Shock vaporization of carbonate and sulfate minerals

NASA Astrophysics Data System (ADS)

Shen, A. H.; Ahrens, T. J.; O'Keefe, J. D.

2001-12-01

Strong shock waves induced by impacts can cause vaporization of rocks and minerals. The products of such process play important roles in planetary differentiation (Yakovlev et al., Geochem. International, 38, 1027, 2000) and in effecting the planetary climate. Many experiments and computer simulations have been performed to simulate the Chicxulub impact at Cretaceous/Tertiary boundary (see, for example, Pierazzo et al., J. Geophys. Res., 103, 28607, 1998 and Pope et al., J. Geophys. Res., 102, 21645, 1997). However, the pressure range for incipient and complete vaporization of carbonates and sulfates are not well constrained, especially, for minerals with various initial porosities. Furthermore, evidence for chemical species in the products of vaporized carbonate and sulfate minerals is almost non-existing. In this study, we employed published Hugoniot data for carbonate and sulfate minerals. By using the methods described in Ahrens (J. Appl. Phys., 43, 2443, 1972) and Ahrens and O'Keefe (The Moon, 4, 214, 1972), we calculated the entropy associated with the thermodynamic states produced by hypervelocity impacts at various velocities for carbonate and sulfate minerals with different initial porosities. The results were compared with the entropy of incipient vaporization and complete vaporization of these minerals to determine the degree of vaporization due to impacts. Moreover, these results are utilized to guide our experimental study in speciation reactions in shock-induced vaporization of carbonates and sulfates.

Toward estimation of origin of methane at ancient seeps — Carbon isotopes of seep carbonates, lipid biomarkers, and adsorbed gas

NASA Astrophysics Data System (ADS)

Miyajima, Yusuke; Watanabe, Yumiko; Ijiri, Akira; Goto, Akiko; Jenkins, Robert; Hasegawa, Takashi; Sakai, Saburo; Matsumoto, Ryo

2017-04-01

Methane is generated mainly by microbial or thermal degradation of organic matter, and the origin of methane can be estimated based on its stable carbon isotopic signature. Seafloor seepages of methane-charged fluids have been a major source of methane to the ocean, and knowing the origin of methane at the methane seeps can provide valuable insights into the subsurface fluid circulation and biogeochemical processes. Methane seeps in the geological past are archived as authigenic methane-derived carbonate rocks, which precipitate via an alkalinity increase facilitated by microbially mediated anaerobic oxidation of methane. Here we attempted to estimate origins of methane at ancient seeps, based on several proxies preserved within the seep carbonates. We examined methane-seep carbonate rocks in the Japan Sea region, collected from lower Miocene to middle Pleistocene sediments at 11 sites on land, and also carbonate nodules collected from the seafloor off Joetsu, where thermogenic methane is seeping. Carbon isotopic compositions of the carbonates and lipid biomarkers of methane-oxidizing archaea within them were analyzed. In order to directly know original isotopic signatures of methane, we also attempted to extract adsorbed methane through acid dissolution of the powdered carbonates. Early-diagenetic carbonate phases show various δ13C values between -64.7 and -4.7‰ vs. VPDB, suggesting either biogenic or thermogenic, or both origins of methane. A lipid biomarker pentamethylicosane (PMI) extracted from the ancient carbonates has δ13C values mostly lower than -100‰ , whereas that from the modern methane-derived carbonate nodule has a higher value (-80‰ ). The δ13C values of the seeping methane (-36‰ ) and PMI in the modern Joetsu seep carbonate shows an offset of -44‰ . If this carbon isotope offset was similar at the ancient seeps, the δ13C values of PMI indicate that methane at ancient seeps in the Japan Sea region was biogenic in origin, with δ13C

Methane Pyrolysis and Disposing Off Resulting Carbon

NASA Technical Reports Server (NTRS)

Sharma, P. K.; Rapp, D.; Rahotgi, N. K.

1999-01-01

Sabatier/Electrolysis (S/E) is a leading process for producing methane and oxygen for application to Mars ISPP. One significant problem with this process is that it produces an excess of methane for combustion with the amount of oxygen that is produced. Therefore, one must discard roughly half of the methane to obtain the proper stoichiometric methane/oxygen mixture for ascent from Mars. This is a waste of hydrogen, which must be brought from Earth and is difficult to transport to Mars and store on Mars. To reduce the problem of transporting hydrogen to Mars, the S/E process can be augmented by another process which reduces overall hydrogen requirement. Three conceptual approaches for doing this are (i) recover hydrogen from the excess methane produced by the S/E process, (ii) convert the methane to a higher hydrocarbon or other organic with a lower H/C ratio than methane, and (iii) use a separate process (such as zirconia or reverse water gas shift reaction) to produce additional oxygen, thus utilizing all the methane produced by the Sabatier process. We report our results here on recovering hydrogen from the excess methane using pyrolysis of methane. Pyrolysis has the advantage that it produces almost pure hydrogen, and any unreacted methane can pass through the S/E process reactor. It has the disadvantage that disposing of the carbon produced by pyrolysis presents difficulties. The goals of a research program on recovery of hydrogen from methane are (in descending priority order): 1) Study the kinetics of pyrolysis to arrive at a pyrolysis reactor design that produces high yields in a confined volume at the lowest possible operating temperature; 2) Study the kinetics of carbon burnoff to determine whether high yields can be obtained in a confined volume at acceptable operating temperatures; and 3) Investigate catalytic techniques for depositing carbon as a fine soot which can be physically separated from the reactor. In the JPL program, we have made significant

METHOD FOR PRODUCING ISOTOPIC METHANES FROM LITHIUM CARBONATE AND LITHIUM HYDRIDE

DOEpatents

Frazer, J.W.

1959-10-27

A process is descrlbed for the production of methane and for the production of methane containing isotopes of hydrogen and/or carbon. Finely divided lithium hydrlde and litldum carbonate reactants are mixed in intimate contact and subsequently compacted under pressures of from 5000 to 60,000 psl. The compacted lithium hydride and lithium carbenate reactunts are dispised in a gas collecting apparatus. Subsequently, the compact is heated to a temperature in the range 350 to 400 deg C whereupon a solid-solid reaction takes place and gaseous methane is evolved. The evolved methane is contaminated with gaseous hydrogen and a very small amount of CO/sub 2/; however, the desired methane product is separated from sald impurities by well known chemical processes, e.g., condensation in a cold trap. The product methane contalns isotopes of carbon and hydrogen, the Isotopic composition being determined by the carbon isotopes originally present In the lithium carbonate and the hydrogen isotopes originally present in the lithium hydride.

Optimal Estimation Retrieval of Mid-Tropospheric Carbon Dioxide and Methane Using the Atmospheric Infrared Sounder (AIRS) Radiances.

NASA Astrophysics Data System (ADS)

Imbiriba, B.

2017-12-01

Carbon dioxide and methane are the most important anthropogenic greenhouse contributions to climate change. Space-based remote sensing measurements of carbon dioxide and methane would help to understand the generation, absorption and transport mechanisms and characterization of such gases. Space-based hyperspectral thermal infrared remote sensing measurements using NASA's Atmospheric Infrared Sounder (AIRS) instrument can provide 14 years of observations of radiances at the top of the atmosphere.Here we present a Optimal Estimation based retrieval system for surface temperature, water vapor, carbon dioxide, methane, and other trace gases, based on selected AIRS channels that allow for CO2 sensitivity down to the lower part of the middle troposphere. We use the SARTA fast forward model developed at University of Maryland Baltimore County, and use the ERA product for prior state atmospheric profiles.We retrieve CO2 and CH4 column concentrations across 14 years of AIRS measurements, for clear only field-of-views, using the AIRS L1B Calibration Subset. We then compare these to the standard AIRS L2 CO2 retrievals, as well TES, and OCO2 data, and the GlobalView/CarbonTracker CO2/CH4 model data from NOAA. We evaluate the hemispheric seasonal cycles, growth rates, and possible interhemispheric transport. We also evaluate the use of atmospheric nitrous oxide concentration to correct for the errors in the temperature profile.

Methane Pyrolysis and Disposing Off Resulting Carbon

NASA Technical Reports Server (NTRS)

Sharma, P. K.; Rapp, D.; Rahotgi, N. K.

1999-01-01

Sabatier/Electrolysis (S/E) is a leading process for producing methane and oxygen for application to Mars ISPP. One significant problem with this process is that it produces an excess of methane for combustion with the amount of oxygen that is produced. Therefore, one must discard roughly half of the methane to obtain the proper stoichiometric methane/oxygen mixture for ascent from Mars. This is wasteful of hydrogen, which must be brought from Earth and is difficult to transport to Mars and store on Mars. To reduced the problem of transporting hydrogen to Mars, the S/E process can be augmented by another process which reduces overall hydrogen requirement. Three conceptual approaches for doing this are (1) recover hydrogen from the excess methane produced by the S/E process, (2) convert the methane to a higher hydrocarbon or other organic with a lower H/C ratio than methane, and (3) use a separate process (such as zirconia or reverse water gas shift reaction) to produce additional oxygen, thus utilizing all the methane produced by the Sabatier process. We report our results here on recovering hydrogen from the excess methane using pyrolysis of methane. Pyrolysis has the advantage that it produces almost pure hydrogen, and any unreacted methane can pass through the S/E process reactor. It has the disadvantage that disposing of the carbon produced by pyrolysis presents difficulties. Hydrogen may be obtained from methane by pyrolysis in the temperature range 10000-12000C. The main reaction products are hydrogen and carbon, though very small amounts of higher hydrocarbons, including aromatic hydrocarbons are formed. The conversion efficiency is about 95% at 12000C. One needs to distinguish between thermodynamic equilibrium conversion and conversion limited by kinetics in a finite reactor.

Process Parameters for Successful Synthesis of Carbon Nanotubes by Chemical Vapor Deposition: Implications for Chemical Mechanisms and Life-cycle Assessment

NASA Astrophysics Data System (ADS)

Xue, Ke

Manufacturing of carbon nanotubes (CNTs) via chemical vapor deposition (CVD) calls for thermal treatment associated with gas-phase rearrangement and catalyst deposition to achieve high cost efficiency and limited influence on environmental impact. Taking advantage of higher degree of structure control and economical efficiency, catalytic chemical vapor deposition (CCVD) has currently become the most prevailing synthesis approach for the synthesis of large-scale pure CNTs in past years. Because the synthesis process of CNTs dominates the potential ecotoxic impacts, materials consumption, energy consumption and greenhouse gas emissions should be further limited to efficiently reduce life cycle ecotoxicity of carbon naotubes. However, efforts to reduce energy and material requirements in synthesis of CNTs by CCVD are hindered by a lack of mechanistic understanding. In this thesis, the effect of operating parameters, especially the temperature, carbon source concentration, and residence time on the synthesis were studied to improve the production efficiency in a different angle. Thus, implications on the choice of operating parameters could be provided to help the synthesis of carbon nanotubes. Here, we investigated the typical operating parameters in conditions that have yielded successful CNT production in the published academic literature of over seventy articles. The data were filtered by quality of the resultant product and deemed either "successful" or "unsuccessful" according to the authors. Furthermore, growth rate data were tabulated and used as performance metric for the process whenever possible. The data provided us an opportunity to prompt possible and common methods for practioners in the synthesis of CNTs and motivate routes to achieve energy and material minimization. The statistical analysis revealed that methane and ethylene often rely on thermal conversion process to form direct carbon precursor; further, methane and ethylene could not be the direct

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.

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

Near room temperature chemical vapor deposition of graphene with diluted methane and molten gallium catalyst.

PubMed

Fujita, Jun-Ichi; Hiyama, Takaki; Hirukawa, Ayaka; Kondo, Takahiro; Nakamura, Junji; Ito, Shin-Ichi; Araki, Ryosuke; Ito, Yoshikazu; Takeguchi, Masaki; Pai, Woei Wu

2017-09-28

Direct growth of graphene integrated into electronic devices is highly desirable but difficult due to the nominal ~1000 °C chemical vapor deposition (CVD) temperature, which can seriously deteriorate the substrates. Here we report a great reduction of graphene CVD temperature, down to 50 °C on sapphire and 100 °C on polycarbonate, by using dilute methane as the source and molten gallium (Ga) as catalysts. The very low temperature graphene synthesis is made possible by carbon attachment to the island edges of pre-existing graphene nuclei islands, and causes no damages to the substrates. A key benefit of using molten Ga catalyst is the enhanced methane absorption in Ga at lower temperatures; this leads to a surprisingly low apparent reaction barrier of ~0.16 eV below 300 °C. The faster growth kinetics due to a low reaction barrier and a demonstrated low-temperature graphene nuclei transfer protocol can facilitate practical direct graphene synthesis on many kinds of substrates down to 50-100 °C. Our results represent a significant progress in reducing graphene synthesis temperature and understanding its mechanism.

Robust IR Remote Sensing Technique of the Total Column of Trace Gases Including Carbon Dioxide and Methane

NASA Technical Reports Server (NTRS)

Georgieva, E. M.; Heaps, W. S.

2011-01-01

Progress on the development of a differential radiometer based upon the Fabry-Perot interferometer (FPI) for methane (CH4) and carbon dioxide (C02) detection in the atmosphere is presented. Methane measurements are becoming increasingly important as a component of NASA's programs to understand the global carbon cycle and quantifY the threat of global warming. Methane is the third most important greenhouse gas in the Earth's radiation budget (after water vapor and carbon dioxide) and the second most important anthropogenic contributor to global warming. The importance of global warming and air quality to society caused the National Research Council to recommend that NASA develop the following missions [1]: ASCENDS (Active Sensing of C02 Emissions over Nights, Days, and Seasons), GEOCAPE (Geostationary Coastal and Air Pollution Events), and GACM (Global Atmosphere Composition Mission). Though methane measurements are not specifically called out in these missions, ongoing environmental changes have raised the importance of understanding the methane budget. In the decadal survey is stated that "to close the carbon budget, we would also address methane, but the required technology is not obvious at this time. If appropriate and cost-effective methane technology becomes available, we strongly recommend adding a methane capability". In its 2007 report the International Panel on Climate Change identified methane as a key uncertainty in our understanding saying that the causes of recent changes in the growth rate of atmospheric CH4 are not well understood. What we do know is that methane arises from a number of natural sources including wet lands and the oceans plus man made sources from agriculture, as well as coal and petroleum production and distribution. It has recently been pointed out that large amount of methane are frozen in the permafrost of Canada and Siberia. There is a fear that melting of this permafrost driven by global warming may release large amounts of

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

Ancient and methane-derived carbon subsidizes contemporary food webs

NASA Astrophysics Data System (ADS)

Delvecchia, Amanda G.; Stanford, Jack A.; Xu, Xiaomei

2016-11-01

While most global productivity is driven by modern photosynthesis, river ecosystems are supplied by locally fixed and imported carbon that spans a range of ages. Alluvial aquifers of gravel-bedded river floodplains present a conundrum: despite no possibility for photosynthesis in groundwater and extreme paucity of labile organic carbon, they support diverse and abundant large-bodied consumers (stoneflies, Insecta: Plecoptera). Here we show that up to a majority of the biomass carbon composition of these top consumers in four floodplain aquifers of Montana and Washington is methane-derived. The methane carbon ranges in age from modern to up to >50,000 years old and is mostly derived from biogenic sources, although a thermogenic contribution could not be excluded. We document one of the most expansive ecosystems to contain site-wide macroinvertebrate biomass comprised of methane-derived carbon and thereby advance contemporary understanding of basal resources supporting riverine productivity.

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.

Methane hydrate-bearing seeps as a source of aged dissolved organic carbon to the oceans

USGS Publications Warehouse

Pohlman, J.W.; Bauer, J.E.; Waite, W.F.; Osburn, C.L.; Chapman, N.R.

2011-01-01

Marine sediments contain about 500-10,000 Gt of methane carbon, primarily in gas hydrate. This reservoir is comparable in size to the amount of organic carbon in land biota, terrestrial soils, the atmosphere and sea water combined, but it releases relatively little methane to the ocean and atmosphere. Sedimentary microbes convert most of the dissolved methane to carbon dioxide. Here we show that a significant additional product associated with microbial methane consumption is methane-derived dissolved organic carbon. We use ??14 C and ??13 C measurements and isotopic mass-balance calculations to evaluate the contribution of methane-derived carbon to seawater dissolved organic carbon overlying gas hydrate-bearing seeps in the northeastern Pacific Ocean. We show that carbon derived from fossil methane accounts for up to 28% of the dissolved organic carbon. This methane-derived material is much older, and more depleted in 13 C, than background dissolved organic carbon. We suggest that fossil methane-derived carbon may contribute significantly to the estimated 4,000-6,000 year age of dissolved organic carbon in the deep ocean, and provide reduced organic matter and energy to deep-ocean microbial communities. ?? 2011 Macmillan Publishers Limited. All rights reserved.

Methane hydrate-bearing seeps as a source of aged dissolved organic carbon to the oceans

USGS Publications Warehouse

Pohlman, John; Waite, William F.; Bauer, James E.; Osburn, Christopher L.; Chapman, N. Ross

2011-01-01

Marine sediments contain about 500–10,000 Gt of methane carbon1, 2, 3, primarily in gas hydrate. This reservoir is comparable in size to the amount of organic carbon in land biota, terrestrial soils, the atmosphere and sea water combined1, 4, but it releases relatively little methane to the ocean and atmosphere5. Sedimentary microbes convert most of the dissolved methane to carbon dioxide6, 7. Here we show that a significant additional product associated with microbial methane consumption is methane-derived dissolved organic carbon. We use Δ14C and δ13C measurements and isotopic mass-balance calculations to evaluate the contribution of methane-derived carbon to seawater dissolved organic carbon overlying gas hydrate-bearing seeps in the northeastern Pacific Ocean. We show that carbon derived from fossil methane accounts for up to 28% of the dissolved organic carbon. This methane-derived material is much older, and more depleted in 13C, than background dissolved organic carbon. We suggest that fossil methane-derived carbon may contribute significantly to the estimated 4,000–6,000 year age of dissolved organic carbon in the deep ocean8, and provide reduced organic matter and energy to deep-ocean microbial communities.

Development of a Field-Deployable Methane Carbon Isotope Analyzer

NASA Astrophysics Data System (ADS)

Dong, Feng; Baer, Douglas

2010-05-01

Methane is a potent greenhouse gas, whose atmospheric surface mixing ratio has almost doubled compared with preindustrial values. Methane can be produced by biogenic processes, thermogenic processes or biomass, with different isotopic signatures. As a key molecule involved in the radiative forcing in the atmosphere, methane is thus one of the most important molecules linking the biosphere and atmosphere. Therefore precise measurements of mixing ratios and isotopic compositions will help scientists to better understand methane sources and sinks. To date, high precision isotope measurements have been exclusively performed with conventional isotope ratio mass spectrometry, which involves intensive labor and is not readily field deployable. Optical studies using infrared laser spectroscopy have also been reported to measure the isotopic ratios. However, the precision of optical-based analyses, to date, is typically unsatisfactory without pre-concentration procedures. We present characterization of the performance of a portable Methane Carbon Isotope Analyzer (MCIA), based on cavity enhanced laser absorption spectroscopy technique, that provides in-situ measurements of the carbon isotope ratio (13C/12C or del_13C) and methane mixing ratio (CH4). The sample is introduced to the analyzer directly without any requirement for pretreatment or preconcentration. A typical precision of less than 1 per mill (< 0.1%) with a 10-ppm methane sample can be achieved in a measurement time of less than 100 seconds. The MCIA can report carbon isotope ratio and concentration measurements over a very wide range of methane concentrations. Results of laboratory tests and field measurements will be presented.

Growth of Carbon Nanostructure Materials Using Laser Vaporization

NASA Technical Reports Server (NTRS)

Zhu, Shen; Su, Ching-Hua; Lehozeky, S.

2000-01-01

Since the potential applications of carbon nanotubes (CNT) was discovered in many fields, such as non-structure electronics, lightweight composite structure, and drug delivery, CNT has been grown by many techniques in which high yield single wall CNT has been produced by physical processes including arc vaporization and laser vaporization. In this presentation, the growth mechanism of the carbon nanostructure materials by laser vaporization is to be discussed. Carbon nanoparticles and nanotubes have been synthesized using pulsed laser vaporization on Si substrates in various temperatures and pressures. Two kinds of targets were used to grow the nanostructure materials. One was a pure graphite target and the other one contained Ni and Co catalysts. The growth temperatures were 600-1000 C and the pressures varied from several torr to 500 torr. Carbon nanoparticles were observed when a graphite target was used, although catalysts were deposited on substrates before growing carbon films. When the target contains catalysts, carbon nanotubes (CNT) are obtained. The CNT were characterized by scanning electron microscopy, x-ray diffraction, optical absorption and transmission, and Raman spectroscopy. The temperature-and pressure-dependencies of carbon nanotubes' growth rate and size were investigated.

Methane and carbon at equilibrium in source rocks

PubMed Central

2013-01-01

Methane in source rocks may not exist exclusively as free gas. It could exist in equilibrium with carbon and higher hydrocarbons: CH4 + C < = > Hydrocarbon. Three lines of evidence support this possibility. 1) Shales ingest gas in amounts and selectivities consistent with gas-carbon equilibrium. There is a 50% increase in solid hydrocarbon mass when Fayetteville Shale is exposed to methane (450 psi) under moderate conditions (100°C): Rock-Eval S2 (mg g-1) 8.5 = > 12.5. All light hydrocarbons are ingested, but with high selectivity, consistent with competitive addition to receptor sites in a growing polymer. Mowry Shale ingests butane vigorously from argon, for example, but not from methane under the same conditions. 2) Production data for a well producing from Fayetteville Shale declines along the theoretical curve for withdrawing gas from higher hydrocarbons in equilibrium with carbon. 3) A new general gas-solid equilibrium model accounts for natural gas at thermodynamic equilibrium, and C6-C7 hydrocarbons constrained to invariant compositions. The results make a strong case for methane in equilibrium with carbon and higher hydrocarbons. If correct, the higher hydrocarbons in source rocks are gas reservoirs, raising the possibility of substantially more gas in shales than analytically apparent, and far more gas in shale deposits than currently recognized. PMID:24330266

A comparison of observed (HALOE) and modeled (CCM2) methane and stratospheric water vapor

NASA Technical Reports Server (NTRS)

Mote, Philip W.; Holton, James R.; Russell, James M., III; Boville, Byron A.

1993-01-01

Recent measurements (21 September-15 October 1992) of methane and water vapor by the Halogen Occultation Experiment (HALOE) on the Upper Atmosphere Research Satellite (UARS) are compared with model results for the same season from a troposphere-middle atmosphere version of the National Center for Atmospheric Research (NCAR) Community Climate Model (CCM2). Several important features of the two constituent fields are well reproduced by the CCM2, despite the use of simplified methane photochemistry in the CCM2 and some notable differences between the model's zonal mean circulation and climatology. Observed features simulated by the model include the following: 1) subsidence over a deep layer in the Southern Hemisphere polar vortex; 2) widespread dehydration in the polar vortex; and 3) existence of a region of low water vapor mixing ratios extending from the Antarctic into the Northern Hemisphere tropics, which suggests that Antarctic dehydration contributes to midlatitude and tropical dryness in the stratosphere.

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.

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.

Determination of Methane Hydrate Solubility in the Absence of Vapor Phase by in-situ Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Lu, W.; Chou, I.; Burruss, R.

2006-12-01

Prediction of the occurrence, distribution, and evolution of methane hydrate in porous marine sediments requires information on solubilities of methane hydrate in water. Solubilities of methane hydrate in the presence of a vapor phase are well established, but those in the absence of a vapor phase are not well defined with differences up to 30%. We have measured methane concentrations in pure water in equilibrium with sI methane hydrate, in the absence of vapor phase, by in-situ Raman spectroscopy at temperatures (T) from 2 to 20 (± 0.3) °C and pressures (P) at 10, 20, 30, and 40 (± 0.4%) MPa. Methane hydrate was synthesized in a high-pressure capillary optical cell (Chou et al., 2005; Advances in High-Pressure Technology for Geophysical Applications. Ed. J. Chen et al., Chapter 24, p. 475, Elsevier). A small quantity of methane was first loaded in an evacuated cell and then pressurized by water. Hydrate crystals were formed near the liquid-vapor interface near the enclosed end of the optical tube at room T, and were then placed at the center of a USGS-type heating-cooling stage. By adjusting sample P and T, the crystals went through dissolution-formation cycles three to four times in three days until the vapor phase was completely consumed and several crystals (typically 40 x 40 x 10 μm) were formed. These crystals were located at about 200 μm from the enclosed end and were about 20 to 40 μm from each other. Raman spectra were collected for the liquid phase adjacent to hydrate crystals near the enclosed end of the tube. A volumetric decrease in crystal size was observed away from the sampling spot; however, no such volumetric decrease was observed in or near the sampling spot. Therefore, equilibrium was likely established locally within the sampling area. The results are represented by the following linear isobaric equations: 10 MPa: ln [X(CH4)] = 0.06175 T - 6.79507; r2 = 0.9991 (n = 6) 20 MPa: ln [X(CH4)] = 0.06170 T - 6.82816; r2 = 0.9985 (n = 6) 30 MPa

CRISM Observations of Water Vapor and Carbon Monoxide

NASA Technical Reports Server (NTRS)

Smith, Michael D.; Wolff, Michael J.; Clancy, R. Todd

2008-01-01

Near-infrared spectra returned by the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM, [1]) on-board the Mars Reconnaissance Orbiter (MRO) contain the clear spectral signature of several atmospheric gases including carbon dioxide (CO2), water vapor (H2O), and carbon monoxide (CO). Here we describe the seasonal and spatial mapping of water vapor and carbon dioxide for one full Martian year using CRISM spectra.

Long open-path instrument for simultaneously monitoring of methane, CO2 and water vapor

NASA Astrophysics Data System (ADS)

Simeonov, Valentin; Parlange, Marc

2013-04-01

A new, long open-path instrument for monitoring of path-averaged methane, CO2 and water vapor concentrations will be presented. The instrument is built on the monostatic scheme (transceiver -distant retroreflector). A VCSEL with a central wavelength of 1654 nm is used as a light source. The receiver is built around a 20 cm Newtonian telescope. The design optical path length is 2000 m but can be further extended. To avoid distortions in the shape of the spectral lines caused by atmospheric turbulences they are scanned within 1 µs. The expected concentration resolution for the above mentioned path length is of the order of 2 ppb for methane, 100 ppb for CO2 and 100 ppm for water vapor. The instrument is developed at the Swiss Federal Institute of Technology - Lausanne (EPFL) Switzerland and will be used within the GAW+ CH program for long-term monitoring of background methane and CO2 concentrations in the Swiss Alps. The initial calibration validation tests at EPFL were completed in December 2012 and the instrument will be installed at the beginning of 2013 at the High Altitude Research Station Jungfraujoch (HARSJ). The HARSJ is located at 3580 m ASL and is one of the 24 global GAW stations. One of the goals of the project is to compare path-averaged to the ongoing point measurements of methane in order to identify possible influence of the station. Future deployments of a copy of the instrument include the Canadian arctic and Siberian wetlands. The instrument can be used for ground truthing of satellite observation as well.

Influence of Oxygenated Compounds on Reaction Products in a Microwave Plasma Methane Pyrolysis Assembly for Post-Processing of Sabatier Methane

NASA Technical Reports Server (NTRS)

Mansell, J. Matthew; Abney, Morgan B.; Miller, Lee A.

2011-01-01

The state-of-the-art Carbon Dioxide Reduction Assembly (CRA) was delivered to the International Space Station (ISS) in April 2010. The system is designed to accept carbon dioxide from the Carbon Dioxide Removal Assembly and hydrogen from the Oxygen Generation Assembly. The two gases are reacted in the CRA in a Sabatier reactor to produce water and methane. Venting of methane results in an oxygen resupply requirement of about 378 lbs per crew member per year. If the oxygen is supplied as water, the total weight for resupply is about 476 lb per crew member per year. For long-term missions beyond low Earth orbit, during which resupply capabilities will be further limited, recovery of hydrogen from methane is highly desirable. For this purpose, NASA is pursuing development of a Plasma Pyrolysis Assembly (PPA) capable of recovering hydrogen from methane. Under certain conditions, water vapor and carbon dioxide (nominally intended to be separated from the CRA outlet stream) may be present in the PPA feed stream. Thus, testing was conducted in 2010 to determine the effect of these "oxygenated" compounds on PPA performance, particularly the effect of inlet carbon dioxide and water variations on the PPA product stream. This paper discusses the test set-up, analysis, and results of this testing

Influence of Oxygenated Compounds on Reaction Products in a Microwave Plasma Methane Pyrolysis Assembly for Post-Processing of Sabatier Methane

NASA Technical Reports Server (NTRS)

Mansell, J. Matthew; Abney, Morgan B.

2012-01-01

The state-of-the-art Carbon Dioxide Reduction Assembly (CRA) was delivered to the International Space Station (ISS) in April 2010. The system is designed to accept carbon dioxide from the Carbon Dioxide Removal Assembly and hydrogen from the Oxygen Generation Assembly. The two gases are reacted in the CRA in a Sabatier reactor to produce water and methane. Venting of methane results in an oxygen resupply requirement of about 378 lbs per crew member per year. If the oxygen is supplied as water, the total weight for resupply is about 476 lb per crew member per year. For long-term missions beyond low Earth orbit, during which resupply capabilities will be further limited, recovery of hydrogen from methane is highly desirable. For this purpose, NASA is pursuing development of a Plasma Pyrolysis Assembly (PPA) capable of recovering hydrogen from methane. Under certain conditions, water vapor and carbon dioxide (nominally intended to be separated from the CRA outlet stream) may be present in the PPA feed stream. Thus, testing was conducted in 2010 to determine the effect of these oxygenated compounds on PPA performance, particularly the effect of inlet carbon dioxide and water variations on the PPA product stream. This paper discusses the test set-up, analysis, and results of this testing.

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.

On morphology of methane-derived authigenic carbonates

NASA Astrophysics Data System (ADS)

Logvina, E.; Matveeva, T.

2009-04-01

Studies of methane-derived carbonates revealed a great variety their morphological types. Although the processes of these carbonates formation is not clearly understood, it has been suggested that in general bacterially mediated processes of hydrocarbon oxidation, coupled with sulphate reduction, produce unusually high levels of alkalinity and dissolved inorganic carbon in the pore fluids that is partitioned between the precipitating carbonate and CO2 rich plumes which emanate into the water column (Aharon, 1994). These carbonates consist by three main CaCO3 polymorphs - calcite, aragonite and dolomite. Carbonates with different petrography cemented from these polymorphs can be classified according to their specific locality mode of formation and biogenic or non-biogenic origin (Greinert et al., 2002). There are classifications for the authigenic carbonates which are based on petrography, morphology, or based on age and origin. In this work we will consider the petrographical and morphological differences of authigenic carbonates. The large structures vary from 10 to 200 m size, named as chemoherm carbonates. Usually they cemented by pure aragonite with minor Mg-calcite admixture. These chemoherms rise up to 50 m above the seafloor. The structures are irregular in shape and have numerous pores and open pathways resulting from plumbing system of fluid expulsion. This type of authigenic carbonates was observed in the NE Black Sea (Michaelis et al., 2002), at the Hydrate Ridge area (Greinert et al., 2001), at Aleutian accretionary margin (Greinert et al., 2002). Diagenetic carbonates - carbonate cemented sediments both growing at the seafloor or within the sediment framework and showing a large variety of shapes (chimneys, crusts, concretions est.), with grey to dark-grey color. Petrographically the carbonate cement represents by Mg-calcite, protodolomite and dolomite. The diagenetic carbonates occur widely in the fluid venting areas. In particular, diagenetic

Cyclic process for producing methane from carbon monoxide with heat removal

DOEpatents

Frost, Albert C.; Yang, Chang-lee

1982-01-01

Carbon monoxide-containing gas streams are converted to methane by a cyclic, essentially two-step process in which said carbon monoxide is disproportionated to form carbon dioxide and active surface carbon deposited on the surface of a catalyst, and said carbon is reacted with steam to form product methane and by-product carbon dioxide. The exothermic heat of reaction generated in each step is effectively removed during each complete cycle so as to avoid a build up of heat from cycle-to-cycle, with particularly advantageous techniques being employed for fixed bed, tubular and fluidized bed reactor operations.

Extreme (13)C depletion of carbonates formed during oxidation of biogenic methane in fractured granite.

PubMed

Drake, Henrik; Åström, Mats E; Heim, Christine; Broman, Curt; Åström, Jan; Whitehouse, Martin; Ivarsson, Magnus; Siljeström, Sandra; Sjövall, Peter

2015-05-07

Precipitation of exceptionally 13C-depleted authigenic carbonate is a result of, and thus a tracer for, sulphate-dependent anaerobic methane oxidation, particularly in marine sediments. Although these carbonates typically are less depleted in 13C than in the source methane, because of incorporation of C also from other sources, they are far more depleted in 13C (δ13C as light as -69‰ V-PDB) than in carbonates formed where no methane is involved. Here we show that oxidation of biogenic methane in carbon-poor deep groundwater in fractured granitoid rocks has resulted in fracture-wall precipitation of the most extremely 13C-depleted carbonates ever reported, δ13C down to -125‰ V-PDB. A microbial consortium of sulphate reducers and methane oxidizers has been involved, as revealed by biomarker signatures in the carbonates and S-isotope compositions of co-genetic sulphide. Methane formed at shallow depths has been oxidized at several hundred metres depth at the transition to a deep-seated sulphate-rich saline water. This process is so far an unrecognized terrestrial sink of methane.

Vaporization characteristics of carbon heat shields under radiative heating.

NASA Technical Reports Server (NTRS)

Davy, W. C.; Bar-Nun, A.

1972-01-01

Study of the vaporization characteristics of samples of ATJ graphite, a material that has been considered for use on a Jovian probe. These samples were subjected to radiative heating loads of approximately 2 kW/sq cm in argon atmospheres of pressures from 0.00046 to 1 atm. Surface temperatures, mass loss rates, and spatially resolved emission spectral data were recorded. These data are analyzed to determine carbon vapor pressure as a function of temperature and are compared with current models for the vapor pressure of carbon. The effects of finite vaporization (i.e., nonequilibrium) rates are considered and compared with experiment. Estimates of the heat of vaporization from an energy balance are also presented.

Biomass-derived carbon composites for enrichment of dilute methane from underground coal mines.

PubMed

Bae, Jun-Seok; Jin, Yonggang; Huynh, Chi; Su, Shi

2018-07-01

Ventilation air methane (VAM), which is the main source of greenhouse gas emissions from coal mines, has been a great challenge to deal with due to its huge flow rates and dilute methane levels (typically 0.3-1.0 vol%) with almost 100% humidity. As part of our continuous endeavor to further improve the methane adsorption capacity of carbon composites, this paper presents new carbon composites derived from macadamia nut shells (MNSs) and incorporated with carbon nanotubes (CNTs). These new carbon composites were fabricated in a honeycomb monolithic structure to tolerate dusty environment and to minimize pressure drop. This paper demonstrates the importance of biomass particle size distributions when formed in a composite and methane adsorption capacities at low pressures relevant to VAM levels. The selectivity of methane over nitrogen was about 10.4 at each relevant partial pressure, which was much greater than that (6.5) obtained conventionally (at very low pressures), suggesting that capturing methane in the presence of pre-adsorbed nitrogen would be a practical option. The equilibrium and dynamic performance of biomass-derived carbon composites were enhanced by 30 and 84%, respectively, compared to those of our previous carbon fiber composites. In addition, the presence of moisture in ventilation air resulted in a negligible effect on the dynamic VAM capture performance of the carbon composites, suggesting that our carbon composites have a great potential for site applications at coal mines because the cost and performance of solid adsorbents are critical factors to consider. Copyright © 2018 Elsevier Ltd. All rights reserved.

Extreme 13C depletion of carbonates formed during oxidation of biogenic methane in fractured granite

PubMed Central

Drake, Henrik; Åström, Mats E.; Heim, Christine; Broman, Curt; Åström, Jan; Whitehouse, Martin; Ivarsson, Magnus; Siljeström, Sandra; Sjövall, Peter

2015-01-01

Precipitation of exceptionally 13C-depleted authigenic carbonate is a result of, and thus a tracer for, sulphate-dependent anaerobic methane oxidation, particularly in marine sediments. Although these carbonates typically are less depleted in 13C than in the source methane, because of incorporation of C also from other sources, they are far more depleted in 13C (δ13C as light as −69‰ V-PDB) than in carbonates formed where no methane is involved. Here we show that oxidation of biogenic methane in carbon-poor deep groundwater in fractured granitoid rocks has resulted in fracture-wall precipitation of the most extremely 13C-depleted carbonates ever reported, δ13C down to −125‰ V-PDB. A microbial consortium of sulphate reducers and methane oxidizers has been involved, as revealed by biomarker signatures in the carbonates and S-isotope compositions of co-genetic sulphide. Methane formed at shallow depths has been oxidized at several hundred metres depth at the transition to a deep-seated sulphate-rich saline water. This process is so far an unrecognized terrestrial sink of methane. PMID:25948095

Trophic state changes can affect the importance of methane-derived carbon in aquatic food webs.

PubMed

Schilder, Jos; van Hardenbroek, Maarten; Bodelier, Paul; Kirilova, Emiliya P; Leuenberger, Markus; Lotter, André F; Heiri, Oliver

2017-06-28

Methane-derived carbon, incorporated by methane-oxidizing bacteria, has been identified as a significant source of carbon in food webs of many lakes. By measuring the stable carbon isotopic composition (δ 13 C values) of particulate organic matter, Chironomidae and Daphnia spp. and their resting eggs (ephippia), we show that methane-derived carbon presently plays a relevant role in the food web of hypertrophic Lake De Waay, The Netherlands. Sediment geochemistry, diatom analyses and δ 13 C measurements of chironomid and Daphnia remains in the lake sediments indicate that oligotrophication and re-eutrophication of the lake during the twentieth century had a strong impact on in-lake oxygen availability. This, in turn, influenced the relevance of methane-derived carbon in the diet of aquatic invertebrates. Our results show that, contrary to expectations, methane-derived relative to photosynthetically produced organic carbon became more relevant for at least some invertebrates during periods with higher nutrient availability for algal growth, indicating a proportionally higher use of methane-derived carbon in the lake's food web during peak eutrophication phases. Contributions of methane-derived carbon to the diet of the investigated invertebrates are estimated to have ranged from 0-11% during the phase with the lowest nutrient availability to 13-20% during the peak eutrophication phase. © 2017 The Author(s).

Patterns of methane-related carbonate formation in the black sea

NASA Astrophysics Data System (ADS)

Reitner, J.; Peckmann, J.; Reimer, A.; Thiel, V.

2003-04-01

Methane seeps on the northwestern Black Sea shelf were investigated during the GHOSTDABS expedition in 2001. Seep areas close to the Dniepr Canyon are sites of intense carbonate formation. In anoxic waters, at depths between 200 and 400 m, we found three different modes of seepage-induced carbonate precipitation. The most spectacular type comprises up to 4 m high Ca-carbonate towers flushed by methane gas (type 1). These buildups are constructed of cm to dm-scale calcified hollow spheres which are made and later surrounded by microbial mats. At the base of these microbial mats the spheres are stabilized by a continuous rim of carbonate cement. At a later stage, the fragile spheres are entirely cemented by fibrous aragonite and Mg calcite. The towers harbour a highly diverse microbial community, which are, at least in part, based on the anaerobic oxidation of methane (AOM). A second variety of methane-derived carbonates was observed in the vicinity of the large carbonate towers and consists of lenticular concretions growing within the sediment (type 2). The concretions are up to several decimeters in size and consist of Mg calcite crystal aggregates that progressively fuse together, thereby incorporating ambient sedimentary matter. Associated biofilms surrounding the concretions clearly show AOM related populations but exhibit a different community structure and a smaller microbial diversity than type 1 carbonates. Type 3 encompasses background sediments irregularly cemented with microcrystalline Mg-calcite (automicrite). These precipitates may show very thin internal biofilms, and are further characterized by small, “birds eye”-type cavities. These cavities appear to arise from ascending gas bubbles, and are partly cemented by granular to blocky Mg calcites. The internal surfaces are frequently coated by thin biofilms resembling those found associated with type 2 concretions. All studied Ca-carbonates have low d13C values (-25 to -35 permille vs. PDB) and show

What controls deposition rate in electron-beam chemical vapor deposition?

