spikes of 7 ppb of methane on Mars. This in situ measurement reorients our understanding of the Martian environment and its potential for life, as the current theories do not entail any active source or sink of methane. In particular, the 10-fold elevation during the southern winter indicates episodic sources of methane that are yet to be discovered. Using the temperature and humidity measurements from the rover, we find that perchlorate salts in the regolith deliquesce to form liquid solutions, and deliquescence progresses to deeper subsurface in the season of the methane spikes. We therefore formulate the following three testable hypotheses as an attempt to explain the apparent variability of the atmospheric methane abundance. The first scenario is that the regolith in Gale Crater adsorbs methane when dry and releases this methane to the atmosphere upon deliquescence. The adsorption energy needs to be 36 kJ mol-1 to explain the magnitude of the methane spikes, higher than laboratory measurements. The second scenario is that microorganisms exist and convert organic matter in the soil to methane when they are in liquid solutions. This scenario does not require regolith adsorption. The third scenario is that deep subsurface aquifers sealed by ice or clathrate produce bursts of methane as a result of freezing and thawing of the permafrost, as the terrestrial arctic tundra. Continued monitoring of methane by Curiosity will test the existence of the near-surface reservoir and its exchange with the atmosphere.

Metabolically active microbial communities in marine sediment under high-CO2 and low-pH extremes

PubMed Central

Yanagawa, Katsunori; Morono, Yuki; de Beer, Dirk; Haeckel, Matthias; Sunamura, Michinari; Futagami, Taiki; Hoshino, Tatsuhiko; Terada, Takeshi; Nakamura, Ko-ichi; Urabe, Tetsuro; Rehder, Gregor; Boetius, Antje; Inagaki, Fumio

2013-01-01

Sediment-hosting hydrothermal systems in the Okinawa Trough maintain a large amount of liquid, supercritical and hydrate phases of CO2 in the seabed. The emission of CO2 may critically impact the geochemical, geophysical and ecological characteristics of the deep-sea sedimentary environment. So far it remains unclear whether microbial communities that have been detected in such high-CO2 and low-pH habitats are metabolically active, and if so, what the biogeochemical and ecological consequences for the environment are. In this study, RNA-based molecular approaches and radioactive tracer-based respiration rate assays were combined to study the density, diversity and metabolic activity of microbial communities in CO2-seep sediment at the Yonaguni Knoll IV hydrothermal field of the southern Okinawa Trough. In general, the number of microbes decreased sharply with increasing sediment depth and CO2 concentration. Phylogenetic analyses of community structure using reverse-transcribed 16S ribosomal RNA showed that the active microbial community became less diverse with increasing sediment depth and CO2 concentration, indicating that microbial activity and community structure are sensitive to CO2 venting. Analyses of RNA-based pyrosequences and catalyzed reporter deposition-fluorescence in situ hybridization data revealed that members of the SEEP-SRB2 group within the Deltaproteobacteria and anaerobic methanotrophic archaea (ANME-2a and -2c) were confined to the top seafloor, and active archaea were not detected in deeper sediments (13–30 cm in depth) characterized by high CO2. Measurement of the potential sulfate reduction rate at pH conditions of 3–9 with and without methane in the headspace indicated that acidophilic sulfate reduction possibly occurs in the presence of methane, even at very low pH of 3. These results suggest that some members of the anaerobic methanotrophs and sulfate reducers can adapt to the CO2-seep sedimentary environment; however, CO2 and pH in the deep-sea sediment were found to severely impact the activity and structure of the microbial community. PMID:23096400

Molecular dynamics simulations of methane hydrate decomposition.

PubMed

Myshakin, Evgeniy M; Jiang, Hao; Warzinski, Robert P; Jordan, Kenneth D

2009-03-12

Molecular dynamics simulations have been carried out to study decomposition of methane hydrate at different cage occupancies. The decomposition rate is found to depend sensitively on the hydration number. The rate of the destruction of the cages displays Arrhenius behavior, consistent with an activated mechanism. During the simulations, reversible formation of partial water cages around methane molecules in the liquid was observed at the interface at temperatures above the computed hydrate decomposition temperature.

Development of Carbon and Sulphur Tolerant Anodes of Solid Oxide Fuel Cells

DTIC Science & Technology

2010-01-14

LSCM/YSZ) composite anode is investigated in detail for the direct utilization of ethanol and methane (the main component of natural gas) in SOFCs...Impregnation of Pd nanoparticles significantly promotes the electrocatalytic activity of LSCM/YSZ composite anodes for the ethanol and methane... electrooxidation reaction. At 800°C, the electrode polarization resistance for the methane oxidation is reduced by a factor of 3 after impregnation of 0.10

Limitations of microbial hydrocarbon degradation at the Amon mud volcano (Nile deep-sea fan)

NASA Astrophysics Data System (ADS)

Felden, J.; Lichtschlag, A.; Wenzhöfer, F.; de Beer, D.; Feseker, T.; Pop Ristova, P.; de Lange, G.; Boetius, A.

2013-05-01

The Amon mud volcano (MV), located at 1250 m water depth on the Nile deep-sea fan, is known for its active emission of methane and non-methane hydrocarbons into the hydrosphere. Previous investigations showed a low efficiency of hydrocarbon-degrading anaerobic microbial communities inhabiting the Amon MV center in the presence of sulfate and hydrocarbons in the seeping subsurface fluids. By comparing spatial and temporal patterns of in situ biogeochemical fluxes, temperature gradients, pore water composition, and microbial activities over 3 yr, we investigated why the activity of anaerobic hydrocarbon degraders can be low despite high energy supplies. We found that the central dome of the Amon MV, as well as a lateral mud flow at its base, showed signs of recent exposure of hot subsurface muds lacking active hydrocarbon degrading communities. In these highly disturbed areas, anaerobic degradation of methane was less than 2% of the methane flux. Rather high oxygen consumption rates compared to low sulfide production suggest a faster development of more rapidly growing aerobic hydrocarbon degraders in highly disturbed areas. In contrast, the more stabilized muds surrounding the central gas and fluid conduits hosted active anaerobic hydrocarbon-degrading microbial communities. The low microbial activity in the hydrocarbon-vented areas of Amon MV is thus a consequence of kinetic limitations by heat and mud expulsion, whereas most of the outer MV area is limited by hydrocarbon transport.

Potential impact of salinity on methane production from food waste anaerobic digestion.

PubMed

Zhao, Jianwei; Liu, Yiwen; Wang, Dongbo; Chen, Fei; Li, Xiaoming; Zeng, Guangming; Yang, Qi

2017-09-01

Previous studies have demonstrated that the presence of sodium chloride (NaCl) inhibited the production of methane from food waste anaerobic digestion. However, the details of how NaCl affects methane production from food waste remain unknown by now and the efficient approach to mitigate the impact of NaCl on methane production was seldom reported. In this paper, the details of how NaCl affects methane production was first investigated via a series of batch experiments. Experimental results showed the effect of NaCl on methane production was dosage dependent. Low level of NaCl improved the hydrolysis and acidification but inhibited the process of methanogenesis whereas high level of NaCl inhibit both steps of acidification and methanogenesis. Then an efficient approach, i.e. co-digestion of food waste and waste activated sludge, to mitigate the impact of NaCl on methane production was reported. Finally, the mechanisms of how co-digestion mitigates the effect on methane production caused by NaCl in co-digestion system were revealed. These findings obtained in this work might be of great importance for the operation of methane recovery from food waste in the presence of NaCl. Copyright © 2017 Elsevier Ltd. All rights reserved.