PubMed

White, William B; Rykaczewski, Konrad; Fedorov, Andrei G

2006-08-25

The key physical processes governing electron-beam-assisted chemical vapor deposition are analyzed via a combination of theoretical modeling and supporting experiments. The scaling laws that define growth of the nanoscale deposits are developed and verified using carefully designed experiments of carbon deposition from methane onto a silicon substrate. The results suggest that the chamber-scale continuous transport of the precursor gas is the rate controlling process in electron-beam chemical vapor deposition.

Methane and carbon dioxide emissions from Shan-Chu-Ku landfill site in northern Taiwan.

PubMed

Hegde, Ullas; Chang, Tsan-Chang; Yang, Shang-Shyng

2003-09-01

To investigate the methane and carbon dioxide emissions from landfill, samples were taken of material up to 5 years old from Shan-Chu-Ku landfill located in the northern part of Taiwan. Atmospheric concentrations of carbon dioxide, methane and nitrous oxide ranged from 310 to 530, 2.64 to 20.16 and 0.358 to 1.516 ppmv with the measurement of gas-type open-path Fourier transform infra-red (FTIR) spectroscopy during February 1998 to March 2000, respectively. Average methane emission rate was 13.17, 65.27 and 0.99 mgm(-2)h(-1) measured by the gas chromatography chamber method in 1-2, 2-3 and 5 year-old landfill, respectively. Similarly, average carbon dioxide emission rate was 93.70, 314.60 and 48.46 mgm(-2)h(-1), respectively. About 2-3 year-old landfill had the highest methane and carbon dioxide emission rates among the tested areas, while 5 year-old landfill was the least. Methane emission rate at night in most tested locations was higher than that in the daytime. Total amount of methane and carbon dioxide emission from this landfill was around 171 and 828 ton in 1999, respectively.

Growth of carbon nanotubes at low powers by impedance-matched microwave plasma enhanced chemical vapor deposition method.

PubMed

Chen, S Y; Chang, L W; Peng, C W; Miao, H Y; Lue, Juh-Tzeng

2005-11-01

A solo carbon nanotube (CNT) was successfully grown on nickel electrodes by a microwave plasma enhanced chemical vapor deposition (MPECVD) method equipped with an impedance-matched substrate holder with the reaction gases composed of hydrogen (H2), carbon dioxide (CO2), and methane (CH4) mixtures. An introduction of carbon dioxide gas before CNTs growth, the substrate temperature can easily be reached above 610 degrees C even heated at a low microwave power. This can be enunciated from fact that carbon dioxide inherits with higher bond energy for molecular dissociation, lower thermal conductivity, and higher heat capacity in comparing to other gases. The electron field emissions for randomly aligned CNTs and well-aligned CNTs grown by MPECVD and by radio frequency assisted hot-filament methods, respectively, are measured and compared. The higher field emission characteristic of the randomly aligned CNTs is presumed to be due to the protruded CNTs, which inheriting with less screening effect and manifesting with defects are crucial to play the effective emission sites.

Determination of methane concentrations in water in equilibrium with sI methane hydrate in the absence of a vapor phase by in situ Raman spectroscopy

USGS Publications Warehouse

Lu, W.; Chou, I.-Ming; Burruss, R.C.

2008-01-01

Most submarine gas hydrates are located within the two-phase equilibrium region of hydrate and interstitial water with pressures (P) ranging from 8 to 60 MPa and temperatures (T) from 275 to 293 K. However, current measurements of solubilities of methane in equilibrium with hydrate in the absence of a vapor phase are limited below 20 MPa and 283.15 K, and the differences among these data are up to 30%. When these data were extrapolated to other P-T conditions, it leads to large and poorly known uncertainties. In this study, in situ Raman spectroscopy was used to measure methane concentrations in pure water in equilibrium with sI (structure one) methane hydrate, in the absence of a vapor phase, at temperatures from 276.6 to 294.6 (??0.3) K and pressures at 10, 20, 30 and 40 (??0.4%) MPa. The relationship among concentration of methane in water in equilibrium with hydrate, in mole fraction [X(CH4)], the temperature in K, and pressure in MPa was derived as: X(CH4) = exp [11.0464 + 0.023267 P - (4886.0 + 8.0158 P)/T]. Both the standard enthalpy and entropy of hydrate dissolution at the studied T-P conditions increase slightly with increasing pressure, ranging from 41.29 to 43.29 kJ/mol and from 0.1272 to 0.1330 kJ/K ?? mol, respectively. When compared with traditional sampling and analytical methods, the advantages of our method include: (1) the use of in situ Raman signals for methane concentration measurements eliminates possible uncertainty caused by sampling and ex situ analysis, (2) it is simple and efficient, and (3) high-pressure data can be obtained safely. ?? 2007 Elsevier Ltd. All rights reserved.

Process for producing methane from gas streams containing carbon monoxide and hydrogen

DOEpatents

Frost, Albert C.

1980-01-01

Carbon monoxide-containing gas streams are passed over a catalyst capable of catalyzing the disproportionation of carbon monoxide so as to deposit a surface layer of active surface carbon on the catalyst essentially without formation of inactive coke thereon. The surface layer is contacted with steam and is thus converted to methane and CO.sub.2, from which a relatively pure methane product may be obtained. While carbon monoxide-containing gas streams having hydrogen or water present therein can be used only the carbon monoxide available after reaction with said hydrogen or water is decomposed to form said active surface carbon. Although hydrogen or water will be converted, partially or completely, to methane that can be utilized in a combustion zone to generate heat for steam production or other energy recovery purposes, said hydrogen is selectively removed from a CO--H.sub.2 -containing feed stream by partial oxidation thereof prior to disproportionation of the CO content of said stream.

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.

Revised methane emissions factors and spatially distributed annual carbon fluxes for global livestock.

PubMed

Wolf, Julie; Asrar, Ghassem R; West, Tristram O

2017-09-29

Livestock play an important role in carbon cycling through consumption of biomass and emissions of methane. Recent research suggests that existing bottom-up inventories of livestock methane emissions in the US, such as those made using 2006 IPCC Tier 1 livestock emissions factors, are too low. This may be due to outdated information used to develop these emissions factors. In this study, we update information for cattle and swine by region, based on reported recent changes in animal body mass, feed quality and quantity, milk productivity, and management of animals and manure. We then use this updated information to calculate new livestock methane emissions factors for enteric fermentation in cattle, and for manure management in cattle and swine. Using the new emissions factors, we estimate global livestock emissions of 119.1 ± 18.2 Tg methane in 2011; this quantity is 11% greater than that obtained using the IPCC 2006 emissions factors, encompassing an 8.4% increase in enteric fermentation methane, a 36.7% increase in manure management methane, and notable variability among regions and sources. For example, revised manure management methane emissions for 2011 in the US increased by 71.8%. For years through 2013, we present (a) annual livestock methane emissions, (b) complete annual livestock carbon budgets, including carbon dioxide emissions, and (c) spatial distributions of livestock methane and other carbon fluxes, downscaled to 0.05 × 0.05 degree resolution. Our revised bottom-up estimates of global livestock methane emissions are comparable to recently reported top-down global estimates for recent years, and account for a significant part of the increase in annual methane emissions since 2007. Our results suggest that livestock methane emissions, while not the dominant overall source of global methane emissions, may be a major contributor to the observed annual emissions increases over the 2000s to 2010s. Differences at regional and local scales may help

Vaporization and Zonal Mixing in Performance Modeling of Advanced LOX-Methane Rockets

NASA Technical Reports Server (NTRS)

Williams, George J., Jr.; Stiegemeier, Benjamin R.

2013-01-01

Initial modeling of LOX-Methane reaction control (RCE) 100 lbf thrusters and larger, 5500 lbf thrusters with the TDK/VIPER code has shown good agreement with sea-level and altitude test data. However, the vaporization and zonal mixing upstream of the compressible flow stage of the models leveraged empirical trends to match the sea-level data. This was necessary in part because the codes are designed primarily to handle the compressible part of the flow (i.e. contraction through expansion) and in part because there was limited data on the thrusters themselves on which to base a rigorous model. A more rigorous model has been developed which includes detailed vaporization trends based on element type and geometry, radial variations in mixture ratio within each of the "zones" associated with elements and not just between zones of different element types, and, to the extent possible, updated kinetic rates. The Spray Combustion Analysis Program (SCAP) was leveraged to support assumptions in the vaporization trends. Data of both thrusters is revisited and the model maintains a good predictive capability while addressing some of the major limitations of the previous version.

Using Mass Spectroscopy to Examine Wetland Carbon Flow from Plants to Methane

NASA Astrophysics Data System (ADS)

Waldo, N.; Tfaily, M. M.; Moran, J.; Hu, D.; Cliff, J. B.; Gough, H. L.; Chistoserdova, L.; Beck, D.; Neumann, R. B.

2017-12-01

In the anoxic soil of wetlands, microbes produce methane (CH4), a greenhouse gas. Prior studies have documented an increase in CH4 emissions as plant productivity increases, likely due to plants releasing more labile organic carbon from roots. But in the field, it is difficult to separate changes in plant productivity and root carbon exudation from other seasonal changes that can affect methane emissions, e.g. temperature. Clarifying the role that root exudation plays in fueling methane production is important because increasing atmospheric temperatures and CO2 levels are projected to increase plant productivity and exudation. To advance understanding of climate-methane feedbacks, this study tracked the flow of carbon from plants into the wetland rhizosphere as plant productivity increased in controlled laboratory conditions. We grew Carex aquatilis, a wetland sedge, in peat-filled rootboxes. Both early and late during the plant growth cycle, we exposed plants to headspace 13CO2, which the plants fixed. Some of this labeled carbon was exuded by the roots and used by rhizosphere microbes. We tracked the isotope ratio of emitted CH4 to establish the time required for plant-released carbon to fuel methanogenesis, and to determine the relative contribution of plant-derived carbon to total CH4 emission. We destructively harvested root and rhizosphere samples from various locations that we characterized by isotope ratio mass spectrometry (MS) to determine isotopic enrichment and therefore relative abundance of root exudates. We analyzed additional aliquots of rhizosphere soil by Fourier transform ion cyclotron resonance MS to track chemical changes in soil carbon as root exudates were converted into methane. To advance mechanistic understanding of the synergistic and competitive microbial interactions that affect methane dynamics in the wetland rhizosphere, we used fluorescence in-situ hybridization to visualize microbial community composition and spatial associations

Vibrationally Excited Carbon Monoxide Produced via a Chemical Reaction Between Carbon Vapor and Oxygen

NASA Astrophysics Data System (ADS)

Jans, Elijah R.; Eckert, Zakari; Frederickson, Kraig; Rich, Bill; Adamovich, Igor V.

2017-06-01

Measurements of the vibrational distribution function of carbon monoxide produced via a reaction between carbon vapor and molecular oxygen has shown a total population inversion on vibrational levels 4-7. Carbon vapor, produced using an arc discharge to sublimate graphite, is mixed with an argon oxygen flow. The excited carbon monoxide is vibrationally populated up to level v=14, at low temperatures, T=400-450 K, in a collision-dominated environment, 15-20 Torr, with total population inversions between v=4-7. The average vibrational energy per CO molecule formed by the reaction is 0.6-1.2 eV/molecule, which corresponds to 10-20% of the reaction enthalpy. Kinetic modeling of the flow reactor, including state specific vibrational processes, was performed to infer the vibrational distribution of the products of the reaction. The results show viability of developing of a new chemical CO laser from the reaction of carbon vapor and oxygen.

Methane in the lunar exosphere: Implications for solar wind carbon escape

NASA Astrophysics Data System (ADS)

Hodges, R. Richard

2016-07-01

A positive identification of methane in the lunar exosphere has been made in data from the neutral mass spectrometer on the Lunar Atmosphere and Dust Environment Explorer (LADEE) spacecraft. Like argon-40, methane is adsorbed on the lunar surface during nighttime. However, higher activation energies for methane delay its desorption at sunrise by about an hour local time, creating a postsunrise bulge with peak concentration of approximately 400-450 molecules cm-3 at a reference altitude of 12 km, which is just above the highest topographic feature on the Moon. The rate of escape of carbon as methane derived from the LADEE data is estimated to be in the range 1.5-4.5 × 1021 s-1. A lower bound for solar carbon escape derived separately from Apollo sample analyses is 3.4 × 1021 s-1.

Effect of Propellant Flowrate and Purity on Carbon Deposition in LO2/Methane Gas Generators

NASA Technical Reports Server (NTRS)

Bossard, J. A.; Burkhardt, W. M.; Niiya, K. Y.; Braam, F.

1989-01-01

The generation and deposition of carbon was studied in the Carbon Deposition Program using subscale hardware with LO2/Liquid Natural Gas (LNG) and LO2/Methane propellants at low mixture ratios. The purpose of the testing was to evaluate the effect of methane purity and full scale injection density on carbon deposition. The LO2/LNG gas generator/preburner testing was performed at mixture ratios between 0.24 and 0.58 and chamber pressures from 5.8 to 9.4 MPa (840 to 1370 psia). A total of seven 200 second duration tests were performed. The LNG testing occurred at low injection densities, similar to the previous LO2/RP-1, LO2/propane, and LO2/methane testing performed on the carbon deposition program. The current LO2/methane test series occurred at an injection density factor of approximately 10 times higher than the previous testing. The high injection density LO2/methane testing was performed at mixture ratios between from 0.23 to 0.81 and chamber pressures from 6.4 to 15.2 MPa (925 to 2210 psia). A total of nine high injection density tests were performed. The testing performed demonstrated that low purity methane (LNG) did not produce any detectable change in carbon deposition when compared to pure methane. In addition, the C* performance and the combustion gas temperatures measured were similar to those obtained for pure methane. Similar results were obtained testing pure methane at higher propellant injection densities with coarse injector elements.

Microbial Methane Production Associated with Carbon Steel Corrosion in a Nigerian Oil Field

PubMed Central

Mand, Jaspreet; Park, Hyung S.; Okoro, Chuma; Lomans, Bart P.; Smith, Seun; Chiejina, Leo; Voordouw, Gerrit

2016-01-01

Microbially influenced corrosion (MIC) in oil field pipeline systems can be attributed to many different types of hydrogenotrophic microorganisms including sulfate reducers, methanogens and acetogens. Samples from a low temperature oil reservoir in Nigeria were analyzed using DNA pyrotag sequencing. The microbial community compositions of these samples revealed an abundance of anaerobic methanogenic archaea. Activity of methanogens was demonstrated by incubating samples anaerobically in a basal salts medium, in the presence of carbon steel and carbon dioxide. Methane formation was measured in all enrichments and correlated with metal weight loss. Methanogens were prominently represented in pipeline solids samples, scraped from the inside of a pipeline, comprising over 85% of all pyrosequencing reads. Methane production was only witnessed when carbon steel beads were added to these pipeline solids samples, indicating that no methane was formed as a result of degradation of the oil organics present in these samples. These results were compared to those obtained for samples taken from a low temperature oil field in Canada, which had been incubated with oil, either in the presence or in the absence of carbon steel. Again, methanogens present in these samples catalyzed methane production only when carbon steel was present. Moreover, acetate production was also found in these enrichments only in the presence of carbon steel. From these studies it appears that carbon steel, not oil organics, was the predominant electron donor for acetate production and methane formation in these low temperature oil fields, indicating that the methanogens and acetogens found may contribute significantly to MIC. PMID:26793176

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

Carbon isotope effect during abiogenic oxidation of methane

NASA Astrophysics Data System (ADS)

Kiyosu, Yasuhiro; Roy Krouse, H.

1989-11-01

The oxidation of methane during flow over CuO and Fe 2O 3 has been examined in the temperature range of 400-650°C. The reaction rate and carbon isotope fractionation are dependent upon the choice of oxide and temperature. The activation energy is lower for hematite (8.0 kcal mole -1) than for cupric oxide (16.6 kcal mole -1). The measured ratios of the isotopic rate constants α =k 12/k 13 were found to have temperature dependences given by: 10 3(α - 1) =2.93 × 10 6/T 2 + 8.11 (cupric oxide) 10 3(α - 1) =7.44 × 10 6/T 2 + 6.56 (hematite) Abiogenic oxidation of methane is probably a significant mechanism for fractionating carbon isotopes in nature.

Methane seep carbonates yield clumped isotope signatures out of equilibrium with formation temperatures

DOE PAGES

Loyd, S. J.; Sample, J.; Tripati, R. E.; ...

2016-07-22

Here, methane cold seep systems typically exhibit extensive buildups of authigenic carbonate minerals, resulting from local increases in alkalinity driven by methane oxidation. Here, we demonstrate that modern seep authigenic carbonates exhibit anomalously low clumped isotope values (Δ47), as much as ~0.2‰ lower than expected values. In modern seeps, this range of disequilibrium translates into apparent temperatures that are always warmer than ambient temperatures, by up to 50 °C. We examine various mechanisms that may induce disequilibrium behaviour in modern seep carbonates, and suggest that the observed values result from several factors including kinetic isotopic effects during methane oxidation, mixingmore » of inorganic carbon pools, pH effects and rapid precipitation. Ancient seep carbonates studied here also exhibit potential disequilibrium signals. Ultimately, these findings indicate the predominance of disequilibrium clumped isotope behaviour in modern cold seep carbonates that must be considered when characterizing environmental conditions in both modern and ancient cold seep settings.« less

Infiltration of carbon in pores within coke and charcoal by methane cracking

NASA Astrophysics Data System (ADS)

Shigeno, Y.; Evans, J. W.

1992-08-01

In order to modify metallurgical coke to increase its resistance to oxidation by CO2, pores within the coke were infiltrated by methane cracking. Carbon produced by methane cracking can impregnate small pores (about 30 nm < pore radius < about 0.3 μm) in which considerable oxidation takes place. This carbon can prevent CO2 from intruding into these pores, reducing the oxidation rate by one third.

A Simulation Model of Carbon Cycling and Methane Emissions in Amazon Wetlands

NASA Technical Reports Server (NTRS)

Potter, Christopher; Melack, John; Hess, Laura; Forsberg, Bruce; Novo, Evlyn Moraes; Klooster, Steven

2004-01-01

An integrative carbon study is investigating the hypothesis that measured fluxes of methane from wetlands in the Amazon region can be predicted accurately using a combination of process modeling of ecosystem carbon cycles and remote sensing of regional floodplain dynamics. A new simulation model has been build using the NASA- CASA concept for predicting methane production and emission fluxes in Amazon river and floodplain ecosystems. Numerous innovations area being made to model Amazon wetland ecosystems, including: (1) prediction of wetland net primary production (NPP) as the source for plant litter decomposition and accumulation of sediment organic matter in two major vegetation classes - flooded forests (varzea or igapo) and floating macrophytes, (2) representation of controls on carbon processing and methane evasion at the diffusive boundary layer, through the lake water column, and in wetland sediments as a function of changes in floodplain water level, (3) inclusion of surface emissions controls on wetland methane fluxes, including variations in daily surface temperature and of hydrostatic pressure linked to water level fluctuations. A model design overview and early simulation results are presented.

More feed efficient sheep produce less methane and carbon dioxide when eating high-quality pellets.

PubMed

Paganoni, B; Rose, G; Macleay, C; Jones, C; Brown, D J; Kearney, G; Ferguson, M; Thompson, A N

2017-09-01

The Australian sheep industry aims to increase the efficiency of sheep production by decreasing the amount of feed eaten by sheep. Also, feed intake is related to methane production, and more efficient (low residual feed intake) animals eat less than expected. So we tested the hypothesis that more efficient sheep produce less methane by investigating the genetic correlations between feed intake, residual feed intake, methane, carbon dioxide, and oxygen. Feed intake, methane, oxygen, and carbon dioxide were measured on Merino ewes at postweaning (1,866 at 223 d old), hogget (1,010 sheep at 607 d old), and adult ages (444 sheep at 1,080 d old). Sheep were fed a high-energy grower pellet ad libitum for 35 d. Individual feed intake was measured using automated feeders. Methane was measured using portable accumulation chambers up to 3 times during this feed intake period. Heritabilities and phenotypic and genotypic correlations between traits were estimated using ASReml. Oxygen (range 0.10 to 0.20) and carbon dioxide (range 0.08 to 0.28) were generally more heritable than methane (range 0.11 to 0.14). Selecting to decrease feed intake or residual feed intake will decrease methane (genetic correlation [] range 0.76 to 0.90) and carbon dioxide ( range 0.65 to 0.96). Selecting to decrease intake ( range 0.64 to 0.78) and methane ( range 0.81 to 0.86) in sheep at postweaning age would also decrease intake and methane in hoggets and adults. Furthermore, selecting for lower residual feed intake ( = 0.75) and carbon dioxide ( = 0.90) in hoggets would also decrease these traits in adults. Similarly, selecting for higher oxygen ( = 0.69) in hoggets would also increase this trait in adults. Given these results, the hypothesis that making sheep more feed efficient will decrease their methane production can be accepted. In addition, carbon dioxide is a good indicator trait for feed intake because it has the highest heritability of the gas traits measured; is cheaper, faster, and

Biogeochemical Cycling of Methane in the Proterozoic and Its Role in the Carbon Isotope Budget

NASA Astrophysics Data System (ADS)

Schrag, D. P.; Laakso, T.

2016-12-01

Various studies have proposed that the biogeochemical cycle of methane has played an important role throughout Earth history, both in contributing to greenhouse stability of climate in the Archean and producing carbon isotope variations and climate fluctuations in the Proterozoic and Phanerozoic. Using a simple box model that couples the geochemical cycles on carbon, oxygen, hydrogen, iron, and sulfur, combined with recent studies of methane cycling in anoxic environments, we reexamine the role of methane in both the Archean and Proterozoic, focusing on methane's role in the carbon isotope budget. We find that methane plays a much more modest role at all times of relative anoxia in the deep ocean, which requires an alternative explanation for the carbon isotope record, in particular the "boring billion" during the Mesoproterozoic. In particular, the high burial efficiency driven by lower oxygen levels drives primary production to much lower levels than has been previously described, resulting in relatively little organic matter available for methanogenesis. In addition, the anoxia in deep water results in a reduced role for methanotrophy at these times, and therefore a change in the mechanisms for production of authigenic carbonate, which may have played a significant role in the carbon isotope budget.

Temperature-pressure conditions in coalbed methane reservoirs of the Black Warrior basin: Implications for carbon sequestration and enhanced coalbed methane recovery

USGS Publications Warehouse

Pashin, J.C.; McIntyre, M.R.

2003-01-01

Sorption of gas onto coal is sensitive to pressure and temperature, and carbon dioxide can be a potentially volatile supercritical fluid in coalbed methane reservoirs. More than 5000 wells have been drilled in the coalbed methane fields of the Black Warrior basin in west-central Alabama, and the hydrologic and geothermic information from geophysical well logs provides a robust database that can be used to assess the potential for carbon sequestration in coal-bearing strata.Reservoir temperature within the coalbed methane target zone generally ranges from 80 to 125 ??F (27-52 ??C), and geothermal gradient ranges from 6.0 to 19.9 ??F/1000 ft (10.9-36.2 ??C/km). Geothermal gradient data have a strong central tendency about a mean of 9.0 ??F/1000 ft (16.4 ??C/km). Hydrostatic pressure gradients in the coalbed methane fields range from normal (0.43 psi/ft) to extremely underpressured (<0.05 psi/ft). Pressure-depth plots establish a bimodal regime in which 70% of the wells have pressure gradients greater than 0.30 psi/ft, and 20% have pressure gradients lower than 0.10 psi/ft. Pockets of underpressure are developed around deep longwall coal mines and in areas distal to the main hydrologic recharge zone, which is developed in structurally upturned strata along the southeastern margin of the basin.Geothermal gradients within the coalbed methane fields are high enough that reservoirs never cross the gas-liquid condensation line for carbon dioxide. However, reservoirs have potential for supercritical fluid conditions beyond a depth of 2480 ft (756 m) under normally pressured conditions. All target coal beds are subcritically pressured in the northeastern half of the coalbed methane exploration fairway, whereas those same beds were in the supercritical phase window prior to gas production in the southwestern half of the fairway. Although mature reservoirs are dewatered and thus are in the carbon dioxide gas window, supercritical conditions may develop as reservoirs

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

Automatic Carbon Dioxide-Methane Gas Sensor Based on the Solubility of Gases in Water

PubMed Central

Cadena-Pereda, Raúl O.; Rivera-Muñoz, Eric M.; Herrera-Ruiz, Gilberto; Gomez-Melendez, Domingo J.; Anaya-Rivera, Ely K.

2012-01-01

Biogas methane content is a relevant variable in anaerobic digestion processing where knowledge of process kinetics or an early indicator of digester failure is needed. The contribution of this work is the development of a novel, simple and low cost automatic carbon dioxide-methane gas sensor based on the solubility of gases in water as the precursor of a sensor for biogas quality monitoring. The device described in this work was used for determining the composition of binary mixtures, such as carbon dioxide-methane, in the range of 0–100%. The design and implementation of a digital signal processor and control system into a low-cost Field Programmable Gate Array (FPGA) platform has permitted the successful application of data acquisition, data distribution and digital data processing, making the construction of a standalone carbon dioxide-methane gas sensor possible. PMID:23112626

Automatic carbon dioxide-methane gas sensor based on the solubility of gases in water.

PubMed

Cadena-Pereda, Raúl O; Rivera-Muñoz, Eric M; Herrera-Ruiz, Gilberto; Gomez-Melendez, Domingo J; Anaya-Rivera, Ely K

2012-01-01

Biogas methane content is a relevant variable in anaerobic digestion processing where knowledge of process kinetics or an early indicator of digester failure is needed. The contribution of this work is the development of a novel, simple and low cost automatic carbon dioxide-methane gas sensor based on the solubility of gases in water as the precursor of a sensor for biogas quality monitoring. The device described in this work was used for determining the composition of binary mixtures, such as carbon dioxide-methane, in the range of 0-100%. The design and implementation of a digital signal processor and control system into a low-cost Field Programmable Gate Array (FPGA) platform has permitted the successful application of data acquisition, data distribution and digital data processing, making the construction of a standalone carbon dioxide-methane gas sensor possible.

Global Methane Budget 2000-2012 (V.1.0, issued June 2016 and V.1.1, issued December 2016)

DOE Data Explorer

Saunois, Marielle [University of Paris - Saclay, Gif-surYvette, France; Bousquet, Phillippe [University of Paris - Saclay, Gif-surYvette, France; Poulter, Ben [NASA Goddard Space Flight Center, Biospheric Science Laboratory, Greenbelt, MD (USA); Peregon, Anna [University of Paris - Saclay, Gif-surYvette, France; Ciais, Philippe [University of Paris - Saclay, Gif-surYvette, France

2016-01-01

After carbon dioxide (CO2), methane (CH4) is the second most important well-mixed greenhouse gas contributing to human-induced climate change. In a time-horizon of 100 years, CH4 has a Global Warming Potential (GWP-100) 28 times larger than CO2. The level of CH4 in the atmosphere is over 150% higher than pre-industrial times (cf. 1750), and it is responsible for 20% of the global warming produced by all well-mixed greenhouse gases. Methane is transformed into water vapor in the stratosphere. Methane also produces ozone in the troposphere, which is a pollutant with negative impacts on human health and ecosystems. The atmospheric life time of methane is 10 ± 2 years. [Copied from the Global Carbon Project, Global Methane Budget Highlights at http://www.globalcarbonproject.org/methanebudget/16/hl-compact.htm

Eddy covariance measurements of methane fluxes over grazed native and improved prairies in Oklahoma

USDA-ARS?s Scientific Manuscript database

Although several studies have reported eddy covariance (EC) measurements at several tallgrass prairie sites to investigate the dynamics of carbon and water vapor fluxes, the EC measurements of methane (CH4) fluxes over grazed tallgrass prairie sites are lacking. CH4 fluxes were measured during the 2...

Seasonal variations in the stable carbon isotopic signature of biogenic methane in a coastal sediment

NASA Technical Reports Server (NTRS)

Martens, C. S.; Green, C. D.; Blair, N. E.; Des Marais, D. J.

1986-01-01

Systematic seasonal variations in the stable carbon isotopic signature of methane gas occur in the anoxic sediments of Cape Lookout Bight, a lagoonal basin on North Carolina's Outer Banks. Values for the carbon isotope ratio of methane range from -57.3 per mil during summer to -68.5 per mil during winter in gas bubbles with an average methane content of 95 percent. The variations are hypothesized to result from changes in the pathways of microbial methane production and cycling of key substrates including acetate and hydrogen. The use of stable isotopic signatures to investigate the global methane cycle through mass balance calculations, involving various sediment and soil biogenic sources, appears to require seasonally averaged data from individual sites.

The carbon isotope biogeochemistry of methane production in anoxic sediments. 1: Field observations

NASA Technical Reports Server (NTRS)

Blair, Neal E.; Boehme, Susan E.; Carter, W. Dale, Jr.

1993-01-01

The natural abundance C-13/C-12 ratio of methane from anoxic marine and freshwater sediments in temperate climates varies seasonally. Carbon isotopic measurements of the methanogenic precursors, acetate and dissolved inorganic carbon, from the marine sediments of Cape Lookout Bight, North Carolina were used to determine the sources of the seasonal variations at that site. Movement of the methanogenic zone over an isotopic gradient within the dissolved CO2 pool appears to be the dominant control of the methane C-13/C-12 ratio from February to June. The onset of acetoclastic methane-production is a second important controlling process during mid-summer. An apparent temperature dependence on the fractionation factor for CO2-reduction may have a significant influence on the isotopic composition of methane throughout the year.

Granular Carbon-Based Electrodes as Cathodes in Methane-Producing Bioelectrochemical Systems

PubMed Central

Liu, Dandan; Roca-Puigros, Marta; Geppert, Florian; Caizán-Juanarena, Leire; Na Ayudthaya, Susakul P.; Buisman, Cees; ter Heijne, Annemiek

2018-01-01

Methane-producing bioelectrochemical systems generate methane by using microorganisms to reduce carbon dioxide at the cathode with external electricity supply. This technology provides an innovative approach for renewable electricity conversion and storage. Two key factors that need further attention are production of methane at high rate, and stable performance under intermittent electricity supply. To study these key factors, we have used two electrode materials: granular activated carbon (GAC) and graphite granules (GG). Under galvanostatic control, the biocathodes achieved methane production rates of around 65 L CH4/m2catproj/d at 35 A/m2catproj, which is 3.8 times higher than reported so far. We also operated all biocathodes with intermittent current supply (time-ON/time-OFF: 4–2′, 3–3′, 2–4′). Current-to-methane efficiencies of all biocathodes were stable around 60% at 10 A/m2catproj and slightly decreased with increasing OFF time at 35 A/m2catproj, but original performance of all biocathodes was recovered soon after intermittent operation. Interestingly, the GAC biocathodes had a lower overpotential than the GG biocathodes, with methane generation occurring at −0.52 V vs. Ag/AgCl for GAC and at −0.92 V for GG at a current density of 10 A/m2catproj. 16S rRNA gene analysis showed that Methanobacterium was the dominant methanogen and that the GAC biocathodes experienced a higher abundance of proteobacteria than the GG biocathodes. Both cathode materials show promise for the practical application of methane-producing BESs. PMID:29946543

Stable carbon isotopic signature of methane from high-emitting wetland sites in discontinuous permafrost landscape

NASA Astrophysics Data System (ADS)

Marushchak, Maija; Liimatainen, Maarit; Lind, Saara; Biasi, Christina; Martikainen, Pertti

2017-04-01

The rising methane concentration in the atmosphere during the past years has been associated with a concurrent change in the carbon isotopic signature: The atmospheric methane is getting more and more depleted in the heavy carbon isotope. The decreasing 13C/12C ratio indicates an increasing contribution of methane from biogenic sources, most importantly wetlands and inland waters, whose global emissions are still poorly constrained. From the climate change perspective, arctic and subarctic wetlands are particularly interesting due to the strong warming and permafrost thaw predicted for these regions that will cause changes in the methane dynamics. Coupling methane flux inventories with determination of the stable isotopic signature can provide useful information about the pathways of methane production, consumption and transport in these ecosystems. Here, we present data on the emissions and carbon isotopic composition of methane from subarctic tundra wetlands at the Seida study site, Northeast European Russia. In this landscape, underlain by discontinuous permafrost, waterlogged fens represent sites of high carbon turnover and high methane release. Despite they cover less than 15% of the region, their methane emissions comprise 98% of the regional mean (± SD) release of 6.7 (± 1.8) g CH4 m-2 y-1 (Marushchak et al. 2016). The methane emission from the studied fens was clearly depleted in 13C compared to the pore water methane. The bulk mean δ13CH4 (± SD) over the growing season was -68.2 (± 2.0) ‰ which is similar to the relatively few values previously reported from tundra wetlands. We explain the depleted methane emissions by the high importance of passive transport via aerenchymous plants, a process that discriminates against the heavier isotopes. This idea is supported by the strong positive correlation observed between the methane emission and the vascular leaf area index (LAI), and the inverse relationship between the δ13CH4 of emitted methane and LAI

Catalyst for the methanation of carbon monoxide in sour gas

DOEpatents

Kustes, William A.; Hausberger, Arthur L.

1985-01-01

The invention involves the synergistic effect of the specific catalytic constituents on a specific series of carriers for the methanation of carbon monoxide in the presence of sulfur at relatively high temperatures and at low steam to gas ratios in the range of 0.2:1 or less. This effect was obtained with catalysts comprising the mixed sulfides and oxides of nickel and chromium supported on carriers comprising magnesium aluminate and magnesium silicate. Conversion of carbon monoxide to methane was in the range of from 40 to 80%. Tests of this combination of metal oxides and sulfides on other carriers and tests of other metal oxides and sulfides on the same carrier produced a much lower level of conversion.

Methane- and dissolved organic carbon-fueled microbial loop supports a tropical subterranean estuary ecosystem

USGS Publications Warehouse

Brankovits, D.; Pohlman, John; Niemann, H.; Leigh, M.B.; Leewis, M.C.; Becker, K. W.; Iliffe, T.M.; Alvarez. F.,; Lehmann, M.F.; Phillips, B.

2017-01-01

Subterranean estuaries extend inland into density-stratified coastal carbonate aquifers containing a surprising diversity of endemic animals (mostly crustaceans) within a highly oligotrophic habitat. How complex ecosystems (termed anchialine) thrive in this globally distributed, cryptic environment is poorly understood. Here, we demonstrate that a microbial loop shuttles methane and dissolved organic carbon (DOC) to higher trophic levels of the anchialine food web in the Yucatan Peninsula (Mexico). Methane and DOC production and consumption within the coastal groundwater correspond with a microbial community capable of methanotrophy, heterotrophy, and chemoautotrophy, based on characterization by 16S rRNA gene amplicon sequencing and respiratory quinone composition. Fatty acid and bulk stable carbon isotope values of cave-adapted shrimp suggest that carbon from methanotrophic bacteria comprises 21% of their diet, on average. These findings reveal a heretofore unrecognized subterranean methane sink and contribute to our understanding of the carbon cycle and ecosystem function of karst subterranean estuaries.

Chemical Production of Vibrationally Excited Carbon Monoxide from Carbon Vapor and Molecular Oxygen Precursors

NASA Astrophysics Data System (ADS)

Frederickson, Kraig; Musci, Ben; Rich, J. William; Adamovich, Igor

2015-09-01

Recent results demonstrating the formation of vibrationally excited carbon monoxide from carbon vapor and molecular oxygen will be presented. Previous reaction dynamics simulations and crossed molecular beam experiments have shown that gas-phase reaction of carbon atoms and molecular oxygen produces vibrationally excited carbon monoxide. The present work examines the product distribution of this reaction in a collision dominated environment, at a pressure of several Torr. Carbon vapor is produced in an AC arc discharge in argon buffer operated at a voltage of approximately 1 kV and current of 10 A, and mixed with molecular oxygen, which may also be excited by an auxiliary RF discharge, in a flowing chemical reactor. Identification of chemical reaction products and inference of their vibrational populations is performed by comparing infrared emission spectra of the flow in the reactor, taken by a Fourier Transform IR spectrometer, with synthetic spectra. Estimates of vibrationally excited carbon monoxide concentration and relative vibrational level populations will be presented.

Numerical simulation of injection process of warm carbon dioxide into layer saturated with methane and its hydrate

NASA Astrophysics Data System (ADS)

Khasanov, M. K.; Stolpovsky, M. V.; Gimaltdinov, I. K.

2018-05-01

In this article, in a flat-one-dimensional approximation, a mathematical model is presented for injecting warm carbon dioxide into a methane hydrate formation of finite length. It is established that the model of formation of hydrate of carbon dioxide in the absence of an area saturated with methane and water, under certain parameters, leads to thermodynamic contradiction. The mathematical model of carbon dioxide injection with formation of the region saturated with methane and water is constructed.

Effects of algal-derived carbon on sediment methane ...

EPA Pesticide Factsheets

Nutrient loading is known to have adverse consequences for aquatic ecosystems, particularly in the form of algal blooms that may result. These blooms pose problems for humans and wildlife, including harmful toxin release, aquatic hypoxia and increased costs for water treatment. Another potential disservice resulting from algal blooms is the enhanced production of methane (CH4), a potent greenhouse gas, in aquatic sediments. Laboratory experiments have shown that algal biomass additions to sediment cores increase rates of CH4 production, but it is unclear whether or not this effect occurs at the ecosystem scale. The goal of this research was to explore the link between algal-derived carbon and methane production in the sediment of a eutrophic reservoir located in southwest Ohio, using a sampling design that capitalized on spatial and temporal gradients in autochthonous carbon input to sediments. Specifically, we aimed to determine if the within-reservoir gradient of sediment algal-derived organic matter and sediment CH4 production rates correlate. This was done by retrieving sediment cores from 15 sites within the reservoir along a known gradient of methane emission rates, at two separate time points in 2016: late spring before the sediments had received large amounts of algal input and mid-summer after algal blooms had been prevalent in the reservoir. Potential CH4 production rates, sediment organic matter source, and microbial community composition were charac

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.

Compact Reconnaissance Imaging Spectrometer Observations of Water Vapor and Carbon Monoxide

NASA Technical Reports Server (NTRS)

Smith, Michael D.; Wolff, Michael J.; Clancy, R. Todd; Murchie, Scott L.

2009-01-01

The Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) onboard the Mars Reconnaissance Orbiter (MRO) spacecraft began taking observations in September 2006 and has now collected more than a full Martian year of data. Retrievals performed using the near-infrared spectra obtained by CRISM are used to characterize the seasonal and spatial variation of the column abundance of water vapor and the column-averaged mixing ratio of carbon monoxide. CRISM retrievals show nominal behavior in water vapor during northern hemisphere spring and summer with maximum abundance reaching 50 precipitable micrometers. Water vapor abundance during the southern hemisphere spring and summer appears significantly reduced compared to observations by other instruments taken during previous years. The CRISM retrievals show the seasonally and globally averaged carbon monoxide mixing ratio to be 700 ppm, but with strong seasonal variations at high latitudes. The summertime near-polar carbon monoxide mixing ratio falls to 200 ppm in the south and 400 ppm in the north as carbon dioxide sublimates from the seasonal polar ice caps and dilutes noncondensable species including carbon monoxide. At low latitudes, the carbon monoxide mixing ratio varies in response to the mean seasonal cycle of surface pressure.

Ground and Airborne Methane Measurements Using Optical Parametric Amplifiers

NASA Technical Reports Server (NTRS)

Numata, Kenji; Riris, Haris; Li, Steve; Wu, Stewart; Kawa, Stephan R.; Abshire, James Brice; Dawsey, Martha; Ramanathan, Anand

2011-01-01

We report on ground and airborne methane measurements with an active sensing instrument using widely tunable, seeded optical parametric generation (OPG). The technique has been used to measure methane, CO2, water vapor, and other trace gases in the near and mid-infrared spectral regions. Methane is a strong greenhouse gas on Earth and it is also a potential biogenic marker on Mars and other planetary bodies. Methane in the Earth's atmosphere survives for a shorter time than CO2 but its impact on climate change can be larger than CO2. Carbon and methane emissions from land are expected to increase as permafrost melts exposing millennial-age carbon stocks to respiration (aerobic-CO2 and anaerobic-CH4) and fires. Methane emissions from c1athrates in the Arctic Ocean and on land are also likely to respond to climate warming. However, there is considerable uncertainty in present Arctic flux levels, as well as how fluxes will change with the changing environment. For Mars, methane measurements are of great interest because of its potential as a strong biogenic marker. A remote sensing instrument that can measure day and night over all seasons and latitudes can localize sources of biogenic gas plumes produced by subsurface chemistry or biology, and aid in the search for extra-terrestrial life. In this paper we report on remote sensing measurements of methane using a high peak power, widely tunable optical parametric generator (OPG) operating at 3.3 micrometers and 1.65 micrometers. We have demonstrated detection of methane at 3.3 micrometers and 1650 nanometers in an open path and compared them to accepted standards. We also report on preliminary airborne demonstration of methane measurements at 1.65 micrometers.

Continuous growth of single-wall carbon nanotubes using chemical vapor deposition

DOEpatents

Grigorian, Leonid [Raymond, OH; Hornyak, Louis [Evergreen, CO; Dillon, Anne C [Boulder, CO; Heben, Michael J [Denver, CO

2008-10-07

The invention relates to a chemical vapor deposition process for the continuous growth of a carbon single-wall nanotube where a carbon-containing gas composition is contacted with a porous membrane and decomposed in the presence of a catalyst to grow single-wall carbon nanotube material. A pressure differential exists across the porous membrane such that the pressure on one side of the membrane is less than that on the other side of the membrane. The single-wall carbon nanotube growth may occur predominately on the low-pressure side of the membrane or, in a different embodiment of the invention, may occur predominately in between the catalyst and the membrane. The invention also relates to an apparatus used with the carbon vapor deposition process.

Continuous growth of single-wall carbon nanotubes using chemical vapor deposition

DOEpatents

Grigorian, Leonid; Hornyak, Louis; Dillon, Anne C; Heben, Michael J

2014-09-23

The invention relates to a chemical vapor deposition process for the continuous growth of a carbon single-wall nanotube where a carbon-containing gas composition is contacted with a porous membrane and decomposed in the presence of a catalyst to grow single-wall carbon nanotube material. A pressure differential exists across the porous membrane such that the pressure on one side of the membrane is less than that on the other side of the membrane. The single-wall carbon nanotube growth may occur predominately on the low-pressure side of the membrane or, in a different embodiment of the invention, may occur predominately in between the catalyst and the membrane. The invention also relates to an apparatus used with the carbon vapor deposition process.

Mars methane engine

NASA Technical Reports Server (NTRS)

Bui, Hung; Coletta, Chris; Debois, Alain

1994-01-01

The feasibility of an internal combustion engine operating on a mixture of methane, carbon dioxide, and oxygen has been verified by previous design groups for the Mars Methane Engine Project. Preliminary stoichiometric calculations examined the theoretical fuel-air ratios needed for the combustion of methane. Installation of a computer data acquisition system along with various ancillary components will enable the performance of the engine, running on the described methane mixture, to be optimized with respect to minimizing excess fuel. Theoretical calculations for stoichiometric combustion of methane-oxygen-carbon dioxide mixtures yielded a ratio of 1:2:4.79 for a methane-oxygen-carbon dioxide mixture. Empirical data shows the values to be closer to 1:2.33:3.69 for optimum operation.

Insights into methane dynamics from analysis of authigenic carbonates and chemosynthetic mussels at newly-discovered Atlantic Margin seeps

USGS Publications Warehouse

Prouty, Nancy G.; Sahy, Diana; Ruppel, Carolyn D.; Roark, E. Brendan; Condon, Dan; Brooke, Sandra; Ross, Steve W.; Demopoulos, Amanda W.J.

2016-01-01

The recent discovery of active methane venting along the US northern and mid-Atlantic margin represents a new source of global methane not previously accounted for in carbon budgets from this region. However, uncertainty remains as to the origin and history of methane seepage along this tectonically inactive passive margin. Here we present the first isotopic analyses of authigenic carbonates and methanotrophic deep-sea mussels, Bathymodiolus   sp., and the first direct constraints on the timing of past methane emission, based on samples collected at the upper slope Baltimore Canyon (∼385 m water depth) and deepwater Norfolk (∼1600 m) seep fields within the area of newly-discovered venting. The authigenic carbonates at both sites were dominated by aragonite, with an average  signature of −47‰, a value consistent with microbially driven anaerobic oxidation of methane-rich fluids occurring at or near the sediment–water interface. Authigenic carbonate U and Sr isotope data further support the inference of carbonate precipitation from seawater-derived fluids rather than from formation fluids from deep aquifers. Carbonate stable and radiocarbon ( and ) isotope values from living Bathymodiolus   sp. specimens are lighter than those of seawater dissolved inorganic carbon, highlighting the influence of fossil carbon from methane on carbonate precipitation. U–Th dates on authigenic carbonates suggest seepage at Baltimore Canyon between 14.7±0.6 ka to 15.7±1.6 ka, and at the Norfolk seep field between 1.0±0.7 ka to 3.3±1.3 ka, providing constraint on the longevity of methane efflux at these sites. The age of the brecciated authigenic carbonates and the occurrence of pockmarks at the Baltimore Canyon upper slope could suggest a link between sediment delivery during Pleistocene sea-level lowstand, accumulation of pore fluid overpressure from sediment compaction, and release of overpressure through subsequent venting. Calculations show that

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.

Combined infrared and ultraviolet-visible spectroscopy matrix-isolated carbon vapor

NASA Technical Reports Server (NTRS)

Kurtz, Joe; Huffman, Donald R.

1990-01-01

Infrared and UV-visible absorption spectra have been measured on the same sample of matrix-isolated carbon vapor in order to establish correlations between absorption intensities of vibrational and electronic transitions as a function of sample annealing. A high degree of correlation has been found between the IR feature at 1998/cm recently assigned to C8 and a UV absorption feature at about 3100 A. Thus, for the first time, direct evidence is given for the assignment of one of the unknown UV-visible features of the long-studied matrix-isolated carbon vapor spectrum.

Revised methane emissions factors and spatially distributed annual carbon fluxes for global livestock

USDA-ARS?s Scientific Manuscript database

Livestock play an important role in carbon cycling through consumption of biomass and emissions of methane. Recent research suggests that existing bottom-up inventories of livestock methane emissions in the U.S., such as those made using 2006 IPCC Tier 1 livestock emissions factors, are too low. Thi...

Fe-rich carbonate chimney in Okinawa Trough Implication for Fe-driven Microbial Anaerobic Oxidation of Methane (AMO)

NASA Astrophysics Data System (ADS)

Peng, X.; Guo, Z.

2016-12-01

Marine sediments associated with cold seeps at continental margins discharge substantial amounts of methane. Microbial anaerobic oxidation of methane (AMO) is a key biogeochemical process in these environments, which can trigger the formation of carbonate chimneys within sediments. The exact biogeochemical mechanism of how AMO control the formation of carbonate chimneys and influence their mineralogy and chemistry remains poorly constrained. Here, we use nano-scale secondary ion mass spectrometry to characterize the petrology and geochemistry of methane-derived Fe-rich carbonate chimneys formed between 5-7 Ma in the Northern Okinawa Trough. We find abundant framboid pyrites formed in the authigenic carbonates in the chimneys, indicating a non-Fe limitation sedimentary system. The δ13C values of carbonate (-18.9‰ to -45.9‰, PDB) show their probable origin from a mixing source of biogenic and thermogenic methane. The δ34S values range from -3.9 ± 0.5‰ to 23.2 ± 0.5‰ (VCDT), indicative of a strong exhaustion of sulfates in a local sulfate pool. We proposed that Fe-rich carbonate chimneys formed at the bottom of the sulfate-methane transition zone, beneath which Fe-driven AOM may happen and provide available ferrous for the extensive precipitation of pyrite in carbonate chimneys. The accumulation of reductive Fe in sediments via this process may widely occur in other analogous settings, with important application for Fe and S biogeochemical cycling within deep sediments at continental margins.

Methane-Oxidizing Bacteria Shunt Carbon to Microbial Mats at a Marine Hydrocarbon Seep

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

Paul, Blair G.; Ding, Haibing; Bagby, Sarah C.

The marine subsurface is a reservoir of the greenhouse gas methane. While microorganisms living in water column and seafloor ecosystems are known to be a major sink limiting net methane transport from the marine subsurface to the atmosphere, few studies have assessed the flow of methane-derived carbon through the benthic mat communities that line the seafloor on the continental shelf where methane is emitted. We analyzed the abundance and isotope composition of fatty acids in microbial mats grown in the shallow Coal Oil Point seep field off Santa Barbara, CA, USA, where seep gas is a mixture of methane andmore » CO 2. We further used stable isotope probing (SIP) to track methane incorporation into mat biomass. We found evidence that multiple allochthonous substrates supported the rich growth of these mats, with notable contributions from bacterial methanotrophs and sulfur-oxidizers as well as eukaryotic phototrophs. Fatty acids characteristic of methanotrophs were shown to be abundant and 13C-enriched in SIP samples, and DNA-SIP identified members of the methanotrophic family Methylococcaceae as major 13CH 4 consumers. Members of Sulfuricurvaceae, Sulfurospirillaceae, and Sulfurovumaceae are implicated in fixation of seep CO 2. The mats’ autotrophs support a diverse assemblage of co-occurring bacteria and protozoa, with Methylophaga as key consumers of methane-derived organic matter. This study identifies the taxa contributing to the flow of seep-derived carbon through microbial mat biomass, revealing the bacterial and eukaryotic diversity of these remarkable ecosystems.« less

Methane-Oxidizing Bacteria Shunt Carbon to Microbial Mats at a Marine Hydrocarbon Seep

DOE PAGES

Paul, Blair G.; Ding, Haibing; Bagby, Sarah C.; ...

2017-02-27

The marine subsurface is a reservoir of the greenhouse gas methane. While microorganisms living in water column and seafloor ecosystems are known to be a major sink limiting net methane transport from the marine subsurface to the atmosphere, few studies have assessed the flow of methane-derived carbon through the benthic mat communities that line the seafloor on the continental shelf where methane is emitted. We analyzed the abundance and isotope composition of fatty acids in microbial mats grown in the shallow Coal Oil Point seep field off Santa Barbara, CA, USA, where seep gas is a mixture of methane andmore » CO 2. We further used stable isotope probing (SIP) to track methane incorporation into mat biomass. We found evidence that multiple allochthonous substrates supported the rich growth of these mats, with notable contributions from bacterial methanotrophs and sulfur-oxidizers as well as eukaryotic phototrophs. Fatty acids characteristic of methanotrophs were shown to be abundant and 13C-enriched in SIP samples, and DNA-SIP identified members of the methanotrophic family Methylococcaceae as major 13CH 4 consumers. Members of Sulfuricurvaceae, Sulfurospirillaceae, and Sulfurovumaceae are implicated in fixation of seep CO 2. The mats’ autotrophs support a diverse assemblage of co-occurring bacteria and protozoa, with Methylophaga as key consumers of methane-derived organic matter. This study identifies the taxa contributing to the flow of seep-derived carbon through microbial mat biomass, revealing the bacterial and eukaryotic diversity of these remarkable ecosystems.« less

Methane-Oxidizing Bacteria Shunt Carbon to Microbial Mats at a Marine Hydrocarbon Seep

PubMed Central

Paul, Blair G.; Ding, Haibing; Bagby, Sarah C.; Kellermann, Matthias Y.; Redmond, Molly C.; Andersen, Gary L.; Valentine, David L.

2017-01-01

The marine subsurface is a reservoir of the greenhouse gas methane. While microorganisms living in water column and seafloor ecosystems are known to be a major sink limiting net methane transport from the marine subsurface to the atmosphere, few studies have assessed the flow of methane-derived carbon through the benthic mat communities that line the seafloor on the continental shelf where methane is emitted. We analyzed the abundance and isotope composition of fatty acids in microbial mats grown in the shallow Coal Oil Point seep field off Santa Barbara, CA, USA, where seep gas is a mixture of methane and CO2. We further used stable isotope probing (SIP) to track methane incorporation into mat biomass. We found evidence that multiple allochthonous substrates supported the rich growth of these mats, with notable contributions from bacterial methanotrophs and sulfur-oxidizers as well as eukaryotic phototrophs. Fatty acids characteristic of methanotrophs were shown to be abundant and 13C-enriched in SIP samples, and DNA-SIP identified members of the methanotrophic family Methylococcaceae as major 13CH4 consumers. Members of Sulfuricurvaceae, Sulfurospirillaceae, and Sulfurovumaceae are implicated in fixation of seep CO2. The mats’ autotrophs support a diverse assemblage of co-occurring bacteria and protozoa, with Methylophaga as key consumers of methane-derived organic matter. This study identifies the taxa contributing to the flow of seep-derived carbon through microbial mat biomass, revealing the bacterial and eukaryotic diversity of these remarkable ecosystems. PMID:28289403

Authigenic carbonates from active methane seeps offshore southwest Africa

NASA Astrophysics Data System (ADS)

Pierre, Catherine; Blanc-Valleron, Marie-Madeleine; Demange, Jérôme; Boudouma, Omar; Foucher, Jean-Paul; Pape, Thomas; Himmler, Tobias; Fekete, Noemi; Spiess, Volkhard

2012-12-01

The southwest African continental margin is well known for occurrences of active methane-rich fluid seeps associated with seafloor pockmarks at water depths ranging broadly from the shelf to the deep basins, as well as with high gas flares in the water column, gas hydrate accumulations, diagenetic carbonate crusts and highly diverse benthic faunal communities. During the M76/3a expedition of R/V METEOR in 2008, gravity cores recovered abundant authigenic carbonate concretions from three known pockmark sites—Hydrate Hole, Worm Hole, the Regab pockmark—and two sites newly discovered during that cruise, the so-called Deep Hole and Baboon Cluster. The carbonate concretions were commonly associated with seep-benthic macrofauna and occurred within sediments bearing shallow gas hydrates. This study presents selected results from a comprehensive analysis of the mineralogy and isotope geochemistry of diagenetic carbonates sampled at these five pockmark sites. The oxygen isotope stratigraphy obtained from three cores of 2-5 m length indicates a maximum age of about 60,000-80,000 years for these sediments. The authigenic carbonates comprise mostly magnesian calcite and aragonite, associated occasionally with dolomite. Their very low carbon isotopic compositions (-61.0 < δ13C ‰ V-PDB < -40.1) suggest anaerobic oxidation of methane (AOM) as the main process controlling carbonate precipitation. The oxygen isotopic signatures (+2.4 < δ18O ‰ V-PDB < +6.2) lie within the range in equilibrium under present-day/interglacial to glacial conditions of bottom seawater; alternatively, the most positive δ18O values might reflect the contribution of 18O-rich water from gas hydrate decomposition. The frequent occurrence of diagenetic gypsum crystals suggests that reduced sulphur (hydrogen sulphide, pyrite) from sub-seafloor sediments has been oxidized by oxygenated bottom water. The acidity released during this process can potentially induce the dissolution of carbonate, thereby

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.

Methane Decomposition and Carbon Growth on Y2O3, Yttria-Stabilized Zirconia, and ZrO2

PubMed Central

2014-01-01

Carbon deposition following thermal methane decomposition under dry and steam reforming conditions has been studied on yttria-stabilized zirconia (YSZ), Y2O3, and ZrO2 by a range of different chemical, structural, and spectroscopic characterization techniques, including aberration-corrected electron microscopy, Raman spectroscopy, electric impedance spectroscopy, and volumetric adsorption techniques. Concordantly, all experimental techniques reveal the formation of a conducting layer of disordered nanocrystalline graphite covering the individual grains of the respective pure oxides after treatment in dry methane at temperatures T ≥ 1000 K. In addition, treatment under moist methane conditions causes additional formation of carbon-nanotube-like architectures by partial detachment of the graphite layers. All experiments show that during carbon growth, no substantial reduction of any of the oxides takes place. Our results, therefore, indicate that these pure oxides can act as efficient nonmetallic substrates for methane-induced growth of different carbon species with potentially important implications regarding their use in solid oxide fuel cells. Moreover, by comparing the three oxides, we could elucidate differences in the methane reactivities of the respective SOFC-relevant purely oxidic surfaces under typical SOFC operation conditions without the presence of metallic constituents. PMID:24587591

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.

Factors that control the stable carbon isotopic composition of methane produced in an anoxic marine sediment

NASA Technical Reports Server (NTRS)

Alperin, M. J.; Blair, Neal E.; Albert, D. B.; Hoehler, T. M.; Martens, C. S.

1993-01-01

The carbon isotopic composition of methane produced in anoxic marine sediment is controlled by four factors: (1) the pathway of methane formation, (2) the isotopic composition of the methanogenic precursors, (3) the isotope fractionation factors for methane production, and (4) the isotope fractionation associated with methane oxidation. The importance of each factor was evaluated by monitoring stable carbon isotope ratios in methane produced by a sediment microcosm. Methane did not accumulate during the initial 42-day period when sediment contained sulfate, indicating little methane production from 'noncompetitive' substrates. Following sulfate depletion, methane accumulation proceeded in three distinct phases. First, CO2 reduction was the dominant methanogenic pathway and the isotopic composition of the methane produced ranged from -80 to -94 per thousand. The acetate concentration increased during this phase, suggesting that acetoclastic methanogenic bacteria were unable to keep pace with acetate production. Second, acetate fermentation became the dominant methanogenic pathway as bacteria responded to elevated acetate concentrations. The methane produced during this phase was progressively enriched in C-13, reaching a maximum delta(C-13) value of -42 per thousand. Third, the acetate pool experienced a precipitous decline from greater than 5 mM to less than 20 micro-M and methane production was again dominated by CO2 reduction. The delta(C-13) of methane produced during this final phase ranged from -46 to -58 per thousand. Methane oxidation concurrent with methane production was detected throughout the period of methane accumulation, at rates equivalent to 1 to 8 percent of the gross methane production rate. Thus methane oxidation was too slow to have significantly modified the isotopic signature of methane. A comparison of microcosm and field data suggests that similar microbial interactions may control seasonal variability in the isotopic composition of methane

Non-linear dynamics of stable carbon and hydrogen isotope signatures based on a biological kinetic model of aerobic enzymatic methane oxidation.

PubMed

Vavilin, Vasily A; Rytov, Sergey V; Shim, Natalia; Vogt, Carsten

2016-06-01

The non-linear dynamics of stable carbon and hydrogen isotope signatures during methane oxidation by the methanotrophic bacteria Methylosinus sporium strain 5 (NCIMB 11126) and Methylocaldum gracile strain 14 L (NCIMB 11912) under copper-rich (8.9 µM Cu(2+)), copper-limited (0.3 µM Cu(2+)) or copper-regular (1.1 µM Cu(2+)) conditions has been described mathematically. The model was calibrated by experimental data of methane quantities and carbon and hydrogen isotope signatures of methane measured previously in laboratory microcosms reported by Feisthauer et al. [ 1 ] M. gracile initially oxidizes methane by a particulate methane monooxygenase and assimilates formaldehyde via the ribulose monophosphate pathway, whereas M. sporium expresses a soluble methane monooxygenase under copper-limited conditions and uses the serine pathway for carbon assimilation. The model shows that during methane solubilization dominant carbon and hydrogen isotope fractionation occurs. An increase of biomass due to growth of methanotrophs causes an increase of particulate or soluble monooxygenase that, in turn, decreases soluble methane concentration intensifying methane solubilization. The specific maximum rate of methane oxidation υm was proved to be equal to 4.0 and 1.3 mM mM(-1) h(-1) for M. sporium under copper-rich and copper-limited conditions, respectively, and 0.5 mM mM(-1) h(-1) for M. gracile. The model shows that methane oxidation cannot be described by traditional first-order kinetics. The kinetic isotope fractionation ceases when methane concentrations decrease close to the threshold value. Applicability of the non-linear model was confirmed by dynamics of carbon isotope signature for carbon dioxide that was depleted and later enriched in (13)C. Contrasting to the common Rayleigh linear graph, the dynamic curves allow identifying inappropriate isotope data due to inaccurate substrate concentration analyses. The non-linear model pretty adequately described experimental

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

PubMed

Burkhardt, M; Koschack, T; Busch, G

2015-02-01

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

Co-production of hydrogen and carbon nanotubes on nickel foam via methane catalytic decomposition

NASA Astrophysics Data System (ADS)

Ping, Dan; Wang, Chaoxian; Dong, Xinfa; Dong, Yingchao

2016-04-01

The co-production of COx-free hydrogen and carbon nanotubes (CNTs) was achieved on 3-dimensional (3D) macroporous nickel foam (NF) via methane catalytic decomposition (MCD) over nano-Ni catalysts using chemical vapor deposition (CVD) technique. By a simple coating of a NiO-Al2O3 binary mixture sol followed by a drying-calcination-reduction treatment, NF supported composite catalysts (denoted as NiyAlOx/NF) with Al2O3 transition-layer incorporated with well-dispersed nano-Ni catalysts were successfully prepared. The effects of Ni loading, calcination temperature and reaction temperature on the performance for simultaneous production of COx-free hydrogen and CNTs were investigated in detail. Catalysts before and after MCD were characterized by XRD, TPR, SEM, TEM, TG and Raman spectroscopy technology. Results show that increasing Ni loading, lowering calcination temperature and optimizing MCD reaction temperature resulted in high production efficiency of COx-free H2 and carbon, but broader diameter distribution of CNTs. Through detailed parameter optimization, the catalyst with a Ni/Al molar ratio of 0.1, calcination temperature of 550 °C and MCD temperature of 650 °C was favorable to simultaneously produce COx-free hydrogen with a growth rate as high as 10.3% and CNTs with uniform size on NF.

Monte Carlo Simulation of the Adsorption of Methane and Tetrafluorocarbon on Single Walled Carbon Nanotubes

NASA Astrophysics Data System (ADS)

Ghadarghadr, Y.; Hashemianzadeh, S. M.

2007-12-01

Alternative fuels must be substantially non-petroleum, provide energy security and environmental benefits, and substitute for conventional fuels such as gasoline and diesel. Natural gas, which consists mainly of methane, fits this definition and is widely available in many countries. One of the strategic goals of the modern automobile manufacturing industry is to replace gasoline and diesel with alternative fuels such as natural gas. In this report, we elucidate the desired characteristics of an optimal adsorbent for gas storage. The U.S. Department of Energy has outlined several requirements that adsorbents must fulfill for natural gas to become economically viable, with a key criterion being the amount adsorbed at 35 bar. We explore the adsorption characteristics of methane on an armchair carbon nanotube and contrast it with the characteristics of CF4. In this research work, adsorptions of pure methane and tetraflouro carbon on (7, 7) armchair carbon nanotubes (CNTs) were studied. Lennard-Jones potential was used for the gas-gas and gas-carbon nanotube interactions. Potential parameters for the carbon-gas and carbon-carbon interactions were obtained from the Lorentz-Berthelot combining rules. Virial equation of state was used to study the pure gas molecules. The work was carried out at a variety of temperatures and pressures.

Seasonal and inter-annual variation in ecosystem scale methane emission from a boreal fen

NASA Astrophysics Data System (ADS)

Rinne, Janne; Li, Xuefei; Raivonen, Maarit; Peltola, Olli; Sallantaus, Tapani; Haapanala, Sami; Smolander, Sampo; Alekseychik, Pavel; Aurela, Mika; Korrensalo, Aino; Mammarella, Ivan; Tuittila, Eeva-Stiina; Vesala, Timo

2016-04-01

Northern wetlands are one of the major sources of atmospheric methane. We have measured ecosystem scale methane emissions from a boreal fen continuously since 2005. The site is an oligotrophic fen in boreal vegetation zone situated in Siikaneva wetland complex in Southern Finland. The mean annual temperature in the area is 3.3°C and total annual precipitation 710 mm. We have conducted the methane emission measurements by the eddy covariance method. Additionally we have measured fluxes of carbon dioxide, water vapor, and sensible heat together with a suite of other environmental parameters. We have analyzed this data alongside with a model run with University of Helsinki methane model. The measured fluxes show generally highest methane emission in late summers coinciding with the highest temperatures in saturated peat zone. During winters the fluxes show small but detectable emission despite the snow and ice cover on the fen. More than 90% of the annual methane emission occurs in snow-free period. The methane emission and peat temperature are connected in exponential manner in seasonal scales, but methane emission does not show the expected behavior with water table. The lack of water table position dependence also contrasts with the spatial variation across microtopography. There is no systematic variation in sub-diurnal time scale. The general seasonal cycle in methane emission is captured well with the methane model. We will show how well the model reproduces the temperature and water table position dependencies observed. The annual methane emission is typically around 10 gC m-2. This is a significant part of the total carbon exchange between the fen and the atmosphere and about twice the estimated carbon loss by leaching from the fen area. The inter-annual variability in the methane emission is modest. The June-September methane emissions from different years, comprising most of the annual emission, correlates positively with peat temperature, but not with

Aerobic Methane Oxidation in Alaskan Lakes Along a Latitudinal Transect

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

Carbon and water vapor fluxes of different ecosystems in Oklahoma

USDA-ARS?s Scientific Manuscript database

Information on exchange of energy, carbon dioxide (CO2), and water vapor (H2O) for major terrestrial ecosystems is vital to quantify carbon and water balances on a large-scale. It is also necessary to develop, test, and improve crop models and satellite-based production efficiency and evapotranspira...

Atmospheric methane removal by methane-oxidizing bacteria immobilized on porous building materials.

PubMed

Ganendra, Giovanni; De Muynck, Willem; Ho, Adrian; Hoefman, Sven; De Vos, Paul; Boeckx, Pascal; Boon, Nico

2014-04-01

Biological treatment using methane-oxidizing bacteria (MOB) immobilized on six porous carrier materials have been used to mitigate methane emission. Experiments were performed with different MOB inoculated in building materials at high (~20 % (v/v)) and low (~100 ppmv) methane mixing ratios. Methylocystis parvus in autoclaved aerated concrete (AAC) exhibited the highest methane removal rate at high (28.5 ± 3.8 μg CH₄ g⁻¹ building material h⁻¹) and low (1.7 ± 0.4 μg CH₄ g⁻¹ building material h⁻¹) methane mixing ratio. Due to the higher volume of pores with diameter >5 μm compared to other materials tested, AAC was able to adsorb more bacteria which might explain for the higher methane removal observed. The total methane and carbon dioxide-carbon in the headspace was decreased for 65.2 ± 10.9 % when M. parvus in Ytong was incubated for 100 h. This study showed that immobilized MOB on building materials could be used to remove methane from the air and also act as carbon sink.

Methane biofiltration in the presence of ethanol vapor under steady and transient state conditions: an experimental study.

PubMed

Ferdowsi, Milad; Ramirez, Antonio Avalos; Jones, Joseph Peter; Heitz, Michèle

2017-09-01

Methane (CH 4 ) removal in the presence of ethanol vapors was performed by a stone-based bed and a hybrid packing biofilter in parallel. In the absence of ethanol, a methane removal efficiency of 55 ± 1% was obtained for both biofilters under similar CH 4 inlet load (IL) of 13 ± 0.5 g CH4  m -3  h -1 and an empty bed residence time (EBRT) of 6 min. The results proved the key role of the bottom section in both biofilters for simultaneous removal of CH 4 and ethanol. Ethanol vapor was completely eliminated in the bottom sections for an ethanol IL variation between 1 and 11 g ethanol  m -3  h -1 . Ethanol absorption and accumulation in the biofilm phase as well as ethanol conversion to CO 2 contributed to ethanol removal efficiency of 100%. In the presence of ethanol vapor, CO 2 productions in the bottom section increased almost fourfold in both biofilters. The ethanol concentration in the leachate of the biofilter exceeding 2200 g ethanol  m -3 leachate in both biofilters demonstrated the excess accumulation of ethanol in the biofilm phase. The biofilters responded quickly to an ethanol shock load followed by a starvation with 20% decrease of their performance. The return to normal operations in both biofilters after the transient conditions took less than 5 days. Unlike the hybrid packing biofilter, excess pressure drop (up to 1.9 cmH 2 O m -1 ) was an important concern for the stone bed biofilter. The biomass accumulation in the bottom section of the stone bed biofilter contributed to 80% of the total pressure drop. However, the 14-day starvation reduced the pressure drop to 0.25 cmH 2 O m -1 .

Biogenic Methane Generation Potential in the Eastern Nankai Trough, Japan: Effect of Reaction Temperature and Total Organic Carbon

NASA Astrophysics Data System (ADS)

Aung, T. T.; Fujii, T.; Amo, M.; Suzuki, K.

2017-12-01

Understanding potential of methane flux from the Pleistocene fore-arc basin filled turbiditic sedimentary formation along the eastern Nankai Trough is important in the quantitative assessment of gas hydrate resources. We considered generated methane could exist in sedimentary basin in the forms of three major components, and those are methane in methane hydrate, free gas and methane dissolved in water. Generation of biomethane strongly depends on microbe activity and microbes in turn survive in diverse range of temperature, salinity and pH. This study aims to understand effect of reaction temperature and total organic carbon on generation of biomethane and its components. Biomarker analysis and cultural experiment results of the core samples from the eastern Nankai Trough reveal that methane generation rate gets peak at various temperature ranging12.5°to 35°. Simulation study of biomethane generation was made using commercial basin scale simulator, PetroMod, with different reaction temperature and total organic carbon to predict how these effect on generation of biomethane. Reaction model is set by Gaussian distribution with constant hydrogen index and standard deviation of 1. Series of simulation cases with peak reaction temperature ranging 12.5°to 35° and total organic carbon of 0.6% to 3% were conducted and analyzed. Simulation results show that linear decrease in generation potential while increasing reaction temperature. But decreasing amount becomes larger in the model with higher total organic carbon. At higher reaction temperatures, >30°, extremely low generation potential was found. This is due to the fact that the source formation modeled is less than 1 km in thickness and most of formation do not reach temperature more than 30°. In terms of the components, methane in methane hydrate and free methane increase with increasing TOC. Drastic increase in free methane was observed in the model with 3% of TOC. Methane amount dissolved in water shows almost

Hydrogen and carbon nanotube production via catalytic decomposition of methane

NASA Astrophysics Data System (ADS)

Deniz, Cansu; Karatepe, Nilgün

2013-09-01

The future energy demand is expected to increase significantly due to an increasing world population and demands for higher standards of living and better air quality. Hydrogen is considered as an energy carrier because of its high conversion efficiency and low pollutant emissions. It can be produced from various sources and transformed into electricity and other energy forms with a low pollution. The catalytic decomposition of hydrocarbon has been seen as a really useful method for production of pure hydrogen and for the environmental concern. The objective of this study was to assess the impact of catalyst composition and processing parameters on COx-free hydrogen production and to produce an available solid form of co-product carbon as carbon nanotubes via catalytic decomposition of methane. The optimum experimental conditions for methane decomposition have been investigated. Fe, Co and Ni are used as catalysts (nano materials) over different substrates as SiO2 and MgO to produce hydrogen at optimum temperatures.

Ecosystem level methane fluxes from tidal freshwater and brackish marshes of the Mississippi River Delta: Implications for coastal wetland carbon projects

USGS Publications Warehouse

Holm, Guerry O.; Perez, Brian C.; McWhorter, David E.; Krauss, Ken W.; Johnson, Darren J.; Raynie, Richard C.; Killebrew, Charles J.

2016-01-01

Sulfate from seawater inhibits methane production in tidal wetlands, and by extension, salinity has been used as a general predictor of methane emissions. With the need to reduce methane flux uncertainties from tidal wetlands, eddy covariance (EC) techniques provide an integrated methane budget. The goals of this study were to: 1) establish methane emissions from natural, freshwater and brackish wetlands in Louisiana based on EC; and 2) determine if EC estimates conform to a methane-salinity relationship derived from temperate tidal wetlands with chamber sampling. Annual estimates of methane emissions from this study were 62.3 g CH4/m2/yr and 13.8 g CH4/m2/yr for the freshwater and brackish (8–10 psu) sites, respectively. If it is assumed that long-term, annual soil carbon sequestration rates of natural marshes are ~200 g C/m2/yr (7.3 tCO2e/ha/yr), healthy brackish marshes could be expected to act as a net radiative sink, equivalent to less than one-half the soil carbon accumulation rate after subtracting methane emissions (4.1 tCO2e/ha/yr). Carbon sequestration rates would need case-by-case assessment, but the EC methane emissions estimates in this study conformed well to an existing salinity-methane model that should serve as a basis for establishing emission factors for wetland carbon offset projects.

A Novel Airborne Carbon Isotope Analyzer for Methane and Carbon Dioxide Source Fingerprinting

NASA Astrophysics Data System (ADS)

Berman, E. S.; Huang, Y. W.; Owano, T. G.; Leifer, I.

2014-12-01

Recent field studies on major sources of the important greenhouse gas methane (CH4) indicate significant underestimation of methane release from fossil fuel industrial (FFI) and animal husbandry sources, among others. In addition, uncertainties still exist with respect to carbon dioxide (CO2) measurements, especially source fingerprinting. CO2 isotopic analysis provides a valuable in situ measurement approach to fingerprint CH4 and CO2as associated with combustion sources, leakage from geologic reservoirs, or biogenic sources. As a result, these measurements can characterize strong combustion source plumes, such as power plant emissions, and discriminate these emissions from other sources. As part of the COMEX (CO2 and MEthane eXperiment) campaign, a novel CO2 isotopic analyzer was installed and collected data aboard the CIRPAS Twin Otter aircraft. Developing methods to derive CH4 and CO2 budgets from remote sensing data is the goal of the summer 2014 COMEX campaign, which combines hyperspectral imaging (HSI) and non-imaging spectroscopy (NIS) with in situ airborne and surface data. COMEX leverages the synergy between high spatial resolution HSI and moderate spatial resolution NIS. The carbon dioxide isotope analyzer developed by Los Gatos Research (LGR) uses LGR's patented Off-Axis ICOS (Integrated Cavity Output Spectroscopy) technology and incorporates proprietary internal thermal control for high sensitivity and optimal instrument stability. This analyzer measures CO2 concentration as well as δ13C, δ18O, and δ17O from CO2 at natural abundance (100-3000 ppm). The laboratory accuracy is ±1.2 ppm (1σ) in CO2 from 370-1000 ppm, with a long-term (1000 s) precision of ±0.012 ppm. The long-term precision for both δ13C and δ18O is 0.04 ‰, and for δ17O is 0.06 ‰. The analyzer was field-tested as part of the COWGAS campaign, a pre-cursor campaign to COMEX in March 2014, where it successfully discriminated plumes related to combustion processes associated with

Direct gas-solid carbonation of serpentinite residues in the absence and presence of water vapor: a feasibility study for carbon dioxide sequestration.

PubMed

Veetil, Sanoopkumar Puthiya; Pasquier, Louis-César; Blais, Jean-François; Cecchi, Emmanuelle; Kentish, Sandra; Mercier, Guy

2015-09-01

Mineral carbonation of serpentinite mining residue offers an environmentally secure and permanent storage of carbon dioxide. The strategy of using readily available mining residue for the direct treatment of flue gas could improve the energy demand and economics of CO2 sequestration by avoiding the mineral extraction and separate CO2 capture steps. The present is a laboratory scale study to assess the possibility of CO2 fixation in serpentinite mining residues via direct gas-solid reaction. The degree of carbonation is measured both in the absence and presence of water vapor in a batch reactor. The gas used is a simulated gas mixture reproducing an average cement flue gas CO2 composition of 18 vol.% CO2. The reaction parameters considered are temperature, total gas pressure, time, and concentration of water vapor. In the absence of water vapor, the gas-solid carbonation of serpentinite mining residues is negligible, but the residues removed CO2 from the feed gas possibly due to reversible adsorption. The presence of small amount of water vapor enhances the gas-solid carbonation, but the measured rates are too low for practical application. The maximum CO2 fixation obtained is 0.07 g CO2 when reacting 1 g of residue at 200 °C and 25 barg (pCO2 ≈ 4.7) in a gas mixture containing 18 vol.% CO2 and 10 vol.% water vapor in 1 h. The fixation is likely surface limited and restricted due to poor gas-solid interaction. It was identified that both the relative humidity and carbon dioxide-water vapor ratio have a role in CO2 fixation regardless of the percentage of water vapor.

Stable carbon isotope ratios in atmospheric methane and some of its sources

NASA Technical Reports Server (NTRS)

Tyler, Stanley C.

1986-01-01

Ratios of C-13/C-12 have been measured in atmospheric methane and in methane collected from sites and biota that represent potentially large sources of atmospheric methane. These include temperate marshes (about -48 percent to about -54 percent), landfills (about -51 percent to about -55 percent), and the first reported values for any species of termite (-72.8 + or - 3.1 percent for Reticulitermes tibialis and -57.3 + or - 1.6 percent for Zootermopsis angusticollis). Numbers in parentheses are delta C-13 values with respect to PDB (Peedee belemnite) carbonate. Most methane sources reported thus far are depleted in C-13 with respect to atmospheric methane (-47.0 + or - 0.3 percent). Individual sources of methane should have C-13/C-12 ratios characteristic of mechanisms of CH4 formation and consumption prior to release to the atmosphere. The mass-weighted average isotopic composition of all sources should equal the mean C-13 of atmospheric methane, corrected for a kinetic isotope effect in the OH attack of CH4. Assuming the kinetic isotope effect to be small (about -3.0 percent correction to -47.0), as in the literature, the new values given here for termite methane do not help to explain the apparent discrepancy between C-13/C-12 ratios of the known CH4 sources and that of atmospheric CH4.

A Novel Framework for Quantifying past Methane Recycling by Sphagnum-Methanotroph Symbiosis Using Carbon and Hydrogen Isotope Ratios of Leaf Wax Biomarkers

NASA Technical Reports Server (NTRS)

Nichols, Jonathan E.; Isles, Peter D. F.; Peteet, Dorothy M.

2014-01-01

The concentration of atmospheric methane is strongly linked to variations in Earth's climate. Currently, we can directly reconstruct the total atmospheric concentration of methane, but not individual terms of the methane cycle. Northern wetlands, dominated by Sphagnum, are an important contributor of atmospheric methane, and we seek to understand the methane cycle in these systems. We present a novel method for quantifying the proportion of carbon Sphagnum assimilates from its methanotrophic symbionts using stable isotope ratios of leaf-wax biomarkers. Carbon isotope ratios of Sphagnum compounds are determined by two competing influences, water content and the isotope ratio of source carbon. We disentangled these effects using a combined hydrogen and carbon isotope approach. We constrained Sphagnum water content using the contrast between the hydrogen isotope ratios of Sphagnum and vascular plant biomarkers. We then used Sphagnum water content to calculate the carbon isotope ratio of Sphagnum's carbon pool. Using a mass balance equation, we calculated the proportion of recycled methane contributed to the Sphagnum carbon pool, 'PRM.' We quantified PRM in peat monoliths from three microhabitats in the Mer Bleue peatland complex. Modern studies have shown that water table depth and vegetation have strong influences on the peatland methane cycle on instrumental time scales. With this new approach, delta C-13 of Sphagnum compounds are now a useful tool for investigating the relationships among hydrology, vegetation, and methanotrophy in Sphagnum peatlands over the time scales of entire peatland sediment records, vital to our understanding of the global carbon cycle through the Late Glacial and Holocene.

Methane formation from the hydrogenation of carbon dioxide on Ni(110) surface--a density functional theoretical study.

PubMed

Bothra, Pallavi; Periyasamy, Ganga; Pati, Swapan K

2013-04-21

The complete hydrogenation mechanisms of CO2 are explored on Ni(110) surface catalyst using density functional theory. We have studied the possible hydrogenation mechanism to form product methane from the stable adsorption-co-adsorption intermediates of CO2 and H2 on Ni(110) surface. Our computations clearly elucidate that the mechanism for the formation of methyl, methoxy and methane moieties from carbon dioxide on the nickel catalyst. Moreover, our studies clearly show that the methane formation via hydroxyl carbonyl intermediate requires a lower energy barrier than via carbon monoxide and formate intermediates on the Ni(110) surface.

First Airborne Lidar Measurements of Methane and Carbon Dioxide Applying the MERLIN Demonstrator CHARM-F

NASA Astrophysics Data System (ADS)

Amediek, Axel; Büdenbender, Christian; Ehret, Gerhard; Fix, Andreas; Gerbig, Christoph; Kiemle, Chritstoph; Quatrevalet, Mathieu; Wirth, Martin

2016-04-01

CHARM-F is the new airborne four-wavelengths lidar for simultaneous soundings of atmospheric CO2 and CH4. Due to its high technological conformity it is also a demonstrator for MERLIN, the French-German satellite mission providing a methane lidar. MERLIN's Preliminary Design Review was successfully passed recently. The launch is planned for 2020. First CHARM-F measurements were performed in Spring 2015 onboard the German research aircraft HALO. The aircraft's maximum flight altitude of 15 km and special features of the lidar, such as a relatively large laser ground spot, result in data similar to those obtained by a spaceborne system. The CHARM-F and MERLIN lidars are designed in the IPDA (integrated path differential absorption) configuration using short double pulses, which gives column averaged gas mixing ratios between the system and ground. The successfully completed CHARM-F flight measurements provide a valuable dataset, which supports the retrieval algorithm development for MERLIN notably. Furthermore, the dataset allows detailed analyses of measurement sensitivities, general studies on the IPDA principle and on system design questions. These activities are supported by another instrument onboard the aircraft during the flight campaign: a cavity ring down spectrometer, providing in-situ data of carbon dioxide, methane and water vapor with high accuracy and precision, which is ideal for validation purposes of the aircraft lidar. For the near future, detailed characterizations of CHARM-F are planned, further support of the MERLIN design, as well as the scientific aircraft campaign CoMet.

Experimental determination of ablation vapor species from carbon phenolic heat-shield materials

NASA Technical Reports Server (NTRS)

Lincoln, K. A.

1981-01-01

The relative concentrations of vapors produced from carbon phenolic composites under thermal loadings approximating those expected at peak heating during vehicle entry into the atmospheres of the outer planets have been determined. The technique of vaporizing the surface of bulk samples by laser irradiation while measuring in situ the vapor species by mass spectrometry is described. Results show that vapor composition varies with irradiance level and with depth of heating (or extent of pyrolysis). Attempts are made to compare these experimental results with the theoretical predictions from computer codes.

Stromatolitic fabric of authigenic carbonate crusts: result of anaerobic methane oxidation at cold seeps in 4,850 m water depth

NASA Astrophysics Data System (ADS)

Greinert, Jens; Bohrmann, Gerhard; Elvert, Marcus

2002-08-01

Methane seepage leads to Mg-calcite and aragonite precipitation at a depth of 4,850 m on the Aleutian accretionary margin. Stromatolitic and oncoid growth structures imply encrustation of microorganisms (microbial mats) in the host sediment with a unique growth direction downward into the sediment, forming crust-shaped lithologies. Biomarker investigations of the residue after carbonate dissolution show strong enrichments in crocetane and archaeol, which contain extremely low δ13C values. This indicates the presence of methane-consuming archaea, and δ13C values of -42 to -51‰ PDB indicate that methane is the carbon source for the carbonate crusts. Thus, it appears that stromatolitic encrustations of methanotrophic anaerobic archaea probably occurs in a consortium with sulphate-reducing bacteria and that carbonate precipitation proceeds downward into the sediment, where ascending cold fluids provide a methane source. Strontium and oxygen isotope analyses as well as 14C ages of the carbonates suggest that the fluids come from deep within the sediment and that carbonate precipitation began about 3,000 years ago.

Methane seepage intensities traced by biomarker patterns in authigenic carbonates from the South China Sea

NASA Astrophysics Data System (ADS)

Guan, H.; Feng, D.

2015-12-01

Authigenic carbonate rocks from an active seep (Site F) at 1120 m water depth of the South China Sea (SCS) were studied using mineralogical and lipid biomarker analyses. Carbonate mineral compositions, in specific samples, were predominantly aragonite, high-Mg calcite (HMC), or a mixture of both. Abundant 13C-depleted lipid biomarkers (various isoprenoids) diagnostic for archaea provide evidence that anaerobic oxidation of methane (AOM) mediated by anaerobic methane oxidizing archaea (ANME) and their bacterial partners is the major process leading to formation of the carbonates. Nearly a pure suite of AOM biomarkers was preserved in aragonitic carbonate in which predominant consortia were most likely ANME-2/Desulfosarcina & Desulfococcus (DSS) assemblages and a mixture of ANME-2/DSS and ANME-1/DSS consortia in the mixed mineral sample, the predominant consortia are in good accordance with the point that the relative higher methane seepage intensity favors the precipitation of aragonite over HMC. In contrast, the completely different biomarker patterns in HMC sample were mainly composed terrestrial organic matter and marine Thaumarchaea, which most likely originally within sediments accompanied with high organic matter input and low methane supply. This environment is known to be favored for archaea of ANME-1 and precipitation of HMC. High concentrations of 13C-depleted hopanoids, including diplopterol, hopanoic acids and hopanols were observed in the aragonite sample that may be sourced by the intermittent presence of oxic conditions in an overall anoxic condition, which was possibly induced by changing seepage intensities.

Carbon kinetic isotope effect in the oxidation of methane by the hydroxyl radical

NASA Technical Reports Server (NTRS)

Cantrell, Christopher A.; Shetter, Richard E.; Mcdaniel, Anthony H.; Calvert, Jack G.; Davidson, James A.

1990-01-01

The reaction of the hydroxyl radical (HO) with the stable carbon isotopes of methane has been studied as a function of temperature from 273 to 353 K. The measued ratio of the rate coefficients for reaction with (C-12)H4 relative to (C-13)H4 (k12/k13) was 1.0054 (+ or - 0.0009 at the 95 percent confidence interval), independent of temperature within the precision of the measurement, over the range studied. The precision of the present value is much improved over that of previous studies, and this result provides important constraints on the current understanding of the cycling of methane through the atmosphere through the use of carbon isotope measurements.

Laser beam methane detector

NASA Technical Reports Server (NTRS)

Hinkley, E. D., Jr.

1981-01-01

Instrument uses infrared absorption to determine methane concentration in liquid natural gas vapor. Two sensors measure intensity of 3.39 mm laser beam after it passes through gas; absorption is proportional to concentration of methane. Instrument is used in modeling spread of LNG clouds and as leak detector on LNG carriers and installations. Unit includes wheels for mobility and is both vertically and horizontally operable.

Adsorption equilibrium of organic vapors on single-walled carbon nanotubes

USGS Publications Warehouse

Agnihotri, S.; Rood, M.J.; Rostam-Abadi, M.

2005-01-01

Gravimetric techniques were employed to determine the adsorption capacities of commercially available purified electric arc and HiPco single-walled carbon nanotubes (SWNTs) for organic compounds (toluene, methyl ethyl ketone (MEK), hexane and cyclohexane) at relative pressures, p/p0, ranging from 1 ?? 10-4 to 0.95 and at isothermal conditions of 25, 37 and 50 ??C. The isotherms displayed both type I and type II characteristics. Adsorption isotherm modeling showed that SWNTs are heterogeneous adsorbents, and the Freundlich equation best describes the interaction between organic molecules and SWNTs. The heats of adsorption were 1-4 times the heats of vaporization, which is typical for physical adsorption of organic vapors on porous carbons. ?? 2005 Elsevier Ltd. All rights reserved.

Authigenic carbon entombed in methane-soaked sediments from the northeastern transform margin of the Guaymas Basin, Gulf of California

NASA Astrophysics Data System (ADS)

Paull, Charles K.; Ussler, William; Peltzer, Edward T.; Brewer, Peter G.; Keaten, Rendy; Mitts, Patrick J.; Nealon, Jeffrey W.; Greinert, Jens; Herguera, Juan-Carlos; Elena Perez, M.

2007-06-01

Extensive ROV-based sampling and exploration of the seafloor was conducted along an eroded transform-parallel fault scarp on the northeastern side of the Guaymas Basin in the Gulf of California to observe the nature of fluids venting from the seafloor, measure the record left by methane-venting on the carbonates from this area, and determine the association with gas hydrate. One gas vent vigorous enough to generate a water-column gas plume traceable for over 800 m above the seafloor was found to emanate from a ˜10-cm-wide orifice on the eroded scarp face. Sediment temperature measurements and topography on a sub-bottom reflector recorded in a transform-parallel seismic reflection profile identified a subsurface thermal anomaly beneath the gas vent. Active chemosynthetic biological communities (CBCs) and extensive authigenic carbonates that coalesce into distinct chemoherm structures were encountered elsewhere along the eroded transform-parallel scarp. The carbon isotopic composition of methane bubbles flowing vigorously from the gas vent (-53.6±0.8‰ PDB) is comparable to methane found in sediment cores taken within the CBCs distributed along the scarp (-51.9±8.1‰ PDB). However, the δ13C value of the CO 2 in the vent gas (+12.4±1.1‰ PDB) is very distinct from those for dissolved inorganic carbon (DIC) (-35.8‰ to -2.9‰ PDB) found elsewhere along the scarp, including underneath CBCs. The δ13C values of the carbonate-rich sediments and rocks exposed on the seafloor today also span an unusually large range (-40.9‰ to +12.9‰ PDB) and suggest two distinct populations of authigenic carbonate materials were sampled. Unconsolidated sediments and some carbonate rocks, which have lithologic evidence for near-seafloor formation, have negative δ13C values, while carbonate rocks that clearly formed in the subsurface have positive δ13C values (up to +23.0‰) close to that measured for CO 2 in the vent gas. There appears to be two carbon sources for the

Implications of CO Bias for Ozone and Methane Lifetime in a CCM

NASA Technical Reports Server (NTRS)

Strode, Sarah; Duncan, Bryan Neal; Yegorova, Elena; Douglass, Anne

2013-01-01

A low bias in carbon monoxide compared to observations at high latitudes is a common feature of chemistry climate models. CO bias can both indicate and contribute to a bias in modeled OH and methane lifetime. This study examines possible causes of CO bias in the ACCMIP simulation of the GEOSCCM, and considers how attributing the CO bias to uncertainty in CO emissions versus biases in other constituents impacts the relationship between CO bias and methane lifetime. We use a simplified model of CO tagged by source with specified OH to quantify the sensitivity of the CO bias to changes in CO emissions or OH concentration, comparing the modeled CO to surface and MOPITT observations. The simplified model shows that decreasing OH in the northern hemisphere removes most of the global mean and inter-hemispheric bias in surface CO. We then use results from this analysis to explore how adjusting CO sources in the CCM impacts the concentrations of ozone, OH and methane. The CCM simulation also exhibits biases in ozone and water vapor compared to observations. We use a parameterized CO-OH-CH4 model that takes ozone and water vapor as inputs to the parameterization to examine whether correcting water and ozone biases can alter OH enough to remove the CO bias. Through this analysis, we aim to better quantify the relationship between CO bias and model biases in ozone concentrations and methane lifetime.

Methane and Carbon Dioxide Concentrations and Fluxes in Amazon Floodplains

NASA Astrophysics Data System (ADS)

Melack, J. M.; MacIntyre, S.; Forsberg, B.; Barbosa, P.; Amaral, J. H.

2016-12-01

Field studies on the central Amazon floodplain in representative aquatic habitats (open water, flooded forests, floating macrophytes) combine measurements of methane and carbon dioxide concentrations and fluxes to the atmosphere over diel and seasonal times with deployment of meteorological sensors and high-resolution thermistors and dissolved oxygen sondes. A cavity ringdown spectrometer is used to determine gas concentrations, and floating chambers and bubble collectors are used to measure fluxes. To further understand fluxes, we measured turbulence as rate of dissipation of turbulent kinetic energy based on microstructure profiling. These results allow calculations of vertical mixing within the water column and of air-water exchanges using surface renewal models. Methane and carbon dioxide fluxes varied as a function of season, habitat and water depth. High CO2 fluxes at high water are related to high pCO2; low pCO2 levels at low water result from increased phytoplankton uptake. CO2 fluxes are highest at turbulent open water sites, and pCO2 is highest in macrophyte beds. Fluxes and pCH4 are high in macrophyte beds.

A 3D Microphysical Model of Titan's Methane Cloud

NASA Astrophysics Data System (ADS)

Xiao, J.; Newman, C.; Inada, A.; Richardson, M.

2006-12-01

A time-dependent idealized 3D microphysical model for Titan's methane cloud is described. This new high resolution microphysical model nests in a Titan WRF GCM model. It assumes the vapor-liquid equilibria of methane-nitrogen mixtures which are based on the recent chemical experiments and thermodynamics models. In particular, the methane is condensed at a given temperature and pressure. Meanwhile nitrogen is dissolved in the methane liquid. The new model first uses the data from the thermodynamic model (Kouvaris et al. 1991), which involves saturation criteria, composition of condensate, and latent heat for a given pressure-temperature profile. For altitudes lower than 14 km, methane is saturated and condensed into liquid phase. However for altitudes from 14 km above to tropopause, methane is changed into supercooled liquid state. Then, we do some testing experiments with 1D model by varying the initial methane vapor mass mixing ratio profile and the initial mole fraction of methane in liquid phase. Based on the steady state results from 1D model, an idealized 3D microphysics model is developed to investigate the convection cloud in Titan's troposphere. Due to lower relative humidity at titan's surface (Samuelson et al. 1997) and the current estimated moist adiabatic lapse rate, convection is hardly to happen without lifting. For this reason, we apply a symmetry cosine ridge in a 100*100 grids box to force the air flow lifted at certain levels, which in turn drives the condensation of methane vapor. In addition to the abundance of methane clouds and its duration provided by the 3D model, our study demonstrates that vertical motion might be likely the major cause of convection clouds in Titan's troposphere. As the future work, we will further investigate size-resolved microphysical scheme to insight into the nature of methane cycle in Titan's atmosphere.

A 4 U Laser Heterodyne Radiometer for Methane (CH4) and Carbon Dioxide (CO2) Measurements from an Occultation-Viewing CubSat

NASA Technical Reports Server (NTRS)

Wilson, Emily L.; DiGregorio, A. J.; Riot, Vincent J.; Ammons, Mark S.; Bruner, WIlliam W.; Carter, Darrell; Mao, Jianping; Ramanathan, Anand; Strahan, Susan E.; Oman, Luke D.;

Investigating physical controls on methane and carbon ...

EPA Pesticide Factsheets

Reservoirs are a globally important source of carbon to the atmosphere. Several recent studies have found that both carbon dioxide (CO2) and methane (CH4) emissions from reservoirs are currently being underestimated by up to 50%. This underestimation is due to inadequate characterization of both spatial variability (e.g. ebullition and CO2 surface water concentration hot spots) and temporal variability (e.g. diurnal patterns, seasonal differences, and pulses driven by weather events or other disturbances). Use of the eddy covariance technique to measure CO2 and CH4 fluxes over reservoirs can help address the issues of spatial and temporal coverage. Here we present results from two eddy covariance measurement campaigns monitoring CO2 and CH4 fluxes over reservoirs in southwestern Ohio, US. The first campaign was part of a study looking at the effects of water level drawdown on reservoir methane ebullition. The eddy covariance results showed a clear response of CH4 emissions to the change in water level, increasing from a baseline of 3440 mg CH4 m-2 d-1 to a maximum of 6740 mg CH4 m-2 d-1 during the drawdown. These results agreed well with the emission rates measured via bubble samplers deployed in the same area as the tower. Conversely, the CO2 fluxes did not show a strong response to the drawdown. In the second campaign the eddy covariance system was deployed longer term at a mid-sized (2.4 km2) lake. Analyses of diurnal patterns in CO2 and CH4 emissions as well

46 CFR 154.1854 - Methane (LNG) as fuel.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 46 Shipping 5 2010-10-01 2010-10-01 false Methane (LNG) as fuel. 154.1854 Section 154.1854... STANDARDS FOR SELF-PROPELLED VESSELS CARRYING BULK LIQUEFIED GASES Operations § 154.1854 Methane (LNG) as fuel. (a) If methane (LNG) vapors are used as fuel in the main propulsion system of a vessel, the...

46 CFR 154.1854 - Methane (LNG) as fuel.

Code of Federal Regulations, 2013 CFR

2013-10-01

... ventilation or detection of gas, the master shall ensure that the methane (LNG) fuel supply is not used until... STANDARDS FOR SELF-PROPELLED VESSELS CARRYING BULK LIQUEFIED GASES Operations § 154.1854 Methane (LNG) as fuel. (a) If methane (LNG) vapors are used as fuel in the main propulsion system of a vessel, the...

46 CFR 154.1854 - Methane (LNG) as fuel.

Code of Federal Regulations, 2011 CFR

2011-10-01

... ventilation or detection of gas, the master shall ensure that the methane (LNG) fuel supply is not used until... STANDARDS FOR SELF-PROPELLED VESSELS CARRYING BULK LIQUEFIED GASES Operations § 154.1854 Methane (LNG) as fuel. (a) If methane (LNG) vapors are used as fuel in the main propulsion system of a vessel, the...

46 CFR 154.1854 - Methane (LNG) as fuel.

Code of Federal Regulations, 2014 CFR

2014-10-01

... ventilation or detection of gas, the master shall ensure that the methane (LNG) fuel supply is not used until... STANDARDS FOR SELF-PROPELLED VESSELS CARRYING BULK LIQUEFIED GASES Operations § 154.1854 Methane (LNG) as fuel. (a) If methane (LNG) vapors are used as fuel in the main propulsion system of a vessel, the...

46 CFR 154.1854 - Methane (LNG) as fuel.

Code of Federal Regulations, 2012 CFR

2012-10-01

... ventilation or detection of gas, the master shall ensure that the methane (LNG) fuel supply is not used until... STANDARDS FOR SELF-PROPELLED VESSELS CARRYING BULK LIQUEFIED GASES Operations § 154.1854 Methane (LNG) as fuel. (a) If methane (LNG) vapors are used as fuel in the main propulsion system of a vessel, the...

Hydrogen production using thermocatalytic decomposition of methane on Ni30/activated carbon and Ni30/carbon black.

PubMed

Srilatha, K; Viditha, V; Srinivasulu, D; Ramakrishna, S U B; Himabindu, V

2016-05-01

Hydrogen is an energy carrier of the future need. It could be produced from different sources and used for power generation or as a transport fuel which mainly in association with fuel cells. The primary challenge for hydrogen production is reducing the cost of production technologies to make the resulting hydrogen cost competitive with conventional fuels. Thermocatalytic decomposition (TCD) of methane is one of the most advantageous processes, which will meet the future demand, hence an attractive route for COx free environment. The present study deals with the production of hydrogen with 30 wt% of Ni impregnated in commercially available activated carbon and carbon black catalysts (samples coded as Ni30/AC and Ni30/CB, respectively). These combined catalysts were not attempted by previous studies. Pure form of hydrogen is produced at 850 °C and volume hourly space velocity (VHSV) of 1.62 L/h g on the activity of both the catalysts. The analysis (X-ray diffraction (XRD)) of the catalysts reveals moderately crystalline peaks of Ni, which might be responsible for the increase in catalytic life along with formation of carbon fibers. The activity of carbon black is sustainable for a longer time compared to that of activated carbon which has been confirmed by life time studies (850 °C and 54 sccm of methane).

Metagenomic analysis of carbon cycling and biogenic methane formation in terrestrial serpentinizing fluid springs

NASA Astrophysics Data System (ADS)

Woycheese, K. M.; Meyer-Dombard, D. R.; Cardace, D.; Arcilla, C. A.; Ono, S.

2016-12-01

The products of serpentinization are proposed to support a hydrogen-driven microbial biosphere in ultrabasic, highly reducing fluids. Shotgun metagenomic analysis of microbial communities collected from terrestrial serpentinizing springs in the Philippines and Turkey suggest that mutualistic relationships may help microbial communities thrive in highly oligotrophic environments. Understanding how these relationships affect production of methane in the deep subsurface is critical to applications such as carbon sequestration and natural gas production. There is conflicting evidence regarding whether methane and C2-C6 alkanes in serpentinizing ecosystems are produced abiogenically or through biotic reactions such as methanogenesis1, 2. While geochemical analysis of methane from serpentinizing ecosystems has previously indicated abiogenic and/or mixed formation3, 4, methanogens have been detected in an increasing number of investigations2. Here, putative metabolisms were identified via assembly and annotation of metagenomic sequence data from the Philippines and Turkey. At both sites, hydrogenotrophic methanogenesis and homoacetogenesis were identified as the principal autotrophic carbon fixation pathways. Heterotrophic acetogenesis and acetoclastic methanogenesis were also detected in sequence data. Other heterotrophic metabolic pathways identified included sulfate reduction, methanotrophy, and biodegradation of aromatic carbon compounds. Many of these metabolic pathways have been shown to be favorable under conditions typical of serpentinizing habitats5. Metagenomic analysis strongly suggests that at least some of the methane originating from these serpentinizing ecosystems may be biologically derived. Ongoing work will further clarify the mechanisms of methane formation by examining the clumped isotopologue ratios of dissolved methane in serpentinizing fluids. 1. Wang et al. (2015). Science. 348. doi: 10.1126/science.aaa4326 2. Kohl et al. (2016). JGR. Biogeosci

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.

Methane-derived carbonates form at the sediment-bedrock interface in a shallow marine gas seep.

NASA Astrophysics Data System (ADS)

Kimball, J.; Ding, H.; Valentine, D. L.

2006-12-01

Hydrocarbon seeps occur world-wide, and release large quantities of oil and natural gas to the ocean and atmosphere. One of the world's most prolific hydrocarbon seep fields is located just offshore from Goleta, CA, and serves as the study site for this investigation. In the course of investigating gas fluxes from a 10 m deep coastal seep, samples of seafloor bedrock were collected by scuba diving during a time of low sediment burden. These samples were found to be concretions composed primarily of carbonate-cemented sand. The delta13C values of the carbonate range from -25 to -32 per mille, and indicate a role for methane oxidation in the formation of the carbonates. Long chain fatty acids were extracted from the concretions and were quantified, identified, and analyzed for their 13C composition. Fatty acids typical of sulfate reducing bacteria were observed, and interpreted as a signature of anoxia. Further mineralogical and isotopic studies are planned. From these observations we interpret a shallow water origin for these concretions, whereby the seasonal migration of sand to the seep environment drives anoxia and anaerobic methane oxidation at the sediment-bedrock interface. The alkalinity generated from sulfate reduction causes the precipitation of methane-derived carbonate- which forms a concretion with sand.

Interference of oxygen, carbon dioxide, and water vapor on the analysis for oxides of nitrogen by chemiluminescence

NASA Technical Reports Server (NTRS)

Maahs, H. G.

1975-01-01

The interference of small concentrations (less than 4 percent by volume) of oxygen, carbon dioxide, and water vapor on the analysis for oxides of nitrogen by chemiluminescence was measured. The sample gas consisted primarily of nitrogen, with less than 100 parts per million concentration of nitric oxide, and with small concentrations of oxygen, carbon dioxide, and water vapor added. Results obtained under these conditions indicate that although oxygen does not measurably affect the analysis for nitric oxide, the presence of carbon dioxide and water vapor causes the indicated nitric oxide concentration to be too low. An interference factor - defined as the percentage change in indicated nitric oxide concentration (relative to the true nitric oxide concentration) divided by the percent interfering gas present - was determined for carbon dioxide to be -0.60 + or - 0.04 and for water vapor to be -2.1 + or - 0.3.

Stratospheric water vapor in the NCAR CCM2

NASA Technical Reports Server (NTRS)

Mote, Philip W.; Holton, James R.

1992-01-01

Results are presented of the water vapor distribution in a 3D GCM with good vertical resolution, a state-of-the-art transport scheme, and a realistic water vapor source in the middle atmosphere. In addition to water vapor, the model transported methane and an idealized clock tracer, which provides transport times to and within the middle atmosphere. The water vapor and methane distributions are compared with Nimbus 7 SAMS and LIMS data and with in situ measurements. It is argued that the hygropause in the model is maintained not by 'freeze-drying' at the tops of tropical cumulonimbus, but by a balance between two sources and one sink. Since the southern winter dehydration is unrealistically intense, this balance most likely does not resemble the balance in the real atmosphere.

Climatic variability, hydrologic anomaly, and methane emission can turn productive freshwater marshes into net carbon sources

Treesearch

Housen Chu; Johan F. Gottgens; Jiquan Chen; Ge Sun; Ankur R. Desai; Zutao Ouyang; Changliang Shao; Kevin Czajkowski

2015-01-01

Freshwater marshes are well-known for their ecological functions in carbon sequestration, but complete carbon budgets that include both methane (CH4) and lateral carbon fluxes for these ecosystems are rarely available. To the best of our knowledge, this is the first full carbon balance for a freshwater marsh where vertical gaseous [carbon dioxide (CO2) and CH4] and...

Sabatier Reactor System Integration with Microwave Plasma Methane Pyrolysis Post-Processor for Closed-Loop Hydrogen Recovery

NASA Technical Reports Server (NTRS)

Abney, Morgan B.; Miller, Lee A.; Williams, Tom

2010-01-01

The Carbon Dioxide Reduction Assembly (CRA) designed and developed for the International Space Station (ISS) represents the state-of-the-art in carbon dioxide reduction (CDRe) technology. The CRA produces water and methane by reducing carbon dioxide with hydrogen via the Sabatier reaction. The water is recycled to the Oxygen Generation Assembly (OGA) and the methane is vented overboard resulting in a net loss of hydrogen. The proximity to earth and the relative ease of logistics resupply from earth allow for a semi-closed system on ISS. However, long-term manned space flight beyond low earth orbit (LEO) dictates a more thoroughly closed-loop system involving significantly higher recovery of hydrogen, and subsequent recovery of oxygen, to minimize costs associated with logistics resupply beyond LEO. The open-loop ISS system for CDRe can be made closed-loop for follow-on missions by further processing methane to recover hydrogen. For this purpose, a process technology has been developed that employs a microwave-generated plasma to reduce methane to hydrogen and acetylene resulting in 75% theoretical recovery of hydrogen. In 2009, a 1-man equivalent Plasma Pyrolysis Assembly (PPA) was delivered to the National Aeronautics and Space Administration (NASA) for technical evaluation. The PPA has been integrated with a Sabatier Development Unit (SDU). The integrated process configuration incorporates a sorbent bed to eliminate residual carbon dioxide and water vapor in the Sabatier methane product stream before it enters the PPA. This paper provides detailed information on the stand-alone and integrated performance of both the PPA and SDU. Additionally, the integrated test stand design and anticipated future work are discussed.

Oxidation of Chemically-Vapor-Deposited Silicon Carbide in Carbon Dioxide

NASA Technical Reports Server (NTRS)

Opila, Elizabeth J.; Nguyen, QuynhGiao N.

1998-01-01

Chemically-vapor-deposited silicon carbide (CVD SiC) was oxidized in carbon dioxide (CO2) at temperatures of 1200-1400 C for times between 96 and 500 h at several gas flow rates. Oxidation weight gains were monitored by thermogravimetric analysis (TGA) and were found to be very small and independent of temperature. Possible rate limiting kinetic mechanisms are discussed. Passive oxidation of SiC by CO2 is negligible compared to the rates measured for other oxidants that are also found in combustion environments, oxygen and water vapor.

Hydrogenation of Carbon Dioxide to Methane by Ruthenium Nanoparticles in Ionic Liquid.

PubMed

Melo, Catarina I; Szczepańska, Anna; Bogel-Łukasik, Ewa; Nunes da Ponte, Manuel; Branco, Luís C

2016-05-23

The efficient transformation of carbon dioxide into fuels can be an excellent alternative to sequestration. In this work, we describe CO2 hydrogenation to methane in imidazolium-based ionic liquid media, using ruthenium nanoparticles prepared in situ as catalyst. The best yield of methane (69 %) was achieved using 0.24 mol % ruthenium catalyst (in [omim][NTf2 ], 1-octyl-3-methylimidazolium bistrifluoromethanesulfonylimide, at 40 bar of hydrogen pressure plus 40 bar of CO2 pressure, and at 150 °C. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Carbon nanotubes accelerate methane production in pure cultures of methanogens and in a syntrophic coculture.

PubMed

Salvador, Andreia F; Martins, Gilberto; Melle-Franco, Manuel; Serpa, Ricardo; Stams, Alfons J M; Cavaleiro, Ana J; Pereira, M Alcina; Alves, M Madalena

2017-07-01

Carbon materials have been reported to facilitate direct interspecies electron transfer (DIET) between bacteria and methanogens improving methane production in anaerobic processes. In this work, the effect of increasing concentrations of carbon nanotubes (CNT) on the activity of pure cultures of methanogens and on typical fatty acid-degrading syntrophic methanogenic coculture was evaluated. CNT affected methane production by methanogenic cultures, although acceleration was higher for hydrogenotrophic methanogens than for acetoclastic methanogens or syntrophic coculture. Interestingly, the initial methane production rate (IMPR) by Methanobacterium formicicum cultures increased 17 times with 5 g·L -1 CNT. Butyrate conversion to methane by Syntrophomonas wolfei and Methanospirillum hungatei was enhanced (∼1.5 times) in the presence of CNT (5 g·L -1 ), but indications of DIET were not obtained. Increasing CNT concentrations resulted in more negative redox potentials in the anaerobic microcosms. Remarkably, without a reducing agent but in the presence of CNT, the IMPR was higher than in incubations with reducing agent. No growth was observed without reducing agent and without CNT. This finding is important to re-frame discussions and re-interpret data on the role of conductive materials as mediators of DIET in anaerobic communities. It also opens new challenges to improve methane production in engineered methanogenic processes. © 2017 The Authors. Environmental Microbiology published by Society for Applied Microbiology and John Wiley & Sons Ltd.

Revised methane emissions factors and spatially distributed annual carbon fluxes for global livestock

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

Wolf, Julie; Asrar, Ghassem R.; West, Tristram O.

Background: Livestock play an important role in carbon cycling through consumption of biomass and emissions of methane. Recent research suggests that existing bottom-up inventories of livestock methane emissions in the US, such as those made using 2006 IPCC Tier 1 livestock emissions factors, are too low. This may be due to outdated information used to develop these emissions factors. In this study, we update information for cattle and swine by region, based on reported recent changes in animal body mass, feed quality and quantity, milk productivity, and management of animals and manure. We then use this updated information to calculatemore » new livestock methane emissions factors for enteric fermentation in cattle, and for manure management in cattle and swine.« less

Pretreatment process for forming a smooth surface diamond film on a carbon-coated substrate

DOEpatents

Feng, Zhu; Brewer, Marilee; Brown, Ian; Komvopoulos, Kyriakos

1994-01-01

A process is disclosed for the pretreatment of a carbon-coated substrate to provide a uniform high density of nucleation sites thereon for the subsequent deposition of a continuous diamond film without the application of a bias voltage to the substrate. The process comprises exposing the carbon-coated substrate, in a microwave plasma enhanced chemical vapor deposition system, to a mixture of hydrogen-methane gases, having a methane gas concentration of at least about 4% (as measured by partial pressure), while maintaining the substrate at a pressure of about 10 to about 30 Torr during the pretreatment.

Pretreatment process for forming a smooth surface diamond film on a carbon-coated substrate

DOEpatents

Feng, Z.; Brewer, M.; Brown, I.; Komvopoulos, K.

1994-05-03

A process is disclosed for the pretreatment of a carbon-coated substrate to provide a uniform high density of nucleation sites thereon for the subsequent deposition of a continuous diamond film without the application of a bias voltage to the substrate. The process comprises exposing the carbon-coated substrate, in a microwave plasma enhanced chemical vapor deposition system, to a mixture of hydrogen-methane gases, having a methane gas concentration of at least about 4% (as measured by partial pressure), while maintaining the substrate at a pressure of about 10 to about 30 Torr during the pretreatment. 6 figures.

A 4 U laser heterodyne radiometer for methane (CH4) and carbon dioxide (CO2) measurements from an occultation-viewing CubeSat

NASA Astrophysics Data System (ADS)

Wilson, Emily L.; DiGregorio, A. J.; Riot, Vincent J.; Ammons, Mark S.; Bruner, William W.; Carter, Darrell; Mao, Jianping; Ramanathan, Anand; Strahan, Susan E.; Oman, Luke D.; Hoffman, Christine; Garner, Richard M.

2017-03-01

We present a design for a 4 U (20 cm  ×  20 cm  ×  10 cm) occultation-viewing laser heterodyne radiometer (LHR) that measures methane (CH4), carbon dioxide (CO2) and water vapor (H2O) in the limb that is designed for deployment on a 6 U CubeSat. The LHR design collects sunlight that has undergone absorption by the trace gas and mixes it with a distributive feedback (DFB) laser centered at 1640 nm that scans across CO2, CH4, and H2O absorption features. Upper troposphere/lower stratosphere measurements of these gases provide key inputs to stratospheric circulation models: measuring stratospheric circulation and its variability is essential for projecting how climate change will affect stratospheric ozone.

Monodeuterated Methane, an Isotopic Tool To Assess Biological Methane Metabolism Rates

PubMed Central

Steele, Joshua A.; Ziebis, Wiebke; Scheller, Silvan; Case, David; Reynard, Linda M.; Orphan, Victoria J.

2017-01-01

ABSTRACT Biological methane oxidation is a globally relevant process that mediates the flux of an important greenhouse gas through both aerobic and anaerobic metabolic pathways. However, measuring these metabolic rates presents many obstacles, from logistical barriers to regulatory hurdles and poor precision. Here we present a new approach for investigating microbial methane metabolism based on hydrogen atom dynamics, which is complementary to carbon-focused assessments of methanotrophy. The method uses monodeuterated methane (CH3D) as a metabolic substrate, quantifying the aqueous D/H ratio over time using off-axis integrated cavity output spectroscopy. This approach represents a nontoxic, comparatively rapid, and straightforward approach that supplements existing radiotopic and stable carbon isotopic methods; by probing hydrogen atoms, it offers an additional dimension for examining rates and pathways of methane metabolism. We provide direct comparisons between the CH3D procedure and the well-established 14CH4 radiotracer method for several methanotrophic systems, including type I and II aerobic methanotroph cultures and methane-seep sediment slurries and carbonate rocks under anoxic and oxic incubation conditions. In all applications tested, methane consumption values calculated via the CH3D method were directly and consistently proportional to 14C radiolabel-derived methane oxidation rates. We also employed this method in a nontraditional experimental setup, using flexible, gas-impermeable bags to investigate the role of pressure on seep sediment methane oxidation rates. Results revealed an 80% increase over atmospheric pressure in methanotrophic rates the equivalent of ~900-m water depth, highlighting the importance of this parameter on methane metabolism and exhibiting the flexibility of the newly described method. IMPORTANCE Microbial methane consumption is a critical component of the global carbon cycle, with wide-ranging implications for climate regulation

Monodeuterated Methane, an Isotopic Tool To Assess Biological Methane Metabolism Rates.

PubMed

Marlow, Jeffrey J; Steele, Joshua A; Ziebis, Wiebke; Scheller, Silvan; Case, David; Reynard, Linda M; Orphan, Victoria J

2017-01-01

Biological methane oxidation is a globally relevant process that mediates the flux of an important greenhouse gas through both aerobic and anaerobic metabolic pathways. However, measuring these metabolic rates presents many obstacles, from logistical barriers to regulatory hurdles and poor precision. Here we present a new approach for investigating microbial methane metabolism based on hydrogen atom dynamics, which is complementary to carbon-focused assessments of methanotrophy. The method uses monodeuterated methane (CH 3 D) as a metabolic substrate, quantifying the aqueous D/H ratio over time using off-axis integrated cavity output spectroscopy. This approach represents a nontoxic, comparatively rapid, and straightforward approach that supplements existing radiotopic and stable carbon isotopic methods; by probing hydrogen atoms, it offers an additional dimension for examining rates and pathways of methane metabolism. We provide direct comparisons between the CH 3 D procedure and the well-established 14 CH 4 radiotracer method for several methanotrophic systems, including type I and II aerobic methanotroph cultures and methane-seep sediment slurries and carbonate rocks under anoxic and oxic incubation conditions. In all applications tested, methane consumption values calculated via the CH 3 D method were directly and consistently proportional to 14 C radiolabel-derived methane oxidation rates. We also employed this method in a nontraditional experimental setup, using flexible, gas-impermeable bags to investigate the role of pressure on seep sediment methane oxidation rates. Results revealed an 80% increase over atmospheric pressure in methanotrophic rates the equivalent of ~900-m water depth, highlighting the importance of this parameter on methane metabolism and exhibiting the flexibility of the newly described method. IMPORTANCE Microbial methane consumption is a critical component of the global carbon cycle, with wide-ranging implications for climate regulation

Phase equilibrium of methane and nitrogen at low temperatures - Application to Titan

NASA Technical Reports Server (NTRS)

Kouvaris, Louis C.; Flasar, F. M.

1991-01-01

Since the vapor phase composition of Titan's methane-nitrogen lower atmosphere is uniquely determined as a function of the Gibbs phase rule, these data are presently computed via integration of the Gibbs-Duhem equation. The thermodynamic consistency of published measurements and calculations of the vapor phase composition is then examined, and the saturated mole fraction of gaseous methane is computed as a function of altitude up to the 700-mbar level. The mole fraction is found to lie approximately halfway between that computed from Raoult's law, for a gas in equilibrium with an ideal solution of liquid nitrogen and methane, and that for a gas in equilibrium with pure liquid methane.

Differentiation of Chemical Components in a Binary Solvent Vapor Mixture Using Carbon/Polymer Composite-Based Chemiresistors

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

Patel, Sanjay V.; Jenkins, Mark W.; Hughes, Robert C.

1999-07-19

We demonstrate a ''universal solvent sensor'' constructed from a small array of carbon/polymer composite chemiresistors that respond to solvents spanning a wide range of Hildebrand volubility parameters. Conductive carbon particles provide electrical continuity in these composite films. When the polymer matrix absorbs solvent vapors, the composite film swells, the average separation between carbon particles increases, and an increase in film resistance results, as some of the conduction pathways are broken. The adverse effects of contact resistance at high solvent concentrations are reported. Solvent vapors including isooctane, ethanol, dlisopropyhnethylphosphonate (DIMP), and water are correctly identified (''classified'') using three chemiresistors, their compositemore » coatings chosen to span the full range of volubility parameters. With the same three sensors, binary mixtures of solvent vapor and water vapor are correctly classified, following classification, two sensors suffice to determine the concentrations of both vapor components. Polyethylene vinylacetate and polyvinyl alcohol (PVA) are two such polymers that are used to classify binary mixtures of DIMP with water vapor; the PVA/carbon-particle-composite films are sensitive to less than 0.25{degree}A relative humidity. The Sandia-developed VERI (Visual-Empirical Region of Influence) technique is used as a method of pattern recognition to classify the solvents and mixtures and to distinguish them from water vapor. In many cases, the response of a given composite sensing film to a binary mixture deviates significantly from the sum of the responses to the isolated vapor components at the same concentrations. While these nonlinearities pose significant difficulty for (primarily) linear methods such as principal components analysis, VERI handles both linear and nonlinear data with equal ease. In the present study the maximum speciation accuracy is achieved by an array containing three or four sensor

The Roles of Sphagnum and Cyperaceae in the Methane Cycle of an Ombrotrophic Bog Revealed by the Carbon Isotope Ratios of Leaf Waxes

NASA Astrophysics Data System (ADS)

Isles, P. D.; Nichols, J. E.; Peteet, D. M.; Kenna, T. C.

2011-12-01

Methane is a strong greenhouse gas, and the role of the terrestrial carbon cycle in the concentrations of atmospheric methane is poorly understood. What is clear, is that northern peatlands are a significant source of methane to the atmosphere. A recent discovery, and a topic of much scrutiny, has been the relationship between Sphagnum in peatlands and symbiotic methanotrophic bacteria. These bacteria oxidize methane produced at depth in peatlands before it is released to the atmosphere, contributing 13C-depleted CO2 to Sphagnum photosynthate. We seek to better understand the fate of methane produced in peatlands at depth, and the relationship between methane release from peatland surfaces and parameters such as temperature, moisture, and vegetation type. We compare carbon isotope ratios of leaf wax n-alkanes from sphagnum and vascular plants and major element chemistry at three different microhabitats, hummock, hollow, and sedge tussock, in Mer Bleue an ombrotrophic peatland near Ottowa, Ontario, Canada. We use these compound-specific carbon isotope measurements to constrain the amount of methane-derived CO2 incorporated by Sphagnum. We also compare our multiannually resolved down-core measurements to data from long-term monitoring of climate parameters and methane flux from the same microhabitats to ground-truth our sedimentary signature of methane with instrumental measurements.

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.

Measurement of Trace Water Vapor in a Carbon Dioxide Removal Assembly Product Stream

NASA Technical Reports Server (NTRS)

Wormhoudt, Joda; Shorter, Joanne H.; McManus, J. Barry; Nelson, David D.; Zahniser, Mark S.; Freedman, Andrew; Campbell, Melissa; Chang, Clarence T.; Smith, Frederick D.

2004-01-01

The International Space Station Carbon Dioxide Removal Assembly (CDRA) uses regenerable adsorption technology to remove carbon dioxide (COP) from cabin air. Product water vapor measurements from a CDRA test bed at the NASA Marshall Space Flight Center were made using a tunable infrared diode laser differential absorption spectrometer (TILDAS) provided by NASA Glenn Research Center. The TILDAS instrument exceeded all the test specifications, including sensitivity, dynamic range, time response, and unattended operation. During the COP desorption phase, water vapor concentrations as low as 5 ppmv were observed near the peak of CO2 evolution, rising to levels of approx. 40 ppmv at the end of a cycle. Periods of high water concentration (>100 ppmv) were detected and shown to be caused by an experimental artifact. Measured values of total water vapor evolved during a single desorption cycle were as low as 1 mg.

Advances in Raman Lidar Measurements of Water Vapor, Cirrus Clouds and Carbon Dioxide

NASA Technical Reports Server (NTRS)

Whiteman, David N.; Potter, John R.; Tola, Rebecca; Rush, Kurt; Veselovskii, Igor; Cadirola, Martin; Comer, Joseph

2006-01-01

Narrow-band interference filters with improved transmission in the ultraviolet have been developed under NASA-funded research and used in the Raman Airborne Spectroscopic Lidar (RASL) in ground- based, upward-looking tests. RASL is an airborne Raman Lidar system designed to measure water vapor mixing ratio, and aerosol backscatter/extinction/depolarization. It also possesses the capability to make experimental measurements of cloud liquid water and carbon dioxide. It is being prepared for first flight tests during the summer of 2006. With the newly developed filters installed in RASL, measurements were made of atmospheric water vapor, cirrus cloud optical properties and carbon dioxide that improve upon any previously demonstrated using Raman lidar. Daytime boundary layer profiling of water vapor mixing ratio is performed with less than 5% random error using temporal and spatial resolution of 2-minutes and 60 - 210, respectively. Daytime cirrus cloud optical depth and extinction- to-backscatter ratio measurements are made using 1-minute average. Sufficient signal strength is demonstrated to permit the simultaneous profiling of carbon dioxide and water vapor mixing ratio into the free troposphere during the nighttime. Downward-looking from an airborne RASL should possess the same measurement statistics with approximately a factor of 5 - 10 decrease in averaging time. A description of the technology improvements are provided followed by examples of the improved Raman lidar measurements.

ECOS E-MATRIX Methane and Volatile Organic Carbon (VOC) Emissions Best Practices Database

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

Parisien, Lia

2016-01-31

This final scientific/technical report on the ECOS e-MATRIX Methane and Volatile Organic Carbon (VOC) Emissions Best Practices Database provides a disclaimer and acknowledgement, table of contents, executive summary, description of project activities, and briefing/technical presentation link.

Factors influencing the stable carbon isotopic signature of methane from combustion and biomass burning

NASA Astrophysics Data System (ADS)

Chanton, Jeffrey P.; Rutkowski, Christine M.; Schwartz, Candace C.; Ward, Darold E.; Boring, Lindsay

2000-01-01

Factors controlling the δ13C of methane released by combustion include the combustion efficiency of the fire and the δ13C of the fuel. Smoldering fires produced 13C-depleted methane relative to hot, flaming fires in controlled forest and grassland burns and within a wood stove. Pine forest burns in the southeastern United States produced methane which ranged from -21 to -30‰, while African grassland burns varied from -17 to -26‰, depending upon combustion phase. African woodland burns produced methane at -30‰. In forest burns in the southeastern United States, the δ13C of methane released with smoldering was significantly 13C depleted relative to methane released under hot flaming conditions. Methane released with smoldering was depleted by 2-3‰ relative to the fuel δ13C, but this difference was not significant. The δ13C of methane produced in a variety of wood stove conditions varied from -9 to -25‰ and also depended upon combustion efficiency. Similar results were found for methane produced by gasoline automobile engines, where the δ13C of methane varied from -9 to -22‰. For combustion occurring within the confining chamber of a wood stove or engine the δ13C of methane was clearly 13C enriched relative to the δ13C of the fuel, possibly because of preferential combustion of 12CH4 in the gas phase. Significant quantities of ethylene (up to 25 to 50% of methane concentrations) were produced in southeastern U.S. forest fires, which may have consequences for physiological and reproductive responses of plants in the ecosystem. Methane production in these fires varied from 0.2 to 8.5% of the carbon dioxide production.

Continuous catalytic decomposition of methane

NASA Technical Reports Server (NTRS)

Clifford, J. E.; Hillenbrand, L. J.; Kim, B. C.; Kolic, E. S.; Zupan, J.

1973-01-01

Water is conserved by employing sequence of reactions whereby 75 percent of methane from Sabatier reaction is decomposed to solid carbon and hydrogen; hydrogen is then separated from residual methane and utilized in usual Sabatier reaction to reduce remaining metabolic carbon dioxide.

Carbon Isotope Fractionations Associated with Methanotrophic Growth with the Soluble and Particulate Methane Monooxygenases

NASA Technical Reports Server (NTRS)

Jahnke, Linda L.; Summons, Roger E.; Chang, Sherwood (Technical Monitor)

1996-01-01

Growth experiments with the RuMP-type methanotroph, Methylococcus capsulatus (Bath), have demonstrated that biomass and lipid biomarkers are significantly depleted in C-13 compared to the substrate methane and that the extent of fractionation is dependent on whether cells express the soluble (s) or particulate (p) methane monooxygenase (MMO). The presence or absence of the characteristic sMMO subunits was monitored using SDS-polyacrylamide gels. In M. capsulatus grown with no Cu supplementation, the characteristic sMMO subunits were observed in the soluble fraction throughout the entire growth period and biomass was depleted in C-13 by approximately 14,700 relative to substrate methane. In cells grown with 5uM Cu, no sMMO bands were observed and a greater fractionation of approximately 27,700 in resultant biomass was obtained. Methanol growth experiments with M. capsulatus and with a RuMP methylotroph, Methylophilus methylotrophus, in which biomass measurements yielded depletions in C-13 of 9 and 5%(sub o), respectively, suggest that oxidation of methane is the major fractionation step. Growth of M. capsulatus at a low level of oxygen, approximately 0.5%, had no significant effect on carbon isotope fractionation by either sMMO or pMMO. These observations are significant for identification of molecular biomarkers; and methanotrophic contributions to carbon isotope composition in natural environments.

Solar-induced chemical vapor deposition of diamond-type carbon films

DOEpatents

Pitts, J.R.; Tracy, C.E.; King, D.E.; Stanley, J.T.

1994-09-13

An improved chemical vapor deposition method for depositing transparent continuous coatings of sp[sup 3]-bonded diamond-type carbon films, comprises: (a) providing a volatile hydrocarbon gas/H[sub 2] reactant mixture in a cold wall vacuum/chemical vapor deposition chamber containing a suitable substrate for said films, at pressure of about 1 to 50 Torr; and (b) directing a concentrated solar flux of from about 40 to about 60 watts/cm[sup 2] through said reactant mixture to produce substrate temperatures of about 750 C to about 950 C to activate deposition of the film on said substrate. 11 figs.

Solar-induced chemical vapor deposition of diamond-type carbon films

DOEpatents

Pitts, J. Roland; Tracy, C. Edwin; King, David E.; Stanley, James T.

1994-01-01

An improved chemical vapor deposition method for depositing transparent continuous coatings of sp.sup.3 -bonded diamond-type carbon films, comprising: a) providing a volatile hydrocarbon gas/H.sub.2 reactant mixture in a cold wall vacuum/chemical vapor deposition chamber containing a suitable substrate for said films, at pressure of about 1 to 50 Torr; and b) directing a concentrated solar flux of from about 40 to about 60 watts/cm.sup.2 through said reactant mixture to produce substrate temperatures of about 750.degree. C. to about 950.degree. C. to activate deposition of the film on said substrate.

Abundant carbon substrates drive extremely high sulfate reduction rates and methane fluxes in Prairie Pothole Wetlands.

PubMed

Dalcin Martins, Paula; Hoyt, David W; Bansal, Sheel; Mills, Christopher T; Tfaily, Malak; Tangen, Brian A; Finocchiaro, Raymond G; Johnston, Michael D; McAdams, Brandon C; Solensky, Matthew J; Smith, Garrett J; Chin, Yu-Ping; Wilkins, Michael J

2017-08-01

Inland waters are increasingly recognized as critical sites of methane emissions to the atmosphere, but the biogeochemical reactions driving such fluxes are less well understood. The Prairie Pothole Region (PPR) of North America is one of the largest wetland complexes in the world, containing millions of small, shallow wetlands. The sediment pore waters of PPR wetlands contain some of the highest concentrations of dissolved organic carbon (DOC) and sulfur species ever recorded in terrestrial aquatic environments. Using a suite of geochemical and microbiological analyses, we measured the impact of sedimentary carbon and sulfur transformations in these wetlands on methane fluxes to the atmosphere. This research represents the first study of coupled geochemistry and microbiology within the PPR and demonstrates how the conversion of abundant labile DOC pools into methane results in some of the highest fluxes of this greenhouse gas to the atmosphere ever reported. Abundant DOC and sulfate additionally supported some of the highest sulfate reduction rates ever measured in terrestrial aquatic environments, which we infer to account for a large fraction of carbon mineralization in this system. Methane accumulations in zones of active sulfate reduction may be due to either the transport of free methane gas from deeper locations or the co-occurrence of methanogenesis and sulfate reduction. If both respiratory processes are concurrent, any competitive inhibition of methanogenesis by sulfate-reducing bacteria may be lessened by the presence of large labile DOC pools that yield noncompetitive substrates such as methanol. Our results reveal some of the underlying mechanisms that make PPR wetlands biogeochemical hotspots, which ultimately leads to their critical, but poorly recognized role in regional greenhouse gas emissions. © 2017 John Wiley & Sons Ltd.

Abundant carbon substrates drive extremely high sulfate reduction rates and methane fluxes in Prairie Pothole Wetlands

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

Dalcin Martins, Paula; Hoyt, David W.; Bansal, Sheel

Inland waters are increasingly recognized as critical sites of methane emissions to the atmosphere, but the biogeochemical reactions driving such fluxes are less well understood. The Prairie Pothole Region (PPR) of North America is one of the largest wetland complexes in the world, containing millions of small, shallow wetlands. The sediment pore waters of PPR wetlands contain some of the highest concentrations of dissolved organic carbon (DOC) and sulfur species ever recorded in terrestrial aquatic environments. Using a suite of geochemical and microbiological analyses we measured the impact of sedimentary carbon and sulfur transformations in these wetlands on methane fluxesmore » to the atmosphere. This research represents the first study of coupled geochemistry and microbiology within the PPR, and demonstrates how the conversion of abundant labile DOC pools into methane results in some of the highest fluxes of this greenhouse gas to the atmosphere ever reported. Abundant DOC and sulfate additionally supported some of the highest sulfate reduction rates ever measured in terrestrial aquatic environments, which we infer to account for a large fraction of carbon mineralization in this system. Methane accumulations in zones of active sulfate reduction may be due to either the transport of free methane gas from deeper locations, or the co-occurrence of methanogenesis and sulfate reduction. If both respiratory processes are concurrent, any competitive inhibition of methanogenesis by sulfate-reducing bacteria may be lessened by the presence of large labile DOC pools that yield non-competitive substrates such as methanol. Our results reveal some of the underlying mechanisms that make PPR wetlands biogeochemical hotspots, which ultimately leads to their critical, but poorly recognized role in regional greenhouse gas emissions.« less

Abundant carbon substrates drive extremely high sulfate reduction rates and methane fluxes in Prairie Pothole Wetlands

USGS Publications Warehouse

Martins, Paula; Hoyt, David W.; Bansal, Sheel; Mills, Christopher T.; Tfaily, Malak; Tangen, Brian; Finocchiaro, Raymond; Johnston, Michael D.; McAdams, Brandon C.; Solensky, Matthew J.; Smith, Garrett J.; Chin, Yu-Ping; Wilkins, Michael J.

2017-01-01

Inland waters are increasingly recognized as critical sites of methane emissions to the atmosphere, but the biogeochemical reactions driving such fluxes are less well understood. The Prairie Pothole Region (PPR) of North America is one of the largest wetland complexes in the world, containing millions of small, shallow wetlands. The sediment pore waters of PPR wetlands contain some of the highest concentrations of dissolved organic carbon (DOC) and sulfur species ever recorded in terrestrial aquatic environments. Using a suite of geochemical and microbiological analyses, we measured the impact of sedimentary carbon and sulfur transformations in these wetlands on methane fluxes to the atmosphere. This research represents the first study of coupled geochemistry and microbiology within the PPR and demonstrates how the conversion of abundant labile DOC pools into methane results in some of the highest fluxes of this greenhouse gas to the atmosphere ever reported. Abundant DOC and sulfate additionally supported some of the highest sulfate reduction rates ever measured in terrestrial aquatic environments, which we infer to account for a large fraction of carbon mineralization in this system. Methane accumulations in zones of active sulfate reduction may be due to either the transport of free methane gas from deeper locations or the co-occurrence of methanogenesis and sulfate reduction. If both respiratory processes are concurrent, any competitive inhibition of methanogenesis by sulfate-reducing bacteria may be lessened by the presence of large labile DOC pools that yield noncompetitive substrates such as methanol. Our results reveal some of the underlying mechanisms that make PPR wetlands biogeochemical hotspots, which ultimately leads to their critical, but poorly recognized role in regional greenhouse gas emissions.

High rate chemical vapor deposition of carbon films using fluorinated gases

DOEpatents

Stafford, Byron L.; Tracy, C. Edwin; Benson, David K.; Nelson, Arthur J.

1993-01-01

A high rate, low-temperature deposition of amorphous carbon films is produced by PE-CVD in the presence of a fluorinated or other halide gas. The deposition can be performed at less than 100.degree. C., including ambient room temperature, with a radio frequency plasma assisted chemical vapor deposition process. With less than 6.5 atomic percent fluorine incorporated into the amorphous carbon film, the characteristics of the carbon film, including index of refraction, mass density, optical clarity, and chemical resistance are within fifteen percent (15%) of those characteristics for pure amorphous carbon films, but the deposition rates are high.

Carbon, oxygen, and strontium isotopic composition of methane-derived authigenic carbonates in methane seep areas, eastern margin of Japan Sea

NASA Astrophysics Data System (ADS)

Kakizaki, Y.; Ishikawa, T.; Hiruta, A.; Matsumoto, R.

2016-12-01

We report the occurrence, mineralogy, and isotopic composition (δ13C; δ18O) of methane-derived authigenic carbonates (MDACs) from three methane seep areas with shallow gas hydrate (Umitaka Spur, Joetsu Knoll, and off-Tobishima Island), in the southeastern margin of Japan Sea. Furthermore, we present strontium isotopic ratios (87Sr/86Sr) of MDACs, pore waters, and seawater from Umitaka Spur. MDACs range from a few mm to several tens of cm in diameter. Their shape is quite varied, e.g. nodular, platy, and indetermine form. Most MDACs are composed of high-Mg calcite. The δ13C values of MDACs from Umitaka Spur range from -30 to -4 permil. These isotopic values are higher than those of Joetsu Knoll and off-Tobishima Island. This difference is dependent upon the formation depth of MDACs in the sediment column. It probably indicates a difference in the formation environment of MDACs (e.g. methane flux). Meanwhile, range of the δ18O values of MDACs from those three areas is mostly equal. The 87Sr/86Sr ratios in MDACs from shallow sediment depth of Umitaka Spur are equal to those of modern surface seawater just above Umitaka Spur. The 87Sr/86Sr ratios of MDACs from deeper sediment depth are lower, and the Sr-isotopic trend indicates an upward increase. This trend can be correlated to the global Sr-isotopic trend of the seawater from late Pleistocene to present. It means that 87Sr/86Sr ratios of MDACs reflect the 87Sr/86Sr ratio of seawater at the formation age. However, the 87Sr/86Sr ratios in pore water are lower than those of MDACs, yet follow a parallel trend. This would suggest that the pore water includes a source of light Sr, presumably released from tuff and volcaniclastics during diagenetic processes. 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).

Methane flux and carbon isotope composition correlate to shifting plant and microbial communities along a permafrost thaw gradient

NASA Astrophysics Data System (ADS)

McCalley, C. K.; Mondav, R.; Chanton, J.; Crill, P. M.; Hodgkins, S. B.; Kim, E.; Rich, V. I.; Wehr, R.; Woodcroft, B. J.; Tyson, G. W.; Saleska, S. R.

2012-12-01

Methane flux from high latitude wetlands is a critical component of the global carbon budget and is highly sensitive to climate change, with observed and predicted increases as permafrost thaws. Microorganisms mediate wetland methane cycling, but connections between ecosystem-scale flux and underlying microbial dynamics are poorly understood. To address this gap we used isotopic (laser absorption spectrometry) and molecular (16S rRNA gene amplicon sequencing) techniques in a high latitude (68° N) wetland to investigate the relationship between microbial community composition and methane emissions across a permafrost thaw gradient. The transition from permafrost dominated, well drained palsas, through intermediate thaw sites dominated by Sphagnum spp., to wet sites with no underlying permafrost dominated by Eriophorum angustifolium is associated with substantial increases in methane emission. Across this thaw progression the carbon isotopic composition of emitted methane increased from -79.5 ‰ in the intermediate-thawing site to -66.4 ‰ in the thawed site, indicating a relative shift from CO2-reductive towards acetoclastic methanogenesis. Increases in methane flux under thaw were correlated with increasing abundance of methane-producing archaeal clades and increases in methane isotopic composition were associated with shifts in the archaeal community. While CO2 reducing methanogens were found throughout thawing and thawed sites, methanogens of the Methanosarcina (the order of Archaea that contains all known acetoclastic methanogens) were most associated with the fully thawed site. These results directly link microbial community composition to ecosystem scale changes in the magnitude and isotopic composition of methane emissions under permafrost thaw. If isotopic shifts of this magnitude are characteristic of methane dynamics under permafrost loss they should also become detectable in global atmospheric methane observations, providing a global scale tracer of

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

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.

Chemical vapor deposition: Stable carbons from low-rank coals

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

Sharma, R.K.; Kulas, R.W.; Olson, E.S.

1996-12-31

A chemical vapor deposition (CVD) technique has been used to increase the oxidative stability of activated carbons. Activated carbons prepared from Gascoyne lignite (North Dakota) by thermal or potassium hydroxide activations were subjected to BCI, in helium at 727{degrees}C with or without benzene for a limited period of time, followed by annealing in helium at 900{degrees}C for three days. Untreated and acid-washed coal samples were used to assess the magnitude of the effect of mineral matter in the coal on the boron coating. The oxidative stability of the boron-modified carbons was determined from the decomposition curves obtained from the thermogravimetricmore » analysis. Modification of the as-received, KOH-treated carbon yielded oxidatively stable carbons up to an initial temperature of 520{degrees}C, compared to about 350{degrees}C for the starting material. Similar results were obtained for the carbonized Gascoyne lignite. Sulfurous acid washing of the Gascoyne significantly enhanced the thermal stability (600{degrees}C) of the boron-modified carbon.« less

Investigating physical controls on methane and carbon dioxide fluxes over reservoirs using the eddy covariance method

EPA Science Inventory

Reservoirs are a globally important source of carbon to the atmosphere. Several recent studies have found that both carbon dioxide (CO2) and methane (CH4) emissions from reservoirs are currently being underestimated by up to 50%. This underestimation is due to inadequate characte...

The effect of heated vapor-phase acidification on organic carbon concentrations and isotopic values in geologic rock samples

NASA Astrophysics Data System (ADS)

Wang, R. Z.; West, A. J.; Yager, J. A.; Rollins, N.; Li, G.; Berelson, W.

2016-12-01

Carbon signatures recorded in the modern and geologic rock record can give insight on the Earth's carbon cycle through time. This is especially true for organic carbon (OC), which can help us understand how the biosphere has evolved over Earth's history. However, carbon recorded in rocks is a combination of OC and inorganic carbon (IC) mostly in the form of carbonate minerals. To measure OC, IC must therefore first be removed through a process called "decarbonation." This is often done through a leaching process with hydrochloric acid (HCl). However, three well known problems exist for the decarbonation process: 1) Incomplete removal of IC, 2) Unintentional removal of OC, and 3) Addition of false carbon blank. Currently, vapor (gas) phase removal of OC is preferred to liquid phase treatment because it has been shown that OC is lost to solubilization during liquid phase acidification. Vapor phase treatment is largely thought to avoid the problem of OC loss, but this has not yet been rigorously investigated. This study investigates that assumption and shows that vapor phase treatment can cause unintentional OC loss. We show that vapor phase treatment must be sensitive to rock type and treatment length to produce robust OC isotopic measurements and concentrations.

A Review of Carbon Nanomaterials' Synthesis via the Chemical Vapor Deposition (CVD) Method.

PubMed

Manawi, Yehia M; Samara, Ayman; Al-Ansari, Tareq; Atieh, Muataz A

2018-05-17

Carbon nanomaterials have been extensively used in many applications owing to their unique thermal, electrical and mechanical properties. One of the prime challenges is the production of these nanomaterials on a large scale. This review paper summarizes the synthesis of various carbon nanomaterials via the chemical vapor deposition (CVD) method. These carbon nanomaterials include fullerenes, carbon nanotubes (CNTs), carbon nanofibers (CNFs), graphene, carbide-derived carbon (CDC), carbon nano-onion (CNO) and MXenes. Furthermore, current challenges in the synthesis and application of these nanomaterials are highlighted with suggested areas for future research.

A Review of Carbon Nanomaterials’ Synthesis via the Chemical Vapor Deposition (CVD) Method

PubMed Central

Manawi, Yehia M.; Samara, Ayman; Al-Ansari, Tareq; Atieh, Muataz A.

2018-01-01

Carbon nanomaterials have been extensively used in many applications owing to their unique thermal, electrical and mechanical properties. One of the prime challenges is the production of these nanomaterials on a large scale. This review paper summarizes the synthesis of various carbon nanomaterials via the chemical vapor deposition (CVD) method. These carbon nanomaterials include fullerenes, carbon nanotubes (CNTs), carbon nanofibers (CNFs), graphene, carbide-derived carbon (CDC), carbon nano-onion (CNO) and MXenes. Furthermore, current challenges in the synthesis and application of these nanomaterials are highlighted with suggested areas for future research. PMID:29772760

Dissociation of methane on the surface of charged defective carbon nanotubes

NASA Astrophysics Data System (ADS)

Guo, Z. H.; Yan, X. H.; Xiao, Y.

2010-03-01

Based on the framework of density functional theory (CASTEP and DMOL 3 codes), we simulate the dissociation of methane (CH 4) molecule on the surface of charged defective carbon nanotubes (CNTs). The results display that a charged CNT with carbon (C) and molybdenum (Mo) dopants can effectively dissociate CH 4 molecule, and the adsorption strength of H and CH 3 can be controlled by the injected negative charges. Moreover, the barrier between the transition state (TS) and the reactant is 0.1014 eV, and a single imaginary frequency of -0.3 cm is found for the transition state structure.

High-Accuracy Measurements of Total Column Water Vapor From the Orbiting Carbon Observatory-2

NASA Technical Reports Server (NTRS)

Nelson, Robert R.; Crisp, David; Ott, Lesley E.; O'Dell, Christopher W.

2016-01-01

Accurate knowledge of the distribution of water vapor in Earth's atmosphere is of critical importance to both weather and climate studies. Here we report on measurements of total column water vapor (TCWV) from hyperspectral observations of near-infrared reflected sunlight over land and ocean surfaces from the Orbiting Carbon Observatory-2 (OCO-2). These measurements are an ancillary product of the retrieval algorithm used to measure atmospheric carbon dioxide concentrations, with information coming from three highly resolved spectral bands. Comparisons to high-accuracy validation data, including ground-based GPS and microwave radiometer data, demonstrate that OCO-2 TCWV measurements have maximum root-mean-square deviations of 0.9-1.3mm. Our results indicate that OCO-2 is the first space-based sensor to accurately and precisely measure the two most important greenhouse gases, water vapor and carbon dioxide, at high spatial resolution [1.3 x 2.3 km(exp. 2)] and that OCO-2 TCWV measurements may be useful in improving numerical weather predictions and reanalysis products.

The use of renewable energy in the form of methane via electrolytic hydrogen generation using carbon dioxide as the feedstock

NASA Astrophysics Data System (ADS)

Hashimoto, Koji; Kumagai, Naokazu; Izumiya, Koichi; Takano, Hiroyuki; Shinomiya, Hiroyuki; Sasaki, Yusuke; Yoshida, Tetsuya; Kato, Zenta

2016-12-01

The history reveals the continuous increase in world energy consumption and carbon emissions. For prevention of intolerable global warming and complete exhaustion of fossil fuels we need complete conversion from fossil fuel consumption to renewable energy. We have been performing the research and development of global carbon dioxide recycling for more than 25 years to supply renewable energy to the world in the form of methane produced by the reaction of carbon dioxide captured from chimney with hydrogen generated electrolytically using electricity generated by renewable energy. We created the cathode and anode for electrolytic hydrogen generation and the catalyst for carbon dioxide methanation by the reaction with hydrogen. The methane formation from renewable energy will be the most convenient and efficient key technology for the use of renewable energy by storage of intermittent and fluctuating electricity generated from renewable energy and by regeneration of stable electricity. Domestic and international cooperation of companies for industrialization is in progress.

Enhanced water vapor separation by temperature-controlled aligned-multiwalled carbon nanotube membranes.

PubMed

Jeon, Wonjae; Yun, Jongju; Khan, Fakhre Alam; Baik, Seunghyun

2015-09-14

Here we present a new strategy of selectively rejecting water vapor while allowing fast transport of dry gases using temperature-controlled aligned-multiwalled carbon nanotubes (aligned-MWNTs). The mechanism is based on the water vapor condensation at the entry region of nanotubes followed by removing aggregated water droplets at the tip of the superhydrophobic aligned-MWNTs. The first condensation step could be dramatically enhanced by decreasing the nanotube temperature. The permeate-side relative humidity was as low as ∼17% and the helium-water vapor separation factor was as high as 4.62 when a helium-water vapor mixture with a relative humidity of 100% was supplied to the aligned-MWNTs. The flow through the interstitial space of the aligned-MWNTs allowed the permeability of single dry gases an order of magnitude higher than the Knudsen prediction regardless of membrane temperature. The water vapor separation performance of hydrophobic polytetrafluoroethylene membranes could also be significantly enhanced at low temperatures. This work combines the membrane-based separation technology with temperature control to enhance water vapor separation performance.

Tunable carbon nanotube-tungsten carbide nanoparticles heterostructures by vapor deposition

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

Xia, Min; Guo, Hongyan; Ge, Changchun

2014-05-14

A simple, versatile route for the synthesis of carbon nanotube (CNT)-tungsten carbide nanoparticles heterostructures was set up via vapor deposition process. For the first time, amorphous CNTs (α-CNTs) were used to immobilized tungsten carbide nanoparticles. By adjusting the synthesis and annealing temperature, α-CNTs/amorphous tungsten carbide, α-CNTs/W{sub 2}C, and CNTs/W{sub 2}C/WC heterostructures were prepared. This approach provides an efficient method to attach other metal carbides and other nanoparticles to carbon nanotubes with tunable properties.

The chemistry and transport of methane and carbon monoxide in the troposphere

NASA Technical Reports Server (NTRS)

Peters, L. K.; Chameides, W. L.

1980-01-01

The present understanding of the physical and chemical behavior of methane, carbon monoxide and the chemical species involved in the conversion of CH4 to CO in the troposphere is reviewed. Following a brief summary of CO and CH4 emission and reactions in urban areas, attention is given to measurements of the spatial and temporal distributions of CO and CH4 in the rural atmosphere, the contribution of the oceans to atmospheric CO and CH4 concentrations, and interactions of CH4 and CO with soils and vegetation. Estimates of the transport of CH4 and CO from the troposphere to the stratosphere are discussed, and photochemical reactions of the constituents are examined. Two- and three-dimensional models for CH4 and CO transport are presented, and possible future variations in atmospheric abundances of the molecules are considered. Finally, present estimates of the global methane and carbon dioxide budgets are summarized, and it is pointed out that, despite the large contribution of anthropogenic sources, the budgets appear to be in balance.

Organic-vapor detection using carbon-nanotubes nanocomposite microacoustic sensors

NASA Astrophysics Data System (ADS)

Penza, M.; Tagliente, M. A.; Aversa, P.; Cassano, G.

2005-06-01

We have developed highly sensitive microacoustic vapor sensors based on surface acoustic waves (SAWs) ST,X quartz 315 and 433 MHz two-port resonator oscillators. A nanocomposite film of single-walled carbon nanotubes (SWCNTs) embedded in a cadmium arachidate (CdA) amphiphilic matrix was prepared by Langmuir-Blodgett technique with a fixed SWCNTs weight filler-content as nanostructured and nanosensing interface, for vapor detection at room temperature. The structural properties and surface morphology of the nanocomposite have been examined by X-ray Specular Reflectivity and Field-Emission Gun Scanning Electron Microscopy, respectively. The measured acoustic sensing characteristics indicate that the SAW sensitivity to polar and nonpolar tested organic molecules (ethanol, ethylacetate, and toluene) of the SWCNTs/CdA nanocomposite is up to two times higher than that of unembedded CdA device; also the SWCNTs/CdA nanocomposite vapor sensitivity results significantly enhanced with respect to traditional organic molecular cavities materials and increases with SAW oscillating frequency with a linear dependence in the frequency change response up to a very low sub-ppm limit of detection.

Measurements of Carbon Dioxide, Methane, and Other Related Tracers at High Spatial and Temporal Resolution in an Urban Environment

NASA Astrophysics Data System (ADS)

Forgeron, J.; Yasuhara, S.; Rella, C.; Jacobson, G. A.; Chiao, S.

2012-12-01

Measurements of Carbon Dioxide, Methane, and Other Related Tracers at High Spatial and Temporal Resolution in an Urban Environment Jeff Forgeron1,2, Scott Yasuhara1,2, Chris Rella1, Gloria Jacobson1, Sen Chiao2 1Picarro Inc., 3105 Patrick Henry Drive, Santa Clara California 95054 USA 2San Jose State University, 1 Washington Square, San Jose California USA JeffAForgeron@gmail.com The ability to quantify sources and sinks of carbon dioxide and methane on the urban scale is essential for understanding the atmospheric drivers to global climate change. In the 'top-down' approach, overall carbon fluxes are determined by combining remote measurements of carbon dioxide concentrations with complex atmospheric transport models, and these emissions measurements are compared to 'bottom-up' predictions based on detailed inventories of the sources and sinks of carbon, both anthropogenic and biogenic in nature. This approach, which has proven to be effective at continental scales, becomes challenging to implement at urban scales, due to poorly understood atmospheric transport models and high variability of the emissions sources in space (e.g., factories, highways, green spaces) and time (rush hours, factory shifts and shutdowns, and diurnal and seasonal variation in residential energy use). New measurement and analysis techniques are required to make sense of the carbon dioxide signal in cities. Here we present detailed, high spatial- and temporal- resolution greenhouse gas measurements made by multiple Picarro-CRDS analyzers in Silicon Valley in California. Real-time carbon dioxide data from a 12-month period are combined with real-time carbon monoxide, methane, acetylene, and carbon-13 measurements to partition the observed carbon dioxide concentrations between different anthropogenic sectors (e.g., transport, residential) and biogenic sources. Real-time wind rose data are also combined with real-time methane data to help identify the direction of local emissions of methane

Initial development and performance evaluation of a process for formation of dense carbon by pyrolysis of methane

NASA Technical Reports Server (NTRS)

Noyes, G. P.; Cusick, R. J.

1985-01-01

The three steps in pyrolytic carbon formation are: (1) gaseous hydrocarbon polymerization and aromatic formation; (2) gas-phase condensation and surface adsorption/impingement of polyaromatic hydrocarbon; and (3) final dehydration to carbon. The structure of the carbon in the various stages of formation is examined. The apparatuses and experimental procedures for the pyrolysis of methane in a 60 cm long quartz reactor tube at temperatures ranging from 1400-1600 K are described. The percentage of carbon converted and its density are calculated and tabularly presented. The results reveal that dense carbon formation is maximized and soot eliminated by this procedure. It is observed that conversion efficiency depends on the composition of the inlet gas and conversion increases with increasing temperature. Based on the experimental data a three-man carbon reactor subsystem (CRS) is developed; the functions of the Sabatier Methanation Reactor, two carbon formation reactors and fluid handling components of the CRS are analyzed. The CRS forms 16 kg of carbon at a rate of 0.8 kg/day for 20 days in a two percent volume density quartz wool packing at temperature of 1500-1600 K.

Adsorption of N-hexane, methanol and water vapor and binary mixtures of N-hexane/water vapor on super activated carbon nanoparticles

NASA Astrophysics Data System (ADS)

Prado, Jesus Antonio

Recent times have seen a large rise in the utilization of engineered nanomaterials (ENMs) within a wide variety of industries due to their unique properties. Consequently, the fabrication, application and disposal of ENMs will inevitably lead to their release to the environment. Once ENMs are in the environment, they may undergo atmospheric transformations, such the sorption of hazardous air pollutants (HAPs) or water vapor. These transformed ENMs may then affect the general public through inhalation -- or other pathways of exposure -- and those employed by the ever-growing nanotechnology sector are of particular vulnerability. As a result, it is important to evaluate the adsorption characteristics of a common carbon-based ENM under the presence of HAPs or water vapor which may adsorb onto them. This study investigated the unary and binary gas-phase adsorption of n-hexane, methanol and water vapor on super activated carbon nanoparticles (SACNPs) with a bench-scale adsorption system. Removal efficiencies, breakthrough tests, throughput ratios, adsorption capacities and kinetics modeling were completed to assess the adsorption behavior of the SACNPs.

Measurements of Carbon Dioxide, Methane, and Other Related Tracers at High Spatial and Temporal Resolution in an Urban Environment

NASA Astrophysics Data System (ADS)

Yasuhara, Scott; Forgeron, Jeff; Rella, Chris; Franz, Patrick; Jacobson, Gloria; Chiao, Sen; Saad, Nabil

2013-04-01

The ability to quantify sources and sinks of carbon dioxide and methane on the urban scale is essential for understanding the atmospheric drivers to global climate change. In the 'top-down' approach, overall carbon fluxes are determined by combining remote measurements of carbon dioxide concentrations with complex atmospheric transport models, and these emissions measurements are compared to 'bottom-up' predictions based on detailed inventories of the sources and sinks of carbon, both anthropogenic and biogenic in nature. This approach, which has proven to be effective at continental scales, becomes challenging to implement at urban scales, due to poorly understood atmospheric transport models and high variability of the emissions sources in space (e.g., factories, highways, green spaces) and time (rush hours, factory shifts and shutdowns, and diurnal and seasonal variation in residential energy use). New measurement and analysis techniques are required to make sense of the carbon dioxide signal in cities. Here we present detailed, high spatial- and temporal- resolution greenhouse gas measurements made by multiple Picarro-CRDS analyzers in Silicon Valley in California. Real-time carbon dioxide data from a 20-month period are combined with real-time carbon monoxide, methane, and acetylene to partition the observed carbon dioxide concentrations between different anthropogenic sectors (e.g., transport, residential) and biogenic sources. Real-time wind rose data are also combined with real-time methane data to help identify the direction of local emissions of methane. High resolution WRF models are also included to better understand the dynamics of the boundary layer. The ratio between carbon dioxide and carbon monoxide is shown to vary over more than a factor of two from season to season or even from day to night, indicating rapid but frequent shifts in the balance between different carbon dioxide sources. Additional information is given by acetylene, a fossil fuel

Sources and turnover of organic carbon and methane in fjord and shelf sediments off northern Norway

NASA Astrophysics Data System (ADS)

Sauer, Simone; Hong, Wei-Li; Knies, Jochen; Lepland, Aivo; Forwick, Matthias; Klug, Martin; Eichinger, Florian; Baranwal, Soma; Crémière, Antoine; Chand, Shyam; Schubert, Carsten J.

2016-10-01

To better understand the present and past carbon cycling and transformation processes in methane-influenced fjord and shelf areas of northern Norway, we compared two sediment cores from the Hola trough and from Ullsfjorden. We investigated (1) the organic matter composition and sedimentological characteristics to study the sources of organic carbon (Corg) and the factors influencing Corg burial, (2) pore water geochemistry to determine the contribution of organoclastic sulfate reduction and methanogenesis to total organic carbon turnover, and (3) the carbon isotopic signature of hydrocarbons to identify the carbon transformation processes and gas sources. High sedimentation and Corg accumulation rates in Ullsfjorden support the notion that fjords are important Corg sinks. The depth of the sulfate-methane-transition (SMT) in the fjord is controlled by the supply of predominantly marine organic matter to the sediment. Organoclastic sulfate reduction accounts for 60% of the total depth-integrated sulfate reduction in the fjord. In spite of the presence of ethane, propane, and butane, we suggest a purely microbial origin of light hydrocarbons in the sediments based on their low δ13C values. In the Hola trough, sedimentation and Corg accumulation rates changed during the deglacial-to-post-glacial transition from approximately 80 cm ka-1 to erosion at present. Thus, Corg burial in this part of the shelf is presently absent. Low organic matter content in the sediment and low rates of organoclastic sulfate reduction (only 3% of total depth-integrated sulfate reduction) entail that the shallow depth of the SMT is controlled mostly by ascending thermogenic methane from deeper sources.

Radiative forcing of carbon dioxide, methane, and nitrous oxide: A significant revision of the methane radiative forcing

NASA Astrophysics Data System (ADS)

Etminan, M.; Myhre, G.; Highwood, E. J.; Shine, K. P.

2016-12-01

New calculations of the radiative forcing (RF) are presented for the three main well-mixed greenhouse gases, methane, nitrous oxide, and carbon dioxide. Methane's RF is particularly impacted because of the inclusion of the shortwave forcing; the 1750-2011 RF is about 25% higher (increasing from 0.48 W m-2 to 0.61 W m-2) compared to the value in the Intergovernmental Panel on Climate Change (IPCC) 2013 assessment; the 100 year global warming potential is 14% higher than the IPCC value. We present new simplified expressions to calculate RF. Unlike previous expressions used by IPCC, the new ones include the overlap between CO2 and N2O; for N2O forcing, the CO2 overlap can be as important as the CH4 overlap. The 1750-2011 CO2 RF is within 1% of IPCC's value but is about 10% higher when CO2 amounts reach 2000 ppm, a value projected to be possible under the extended RCP8.5 scenario.

Carbon Nanotubes Growth on Graphite Fibers

NASA Technical Reports Server (NTRS)

Zhu, Shen; Su, Ching-Hua; Lehoczky, S. L.; Muntele, I.; Ila, D.; Curreri, Peter A. (Technical Monitor)

2002-01-01

Carbon nanotubes (CNT) were synthesized on graphite fibers by thermal Chemical Vapor Deposition (CVD). On the fiber surface, iron nanoparticles are coated and act as catalysts for CNT growth. The growth temperature ranges from 550 to 1000 C at an ambient pressure. Methane and hydrogen gases with methane contents of 10% to 100% are used for the CNT synthesis. At high growth temperatures (greater than 800 C), the rapid inter-diffusion of the transition metal iron on the graphite surface results in a rough fiber surface with no CNT grown on the surface. When the growth temperature is relatively low (650 - 800 C), CNT are fabricated on the graphite surface with catalytic particles on the nanotube top ends. Using micro Raman spectroscopy in the breath mode region, single-walled or multi-walled CNT can be determined, depending on methane concentrations.

Investigating physical controls on methane and carbon dioxide fluxes over reservoirs using the eddy covariance method-abstract

EPA Science Inventory

Reservoirs are a globally important source of carbon to the atmosphere. Several recent studies have found that both carbon dioxide (CO2) and methane (CH4) emissions from reservoirs are currently being underestimated by up to 50%. This underestimation is due to inadequate characte...

Biofiltration for control of carbon disulfide and hydrogen sulfide vapors

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

Fucich, W.J.; Yang, Y.; Togna, A.P.

1997-12-31

A full-scale biofiltration system has been installed to control carbon disulfide (CS{sub 2}) and hydrogen sulfide (H{sub 2}S) vapor emissions at Nylonge Corporation (Nylonge), a cellulose sponge manufacturing facility in Elyria, Ohio. Both CS{sub 2} and H{sub 2}S are toxic and odorous. In addition, the US Environmental Protection Agency (EPA) has classified CS{sub 2} as one of the 189 hazardous air pollutants listed under Title 3 of the 1990 Clean Air Act Amendments. Nylonge evaluated several technologies to control CS{sub 2} and H{sub 2}S vapor emissions. After careful consideration of both removal efficiency requirements and cost, Nylonge selected biological treatmentmore » as the best overall technology for their application. A biological based technology has been developed to effectively degrade CS{sub 2} and H{sub 2}S vapors. Biofiltration is a process that aerobically converts particular vapor phase compounds into CO{sub 2}, biomass, and water vapor. In this process, microorganisms, in the form of a moistened biofilm layer, immobilized on an organic packing material, such as compost, peat, wood chips, etc., are used to catalyze beneficial chemical reactions. As a contaminated vapor stream passes through the biofilter bed, the contaminants are transferred to the biofilm and are degraded by the microorganisms. This paper describes the CS{sub 2} and H{sub 2}S biofiltration process and the full-scale biofilter system installed at Nylonge`s facility. The system was started in October of 1995, and is designed to treat a 30,000 CFM exhaust stream contaminated with CS{sub 2} and H{sub 2}S vapors.« less

Geochemical record of methane seepage in authigenic carbonates and surrounding host sediments: A case study from the South China Sea

NASA Astrophysics Data System (ADS)

Hu, Yu; Chen, Linying; Feng, Dong; Liang, Qianyong; Xia, Zhen; Chen, Duofu

2017-05-01

Sediments at marine methane seep sites provide potential archives of past fluid flow that serve to explore seepage activities over time. Three gravity cores (D-8, D-F, and D-7) were collected from seep sites on the northern slope of the South China Sea where gas hydrates were drilled in the subsurface. Various carbon and sulfur contents, δ13C values of total inorganic carbon (δ13CTIC), δ34S values of chromium reducible sulfur (δ34SCRS), trace element contents, grain size, and AMS 14C dating of planktonic Foraminifera in the sediments were determined to explore the availability of related proxies at seeps and to trace past methane seepage activities. Evidence for the presence of methane seepage and consequently anaerobic oxidation of methane comes from the occurrence of 13C-depleted authigenic carbonate nodules (δ13C values as low as -49‰) discovered at an interval of 150-200 cm in core D-7. This finding is supported by high S/C ratios and molybdenum enrichment in the same interval. However, low contents of CRS and negative δ34SCRS values are present. It is suggested to reflect a transient methane seepage event, which continued for about 1 ka based on the 14C ages. Cores D-8 and D-F have δ13CTIC values close to zero, low S/C ratios and CRS contents, negative δ34SCRS values, and no trace element enrichment, suggesting a negligible impact of methane-seepage on the sediments. The negative δ34SCRS values of the studied seep-impacted and background sediments suggest that the application of δ34SCRS alone as a proxy to identify AOM-related process may be insufficient. Sediment carbon-sulfur-trace element systematics and 14C ages used here have the potential to be a promising tool to recognize transient methane seepages and constrain their timescales.

Molecular simulation investigation into the performance of Cu-BTC metal-organic frameworks for carbon dioxide-methane separations.

PubMed

Gutiérrez-Sevillano, Juan José; Caro-Pérez, Alejandro; Dubbeldam, David; Calero, Sofía

2011-12-07

We report a molecular simulation study for Cu-BTC metal-organic frameworks as carbon dioxide-methane separation devices. For this study we have computed adsorption and diffusion of methane and carbon dioxide in the structure, both as pure components and mixtures over the full range of bulk gas compositions. From the single component isotherms, mixture adsorption is predicted using the ideal adsorbed solution theory. These predictions are in very good agreement with our computed mixture isotherms and with previously reported data. Adsorption and diffusion selectivities and preferential sitings are also discussed with the aim to provide new molecular level information for all studied systems.

Bifunctional catalyst of graphite-encapsulated iron compound nanoparticle for magnetic carbon nanotubes growth by chemical vapor deposition

NASA Astrophysics Data System (ADS)

Saraswati, Teguh Endah; Prasiwi, Oktaviana Dewi Indah; Masykur, Abu; Anwar, Miftahul

2017-01-01

The carbon nanotube has widely taken great attractive in carbon nanomaterial research and application. One of its preparation methods is catalytic chemical vapor deposition (CCVD) using catalyst i.e. iron, nickel, etc. Generally, except the catalyst, carbon source gasses as the precursor are still required. Here, we report the use of the bifunctional material of Fe3O4/C which has an incorporated core/shell structures of carbon-encapsulated iron compound nanoparticles. The bifunctional catalyst was prepared by submerged arc discharge that simply performed using carbon and carbon/iron oxide electrodes in ethanol 50%. The prepared material was then used as a catalyst in thermal chemical vapor deposition at 800°C flown with ethanol vapor as the primer carbon source in a low-pressure condition. This catalyst might play a dual role as a catalyst and secondary carbon source for growing carbon nanotubes at the time. The synthesized products were characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD) analysis. The successful formation of carbon nanotubes was assigned by the shifted X-ray diffracted peak of carbon C(002), the iron oxides of Fe3O4 and γ-Fe2O3, and the other peaks which were highly considered to the other carbon allotropes with sp2 hybridization structures. The other assignment was studied by electron microscopy which successfully observed the presence of single-wall carbon nanotubes. In addition, the as-prepared carbon nanotubes have a magnetic property which was induced by the remaining of metal catalyst inside the CNT.

Carbon and hydrogen isotopic characterization of methane from wetlands and lakes of the Yukon-Kuskokwim Delta, Western Alaska

NASA Technical Reports Server (NTRS)

Martens, Christopher S.; Kelley, Cheryl A.; Chanton, Jeffrey P.; Showers, William J.

1992-01-01

The results are reported of a study of the carbon and hydrogen isotopic composition of methane from tundra environments of the Yukon-Kuskokwin Delta of western Alaska. The delta C-13 value of diffusive methane emissions from wet meadow tundra of the Delta is -65.82 +/- 2.21 per mil (n=18). Detritus-rich sediments of tundra lakes are loaded with methane-rich gas bubbles during the warm season. Spatial trend is the major gas concentration and isotopic values of methane in these gas bubbles appear to reflect processes associated with production rate and mechanisms; high methane concentrations, lightest delta C-13 values, the heaviest delta D value occur in detritus-rich sediments isolated from emergent vegetation. Heavier delta C-13 and lighter delta D values in methane from heavily vegetated lake margins suggest a shift toward a larger role for acetate fermentation in association with aquatic plants and plant detritus. Bubble ebullition is estimated to account for up to 17 percent of total Delta methane emissions.

Methane-derived authigenic carbonates along the North Anatolian fault system in the Sea of Marmara (Turkey)

NASA Astrophysics Data System (ADS)

Crémière, Antoine; Pierre, Catherine; Blanc-Valleron, Marie-Madeleine; Zitter, Tiphaine; Çağatay, M. Namik; Henry, Pierre

2012-08-01

The Marnaut cruise (May-June 2007) investigated the submerged part of the North Anatolian fault system, an active tectonic area in the Sea of Marmara. Already known and new fluid venting sites along the fault system were visited by submersible diving. Cold seeps present a considerable diversity of geochemical background associated with occurrences of authigenic carbonate crusts outcropping at the seafloor. Buried carbonate concretions were also recovered by coring within the sediments of the Tekirdağ Basin and of the Western-High ridge that separates the Tekirdağ and Central Basins. Interestingly, numerous of these early diagenetic carbonates were found within the transitional sediments from lacustrine to marine environment deposited after the late glacial maximum. The authigenic carbonates are mainly composed of aragonite, Mg-calcite and minor amounts of dolomite, and are often associated with pyrite and barite. The carbon isotopic compositions of carbonates present a wide range of values from -50.6‰ to +14.2‰ V-PDB indicating different diagenetic settings and complex mixtures of dissolved inorganic carbon from different sources. The low δ13C values of the seafloor crusts and of most buried concretions indicate that the carbon source was a mixture of microbial and thermogenic methane and possibly other hydrocarbons that were oxidized by anaerobic microbial processes. The positive δ13C values of a few buried concretions from the Western-High ridge reflect the mineralization of heavy CO2, which is thought to represent the residual by-product of oil biodegradation in a subsurface petroleum reservoir that migrated up with brines. Most of the oxygen isotopic compositions of seafloor carbonates are close to the isotopic equilibrium with the present-day bottom water conditions but a few values as low as -1.9‰ V-PDB indicate precipitation from brackish waters. In buried carbonate concretions, δ18O values as high as +4.9‰ V-PDB reflect the contribution of

Carbon isotopes of benthic foraminifera associated with methane seeps in Four-Way Closure Ridge, offshore southwestern Taiwan

NASA Astrophysics Data System (ADS)

Wang, W. R.; Wei, K. Y.; Mii, H. S.; Lin, Y. S.; Huang, J. J.; Wang, P. L.; Lin, A. T.

2015-12-01

Release of large amounts of methane from marine gas hydrate reservoirs has been considered as a possible trigger of climate change, which can be recorded by the variation of carbon isotopes (δ13C) of the benthic foraminifera. In modern analogs, previous studies have suggested that δ13C becomes more negative when influenced by methane seeps. However, values of δ13C of benthic foraminifera might vary with different species and sedimentary settings in different regions. Seismic profiles in offshore southwestern Taiwan show the existence of Bottom Simulating Reflector (BSR) in the region, indicative of gas hydrate reservoirs. Various methane seepages have been found, and they are suspected to be related to the gas hydrates buried underneath. A better understanding of the δ13C signals of benthic foraminifera near the methane seepages can further clarify the origin of the methane and to evaluate it as a proxy of methane release for the geologic past. We have analyzed δ13C of benthic foraminifera Uvigerina proboscidea (150-250 mm) in the topmost 15 cm sediments in five marine cores (OR1-1092-WFWC-1, OR1-1092-WFWC-4, OR1-1092-WFWC-6, OR3-1806-C5-2 and OR3-1806-C10) collected from the Four-Way Closure Ridge in offshore southwestern Taiwan (water depth from 1330 to 1580 m). Our results show that δ13C values of U. proboscidea range from -0.98‰ to -6.21‰ (VPDB) for core OR3-1806-C5-2, which is considered as a seeps-influenced site. On the other hand, δ13C values of U. proboscidea from the background sites range from -0.40‰ to -1.00‰. The difference between the methane seep-affected and the background sites is in the range of 0.00‰ to 5.01‰, comparable to those documented in previous studies in other areas. The significant negative excursion in carbon isotopes in the seep site foraminifera is likely caused by incorporation of light inorganic carbon generated by methanotrophy in the system.

Methane cycling. Nonequilibrium clumped isotope signals in microbial methane.

PubMed

Wang, David T; Gruen, Danielle S; Lollar, Barbara Sherwood; Hinrichs, Kai-Uwe; Stewart, Lucy C; Holden, James F; Hristov, Alexander N; Pohlman, John W; Morrill, Penny L; Könneke, Martin; Delwiche, Kyle B; Reeves, Eoghan P; Sutcliffe, Chelsea N; Ritter, Daniel J; Seewald, Jeffrey S; McIntosh, Jennifer C; Hemond, Harold F; Kubo, Michael D; Cardace, Dawn; Hoehler, Tori M; Ono, Shuhei

2015-04-24

Methane is a key component in the global carbon cycle, with a wide range of anthropogenic and natural sources. Although isotopic compositions of methane have traditionally aided source identification, the abundance of its multiply substituted "clumped" isotopologues (for example, (13)CH3D) has recently emerged as a proxy for determining methane-formation temperatures. However, the effect of biological processes on methane's clumped isotopologue signature is poorly constrained. We show that methanogenesis proceeding at relatively high rates in cattle, surface environments, and laboratory cultures exerts kinetic control on (13)CH3D abundances and results in anomalously elevated formation-temperature estimates. We demonstrate quantitatively that H2 availability accounts for this effect. Clumped methane thermometry can therefore provide constraints on the generation of methane in diverse settings, including continental serpentinization sites and ancient, deep groundwaters. Copyright © 2015, American Association for the Advancement of Science.

Ammonia and methane emissions from cattle and dairy feedlots in Colorado

NASA Astrophysics Data System (ADS)

Golston, L.; Pan, D.; Stanton, L. G.; Tao, L.; Sun, K.; Zondlo, M. A.

2014-12-01

Concentrated animal feeding operations (CAFOs) are recognized as a major contributor of both methane and ammonia to the atmosphere. Ammonia is released by volatilization of urea and nitrogen containing wastes from the feedlot surface and waste management systems, while methane is produced from enteric fermentation and primarily exhaled into the atmosphere. Our objective was to survey plumes downwind of open lot feedyards near Greeley, Colorado and surrounding areas, to quantify the spatial and temporal variability of agricultural emissions in this area. Research was conducted during the month-long NASA DISCOVER-AQ campaign in July-August 2014, with over 4000 km of on-road measurements. Methane and ammonia concentrations were measured using open-path laser spectroscopy, along with water vapor, carbon monoxide, and carbon dioxide on a roof-mounted, mobile platform. The open-path design enables high resolution measurements of ammonia with minimized sampling issues. Concurrent measurements during the campaign by other groups on stationary and aircraft platforms help characterize the meteorological conditions and atmospheric chemistry. We present measurements from 65 of the 67 registered CAFOs in Weld County, which contain up to 660,000 cattle-equivalent animals units. The ammonia to methane enhancement ratio, ΔNH3:ΔCH4, was positively skewed with a median of 0.14 ± 0.04 ppmv/ppmv, consistent with our previous measurements during DISCOVER-AQ California. Due to the much greater variability of ammonia compared to methane, the emissions ratio is used to provide an estimate of feedyard ammonia emissions, with results divided for cattle, dairy, and sheep. Using the most recent emissions estimates of methane, we calculated a total of ≈28.8 TgNH3/yr released globally from feedlots alone, nearly as large as the IPCC's estimate of 30.4 Tg/yr from all agriculture sources. This discrepancy suggests feedyard ammonia is underrepresented in current inventories and models, and

Method and apparatus for vapor detection

NASA Technical Reports Server (NTRS)

Lerner, Melvin (Inventor); Hood, Lyal V. (Inventor); Rommel, Marjorie A. (Inventor); Pettitt, Bruce C. (Inventor); Erikson, Charles M. (Inventor)

1980-01-01

The method disclosed herein may be practiced by passing the vapors to be sampled along a path with halogen vapor, preferably chlorine vapor, heating the mixed vapors to halogenate those of the sampled vapors subject to halogenation, removing unreacted halogen vapor, and then sensing the vapors for organic halogenated compounds. The apparatus disclosed herein comprises means for flowing the vapors, both sample and halogen vapors, into a common path, means for heating the mixed vapors to effect the halogenation reaction, means for removing unreacted halogen vapor, and a sensing device for sensing halogenated compounds. By such a method and means, the vapors of low molecular weight hydrocarbons, ketones and alcohols, when present, such as methane, ethane, acetone, ethanol, and the like are converted, at least in part, to halogenated compounds, then the excess halogen removed or trapped, and the resultant vapors of the halogenated compounds sensed or detected. The system is highly sensitive. For example, acetone in a concentration of 30 parts per billion (volume) is readily detected.

Annual net ecosystem exchanges of carbon dioxide and methane from a temperate brackish marsh: should the focus of marsh restoration be on brackish environments?

NASA Astrophysics Data System (ADS)

Windham-Myers, L.; Anderson, F. E.; Bergamaschi, B. A.; Ferner, M. C.; Schile, L. M.; Spinelli, G.

2015-12-01

The exchange and transport of carbon in tidally driven, saline marsh ecosystems provide habitat and trophic support for coastal wildlife and fisheries, while potentially accumulating and storing carbon at some of the highest rates compared to other ecosystems. However, due to the predicted rise in sea level over the next century, the preservation and restoration of estuarine habitats is necessary to compensate for their expected decline. In addition, restoration of these marsh systems can also reduce the impacts of global climate change as they assimilate as much carbon as their freshwater counterparts, while emitting less methane due to the higher concentrations of sulfate in seawater. Unfortunately, in brackish marshes, with salinity concentrations less than 18 parts per thousand (ppt), simple relationships between methane production, salinity and sulfate concentrations are not well known. Here we present the net ecosystem exchange (NEE) of carbon dioxide and methane, as calculated by the eddy covariance method, from a brackish marsh ecosystem in the San Francisco Estuary where salinity ranges from oligohaline (0.5-5 ppt) to mesohaline (5-18 ppt) conditions. Daily rates of carbon dioxide and methane NEE ranged from approximately 10 gC-CO2 m-2 d-1 and 0 mgC-CH4 m-2 d-1, during the winter to -15 gC-CO2 m-2 d-1 and 30 mgC-CH4 m-2 d-1, in the summer growing season. A comparison between similar measurements made from freshwater wetlands in the Sacramento-San Joaquin Delta found that the daily rates of carbon dioxide NEE were similar, but daily rates of methane NEE were just a small fraction (0-15%). Our research also shows that the daily fluxes of carbon dioxide and methane at the brackish marsh were highly variable and may be influenced by the tidal exchanges of seawater. Furthermore, the observed decline in methane production from summer to fall may have resulted from a rise in salinity and/or a seasonal decline in water and air temperatures. Our research goals are

Activated carbon derived from waste coffee grounds for stable methane storage.

PubMed

Kemp, K Christian; Baek, Seung Bin; Lee, Wang-Geun; Meyyappan, M; Kim, Kwang S

2015-09-25

An activated carbon material derived from waste coffee grounds is shown to be an effective and stable medium for methane storage. The sample activated at 900 °C displays a surface area of 1040.3 m(2) g(-1) and a micropore volume of 0.574 cm(3) g(-1) and exhibits a stable CH4 adsorption capacity of ∼4.2 mmol g(-1) at 3.0 MPa and a temperature range of 298 ± 10 K. The same material exhibits an impressive hydrogen storage capacity of 1.75 wt% as well at 77 K and 100 kPa. Here, we also propose a mechanism for the formation of activated carbon from spent coffee grounds. At low temperatures, the material has two distinct types with low and high surface areas; however, activation at elevated temperatures drives off the low surface area carbon, leaving behind the porous high surface area activated carbon.

Activated carbon derived from waste coffee grounds for stable methane storage

NASA Astrophysics Data System (ADS)

Kemp, K. Christian; Baek, Seung Bin; Lee, Wang-Geun; Meyyappan, M.; Kim, Kwang S.

2015-09-01

An activated carbon material derived from waste coffee grounds is shown to be an effective and stable medium for methane storage. The sample activated at 900 °C displays a surface area of 1040.3 m2 g-1 and a micropore volume of 0.574 cm3 g-1 and exhibits a stable CH4 adsorption capacity of ˜4.2 mmol g-1 at 3.0 MPa and a temperature range of 298 ± 10 K. The same material exhibits an impressive hydrogen storage capacity of 1.75 wt% as well at 77 K and 100 kPa. Here, we also propose a mechanism for the formation of activated carbon from spent coffee grounds. At low temperatures, the material has two distinct types with low and high surface areas; however, activation at elevated temperatures drives off the low surface area carbon, leaving behind the porous high surface area activated carbon.

Biophysical controls on carbon and water vapor fluxes across a grassland climatic gradient in the United States

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

Wagle, Pradeep; Xiao, Xiangming; Scott, Russell L.

Understanding of the underlying causes of spatial variation in exchange of carbon and water vapor fluxes between grasslands and the atmosphere is crucial for accurate estimates of regional and global carbon and water budgets, and for predicting the impact of climate change on biosphere–atmosphere feedbacks of grasslands. We used ground-based eddy flux and meteorological data, and the Moderate Resolution Imaging Spectroradiometer (MODIS) enhanced vegetation index (EVI) from 12 grasslands across the United States to examine the spatial variability in carbon and water vapor fluxes and to evaluate the biophysical controls on the spatial patterns of fluxes. Precipitation was strongly associatedmore » with spatial and temporal variability in carbon and water vapor fluxes and vegetation productivity. Grasslands with annual average precipitation <600 mm generally had neutral annual carbon balance or emitted small amount of carbon to the atmosphere. Despite strong coupling between gross primary production (GPP)and evapotranspiration (ET) across study sites, GPP showed larger spatial variation than ET, and EVI had a greater effect on GPP than on ET. Consequently, large spatial variation in ecosystem water use efficiency (EWUE = annual GPP/ET; varying from 0.67 ± 0.55 to 2.52 ± 0.52 g C mm⁻¹ET) was observed. Greater reduction in GPP than ET at high air temperature and vapor pressure deficit caused a reduction in EWUE in dry years, indicating a response which is opposite than what has been reported for forests. Our results show that spatial and temporal variations in ecosystem carbon uptake, ET, and water use efficiency of grasslands were strongly associated with canopy greenness and coverage, as indicated by EVI.« less

Inverse Modeling of Tropospheric Methane Constrained by 13C Isotope in Methane

NASA Astrophysics Data System (ADS)

Mikaloff Fletcher, S. E.; Tans, P. P.; Bruhwiler, L. M.

2001-12-01

Understanding the budget of methane is crucial to predicting climate change and managing earth's carbon reservoirs. Methane is responsible for approximately 15% of the anthropogenic greenhouse forcing and has a large impact on the oxidative capacity of Earth's atmosphere due to its reaction with hydroxyl radical. At present, many of the sources and sinks of methane are poorly understood, due in part to the large spatial and temporal variability of the methane flux. Model calculations of methane mixing ratios using most process-based source estimates typically over-predict the inter-hemispheric gradient of atmospheric methane. Inverse models, which estimate trace gas budgets by using observations of atmospheric mixing ratios and transport models to estimate sources and sinks, have been used to incorporate features of the atmospheric observations into methane budgets. While inverse models of methane generally tend to find a decrease in northern hemisphere sources and an increase in southern hemisphere sources relative to process-based estimates,no inverse study has definitively associated the inter-hemispheric gradient difference with a specific source process or group of processes. In this presentation, observations of isotopic ratios of 13C in methane and isotopic signatures of methane source processes are used in conjunction with an inverse model of methane to further constrain the source estimates of methane. In order to investigate the advantages of incorporating 13C, the TM3 three-dimensional transport model was used. The methane and carbon dioxide measurements used are from a cooperative international effort, the Cooperative Air Sampling Network, lead by the Climate Monitoring Diagnostics Laboratory (CMDL) at the National Oceanic and Atmospheric Administration (NOAA). Experiments using model calculations based on process-based source estimates show that the inter-hemispheric gradient of δ 13CH4 is not reproduced by these source estimates, showing that the

Catalytic aromatization of methane.

PubMed

Spivey, James J; Hutchings, Graham

2014-02-07

Recent developments in natural gas production technology have led to lower prices for methane and renewed interest in converting methane to higher value products. Processes such as those based on syngas from methane reforming are being investigated. Another option is methane aromatization, which produces benzene and hydrogen: 6CH4(g) → C6H6(g) + 9H2(g) ΔG°(r) = +433 kJ mol(-1) ΔH°(r) = +531 kJ mol(-1). Thermodynamic calculations for this reaction show that benzene formation is insignificant below ∼600 °C, and that the formation of solid carbon [C(s)] is thermodynamically favored at temperatures above ∼300 °C. Benzene formation is insignificant at all temperatures up to 1000 °C when C(s) is included in the calculation of equilibrium composition. Interestingly, the thermodynamic limitation on benzene formation can be minimized by the addition of alkanes/alkenes to the methane feed. By far the most widely studied catalysts for this reaction are Mo/HZSM-5 and Mo/MCM-22. Benzene selectivities are generally between 60 and 80% at methane conversions of ∼10%, corresponding to net benzene yields of less than 10%. Major byproducts include lower molecular weight hydrocarbons and higher molecular weight substituted aromatics. However, carbon formation is inevitable, but the experimental findings show this can be kinetically limited by the use of H2 or oxidants in the feed, including CO2 or steam. A number of reactor configurations involving regeneration of the carbon-containing catalyst have been developed with the goal of minimizing the cost of regeneration of the catalyst once deactivated by carbon deposition. In this tutorial review we discuss the thermodynamics of this process, the catalysts used and the potential reactor configurations that can be applied.

Potential methane reservoirs beneath Antarctica.

PubMed

Wadham, J L; Arndt, S; Tulaczyk, S; Stibal, M; Tranter, M; Telling, J; Lis, G P; Lawson, E; Ridgwell, A; Dubnick, A; Sharp, M J; Anesio, A M; Butler, C E H

2012-08-30

Once thought to be devoid of life, the ice-covered parts of Antarctica are now known to be a reservoir of metabolically active microbial cells and organic carbon. The potential for methanogenic archaea to support the degradation of organic carbon to methane beneath the ice, however, has not yet been evaluated. Large sedimentary basins containing marine sequences up to 14 kilometres thick and an estimated 21,000 petagrams (1 Pg equals 10(15) g) of organic carbon are buried beneath the Antarctic Ice Sheet. No data exist for rates of methanogenesis in sub-Antarctic marine sediments. Here we present experimental data from other subglacial environments that demonstrate the potential for overridden organic matter beneath glacial systems to produce methane. We also numerically simulate the accumulation of methane in Antarctic sedimentary basins using an established one-dimensional hydrate model and show that pressure/temperature conditions favour methane hydrate formation down to sediment depths of about 300 metres in West Antarctica and 700 metres in East Antarctica. Our results demonstrate the potential for methane hydrate accumulation in Antarctic sedimentary basins, where the total inventory depends on rates of organic carbon degradation and conditions at the ice-sheet bed. We calculate that the sub-Antarctic hydrate inventory could be of the same order of magnitude as that of recent estimates made for Arctic permafrost. Our findings suggest that the Antarctic Ice Sheet may be a neglected but important component of the global methane budget, with the potential to act as a positive feedback on climate warming during ice-sheet wastage.

Carbon dioxide and water vapor high temperature electrolysis

NASA Technical Reports Server (NTRS)

Isenberg, Arnold O.; Verostko, Charles E.

1989-01-01

The design, fabrication, breadboard testing, and the data base obtained for solid oxide electrolysis systems that have applications for planetary manned missions and habitats are reviewed. The breadboard tested contains sixteen tubular cells in a closely packed bundle for the electrolysis of carbon dioxide and water vapor. The discussion covers energy requirements, volume, weight, and operational characteristics related to the measurement of the reactant and product gas compositions, temperature distribution along the electrolyzer tubular cells and through the bundle, and thermal energy losses. The reliability of individual cell performance in the bundle configuration is assessed.

Environmental controls over carbon dioxide and water vapor exchange of terrestrial vegetation

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

B. E. Law; E. Falgeb; L. Guc

2002-12-02

The objective of this research was to compare seasonal and annual estimates of CO2 and water vapor exchange across sites in forests, grasslands, crops, and tundra that are part of an international network called FLUXNET, and to investigating the responses of vegetation to environmental variables. FLUXNETs goals are to understand the mechanisms controlling the exchanges of CO2, water vapor and energy across a spectrum of time and space scales, and to provide information for modeling of carbon and water cycling across regions and the globe. At a subset of sites, net carbon uptake (net ecosystem exchange, the net of photosynthesismore » and respiration) was greater under diffuse than under direct radiation conditions, perhaps because of a more efficient distribution of non-saturating light conditions for photosynthesis, lower vapor pressure deficit limitation to photosynthesis, and lower respiration associated with reduced temperature. The slope of the relation between monthly gross ecosystem production and evapotranspiration was similar between biomes, except for tundra vegetation, showing a strong linkage between carbon gain and water loss integrated over the year (slopes=3.4 g CO2/kg H2O for grasslands, 3.2 for deciduous broadleaf forests, 3.1 for crops, 2.4 for evergreen conifers, and 1.5 for tundra vegetation). The ratio of annual ecosystem respiration to gross photosynthesis averaged 0.83, with lower values for grasslands, presumably because of less investment in respiring plant tissue compared with forests. Ecosystem respiration was weakly correlated with mean annual temperature across biomes, in spite of within site sensitivity over shorter temporal scales. Mean annual temperature and site water balance explained much of the variation in gross photosynthesis. Water availability limits leaf area index over the long-term, and inter-annual climate variability can limit carbon uptake below the potential of the leaf area present.« less

Highly biocompatible yogurt-derived carbon dots as multipurpose sensors for detection of formic acid vapor and metal ions

NASA Astrophysics Data System (ADS)

Moonrinta, Sasaluck; Kwon, Binhee; In, Insik; Kladsomboon, Sumana; Sajomsang, Warayuth; Paoprasert, Peerasak

2018-07-01

Carbon dots are fascinating nanomaterials given their straightforward synthesis, unique optical properties, sensing capabilities, and biocompatibility. In this work, biocompatible carbon dots were prepared from yogurt using a two-step pyrolysis/hydrothermal method. The dots were spherical in shape with an average size of 4.7 nm. They showed blue emission under UV illumination with a quantum yield of 1.5%. Their photoluminescence was stable over three months and in both strong buffer solutions and highly concentrated salt solutions. The optical absorption and photoluminescence properties of the dots were employed for vapor and metal ion sensing, respectively. For the first time, the carbon dots were integrated into an optical electronic nose, and used for the detection of formic acid vapor at room temperature. Sensing was based on monitoring the optical transmission through a carbon dot film upon exposure to vapor, and the results were confirmed by UV-visible spectroscopy. The carbon dot-integrated electronic nose was able to distinguish vapor from formic acid/water solutions at different concentrations, with a detection limit of 7.3% v/v. The sensitivity of the dots to metal ions was tested by measuring the photoluminescence emission intensity at different excitation wavelengths. Principal component analysis was used to differentiate between the ions. The results suggested that interactions between carbon dots and metals ions occurred at a range of binding sites. The biocompability of the dots was demonstrated to be excellent. The study identified carbon dots produced from yogurt as multipurpose fluorescent nanomaterials with potential sensing and biomedical applications.

Effect of temperature for synthesizing single-walled carbon nanotubes by catalytic chemical vapor deposition over Mo-Co-MgO catalyst

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

Niu Zhiqiang; Fang Yan

2008-06-03

The influence of temperature on synthesizing single-walled carbon nanotubes (SWCNTs) by catalytic chemical vapor deposition of methane over Mo-Co-MgO catalyst was studied by Transmission Electron Microscope (TEM) and Raman scattering. The Mo-Co-MgO bimetallic catalyst was prepared by decomposing the mixture of magnesium nitrate, ammonium molybdate, citric acid, and cobalt nitrate. The results show that Mo-Co-MgO bimetallic catalyst is effective to synthesize SWCNTs. By using Mo-Co-MgO bimetallic catalyst, generation of SWCNTs even at 940 K was demonstrated. The optimum temperature of synthesizing SWCNTs over Mo-Co-MgO bimetallic catalyst may be about 1123 K. At 1123 K, the diameters of SWCNTs are inmore » the range of 0.75-1.65 nm. The content of SWCNTs is increased with the increase of temperature below 1123 K and the carbon yield rate is also increased with the increase of synthesis temperature. Therefore, the amount of SWCNTs increases with the increase of temperature below 1123 K. However, above 1123 K, the content of SWCNTs is decreased with the increase of temperature; therefore, it is not effective to increase the amount of SWCNTs through increasing synthesis temperature above 1123 K.« less

Infectious papillomavirus in the vapor of warts treated with carbon dioxide laser or electrocoagulation: Detection and protection

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

Sawchuk, W.S.; Weber, P.J.; Lowy, D.R.

1989-07-01

Papillomavirus DNA has been reported recently in the vapor (smoke plume) derived from warts treated with carbon dioxide laser; this raises concerns for operator safety. We therefore have studied a group of human and bovine warts to define further the potential risk of wart therapy and to test whether a surgical mask could reduce exposure. Half of each wart was treated with carbon dioxide laser and the other half with electrocoagulation. The vapor produced by each form of therapy was collected with a dry filter vacuum apparatus and analyzed for the presence of papillomavirus. Vapor from human plantar warts wasmore » analyzed for the presence of human papillomavirus DNA, because there is no infectivity assay for human papillomavirus. Of plantar warts treated, five of eight laser-derived vapors and four of seven electrocoagulation-derived vapors were positive for human papillomavirus DNA. Greater amounts of papillomavirus DNA were usually recovered in the laser vapor than in the electrocoagulation vapor from the same wart. Bioassay readily detected infectious bovine papillomavirus in the vapor from bovine warts treated with either modality; more virus was present in laser-derived material. A surgical mask was found capable of removing virtually all laser- or electrocoagulation-derived virus, strongly suggesting that such masks can protect operators from potential inhalation exposure to papillomavirus.« less

Atmospheric Methane Measurements from an Aircraft Based at NASA Ames: Five Years of Observations by the AJAX Project

NASA Technical Reports Server (NTRS)

Iraci, Laura

2016-01-01

The Alpha Jet Atmospheric eXperiment (AJAX) is a research project based at Moffett Field, CA, which collects airborne measurements of ozone, carbon dioxide, methane, water vapor, and formaldehyde, as well as 3-D winds, temperature, pressure, and location. Since its first science flight in 2011, AJAX has developed a wide a variety of mission types, combining vertical profiles (from approx. 8 km to near surface),boundary layer legs, and plume sampling as needed. With an ongoing five-year data set, the team has sampled over 160 vertical profiles, a dozen wildfires, and numerous stratospheric ozone intrusions. This talk will present an overview of our flights flown to date, with particular focus on methane observations in the San Francisco Bay Area, Sacramento, and the delta region.

The role of molecular hydrogen and methane oxidation in the water vapour budget of the stratosphere

NASA Technical Reports Server (NTRS)

Le Texier, H.; Solomon, S.; Garcia, R. R.

1988-01-01

The detailed photochemistry of methane oxidation has been studied in a coupled chemical/dynamical model of the middle atmosphere. The photochemistry of formaldehyde plays an important role in determining the production of water vapor from methane oxidation. At high latitudes, the production and transport of molecular hydrogen is particularly important in determining the water vapor distribution. It is shown that the ratio of the methane vertical gradient to the water vapor vertical gradient at any particular latitude should not be expected to be precisely 2, due both to photochemical and dynamical effects. Modeled H2O profiles are compared with measurements from the Limb Infrared Monitor of the Stratosphere (LIMS) experiment at various latitudes. Molecular hydrogen is shown to be responsible for the formation of a secondary maximum displayed by the model water vapor profiles in high latitude summer, a feature also found in the LIMS data.

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.

Investigation of Methane and Soil Carbon Dynamics Using Near Surface Geophysical Methods at the Tanoma Educational Wetland Site, Tanoma, Pennsylvania

NASA Astrophysics Data System (ADS)

Seidel, A. D.; Mount, G.

2017-12-01

Studies to constrain methane budgets of Pennsylvania have sought to quantify the amount and rate of fugitive methane released during industrial natural gas development. However, contributions from other environmental systems such as artificial wetlands used to treat part of the 300 million gallons per day of acid mine drainage (AMD) are often not understated or not considered. The artificial wetlands are sources of both biogenic and thermogenic methane and are used to treat AMD which would otherwise flow untreated into Pennsylvania surface waters. Our research utilizes a combination of indirect non-invasive geophysical methods (ground penetrating radar, GPR) and the complex refractive index model, aerial imagery, and direct measurements (coring and gas traps) to estimate the contribution of biogenic methane from wetlands and legacy thermogenic methane from acid mine drainage from a flooded coal mine at an artificial wetland designed to treat these polluted waters at Tanoma, Pennsylvania. Our approach uses (3D) GPR surveys to define the thickness of the soil from the surface to the regolith-bedrock interface to create a volume model of potential biogenic gas stores. Velocity data derived from the GPR is then used to calculate the dielectric permittivity of the soil and then modeled for gas content when considering the saturation, porosity and amount of soil present. Depth-profile cores are extracted to confirm soil column interfaces and determine changes in soil carbon content. Comparisons of gas content are made with gas traps placed across the wetlands that measure the variability of gaseous methane released. In addition, methane dissolved in the waters from biogenic processes in the wetland and thermogenic processes underground are analyzed by a gas chromatograph to quantify those additions. In sum, these values can then be extrapolated to estimate carbon stocks in AMD areas such as those with similar water quality and vegetation types in the Appalachian region

Ca-Rich Carbonate Melts: A Regular-Solution Model, with Applications to Carbonatite Magma + Vapor Equilibria and Carbonate Lavas on Venus

NASA Technical Reports Server (NTRS)

Treiman, Allan H.

1995-01-01

A thermochemical model of the activities of species in carbonate-rich melts would be useful in quantifying chemical equilibria between carbonatite magmas and vapors and in extrapolating liquidus equilibria to unexplored PTX. A regular-solution model of Ca-rich carbonate melts is developed here, using the fact that they are ionic liquids, and can be treated (to a first approximation) as interpenetrating regular solutions of cations and of anions. Thermochemical data on systems of alkali metal cations with carbonate and other anions are drawn from the literature; data on systems with alkaline earth (and other) cations and carbonate (and other) anions are derived here from liquidus phase equilibria. The model is validated in that all available data (at 1 kbar) are consistent with single values for the melting temperature and heat of fusion for calcite, and all liquidi are consistent with the liquids acting as regular solutions. At 1 kbar, the metastable congruent melting temperature of calcite (CaCO3) is inferred to be 1596 K, with (Delta)bar-H(sub fus)(calcite) = 31.5 +/- 1 kJ/mol. Regular solution interaction parameters (W) for Ca(2+) and alkali metal cations are in the range -3 to -12 kJ/sq mol; W for Ca(2+)-Ba(2+) is approximately -11 kJ/sq mol; W for Ca(2+)-Mg(2+) is approximately -40 kJ/sq mol, and W for Ca(2+)-La(3+) is approximately +85 kJ/sq mol. Solutions of carbonate and most anions (including OH(-), F(-), and SO4(2-)) are nearly ideal, with W between 0(ideal) and -2.5 kJ/sq mol. The interaction of carbonate and phosphate ions is strongly nonideal, which is consistent with the suggestion of carbonate-phosphate liquid immiscibility. Interaction of carbonate and sulfide ions is also nonideal and suggestive of carbonate-sulfide liquid immiscibility. Solution of H2O, for all but the most H2O-rich compositions, can be modeled as a disproportionation to hydronium (H3O(+)) and hydroxyl (OH(-)) ions with W for Ca(2+)-H3O(+) (approximately) equals 33 kJ/sq mol. The

Measurement of the Carbon Isotopic Composition of Methane Using Helicoidal Laser Eigenstates

NASA Astrophysics Data System (ADS)

Jacob, D.; Le Floch, A.; Bretenaker, F.; Guenot, P.

1996-06-01

The spatially generalized Jones matrix formalism is used to design a laser cavity to make intracavity measurements of the carbon isotopic composition of methane. the method is based on a double optical lever effect for helicoidally polarized eigenstates, permitting to measure successively the ^{12}CH_4 and ^{13}CH_4 concentrations. To choose the probed isotope, one simply tunes the frequency of the laser by Zeeman effect. The experiment exhibits a good agreement with the predictions and permits to measure the ^{13}CH4/^{12}CH_4 composition ratio of methane with an uncertainty of the order of ± 0.07% for a sample containing only 6× 10^{-9} mole of methane. On utilise le formalisme des matrices de Jones généralisées spatialement pour concevoir une cavité laser permettant la mesure intra-cavité de la composition isotopique du carbone présent dans le méthane. La méthode est fondée sur une double application de l'effet de levier optique pour les états propres hélicoïdaux, permettant de mesurer successivement les concentrations de ^{12}CH_4 et de ^{13}CH_4. Pour passer d'un isotope à l'autre, on ajuste simplement la fréquence du laser par effet Zeeman. L'expérience est en bon accord avec les prédictions et permet d'effectuer la mesure du rapport isotopique ^{13}CH4/^{12}CH_4 avec une fourchette d'incertitude de ± 0,07% pour des échantillons de gaz ne contenant que 6× 10^{-9} mole de méthane.

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.

Atmospheric methane from organic carbon mobilization in sedimentary basins — The sleeping giant?

NASA Astrophysics Data System (ADS)

Kroeger, K. F.; di Primio, R.; Horsfield, B.

2011-08-01

The mass of organic carbon in sedimentary basins amounts to a staggering 10 16 t, dwarfing the mass contained in coal, oil, gas and all living systems by ten thousand-fold. The evolution of this giant mass during subsidence and uplift, via chemical, physical and biological processes, not only controls fossil energy resource occurrence worldwide, but also has the capacity for driving global climate: only a tiny change in the degree of leakage, particularly if focused through the hydrate cycle, can result in globally significant greenhouse gas emissions. To date, neither climate models nor atmospheric CO 2 budget estimates have quantitatively included methane from thermal or microbial cracking of sedimentary organic matter deep in sedimentary basins. Recent estimates of average low latitude Eocene surface temperatures beyond 30 °C require extreme levels of atmospheric CO 2. Methane degassing from sedimentary basins may be a mechanism to explain increases of atmospheric CO 2 to values as much as 20 times higher than pre-industrial values. Increased natural gas emission could have been set in motion either by global tectonic processes such as pulses of activity in the global alpine fold belt, leading to increased basin subsidence and maturation rates in the prolific Jurassic and Cretaceous organic-rich sediments, or by increased magmatic activity such as observed in the northern Atlantic around the Paleocene-Eocene boundary. Increased natural gas emission would have led to global warming that was accentuated by long lasting positive feedback effects through temperature transfer from the surface into sedimentary basins. Massive gas hydrate dissociation may have been an additional positive feedback factor during hyperthermals superimposed on long term warming, such as the Paleocene-Eocene Thermal Maximum (PETM). As geologic sources may have contributed over one third of global atmospheric methane in pre-industrial time, variability in methane flux from sedimentary

Carbon-dependent control of electron transfer and central carbon pathway genes for methane biosynthesis in the Archaean, Methanosarcina acetivorans strain C2A

PubMed Central

2010-01-01

Background The archaeon, Methanosarcina acetivorans strain C2A forms methane, a potent greenhouse gas, from a variety of one-carbon substrates and acetate. Whereas the biochemical pathways leading to methane formation are well understood, little is known about the expression of the many of the genes that encode proteins needed for carbon flow, electron transfer and/or energy conservation. Quantitative transcript analysis was performed on twenty gene clusters encompassing over one hundred genes in M. acetivorans that encode enzymes/proteins with known or potential roles in substrate conversion to methane. Results The expression of many seemingly "redundant" genes/gene clusters establish substrate dependent control of approximately seventy genes for methane production by the pathways for methanol and acetate utilization. These include genes for soluble-type and membrane-type heterodisulfide reductases (hdr), hydrogenases including genes for a vht-type F420 non-reducing hydrogenase, molybdenum-type (fmd) as well as tungsten-type (fwd) formylmethanofuran dehydrogenases, genes for rnf and mrp-type electron transfer complexes, for acetate uptake, plus multiple genes for aha- and atp-type ATP synthesis complexes. Analysis of promoters for seven gene clusters reveal UTR leaders of 51-137 nucleotides in length, raising the possibility of both transcriptional and translational levels of control. Conclusions The above findings establish the differential and coordinated expression of two major gene families in M. acetivorans in response to carbon/energy supply. Furthermore, the quantitative mRNA measurements demonstrate the dynamic range for modulating transcript abundance. Since many of these gene clusters in M. acetivorans are also present in other Methanosarcina species including M. mazei, and in M. barkeri, these findings provide a basis for predicting related control in these environmentally significant methanogens. PMID:20178638

The Geologic Signature of Anaerobic Oxidation of Methane (Invited)

NASA Astrophysics Data System (ADS)

Ussler, W.; Paull, C. K.

2010-12-01

Anaerobic oxidation of methane (AOM) is an enormous sink in anoxic marine sediments for methane produced in situ or ascending through the sediment column towards the seafloor. Existing estimates indicate that between 75 and 382 Tg of sedimentary methane are oxidized each year before reaching the sediment-water interface making AOM a diagenetic process of global significance. This methane is derived from a variety of sources including microbial production, thermocatalytic cracking of complex organic matter, decomposing gas hydrates, and possibly abiogenic processes. Stables isotopes of membrane lipid biomarkers and authigenic carbonates associated with zones of AOM, fluorescence in situ hybridization, and anaerobic methane incubations have substantiated the role Archaea and sulfate-reducing bacteria have in driving AOM. The products of AOM are dissolved inorganic carbon (predominantly HCO3-) and bisulfide (HS-). Stable isotope measurements of authigenic carbonates associated with zones of AOM are consistent with the diagenetic carbon being primarily methane derived. These methane-derived carbonates occur in a variety of forms including sedimentary nodules and thin lenses within and below zones of contemporary AOM; outcrops of slabs, ledges, and jagged authigenic carbonates exhumed on the seafloor; and authigenic carbonate mounds associated with near-subsurface methane gas accumulations. Examples of exhumed authigenic carbonates include rugged outcrops along the Guaymas Transform in the Gulf of California, extensive slabs and ledges in the Eel River Basin, and mounds in various stages of development near Bullseye Vent, off Vancouver Island and in the Santa Monica Basin. It is clear from basic microbial biogeochemistry and the occurrences of massive authigenic carbonate which span a large range in size that DIC produced by AOM is preserved as authigenic carbonate within the seafloor and not on the seafloor. These exhumed authigenic carbonate provide a glimpse of how

Methane production by attached film

DOEpatents

Jewell, William J.

1981-01-01

A method for purifying wastewater of biodegradable organics by converting the organics to methane and carbon dioxide gases is disclosed, characterized by the use of an anaerobic attached film expanded bed reactor for the reaction process. Dilute organic waste material is initially seeded with a heterogeneous anaerobic bacteria population including a methane-producing bacteria. The seeded organic waste material is introduced into the bottom of the expanded bed reactor which includes a particulate support media coated with a polysaccharide film. A low-velocity upward flow of the organic waste material is established through the bed during which the attached bacterial film reacts with the organic material to produce methane and carbon dioxide gases, purified water, and a small amount of residual effluent material. The residual effluent material is filtered by the film as it flows upwardly through the reactor bed. In a preferred embodiment, partially treated effluent material is recycled from the top of the bed to the bottom of the bed for further treatment. The methane and carbon dioxide gases are then separated from the residual effluent material and purified water.

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

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.

Electrospun carbon nanofibers surface-grafted with vapor-grown carbon nanotubes as hierarchical electrodes for supercapacitors

NASA Astrophysics Data System (ADS)

Zhou, Zhengping; Wu, Xiang-Fa; Fong, Hao

2012-01-01

This letter reports the fabrication and electrochemical properties of electrospun carbon nanofibers surface-grafted with vapor-grown carbon nanotubes (CNTs) as hierarchical electrodes for supercapacitors. The specific capacitance of the fabricated electrodes was measured up to 185 F/g at the low discharge current density of 625 mA/g; a decrease of 38% was detected at the high discharge current density of 2.5 A/g. The morphology and microstructure of the electrodes were examined by electron microscopy, and the unique connectivity of the hybrid nanomaterials was responsible for the high specific capacitance and low intrinsic contact electric resistance of the hierarchical electrodes.

What's the Deal with Methane at LUST Spill Sites? Part 2: Vapor Intrusion

EPA Science Inventory

This article is specifically intended to discuss methane produced from releases of ethanol and gasoline-ethanol mixtures. There may be other sources of methane at a site, including leaks of natural gas or methane produced from the natural decay of buried plant tissues or from the...

Reconstruction of past methane availability in an Arctic Alaska wetland indicates climate influenced methane release during the past ~12,000 years

USGS Publications Warehouse

Wooller, Matthew J.; Pohlman, John W.; Gaglioti, Benjamin V.; Langdon, Peter; Jones, Miriam; Anthony, Katey M. Walter; Becker, Kevin W.; Hinrichs, Kai-Uwe; Elvert, Marcus

2012-01-01

Atmospheric contributions of methane from Arctic wetlands during the Holocene are dynamic and linked to climate oscillations. However, long-term records linking climate variability to methane availability in Arctic wetlands are lacking. We present a multi-proxy ~12,000 year paleoecological reconstruction of intermittent methane availability from a radiocarbon-dated sediment core (LQ-West) taken from a shallow tundra lake (Qalluuraq Lake) in Arctic Alaska. Specifically, stable carbon isotopic values of photosynthetic biomarkers and methane are utilized to estimate the proportional contribution of methane-derived carbon to lake-sediment-preserved benthic (chironomids) and pelagic (cladocerans) components over the last ~12,000 years. These results were compared to temperature, hydrologic, and habitat reconstructions from the same site using chironomid assemblage data, oxygen isotopes of chironomid head capsules, and radiocarbon ages of plant macrofossils. Cladoceran ephippia from ~4,000 cal year BP sediments have δ13C values that range from ~−39 to −31‰, suggesting peak methane carbon assimilation at that time. These low δ13C values coincide with an apparent decrease in effective moisture and development of a wetland that included Sphagnum subsecundum. Incorporation of methane-derived carbon by chironomids and cladocerans decreased from ~2,500 to 1,500 cal year BP, coinciding with a temperature decrease. Live-collected chironomids with a radiocarbon age of 1,640 cal year BP, and fossil chironomids from 1,500 cal year BP in the core illustrate that ‘old’ carbon has also contributed to the development of the aquatic ecosystem since ~1,500 cal year BP. The relatively low δ13C values of aquatic invertebrates (as low as −40.5‰) provide evidence of methane incorporation by lake invertebrates, and suggest intermittent climate-linked methane release from the lake throughout the Holocene.

Methane, Black Carbon, and Ethane Emissions from Natural Gas Flares in the Bakken Shale, North Dakota.

PubMed

Gvakharia, Alexander; Kort, Eric A; Brandt, Adam; Peischl, Jeff; Ryerson, Thomas B; Schwarz, Joshua P; Smith, Mackenzie L; Sweeney, Colm

2017-05-02

Incomplete combustion during flaring can lead to production of black carbon (BC) and loss of methane and other pollutants to the atmosphere, impacting climate and air quality. However, few studies have measured flare efficiency in a real-world setting. We use airborne data of plume samples from 37 unique flares in the Bakken region of North Dakota in May 2014 to calculate emission factors for BC, methane, ethane, and combustion efficiency for methane and ethane. We find no clear relationship between emission factors and aircraft-level wind speed or between methane and BC emission factors. Observed median combustion efficiencies for methane and ethane are close to expected values for typical flares according to the US EPA (98%). However, we find that the efficiency distribution is skewed, exhibiting log-normal behavior. This suggests incomplete combustion from flares contributes almost 1/5 of the total field emissions of methane and ethane measured in the Bakken shale, more than double the expected value if 98% efficiency was representative. BC emission factors also have a skewed distribution, but we find lower emission values than previous studies. The direct observation for the first time of a heavy-tail emissions distribution from flares suggests the need to consider skewed distributions when assessing flare impacts globally.

Enhanced Synthesis of Carbon Nanomaterials Using Acoustically Excited Methane Diffusion Flames

PubMed Central

Hou, Shuhn-Shyurng; Chen, Kuan-Ming; Yang, Zong-Yun; Lin, Ta-Hui

2015-01-01

Acoustically modulated methane jet diffusion flames were used to enhance carbon nanostructure synthesis. A catalytic nickel substrate was employed to collect the deposit materials at sampling position z = 10 mm above the burner exit. The fabrication of carbon nano-onions (CNOs) and carbon nanotubes (CNTs) was significantly enhanced by acoustic excitation at frequencies near the natural flickering frequency (ƒ = 20 Hz) and near the acoustically resonant frequency (ƒ = 90 Hz), respectively. At these characteristic frequencies, flow mixing was markedly enhanced by acoustic excitation, and a flame structure with a bright slender core flame was generated, which provided a favorable flame environment for the growth of carbon nanomaterials. The production rate of CNOs was high at 20 Hz (near the natural flickering frequency), at which the gas temperature was about 680 °C. Additionally, a quantity of CNTs was obtained at 70–95 Hz, near the acoustically resonant frequency, at which the gas temperature was between 665 and 830 °C. However, no carbon nanomaterials were synthesized at other frequencies. The enhanced synthesis of CNOs and CNTs is attributed to the strong mixing of the fuel and oxidizer due to the acoustic excitation at resonant frequencies. PMID:28793473

Analysis of methane biodegradation by Methylosinus trichosporium OB3b

PubMed Central

Rodrigues, Andréa dos Santos; Salgado, Belkis Valdman e Andréa Medeiros

2009-01-01

The microbial oxidation of methane in the atmosphere is performed by methanotrophic bacteria that use methane as a unique source of carbon and energy. The objective of this work consisted of the investigation of the best conditions of methane biodegradation by methanotrophic bacteria Methylosinus trichosporium OB3b that oxidize it to carbon dioxide, and the use of these microorganisms in monitoring methods for methane. The results showed that M. trichosporium OB3b was capable to degrade methane in a more effective way with an initial microorganism concentration of 0.0700 g.L-1, temperature of 30ºC, pH 6.5 and using 1.79 mmol of methane. In these same conditions, there was no bacterial growth when 2.69 mmol of methane was used. The specific rate of microorganism growth, the conversion factor, the efficiency and the volumetric productivity, for the optimized conditions of biodegradation were, respectively, 0.0324 h-1, 0.6830 gcells/gCH4, 73.73% and 2.7732.10-3 gcells/L.h. The final product of methane microbiological degradation, carbon dioxide, was quantified through the use of a commercial electrode, and, through this, the grade of methane conversion in carbon dioxide was calculated. PMID:24031362

Triton's Summer Sky of Methane and Carbon Monoxide

NASA Astrophysics Data System (ADS)

2010-04-01

According to the first ever infrared analysis of the atmosphere of Neptune's moon Triton, summer is in full swing in its southern hemisphere. The European observing team used ESO's Very Large Telescope and discovered carbon monoxide and made the first ground-based detection of methane in Triton's thin atmosphere. These observations revealed that the thin atmosphere varies seasonally, thickening when warmed. "We have found real evidence that the Sun still makes its presence felt on Triton, even from so far away. This icy moon actually has seasons just as we do on Earth, but they change far more slowly," says Emmanuel Lellouch, the lead author of the paper reporting these results in Astronomy & Astrophysics. On Triton, where the average surface temperature is about minus 235 degrees Celsius, it is currently summer in the southern hemisphere and winter in the northern. As Triton's southern hemisphere warms up, a thin layer of frozen nitrogen, methane, and carbon monoxide on Triton's surface sublimates into gas, thickening the icy atmosphere as the season progresses during Neptune's 165-year orbit around the Sun. A season on Triton lasts a little over 40 years, and Triton passed the southern summer solstice in 2000. Based on the amount of gas measured, Lellouch and his colleagues estimate that Triton's atmospheric pressure may have risen by a factor of four compared to the measurements made by Voyager 2 in 1989, when it was still spring on the giant moon. The atmospheric pressure on Triton is now between 40 and 65 microbars - 20 000 times less than on Earth. Carbon monoxide was known to be present as ice on the surface, but Lellouch and his team discovered that Triton's upper surface layer is enriched with carbon monoxide ice by about a factor of ten compared to the deeper layers, and that it is this upper "film" that feeds the atmosphere. While the majority of Triton's atmosphere is nitrogen (much like on Earth), the methane in the atmosphere, first detected by

Project identification for methane reduction options

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

Kerr, T.

1996-12-31

This paper discusses efforts directed at reduction in emission of methane to the atmosphere. Methane is a potent greenhouse gas, which on a 20 year timeframe may present a similar problem to carbon dioxide. In addition, methane causes additional problems in the form of smog and its longer atmospheric lifetime. The author discusses strategies for reducing methane emission from several major sources. This includes landfill methane recovery, coalbed methane recovery, livestock methane reduction - in the form of ruminant methane reduction and manure methane recovery. The author presents examples of projects which have implemented these ideas, the economics of themore » projects, and additional gains which come from the projects.« less

Biocatalytic conversion of methane to methanol as a key step for development of methane-based biorefineries.

PubMed

Hwang, In Yeub; Lee, Seung Hwan; Choi, Yoo Seong; Park, Si Jae; Na, Jeong Geol; Chang, In Seop; Kim, Choongik; Kim, Hyun Cheol; Kim, Yong Hwan; Lee, Jin Won; Lee, Eun Yeol

2014-12-28

Methane is considered as a next-generation carbon feedstock owing to the vast reserves of natural and shale gas. Methane can be converted to methanol by various methods, which in turn can be used as a starting chemical for the production of value-added chemicals using existing chemical conversion processes. Methane monooxygenase is the key enzyme that catalyzes the addition of oxygen to methane. Methanotrophic bacteria can transform methane to methanol by inhibiting methanol dehydrogenase. In this paper, we review the recent progress made on the biocatalytic conversion of methane to methanol as a key step for methane-based refinery systems and discuss future prospects for this technology.

Differential responses of carbon and water vapor fluxes to climate among evergreen needleleaf forests in the USA

DOE PAGES

Wagle, Pradeep; Xiao, Xiangming; Kolb, Thomas E.; ...

2016-05-31

Here, understanding the differences in carbon and water vapor fluxes of spatially distributed evergreen needleleaf forests (ENFs) is crucial for accurately estimating regional or global carbon and water budgets and when predicting the responses of ENFs to current and future climate. We compared the fluxes of ten AmeriFlux ENF sites to investigate cross-site variability in net ecosystem exchange of carbon (NEE), gross primary production (GPP), and evapotranspiration (ET). We used wavelet cross-correlation analysis to examine responses of NEE and ET to common climatic drivers over multiple timescales and also determined optimum values of air temperature (T a) and vapor pressuremore » deficit (VPD) for NEE and ET.« less

Differential responses of carbon and water vapor fluxes to climate among evergreen needleleaf forests in the USA

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

Wagle, Pradeep; Xiao, Xiangming; Kolb, Thomas E.

Here, understanding the differences in carbon and water vapor fluxes of spatially distributed evergreen needleleaf forests (ENFs) is crucial for accurately estimating regional or global carbon and water budgets and when predicting the responses of ENFs to current and future climate. We compared the fluxes of ten AmeriFlux ENF sites to investigate cross-site variability in net ecosystem exchange of carbon (NEE), gross primary production (GPP), and evapotranspiration (ET). We used wavelet cross-correlation analysis to examine responses of NEE and ET to common climatic drivers over multiple timescales and also determined optimum values of air temperature (T a) and vapor pressuremore » deficit (VPD) for NEE and ET.« less

Methane dynamics regulated by microbial community response to permafrost thaw.

PubMed

McCalley, Carmody K; Woodcroft, Ben J; Hodgkins, Suzanne B; Wehr, Richard A; Kim, Eun-Hae; Mondav, Rhiannon; Crill, Patrick M; Chanton, Jeffrey P; Rich, Virginia I; Tyson, Gene W; Saleska, Scott R

2014-10-23

Permafrost contains about 50% of the global soil carbon. It is thought that the thawing of permafrost can lead to a loss of soil carbon in the form of methane and carbon dioxide emissions. The magnitude of the resulting positive climate feedback of such greenhouse gas emissions is still unknown and may to a large extent depend on the poorly understood role of microbial community composition in regulating the metabolic processes that drive such ecosystem-scale greenhouse gas fluxes. Here we show that changes in vegetation and increasing methane emissions with permafrost thaw are associated with a switch from hydrogenotrophic to partly acetoclastic methanogenesis, resulting in a large shift in the δ(13)C signature (10-15‰) of emitted methane. We used a natural landscape gradient of permafrost thaw in northern Sweden as a model to investigate the role of microbial communities in regulating methane cycling, and to test whether a knowledge of community dynamics could improve predictions of carbon emissions under loss of permafrost. Abundance of the methanogen Candidatus 'Methanoflorens stordalenmirensis' is a key predictor of the shifts in methane isotopes, which in turn predicts the proportions of carbon emitted as methane and as carbon dioxide, an important factor for simulating the climate feedback associated with permafrost thaw in global models. By showing that the abundance of key microbial lineages can be used to predict atmospherically relevant patterns in methane isotopes and the proportion of carbon metabolized to methane during permafrost thaw, we establish a basis for scaling changing microbial communities to ecosystem isotope dynamics. Our findings indicate that microbial ecology may be important in ecosystem-scale responses to global change.

Plasma-enhanced chemical vapor deposition of multiwalled carbon nanofibers.

PubMed

Matthews, Kristopher; Cruden, Brett A; Chen, Bin; Meyyappan, M; Delzeit, Lance

2002-10-01

Plasma-enhanced chemical vapor deposition is used to grow vertically aligned multiwalled carbon nanofibers (MWNFs). The graphite basal planes in these nanofibers are not parallel as in nanotubes; instead they exhibit a small angle resembling a stacked cone arrangement. A parametric study with varying process parameters such as growth temperature, feedstock composition, and substrate power has been conducted, and these parameters are found to influence the growth rate, diameter, and morphology. The well-aligned MWNFs are suitable for fabricating electrode systems in sensor and device development.

Plasma-enhanced chemical vapor deposition of multiwalled carbon nanofibers

NASA Technical Reports Server (NTRS)

Matthews, Kristopher; Cruden, Brett A.; Chen, Bin; Meyyappan, M.; Delzeit, Lance

2002-01-01

Plasma-enhanced chemical vapor deposition is used to grow vertically aligned multiwalled carbon nanofibers (MWNFs). The graphite basal planes in these nanofibers are not parallel as in nanotubes; instead they exhibit a small angle resembling a stacked cone arrangement. A parametric study with varying process parameters such as growth temperature, feedstock composition, and substrate power has been conducted, and these parameters are found to influence the growth rate, diameter, and morphology. The well-aligned MWNFs are suitable for fabricating electrode systems in sensor and device development.

Evidence of Sulfate-Dependent Anaerobic Methane Oxidation within an Area Impacted by Coalbed Methane-Related Gas Migration

NASA Astrophysics Data System (ADS)

Wolfe, A. L.; Wikin, R. T.

2017-12-01

We evaluated water quality characteristics in the northern Raton Basin of Colorado and documented the response of the Poison Canyon aquifer system several years after upward migration of methane gas occurred from the deeper Vermejo Formation coalbed production zone. Over a 17-month study period, water samples were obtained from domestic water wells and monitoring wells located within the impacted area, and analyzed for 245 constituents, including organic compounds, nutrients, major and trace elements, dissolved gases, and isotopic tracers for carbon, sulfur, oxygen, and hydrogen. Multiple lines of evidence suggest that sulfate-dependent methane biodegradation, which involves the oxidation of methane (CH4) to carbon dioxide (CO2) using sulfate (SO42-) as the terminal electron acceptor, is occurring: (i) consumption of methane and sulfate and production of sulfide and bicarbonate, (ii) methane loss coupled to production of higher molecular weight (C2+) gaseous hydrocarbons, (iii) patterns of 13C enrichment and depletion in methane and dissolved inorganic carbon, and (iv) a systematic shift in sulfur and oxygen isotope ratios of sulfate, indicative of microbial sulfate reduction. Groundwater-methane attenuation is linked to the production of dissolved sulfide, and elevated dissolved sulfide concentrations represent an undesirable secondary water quality impact. The biogeochemical response of the aquifer system has not mobilized naturally occurring trace metals, including arsenic, chromium, cobalt, nickel, and lead, likely due to the microbial production of hydrogen sulfide, which favors stabilization of metals in aquifer solids.

Enhanced cyclic stability of SnS microplates with conformal carbon coating derived from ethanol vapor deposition for sodium-ion batteries

NASA Astrophysics Data System (ADS)

Li, Xiang; Liu, Jiangwen; Ouyang, Liuzhang; Yuan, Bin; Yang, Lichun; Zhu, Min

2018-04-01

Carbon coated SnS microplates (SnS@C MPs) were prepared via a facile chemical vapor deposition method using SnS2 nanoflakes as precursor and ethanol vapor as carbon source. The carbon coating restrains the growth of SnS during the heat treatment. Furthermore, it improves the electronic conductivity as well as accommodates volume variations of SnS during the sodiation and desodiation processes. Therefore, the rate capability and cycle performance of the SnS@C MPs as anode materials for sodium-ion batteries are remarkably enhanced compared with the bare SnS and the SnS2 precursor. At current densities of 0.1, 0.2, 0.5, 1 and 2 A g-1, the optimized SnS@C MPs exhibit stable capacities of 602.9, 532.1, 512.2, 465.9 and 427.2 mAh g-1, respectively. At 1 A g-1, they show a reversible capacity of 528.8 mAh g-1 in the first cycle, and maintain 444.7 mAh g-1 after 50 cycles, with capacity retention of 84.1%. The carbon coating through chemical vapor deposition using ethanol vapor as carbon sources is green, simple and cost-effective, which shows great promise to improve the reversible Na+ storage of electrode materials.

Technical note: Methionine, a precursor of methane in living plants

NASA Astrophysics Data System (ADS)

Lenhart, K.; Althoff, F.; Greule, M.; Keppler, F.

2014-11-01

When terrestrial plants were identified as producers of the greenhouse gas methane, much discussion and debate ensued, not only about their contribution to the global methane budget, but also with regard to the validity of the observation itself. Although the phenomenon has now become more accepted for both living and dead plants, the mechanism of methane formation in living plants remains to be elucidated and its precursor compounds identified. We made use of stable isotope techniques to verify in vivo formation of methane and, in order to identify the carbon precursor, 13C-positionally labelled organic compounds were employed. Here we show that the amino acid L-methionine acts as a methane precursor in living plants. Employing 13C-labelled methionine clearly identified the sulphur-bound methyl group of methionine as a carbon precursor of methane released from lavender (Lavandula angustifolia). Furthermore, when lavender plants were stressed physically, methane release rates and the stable carbon isotope values of the emitted methane greatly increased. Our results provide additional support that plants possess a mechanism for methane production and suggest that methionine might play an important role in the formation of methane in living plants, particularly under stress conditions.

Vapor-condensation-assisted optical microscopy for ultralong carbon nanotubes and other nanostructures.

PubMed

Wang, Jiangtao; Li, Tianyi; Xia, Bingyu; Jin, Xiang; Wei, Haoming; Wu, Wenyun; Wei, Yang; Wang, Jiaping; Liu, Peng; Zhang, Lina; Li, Qunqing; Fan, Shoushan; Jiang, Kaili

2014-06-11

Here we present a simple yet powerful approach for the imaging of nanostructures under an optical microscope with the help of vapor condensation on their surfaces. Supersaturated water vapor will first form a nanometer-sized water droplet on the condensation nuclei on the surface of nanostructures, and then the water droplet will grow bigger and scatter more light to make the outline of the nanostructure be visible under dark-field optical microscope. This vapor-condensation-assisted (VCA) optical microscopy is applicable to a variety of nanostructures from ultralong carbon nanotubes to functional groups, generating images with contrast coming from the difference in density of the condensation sites, and does not induce any impurities to the specimens. Moreover, this low-cost and efficient technique can be conveniently integrated with other facilities, such as Raman spectroscope and so forth, which will pave the way for widespread applications.

Wetland Resiliency: How does multi-year water table level decline and recovery influence carbon dioxide and methane fluxes?

NASA Astrophysics Data System (ADS)

Pugh, C.; Reed, D. E.; Desai, A. R.; Sulman, B. N.

2016-12-01

Wetlands play a disproportionately large role in the global carbon budget, and individual wetlands can fluctuate between carbon sinks and sources depending on factors such as hydrology, biogeochemistry, and land use. Although much research has been done on wetland biogeochemical cycles, there is a lack of experimental evidence concerning how changes in wetland hydrology influence these cycles over interannual timescales. Over a seven-year period, Sulman et al. (2009) found that a drought-induced declining water table at a shrub wetland in northern Wisconsin coincided with increased ecosystem respiration (ER) and gross ecosystem productivity (GEP) (Sulman et al. 2009). Since then, however, the average water table level at this site has begun to increase, thus allowing a unique opportunity to explore how wetland carbon storage is impacted by water table recovery. With the addition of three more years of eddy covariance observations post recovery and new methane flux observations, we found that water table level no longer had a significant correlation with GEP, ER, or methane flux. Air temperature, however, had a strong correlation with all three. Average methane flux stayed relatively constant under 14 °C, before increasing an order of magnitude from 3.7 nmol m-2 s-1 in April to 36 nmol m-2 s-1 in July. These results suggest that, over decadal timescales, temperature, rather than water level, is a stronger limiting factor for both aerobic and anaerobic respiration in shrub fen wetlands. Wetlands play a disproportionately large role in the global carbon budget, and individual wetlands can fluctuate between carbon sinks and sources depending on factors such as hydrology, biogeochemistry, and land use. Although much research has been done on wetland biogeochemical cycles, there is a lack of experimental evidence concerning how changes in wetland hydrology influence these cycles over interannual timescales. Over a seven-year period, Sulman et al. (2009) found that a

Trends of total water vapor column above the Arctic from satellites observations

NASA Astrophysics Data System (ADS)

Alraddawi, Dunya; Sarkissian, Alain; Keckhut, Philippe; Bock, Olivier; Claud, Chantal; Irbah, Abdenour

2016-04-01

Atmospheric water vapor (H2O) is the most important natural (as opposed to man-made) greenhouse gas, accounting for about two-thirds of the natural greenhouse effect. Despite this importance, its role in climate and its reaction to climate change are still difficult to assess. Many details of the hydrological cycle are poorly understood, such as the process of cloud formation and the transport and release of latent heat contained in the water vapor. In contrast to other important greenhouse gases like carbon dioxide (CO2) and methane, water vapor has a much higher temporal and spatial variability. Total precipitable water (TPW) or the total column of water vapor (TCWV) is the amount of liquid water that would result if all the water vapor in the atmospheric column of unit area were condensed. TCWV distribution contains valuable information on the vigor of the hydrological processes and moisture transport in the atmosphere. Measurement of TPW can be obtained based on atmospheric water vapor absorption or emission of radiation in the spectral range from UV to MW. TRENDS were found over the terrestrial Arctic by means of TCWV retrievals (using Moderate Resolution Imaging Spectro-radiometer (MODIS) near-infrared (2001-2015) records). More detailed approach was made for comparisons with ground based instruments over Sodankyla - Finland (TCWV from: SCIAMACHY 2003-2011, GOME-2A 2007-2011, SAOZ 2003-2011, GPS 2003-2011, MODIS 2003-2011)

Authigenic minerals related to carbon and sulfur biogeochemical cycling from deep-sea active methane seeps offshore South-West Africa

NASA Astrophysics Data System (ADS)

Pierre, C.; Blanc-Valleron, M.; Demange, J.; Boudouma, O.; Pape, T.; Himmler, T.; Fekete, N.; Spiess, V.

2011-12-01

The South-West African continental margin is well known for occurrences of active methane-rich fluid seeps that are associated with seafloor pockmarks in a broad range of water depths, from the shelf to the deep basins. High gas flares in the water column, luxurious oases of benthic fauna, gas hydrate accumulations and diagenetic carbonate crusts have been observed at these seeps. During the M76/3a expedition of R/V METEOR (summer 2008) gravity cores recovered abundant authigenic carbonate concretions from five pockmarks of the South-West African margin including previously studied sites (Hydrate Hole, Worm Hole, Regab Pockmark) and two sites (Deep Hole, Baboon Cluster) newly discovered during the cruise. Carbonate concretions were mostly associated to sediments settled by seep-associated benthic macrofauna and bearing shallow gas hydrates. We present new results of the comprehensive analysis of the mineralogy and isotope geochemistry of the diagenetic carbonates sampled in the five pockmarks. The mineralogy of authigenic carbonates is dominated by magnesian calcite and aragonite, associated occasionally with dolomite. The oxygen and carbon isotopic compositions of authigenic carbonates (+2.4 < δ18O % V-PDB < +6.2 ; -61.0 < δ13C % V-PDB < -40.1) indicate that microbial anaerobic oxidation of methane (AOM) was the main process controling carbonate precipitation within sub-seafloor sediments deposited from the glacial-time up to the present. The frequent occurrence of diagenetic gypsum crystals within the sediments demonstrates that bio-irrigation with oxygenated bottom water by the burrowing activity of benthic fauna caused the secondary oxidation of reduced sulfur (hydrogen sulfide and pyrite) that was produced by sulfate reducting bacteria as a by-product of AOM; during the sulfide oxidation process, the released acidity induced the partial dissolution of carbonates. Our results demonstrate also the strong link that existed between the carbon and sulfur cycles

Microbial production and oxidation of methane in deep subsurface

NASA Astrophysics Data System (ADS)

Kotelnikova, Svetlana

2002-10-01

The goal of this review is to summarize present studies on microbial production and oxidation of methane in the deep subterranean environments. Methane is a long-living gas causing the "greenhouse" effect in the planet's atmosphere. Earlier, the deep "organic carbon poor" subsurface was not considered as a source of "biogenic" methane. Evidence of active methanogenesis and presence of viable methanogens including autotrophic organisms were obtained for some subsurface environments including water-flooded oil-fields, deep sandy aquifers, deep sea hydrothermal vents, the deep sediments and granitic groundwater at depths of 10 to 2000 m below sea level. As a rule, the deep subterranean microbial populations dwell at more or less oligotrophic conditions. Molecular hydrogen has been found in a variety of subsurface environments, where its concentrations were significantly higher than in the tested surface aquatic environments. Chemolithoautotrophic microorganisms from deep aquifers that could grow on hydrogen and carbon dioxide can act as primary producers of organic carbon, initiating heterotrophic food chains in the deep subterranean environments independent of photosynthesis. "Biogenic" methane has been found all over the world. On the basis of documented occurrences, gases in reservoirs and older sediments are similar and have the isotopic character of methane derived from CO 2 reduction. Groundwater representing the methanogenic end member are characterized by a relative depletion of dissolved organic carbon (DOC) in combination with an enrichment in 13C in inorganic carbon, which is consistent with the preferential reduction of 12CO 2 by autotrophic methanogens or acetogens. The isotopic composition of methane formed via CO 2 reduction is controlled by the δ13C of the original CO 2 substrate. Literature data shows that CH 4 as heavy as -40‰ or -50‰ can be produced by the microbial reduction of isotopically heavy CO 2. Produced methane may be oxidized

Experimental investigation on the carbon isotope fractionation of methane during gas migration by diffusion through sedimentary rocks at elevated temperature and pressure

NASA Astrophysics Data System (ADS)

Zhang, Tongwei; Krooss, Bernhard M.

2001-08-01

Molecular transport (diffusion) of methane in water-saturated sedimentary rocks results in carbon isotope fractionation. In order to quantify the diffusive isotope fractionation effect and its dependence on total organic carbon (TOC) content, experimental measurements have been performed on three natural shale samples with TOC values ranging from 0.3 to 5.74%. The experiments were conducted at 90°C and fluid pressures of 9 MPa (90 bar). Based on the instantaneous and cumulative composition of the diffused methane, effective diffusion coefficients of the 12CH4 and 13CH4 species, respectively, have been calculated. Compared with the carbon isotopic composition of the source methane (δ13C1 = -39.1‰), a significant depletion of the heavier carbon isotope (13C) in the diffused methane was observed for all three shales. The degree of depletion is highest during the initial non-steady state of the diffusion process. It then gradually decreases and reaches a constant difference (Δ δ = δ13Cdiff -δ13Csource) when approaching the steady-state. The degree of the isotopic fractionation of methane due to molecular diffusion increases with the TOC content of the shales. The carbon isotope fractionation of methane during molecular migration results practically exclusively from differences in molecular mobility (effective diffusion coefficients) of the 12CH4 and 13CH4 entities. No measurable solubility fractionation was observed. The experimental isotope-specific diffusion data were used in two hypothetical scenarios to illustrate the extent of isotopic fractionation to be expected as a result of molecular transport in geological systems with shales of different TOC contents. The first scenario considers the progression of a diffusion front from a constant source (gas reservoir) into a homogeneous ;semi-infinite; shale caprock over a period of 10 Ma. In the second example, gas diffusion across a 100 m caprock sequence is analyzed in terms of absolute quantities and isotope

Characterization of Methane Hydrate Growth from Aqueous Solution by Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Chou, I.; Lu, W.; Yuan, S.; Li, J.; Burruss, R. C.

2009-12-01

We observed the growth of methane hydrate from aqueous solution in fused silica capillaries near room temperature (RT) in two different experiments. In the first, we sealed methane together with ~2 wt% Na2SO4 solution in a fused silica capillary (0.3x0.3 mm cross-section with 0.05x0.05 mm cavity, and ~6 cm long), using the method of Chou et al. (2008, Geochim. Cosmochim. Acta, 72, 2517). The hydrate, liquid, and vapor coexist at ~23 °C and ~36.5 MPa. The behavior of two methane bubbles, one of which was enclosed by a hydrate crystal and the other near a small hydrate crystal, was monitored. These two bubbles are the only methane sources near the hydrate crystals. The system was slowly cooled to RT (~21 °C), and images were recorded continuously for a period of ~1.5 hours, together with temperature and time information. The images show the exposed bubble decreased in size, while both of the hydrate crystals increased in size, which was caused by the transfer of methane in solution. According to our previous report (Fig. 8 of Lu et al., 2008, Geochim. Cosmochim. Acta, 72, 412), the concentrations of methane in the solution near the exposed bubble are higher than those near the hydrate crystals. Most of the dissolved methane, transferred down the concentration gradient, was consumed and encaged in the nearby crystal, with only a small fraction of methane being consumed by the more distant crystal. Eventually, the exposed vapor bubble was totally consumed, but the bubble shielded by the hydrate crystal remained. This shows hydrate can grow from dissolved methane in the solution far away from free gas. In the 2nd experiment, we sealed methane, together with pure H2O and glass beads (0.04 to 0.07 mm in dia.), in a fused silica capillary (0.3 mm OD, 0.1 mm ID, and ~6 cm long) using the method cited above. We separated the vapor phase from the solution and glass beads by centrifuging the sealed capsule, then imposed a T gradient to the sample by cooling the solution end

An advanced carbon reactor subsystem for carbon dioxide reduction

NASA Technical Reports Server (NTRS)

Noyes, Gary P.; Cusick, Robert J.

1986-01-01

An evaluation is presented of the development status of an advanced carbon-reactor subsystem (ACRS) for the production of water and dense, solid carbon from CO2 and hydrogen, as required in physiochemical air revitalization systems for long-duration manned space missions. The ACRS consists of a Sabatier Methanation Reactor (SMR) that reduces CO2 with hydrogen to form methane and water, a gas-liquid separator to remove product water from the methane, and a Carbon Formation Reactor (CFR) to pyrolize methane to carbon and hydrogen; the carbon is recycled to the SMR, while the produce carbon is periodically removed from the CFR. A preprototype ACRS under development for the NASA Space Station is described.

Lipid biomarker patterns of methane-derived carbonates from Dongsha area, the northern of South China Sea

NASA Astrophysics Data System (ADS)

Yu, X.; Lei, J.; Yang, K.; Fang, Y.

2012-12-01

Carbonate and sediment samples collected from the Dongsha area the South China by TV-grab. The δ13C values of the carbonate indicate that the carbonate carbon is mainly derived from the oxidation of methane. According to the δ13C value of two groups carbonates could be divided: Group1 (G1) is 13C-depleted as reported previously, the δ13C value lighter than -50‰ PDB; group2 (G2) is enriched in 13C relatively, the δ13C value is around -30‰PDB. The δ13C value of sediments associated with carbonate varying from -19.2 to -30.4‰PDB. G1 and G2 have similar n-alkanes distribution and with 13C-depleted PMI, but glycerol dialkyl glycerol tetraethers (GDGTs) patterns obviously different. The G1 with the higher GDGTs concentration, up to 0.37 ug/g (dry weight), and the isoprenoid GDGTs is dominantly, with a acyclic > monocyclic > bicyclic > tricyclic > tetracyclic biphytane distribution, the branch GDGTs is less than 2%. The G2 with the quite lower GDGTs concentration, varying from 0.025~0.063ug/g (dry weight), the isoprenoid GDGTs content is less than 70%, with a acyclic > tetracyclic > bicyclic > monocyclic > tricyclic biphytane distribution, the branch GDGT is more than 30%. The sediment associated with carbonate has the similar GDGTs pattern with the G2, but the GDGTs concentration is between G1 and G2. The molecular structure and their carbon isotopic composition suggest that the organism mainly derived from methane oxidizing archaea and more carbonate precipitation by AOM within the G1 carbonates. Meanwhile, partly organism derived from crenachaeol and terrestrial, some carbonate precipitation originated from water column within the G2 carbonates. The G2 carbonates contain the similar biomarkers as found in nearby sediments, suggesting that the organisms associated with carbonate precipitation are the similar

Using carbon isotopes of methane from porewater to understand methane emissions across a permafrost thaw gradient

NASA Astrophysics Data System (ADS)

Varner, R. K.; McCalley, C. K.; Clarizia, P. E.; Verbeke, B. A.; Werner, S. L.; Burke, S. A.; Malhotra, A.; Rocci, K.

2016-12-01

Methane (CH4) emissions from high latitude ecosystems are controlled in part by the presence/absence of permafrost and concomitant modifications in vegetation composition. Rapid transitions in habitat impact CH4 emissions both by changing the moisture regime as well as the production and emission pathways. Measurement of the isotopic composition of CH4 in porewater in these thawed ecosystems can indicate shifts in production pathways of CH4. We measured CH4 and carbon dioxide (CO2) emission, belowground CH4 concentration and 13CH4 of porewater, vegetative type, and vascular greenness area (VGA) along a thaw gradient during summers 2012-2016 in Stordalen Mire, Sweden. Concentrations of CH4 belowground showed positive correlation with aboveground emissions. Carbon isotopic signatures of CH4 varied varied between sites with more hydrogenotrophic signatures in sites dominated by Sphagnum spp. and acetate fermentation signatures in sedge dominated sites (Carex and Eriophorum spp.). These data indicate that these ecosystems transition from thaw, their 13CH4 emissions will change and therefore need to be accounted for in global atmospheric budgets and models.

Methane and carbon dioxide fluxes in the waterlogged forests of south and middle taiga of Western Siberia

NASA Astrophysics Data System (ADS)

Glagolev, M. V.; Ilyasov, D. V.; Terentieva, I. E.; Sabrekov, A. F.; Mochenov, S. Yu; Maksutov, S. S.

2018-03-01

Field measurements of methane and carbon dioxide flux were carried out using portable static chambers in south (ST) and middle taiga subzones (MT) of Western Siberia (WS) from 16 to 24 August 2015. Two sites were investigated: Bakchar bog in the Tomsk region (in typical ecosystems for this area: oligotrophic bog/forest border and waterlogged forest) and Shapsha in Khanty-Mansiysk region (in waterlogged forest). The highest values of methane fluxes (mgC·m-2·h-1) were obtained in burnt wet birch forest (median 6.96; first quartile 3.12; third quartile 8.95). The lowest values of methane fluxes (among the sites mentioned above) were obtained in seasonally waterlogged forests (median -0.08; first and third quartiles are -0.14 and -0.03 mgC·m-2·h-1 respectively). These data will help to estimate the regional methane flux from the waterlogged and periodically flooded forests and to improve its prediction.

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.

Negative Ion Drift Velocity and Longitudinal Diffusion in Mixtures of Carbon Disulfide and Methane

NASA Technical Reports Server (NTRS)

Dion, Michael P.; Son, S.; Hunter, S. D.; deNolfo, G. A.

2011-01-01

Negative ion drift velocity and longitudinal diffusion has been measured for gas mixtures of carbon disulfide (CS2) and methane (CH4)' Measurements were made as a function of total pressure, CS2 partial pressure and electric field. Constant mobility and thermal-limit longitudinal diffusion is observed for all gas mixtures tested. Gas gain for some of the mixtures is also included.

Technical Note: Methionine, a precursor of methane in living plants

NASA Astrophysics Data System (ADS)

Lenhart, K.; Althoff, F.; Greule, M.; Keppler, F.

2015-03-01

When terrestrial plants were identified as producers of the greenhouse gas methane, much discussion and debate ensued not only about their contribution to the global methane budget but also with regard to the validity of the observation itself. Although the phenomenon has now become more accepted for both living and dead plants, the mechanism of methane formation in living plants remains to be elucidated and its precursor compounds to be identified. We made use of stable isotope techniques to verify the in vivo formation of methane, and, in order to identify the carbon precursor, 13C positionally labeled organic compounds were employed. Here we show that the amino acid L-methionine acts as a methane precursor in living plants. Employing 13C-labeled methionine clearly identified the sulfur-bound methyl group of methionine as a carbon precursor of methane released from lavender (Lavandula angustifolia). Furthermore, when lavender plants were stressed physically, methane release rates and the stable carbon isotope values of the emitted methane greatly increased. Our results provide additional support that plants possess a mechanism for methane production and suggest that methionine might play an important role in the formation of methane in living plants, particularly under stress conditions.

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.

Seasonal C-13 variations of methane from an anoxic marine sediment

NASA Technical Reports Server (NTRS)

Blair, Neal; Desmarais, David S.; Martens, Christopher S.

1985-01-01

Recent analyses of glacial ice suggest that the atmospheric concentration of methane has doubled in the last several hundred years, presumably due to anthropogenic perturbations of the relevant biogeochemical cycles. In principal, carbon isotopic measurements of atmospheric methane would provide information concerning changes in the sources and sinks of methane. The isotopic composition of methane is dependent on the source of the methane carbon, the mechanism of methane synthesis, and the degree and mode of oxidation which the methane has experienced. Unfortunately, few carbon isotopic measurements of atmospheric variations have been reported, so conclusions about temporal isotopic variations cannot be made. Also, before isotopic measurements of atmospheric methane can be used to identify changes in methane isotopic composition from different sources must be obtained. Methane bubbles from the anoxic sediments of Cape Lookout Bight, NC exhibit seasonal C-13 variations. The C-13 values ranged from -58 in August to -64 in the winter months with the evolution of the C-13 enriched gas occurring during periods of peak methane production. Even though a few intramolecular C-13 measurements of the pore water acetate have been made (methyl group, -26 per mil; carbonyl, -6 per mil), it is not clear how the acetate fermentation pathway affects the methane C-13/C-12 composition.

Carbon dioxide and methane emission dynamics in central London (UK)

NASA Astrophysics Data System (ADS)

Helfter, Carole; Nemitz, Eiko; Barlow, Janet F.; Wood, Curtis R.

2013-04-01

London, with a population of 8.2 million, is the largest city in Europe. It is heavily built-up (typically 8% vegetation cover within the central boroughs) and boasts some of the busiest arteries in Europe despite efforts to reduce traffic in the city centre with the introduction of a congestion charging scheme in 2007. We report on two substantial pollution monitoring efforts in the heart of London between October 2006 and present. Fluxes of carbon dioxide (CO2) and water (H2O) were measured continuously by eddy-covariance in central London from October 2006 until May 2008 from a 190 m telecommunication tower (BT tower; 51° 31' 17.4'' N 0° 8' 20.04'' W). The eddy-covariance system consisted of a Gill R3-50 ultrasonic anemometer operated at 20 Hz and a LI-COR 6262 infrared gas analyser. Air was sampled 0.3 m below the sensor head of the ultrasonic anemometer - which was itself mounted on a 3 m mast to the top of a 15 m lattice tower situated on the roof of the tower (instrument head at 190 m above street level) - and pulled down 45 m of 12.7 mm OD Teflon tubing. In addition, meteorological variables (temperature, relative humidity, pressure, precipitation, wind speed and direction) were also measured with a multi-sensor (Weather Transmitter WXT510, Vaisala). Eddy-covariance measurements at the BT tower location were reinstated in July 2011 and include methane (CH4), CO2 and H2O concentrations measured by a Picarro fast methane analyser (G2301-f). CO2 emissions were found to be mainly controlled by fossil fuel combustion (e.g. traffic, commercial and domestic heating). Diurnal averages of CO2 fluxes were found to be highly correlated to traffic. However changes in heating-related natural gas consumption and, to a lesser extent, photosynthetic activity in two large city centre green spaces (Hyde Park and Regent's Park) explained the seasonal variability. Annual estimates of net exchange of CO2 obtained by eddy-covariance agreed well with up-scaled data from the UK

Optical fiber network sensor system for monitoring methane concentration

NASA Astrophysics Data System (ADS)

Zhang, Zhi-wei; Zhang, Ji-long

2011-08-01

With regard to the high accuracy optic-fiber sensor for monitoring methane concentration, the choice of light source depends on methane peak values. Besides, the environment of mine should be considered, that is to say other gas should be considered, such as vapor, CO and CO2 etc, without absorbent spectrum in the decided wavelength. It has been reported that vapor, CO and CO2 have no obvious absorption in 0.85μm, 1.3μm and 1.66μm area, CH4 has no obvious absorption in 0.85μm area. So diode laser with 1.3μm or 1.66μm peak wavelength is chosen as the optic-fiber sensor's light source for detecting methane concentration. On the basis of the principle of optic absorption varied with methane concentration at its characteristic absorbent wavelength, the advantage of optic-fiber sensor technology and the circumstance characteristic of the coal mine. An optic-fiber sensor system is presented for monitoring methane concentration. Space Division Multiple Access Technology (SDMAT) and long optical path absorbent pool technology are combined in the study. Considering the circumstance characteristic of the coal mine, the optic-fiber network sensors for detecting methane concentration from mix gas of vapor, CO, CH4 and CO2 are used. It introduces the principle of an optic-fiber sensor system for monitoring methane concentration in coal mine. It contains the structure block diagram of monitoring system, the system is mainly made up of diode laser for monitoring methane concentration, Y-shaped photo-coupler with coupled rate 50:50, optical switch 1×2, gas absorbent cell, the computer data process and control system and photoelectric transformer. In this study, in order to decrease to the influence of the dark-current of photodiode, intensity in light sources and temperature drifts of processing circuit on the system accuracy in measurement, a beam of light is broken down into two beams in the coupler of Y-shaped coupler, the one acts as the reference optical path, the

Combustion of Methane Hydrate

NASA Astrophysics Data System (ADS)

Roshandell, Melika

from the experimental component of the research was that hydrates can burn completely, and that they burn most rapidly just after ignition and then burn steadily when some of the water in the dissociated zone is allowed to drain away. Excessive surfactant in the water creates a foam layer around the hydrate that acts as an insulator. The layer prevents sufficient heat flux from reaching the hydrate surface below the foam to release additional methane and the hydrate flame extinguishes. No self-healing or ice-freezing processes were observed in any of the combustion experiments. There is some variability, but a typical hydrate flame is receiving between one and two moles of water vapor from the liquid dissociated zone of the hydrate for each mole of methane it receives from the dissociating solid region. This limits the flame temperature to approximately 1800 K. In the theoretical portion of the study, a physical model using an energy balance from methane combustion was developed to understand the energy transfer between the three phases of gas, liquid and solid during the hydrate burn. Also this study provides an understanding of the different factors impacting the hydrate's continuous burn, such as the amount of water vapor in the flame. The theoretical study revealed how the water layer thickness on the hydrate surface, and its effect on the temperature gradient through the dissociated zone, plays a significant role in the hydrate dissociation rate and methane release rate. Motivated by the above mentioned observation from the theoretical analysis, a 1-D two-phase numerical simulation based on a moving front model for hydrate dissociation from a thermal source was developed. This model was focused on the dynamic growth of the dissociated zone and its effect on the dissociation rate. The model indicated that the rate of hydrate dissociation with a thermal source is a function of the dissociated zone thickness. It shows that in order for a continuous dissociation and

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

Emissions of organic carbon and methane from petroleum and dairy operations in California's San Joaquin Valley

NASA Astrophysics Data System (ADS)

Gentner, D. R.; Ford, T. B.; Guha, A.; Boulanger, K.; Brioude, J.; Angevine, W. M.; de Gouw, J. A.; Warneke, C.; Gilman, J. B.; Ryerson, T. B.; Peischl, J.; Meinardi, S.; Blake, D. R.; Atlas, E.; Lonneman, W. A.; Kleindienst, T. E.; Beaver, M. R.; St. Clair, J. M.; Wennberg, P. O.; VandenBoer, T. C.; Markovic, M. Z.; Murphy, J. G.; Harley, R. A.; Goldstein, A. H.

2014-05-01

Petroleum and dairy operations are prominent sources of gas-phase organic compounds in California's San Joaquin Valley. It is essential to understand the emissions and air quality impacts of these relatively understudied sources, especially for oil/gas operations in light of increasing US production. Ground site measurements in Bakersfield and regional aircraft measurements of reactive gas-phase organic compounds and methane were part of the CalNex (California Research at the Nexus of Air Quality and Climate Change) project to determine the sources contributing to regional gas-phase organic carbon emissions. Using a combination of near-source and downwind data, we assess the composition and magnitude of emissions, and provide average source profiles. To examine the spatial distribution of emissions in the San Joaquin Valley, we developed a statistical modeling method using ground-based data and the FLEXPART-WRF transport and meteorological model. We present evidence for large sources of paraffinic hydrocarbons from petroleum operations and oxygenated compounds from dairy (and other cattle) operations. In addition to the small straight-chain alkanes typically associated with petroleum operations, we observed a wide range of branched and cyclic alkanes, most of which have limited previous in situ measurements or characterization in petroleum operation emissions. Observed dairy emissions were dominated by ethanol, methanol, acetic acid, and methane. Dairy operations were responsible for the vast majority of methane emissions in the San Joaquin Valley; observations of methane were well correlated with non-vehicular ethanol, and multiple assessments of the spatial distribution of emissions in the San Joaquin Valley highlight the dominance of dairy operations for methane emissions. The petroleum operations source profile was developed using the composition of non-methane hydrocarbons in unrefined natural gas associated with crude oil. The observed source profile is

Economic Analysis of Planting Forests on Rice Lands in Texas: Sequestering Carbon and Avoiding Methane Production

NASA Astrophysics Data System (ADS)

Kronrad, G. D.; Huang, C.

2005-12-01

Global climate change is predicted due to increases in greenhouse gasses (i.e. CO2, CH4, CFCs, N2O, O3) in the atmosphere caused by human activities. The atmospheric concentration of methane (CH4), which absorbs and retains heat 21 times more effectively than CO2, has increased. Anaerobic bacterial activity in rice paddies constitutes one of major emission sources of CH4. The rice fields of Texas, for example, accounted for an annual CH4 emission of between 1.1 and 1.6 million tons of CO2 equivalent between 1990 and 2000. Converting marginal rice fields to forests plantations will remove CO2 from the atmosphere, sequester carbon in the forests and prevent the production of CH4. Therefore, carbon credits can be claimed for the carbon sequestered and the avoidance of CH4 production. Analyses were conducted to calculate the amount of carbon sequestered and methane avoided, and the profitability, measured in net present worth (NPW), of managing loblolly pine plantation for 1) timber production only, 2) the dual products of timber products and carbon credits in forests planted on marginal agricultural and unused pastureland and 3) the dual products of timber and carbon storage in forests planted on marginal rice lands. Calculations were performed using three discount rates, three site qualities and five prices for carbon credits. The results indicate that on average quality land, using a discount rate of 8 percent, forests planted on marginal agricultural and unused pastureland earn a NPW of 346 per acre from timber production only; a NPW of 438 per acre from timber and carbon credits (54.4 tons of carbon sequestered), assuming carbon is worth 10 per ton, during one rotation (32 years). The profitability of forest management increases due to the inclusion of carbon credits. The profitability of planting forests on marginal rice fields is even higher, earning a NPW of 566 per acre from timber and carbon credits (54.4 tons of C sequestered and 33.3 tons of C emission

Differential responses of carbon and water vapor fluxes to climate among evergreen needleleaf forests in the USA

USDA-ARS?s Scientific Manuscript database

Understanding of differences in carbon and water vapor fluxes of spatially distributed evergreen needle leaf forests (ENFs) is crucial to accurately estimating regional carbon and water budgets and when predicting the responses of ENFs to future climate. We investigated cross-site variability in car...

Microbial methane from in situ biodegradation of coal and shale: A review and reevaluation of hydrogen and carbon isotope signatures

USGS Publications Warehouse

Vinson, David S.; Blair, Neal E.; Martini, Anna M.; Larter, Steve; Orem, William H.; McIntosh, Jennifer C.

2017-01-01

Stable carbon and hydrogen isotope signatures of methane, water, and inorganic carbon are widely utilized in natural gas systems for distinguishing microbial and thermogenic methane and for delineating methanogenic pathways (acetoclastic, hydrogenotrophic, and/or methylotrophic methanogenesis). Recent studies of coal and shale gas systems have characterized in situ microbial communities and provided stable isotope data (δD-CH4, δD-H2O, δ13C-CH4, and δ13C-CO2) from a wider range of environments than available previously. Here we review the principal biogenic methane-yielding pathways in coal beds and shales and the isotope effects imparted on methane, document the uncertainties and inconsistencies in established isotopic fingerprinting techniques, and identify the knowledge gaps in understanding the subsurface processes that govern H and C isotope signatures of biogenic methane. We also compare established isotopic interpretations with recent microbial community characterization techniques, which reveal additional inconsistencies in the interpretation of microbial metabolic pathways in coal beds and shales. Collectively, the re-assessed data show that widely-utilized isotopic fingerprinting techniques neglect important complications in coal beds and shales.Isotopic fingerprinting techniques that combine δ13C-CH4 with δD-CH4 and/or δ13C-CO2have significant limitations: (1) The consistent ~ 160‰ offset between δD-H2O and δD-CH4 could imply that hydrogenotrophic methanogenesis is the dominant metabolic pathway in microbial gas systems. However, hydrogen isotopes can equilibrate between methane precursors and coexisting water, yielding a similar apparent H isotope signal as hydrogenotrophic methanogenesis, regardless of the actual methane formation pathway. (2) Non-methanogenic processes such as sulfate reduction, Fe oxide reduction, inputs of thermogenic methane, anaerobic methane oxidation, and/or formation water interaction can cause the apparent carbon

Assessing Near-surface Heat, Water Vapor and Carbon Dioxide Exchange Over a Coastal Salt-marsh

NASA Astrophysics Data System (ADS)

Bogoev, I.; O'Halloran, T. L.; LeMoine, J.

2017-12-01

Coastal ecosystems play an important role in mitigating the effects of climate change by storing significant quantities of carbon. A growing number of studies suggest that vegetated estuarine habitats, specifically salt marshes, have high long-term rates of carbon sequestration, perhaps even higher than mature tropical and temperate forests. Large amounts of carbon, accumulated over thousands of years, are stored in the plant materials and sediment. Improved understanding of the factors that control energy and carbon exchange is needed to better guide restoration and conservation management practices. To that end, we recently established an observation system to study marsh-atmosphere interactions within the North Inlet-Winyah Bay National Estuarine Research Reserve. Near-surface fluxes of heat, water vapor (H2O) and carbon dioxide (CO2) were measured by an eddy-covariance system consisting of an aerodynamic open-path H2O / CO2 gas analyzer with a spatially integrated 3D sonic anemometer/thermometer (IRGASON). The IRGASON instrument provides co-located and highly synchronized, fast response H2O, CO2 and air- temperature measurements, which eliminates the need for spectral corrections associated with the separation between the sonic anemometer and the gas analyzer. This facilitates calculating the instantaneous CO2 molar mixing ratio relative to dry air. Fluxes computed from CO2 and H2O mixing ratios, which are conserved quantities, do not require post-processing corrections for air-density changes associated with temperature and water vapor fluctuations. These corrections are particularly important for CO2, because they could be even larger than the measured flux. Here we present the normalized frequency spectra of air temperature, water vapor and CO2, as well as their co-spectra with the co-located vertical wind. We also show mean daily cycles of sensible, latent and CO2 fluxes and analyze correlations with air/water temperature, wind speed and light availability.

Spatial variability in nitrous oxide and methane emissions from beef cattle feedyard pen surfaces

USDA-ARS?s Scientific Manuscript database

Greenhouse gas emissions from beef cattle feedlots include enteric carbon dioxide and methane, and manure-derived methane, nitrous oxide and carbon dioxide. Enteric methane comprises the largest portion of the greenhouse gas footprint of beef cattle feedyards. For the manure component, methane is th...

First Airborne IPDA Lidar Measurements of Methane and Carbon Dioxide Applying the DLR Greenhouse Gas Sounder CHARM-F

NASA Astrophysics Data System (ADS)

Amediek, A.; Ehret, G.; Fix, A.; Wirth, M.; Quatrevalet, M.; Büdenbender, C.; Kiemle, C.; Loehring, J.; Gerbig, C.

2015-12-01

First airborne measurement using CHARM-F, the four-wavelengths lidar for simultaneous soundings of atmospheric CO2 and CH4, were performed in Spring 2015 onboard the German research aircraft HALO. The lidar is designed in the IPDA (integrated path differential absorption) configuration using short double pulses, which gives column averaged gas mixing ratios between aircraft and ground. HALO's maximum flight altitude of 15 km and special features of the lidar, such as a relatively large laser ground spot, enable the CHARM-F system to be an airborne demonstrator for future spaceborne greenhouse gas lidars. Due to a high technological conformity this applies in particular to the French-German satellite mission MERLIN, the spaceborne methane IPDA lidar. The successfully completed flight measurements provide a valuable dataset, which supports the retrieval algorithm development for MERLIN notably. The flights covered different ground cover types, different orography types as well as the sea. Additionally, we captured different cloud conditions, at which the broken cloud case is a matter of particular interest. This dataset allows detailed analyses of measurement sensitivities, general studies on the IPDA principle and on technical details of the system. These activities are supported by another instrument onboard: a cavity ring down spectrometer, providing in-situ data of carbon dioxide, methane and water vapor with high accuracy and precision, which is ideal for validation purposes of the lidar. Additionally the onboard instrumentation of HALO gives information about pressure and temperature for cross-checking the ECMWF data, which are intended to be used for calculating the weighting function, the key quantity for the retrieval of gas column mixing ratios from the measured gas optical depths. In combination with dedicated descents into the boundary layer and subsequent ascents, a self-contained dataset for characterizations of CHARM-F is available.

Catalytic chemical vapor deposition synthesis and electron microscopy observation of coiled carbon nanotubes

NASA Astrophysics Data System (ADS)

Xie, Jining; Mukhopadyay, K.; Yadev, J.; Varadan, V. K.

2003-10-01

Coiled carbon nanotubes exhibit excellent mechanical and electrical properties because of the combination of coil morphology and properties of nanotubes. They could have potential novel applications in nanocomposites and nano-electronic devices as well as nano-electromechanical systems. In this work, synthesis of regularly coiled carbon nanotubes is presented. It involves pyrolysis of hydrocarbon gas over metal/support catalyst by both thermal filament and microwave catalytic chemical vapor deposition methods. Scanning electron microscopy and transmission electron microscopy were performed to observe the coil morphology and nanostructure of coiled nanotubes. The growth mechanism and structural and electrical properties of coiled carbon nanotubes are also discussed.

Chemical structural analysis of diamondlike carbon films: I. Surface growth model

NASA Astrophysics Data System (ADS)

Takabayashi, Susumu; Ješko, Radek; Shinohara, Masanori; Hayashi, Hiroyuki; Sugimoto, Rintaro; Ogawa, Shuichi; Takakuwa, Yuji

2018-02-01

The surface growth mechanisms of diamondlike carbon (DLC) films has been clarified. DLC films were synthesized in atmospheres with a fixed methane-to-argon ratio at different temperatures up to 700 °C by the photoemission-assisted glow discharge of photoemission-assisted plasma-enhanced chemical vapor deposition. The electrical resistivity of the films decreased logarithmically as the synthesis temperature was increased. Conversely, the dielectric constant of the films increased and became divergent at high temperature. However, the very high electrical resistivity of the film synthesized at 150 °C was retained even after post-annealing treatments at temperatures up to 500 °C, and divergence of the dielectric constant was not observed. Such films exhibited excellent thermal stability and retained large amounts of hydrogen, even after post-annealing treatments. These results suggest that numerous hydrogen atoms were incorporated into the DLC films during synthesis at low temperatures. Hydrogen atoms terminate carbon dangling bonds in the films to restrict π-conjugated growth. During synthesis at high temperature, hydrogen was desorbed from the interior of the growing films and π-conjugated conductive films were formed. Moreover, hydrogen radicals were chemisorbed by carbon atoms at the growing DLC surface, leading to removal of carbon atoms from the surface as methane gas. The methane molecules decomposed into hydrocarbons and hydrogen radicals through the attack of electrons above the surface. Hydrogen radicals contributed to the etching reaction cycle of the film; the hydrocarbon radicals were polymerized by reacting with other radicals and the methane source. The polymer radicals remained above the film, preventing the supply of the methane source and disrupting the action of argon ions. At high temperatures, the resultant DLC films were rough and thin.

Ruminant Methane δ (13C/12C) - Values: Relation to Atmospheric Methane

NASA Astrophysics Data System (ADS)

Rust, Fleet

1981-03-01

The δ (13C/12C) - values of methane produced by fistulated steers, dairy cattle, and wethers, and dairy and beef cattle herds show a bimodal distribution that appears to be correlated with the plant type (C3 or C4, that is, producing either a three- or a four-carbon acid in the first step of photosynthesis) consumed by the animals. These results indicate that cattle and sheep, on a global basis, release methane with an average δ (13C/12C) value of -60 and -63 per mil, respectively. Together they are a source of atmospheric methane whose δ (13C/12C) is similar to published values for marsh gas and cannot explain the 20 per mil higher values for atmospheric methane.

Biophysical controls on carbon and water vapor fluxes across a grassland climatic gradient in the United States

USDA-ARS?s Scientific Manuscript database

Understanding of the underlying causes of spatial variation in exchange of carbon and water vapor fluxes between grasslands and the atmosphere is crucial for accurate estimates of regional and global carbon and water budgets, and for predicting the impact of climate change on biosphere–atmosphere fe...

Deep peat warming increases surface methane and carbon dioxide emissions in a black spruce-dominated ombrotrophic bog.

PubMed

Gill, Allison L; Giasson, Marc-André; Yu, Rieka; Finzi, Adrien C

2017-12-01

Boreal peatlands contain approximately 500 Pg carbon (C) in the soil, emit globally significant quantities of methane (CH 4 ), and are highly sensitive to climate change. Warming associated with global climate change is likely to increase the rate of the temperature-sensitive processes that decompose stored organic carbon and release carbon dioxide (CO 2 ) and CH 4 . Variation in the temperature sensitivity of CO 2 and CH 4 production and increased peat aerobicity due to enhanced growing-season evapotranspiration may alter the nature of peatland trace gas emission. As CH 4 is a powerful greenhouse gas with 34 times the warming potential of CO 2 , it is critical to understand how factors associated with global change will influence surface CO 2 and CH 4 fluxes. Here, we leverage the Spruce and Peatland Responses Under Changing Environments (SPRUCE) climate change manipulation experiment to understand the impact of a 0-9°C gradient in deep belowground warming ("Deep Peat Heat", DPH) on peat surface CO 2 and CH 4 fluxes. We find that DPH treatments increased both CO 2 and CH 4 emission. Methane production was more sensitive to warming than CO 2 production, decreasing the C-CO 2 :C-CH 4 of the respired carbon. Methane production is dominated by hydrogenotrophic methanogenesis but deep peat warming increased the δ 13 C of CH 4 suggesting an increasing contribution of acetoclastic methanogenesis to total CH 4 production with warming. Although the total quantity of C emitted from the SPRUCE Bog as CH 4 is <2%, CH 4 represents >50% of seasonal C emissions in the highest-warming treatments when adjusted for CO 2 equivalents on a 100-year timescale. These results suggest that warming in boreal regions may increase CH 4 emissions from peatlands and result in a positive feedback to ongoing warming. © 2017 John Wiley & Sons Ltd.

Methane and carbon dioxide exchange in a post-extraction, unrestored peatland in Eastern Quebec, Canada

NASA Astrophysics Data System (ADS)

Rankin, Tracy; Strachan, Ian; Strack, Maria

2017-04-01

Peatlands, in their pristine state, are important long-term sinks of carbon. The extraction of peat for agricultural purposes or for biofuel leads to a shift in the carbon dynamics. Changes in environmental conditions post extraction may also allow for invasive species to establish and spread across the peatland. Many studies have shown the benefits and advantages of various restoration management practices, but few studies have explored the carbon exchange from unrestored peatlands. Our study reports the methane (CH4) and carbon dioxide (CO2) fluxes from a post-extraction, unrestored peatland in Eastern Québec at both the plant community scale using static chambers, and at the ecosystem scale using an eddy covariance flux tower, over two complete years. Extraction of the Saint-Alexandre-de-Kamouraska peatland (SAK) started in the early 1970's and was halted in 1999. No restoration efforts have been implemented and the remnant ditches remain unblocked. The site consists of sparse patches of Eriophorum and a vast area of bare peat. Consequently, SAK is an overall source of carbon to the atmosphere, releasing an annual total of 153 g C m-2 and 241 g C m-2 in CO2 emissions for 2014 and 2015, respectively, and an average annual total of 1 g C m-2yr-1 in CH4 emissions. Phragmites and Typha, both invasive species, have established themselves in the ditches and are sources of methane; partly explaining the increased emissions in carbon fluxes to the atmosphere post extraction. Results from this study will help managers assess the importance of post-extraction peatland restoration, by comparing the differences in CO2 and CH4 exchange between restored and unrestored peatlands.

Release of Methane from Bering Sea Sediments During the Last Glacial Period

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

Mea Cook; Lloyd Keigwin

2007-11-30

Several lines of evidence suggest that during times of elevated methane flux the sulfate-methane transition zone (SMTZ) was positioned near the sediment-water interface. We studied two cores (from 700 m and 1457 m water depth) from the Umnak Plateau region. Anomalously low d13C and high d18O in benthic and planktonic foraminifera in these cores are the consequence of diagenetic overgrowths of authigenic carbonates. There are multiple layers of authigenic-carbonate-rich sediment in these cores, and the stable isotope compositions of the carbonates are consistent with those formed during anaerobic oxidation of methane (AOM). The carbonate-rich layers are associated with biomarkers producedmore » by methane-oxidizing archaea, archaeol and glyceryl dibiphytanyl glyceryl tetraether (GDGT). The d13C of the archaeol and certain GDGTs are isotopically depleted. These carbonate- and AOM-biomarker-rich layers were emplaced in the SMTZ during episodes when there was a high flux of methane or methane-rich fluids upward in the sediment column. The sediment methane in the Umnak Plateau region appears to have been very dynamic during the glacial period, and interacted with the ocean-atmosphere system at millennial time scales. The upper-most carbonate-rich layers are in radiocarbon-dated sediment deposited during interstitials 2 and 3, 28-20 ka, and may be associated with the climate warming during this time.« less

Optical properties of hydrogenated amorphous carbon films grown from methane plasma

NASA Technical Reports Server (NTRS)

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

1985-01-01

A 30 kHz ac glow discharge formed from methane gas was used to grow carbon films on InP substrates. Both the growth rate, and the realitive Ar ion sputtering rate at 3 keV varied monotonically with deposition power. Results from the N-15 nuclear reaction profile experiments indicated a slight drop in the hydrogen concentration as more energy was dissipated in the ac discharge. Values for the index of refraction and extinction coefficient ranged from 1.721 to 1.910 and 0 to -0.188, respectively. Optical bandgaps as high as 2.34 eV were determined.

The annual cycle of stratospheric water vapor in a general circulation model

NASA Technical Reports Server (NTRS)

Mote, Philip W.

1995-01-01

The application of general circulation models (GCM's) to stratospheric chemistry and transport both permits and requires a thorough investigation of stratospheric water vapor. The National Center for Atmospheric Research has redesigned its GCM, the Community Climate Model (CCM2), to enable studies of the chemistry and transport of tracers including water vapor; the importance of water vapor to the climate and chemistry of the stratosphere requires that it be better understood in the atmosphere and well represented in the model. In this study, methane is carried as a tracer and converted to water; this simple chemistry provides an adequate representation of the upper stratospheric water vapor source. The cold temperature bias in the winter polar stratosphere, which the CCM2 shares with other GCM's, produces excessive dehydration in the southern hemisphere, but this dry bias can be ameliorated by setting a minimum vapor pressure. The CCM2's water vapor distribution and seasonality compare favorably with observations in many respects, though seasonal variations including the upper stratospheric semiannual oscillation are generally too small. Southern polar dehydration affects midlatitude water vapor mixing ratios by a few tenths of a part per million, mostly after the demise of the vortex. The annual cycle of water vapor in the tropical and northern midlatitude lower stratosphere is dominated by drying at the tropical tropopause. Water vapor has a longer adjustment time than methane and had not reached equilibrium at the end of the 9 years simulated here.

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.

Methane and Dissolved Organic Carbon Sustain an Ecosystem within a Density Stratified Coastal Aquifer of the Yucatan Peninsula, Mexico. Evidence for a Subterranean Microbial Loop?

NASA Astrophysics Data System (ADS)

Brankovits, David; Pohlman, John W.; Niemann, Helge; Leigh, Mary Beth; Casso, Michael; Alvarez Noguera, Fernando; Lehmann, Moritz F.; Iliffe, Thomas M.

2016-04-01

In coastal karst terrains, anchialine caves that meander in density stratified aquifers provide an exceptional opportunity for scientists to study in situ biogeochemical processes within the groundwater. The Caribbean coast of Mexico's Yucatan Peninsula contains over 1000 km of mapped cave passages, the densest known accumulation of anchialine caves in the world. A decades-old study based on the simple observation of 13C-depleted biomass in the cave-adapted fauna suggested biogeochemical processes related to methane-linked carbon cycling and/or other chemoautotrophic pathways as a source of energy and carbon. In this study, we utilized cave diving and a novel sampling device (the Octopipi) to obtain cm-scale water column profiles of methane, DOC and DIC concentrations and stable carbon isotope ratios to identify the energy sources and microbial processes that sustain life in these subterranean estuaries. High concentrations (up to 9522 nM) low-δ13C (as low as -67.5 permil) methane near the ceiling of the cave (in the fresh water section of the stratified water column) and evidence for methane oxidation in the brackish water portion of the water column suggest methane availability and consumption. Profiles obtained by the Octopipi demonstrate that virtually all of the methane (˜99%) is oxidized at the interface of anoxic freshwater and hypoxic brackish water masses. The high-methane water mass near the ceiling also contained elevated concentrations of DOC (851 μM) that displayed comparatively high δ13C (-27.8 to -28.2 permil), suggesting terrestrial organic matter input from the overlying soils. Low-methane brackish and saline water was characterized by lower DOC concentration (15 to 97 μM), yet with similar δ13C (-25.9 to -27.2 permil), suggesting significant terrestrial organic matter consumption or removal with increasing depth, from fresh to saline water, within the water column. The presence of 13C-depleted fatty acids (e.g., C16:1ω7c with δ13C

Carbon-Electrode-Tailored All-Inorganic Perovskite Solar Cells To Harvest Solar and Water-Vapor Energy.

PubMed

Duan, Jialong; Hu, Tianyu; Zhao, Yuanyuan; He, Benlin; Tang, Qunwei

2018-05-14

Moisture is the worst enemy for state-of-the-art perovskite solar cells (PSCs). However, the flowing water vapor within nanoporous carbonaceous materials can create potentials. Therefore, it is a challenge to integrate water vapor and solar energies into a single PSC device. We demonstrate herein all-inorganic cesium lead bromide (CsPbBr 3 ) solar cells tailored with carbon electrodes to simultaneously harvest solar and water-vapor energy. Upon interfacial modification and plasma treatment, the bifunctional PSCs yield a maximum power conversion efficiency up to 9.43 % under one sun irradiation according to photoelectric conversion principle and a power output of 0.158 μW with voltage of 0.35 V and current of 0.45 μA in 80 % relative humidity through the flowing potentials at the carbon/water interface. The initial efficiency is only reduced by 2 % on exposing the inorganic PSC with 80 % humidity over 40 days. The successful realization of physical proof-of-concept multi-energy integrated solar cells provides new opportunities of maximizing overall power output. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Interannual, seasonal, and retrospective analysis of the methane and carbon dioxide budgets of a temperate peatland

Treesearch

D.M. Olson; T.J. Griffis; A. Noormets; R. Kolka; J. Chen

2013-01-01

Three years (2009-2011) of near-continuous methane (CH4) and carbon dioxide (CO2) fluxes were measured with the eddy covariance (EC) technique at a temperate peatland located within the Marcell Experimental Forest, in northern Minnesota, USA. The peatland was a net source of CH4 and a net sink of CO...

The Real Difference between Biotic and Abiotic Methane

NASA Astrophysics Data System (ADS)

Cao, X.; Bao, H.; Peng, Y.

2017-12-01

Methane has both biotic and abiotic origins, and the identification of these two origins has important implications not only in understanding terrestrial processes but also in searching for extraterrestrial life. Carbon and hydrogen isotopes in methane have been used to identify certain biosignatures, but such efforts often suffer from ambiguity. Recent advancement in our capability in measuring multiply substituted isotopologues of methane (i.e. 13CDH3 and 12CD2H2) has found large 12CD2H2 depletion in abiotic methane. Quantum tunneling has been proposed to account for the apparent abiotic signature. However, quantum tunneling is neither unique to abiotic processes nor consistent with the observed not-so-depleted hydrogen isotope composition. Here we constructed a general kinetic model for methane formation from CO2, and validated it by fitting its parameters to observed 13CDH3, 12CD2H2, and 12CDH3. Our model revealed that the fundamental difference between biotic and abiotic methane isotopic signatures is in the source of hydrogens during methane formation. Hydrogens in biotic methane originate from the stronger carbon-hydrogen and sulfur-hydrogen bonds, while hydrogens in abiotic methane originate from the much weaker metal-hydrogen adsorption bond. This hydrogen source difference results in abiotic methane being more depleted in 12CD2H2 than the biotic one. Our model also shows that the primary kinetic hydrogen isotope effect is at approximately 0.6 for both abiotic and biotic pathways, a normal value further nullifying the role of quantum tunneling. The active and exclusive shuttling of reduced hydrogen via strong chemical bonds like carbon-hydrogen and sulfur-hydrogen in coenzymes is proposed here to be a unique signature of life. In an ironic sense, it is the equilibrated hydrogen isotope composition in the hydrogen donors that distinguishes the living from the non-living.

Bioelectrochemical approach for control of methane emission from wetlands.

PubMed

Liu, Shentan; Feng, Xiaojuan; Li, Xianning

2017-10-01

To harvest electricity and mitigate methane emissions from wetlands, a novel microbial fuel cell coupled constructed wetland (MFC-CW) was assembled with an anode placing in the rhizosphere and a cathode on the water surface. Plant-mediated methane accounted for 71-82% of the total methane fluxes. The bioanode served as an inexhaustible source of electron acceptors and resulted in reduced substantial methane emissions owing to electricigens outcompeting methanogens for carbon and electrons when substrate was deficient. However, when supplying sufficient organic carbon, both electricity and methane increased, indicating that electrogenesis and methanogenesis could co-exist in harmony. Direct methane emission (diffusion/ebullition) and plant-mediated methane emission were affected by operating conditions. Methanogenesis was significantly suppressed (∼98%) at HRT of 96h and with external resistance of 200Ω, accompanied with improved coulombic efficiency of 14.9% and current density of 187mA/m 2 . Contrarily, change of electrode polarity in the rhizosphere led to more methane efflux. Copyright © 2017 Elsevier Ltd. All rights reserved.

Methane mitigation shows significant benefits towards achieving the 1.5 degree target.

NASA Astrophysics Data System (ADS)

Collins, W.; Webber, C.; Cox, P. M.; Huntingford, C.; Lowe, J. A.; Sitch, S.

2017-12-01

Most analyses of allowable carbon emissions to achieve the 1.5 degree target implicitly assume that the ratio of CO2 to non-CO2 greenhouse gases remains near constant, and that all radiative forcing factors have similar impacts on land and ocean carbon storage. Here we determine how plausible reductions in methane emissions will make the carbon targets more feasible. We account for the latest estimates of the methane radiative effect as well as the indirect effects of methane on ozone. We particularly address the differing effects of methane and CO2 mitigation on the land carbon storage including via reduced concentrations of surface ozone. The methodology uses an intermediate complexity climate model (IMOGEN) coupled to a land surface model (JULES) which represents the details of the terrestrial carbon cycle. The carbon emissions inputs to IMOGEN are varied to find allowable pathways consistent with the Paris 1.5 K or 2.0 K targets. The IMOGEN physical parameters are altered to represent the climate characteristics of 38 CMIP5 models (such as climate sensitivity) to provide bounds on the range of allowable CO2 emissions. We examine the effects of three different methane mitigation options that are broadly consistent with the ranges in the SSP scenarios: little mitigation, cost-optimal mitigation, and maximal mitigation. The land and ocean carbon storage increases with methane mitigation, allowing more flexibility in CO2 emission reduction. This is mostly since CO2 fertilisation is reduced less with high methane mitigation, with a small contribution from reduced plant damage with lower surface ozone levels.

ZnO Functionalization of Multi-walled Carbon Nanotubes for Methane Sensing at Single Parts Per Million Concentration Levels

EPA Science Inventory

This paper presents a novel atomic layer deposition (ALD) based ZnO functionalization of surface pre-treated multi-walled carbon nanotubes (MWCNTs) for highly sensitive methane chemoresistive sensors. The temperature optimization of the ALD process leads to enhanced ZnO nanopart...

Ebullitive methane emissions from oxygenated wetland streams

USGS Publications Warehouse

Crawford, John T.; Stanley, Emily H.; Spawn, Seth A.; Finlay, Jacques C.; Striegl, Robert G.

2014-01-01

Stream and river carbon dioxide emissions are an important component of the global carbon cycle. Methane emissions from streams could also contribute to regional or global greenhouse gas cycling, but there are relatively few data regarding stream and river methane emissions. Furthermore, the available data do not typically include the ebullitive (bubble-mediated) pathway, instead focusing on emission of dissolved methane by diffusion or convection. Here, we show the importance of ebullitive methane emissions from small streams in the regional greenhouse gas balance of a lake and wetland-dominated landscape in temperate North America and identify the origin of the methane emitted from these well-oxygenated streams. Stream methane flux densities from this landscape tended to exceed those of nearby wetland diffusive fluxes as well as average global wetland ebullitive fluxes. Total stream ebullitive methane flux at the regional scale (103 Mg C yr−1; over 6400 km2) was of the same magnitude as diffusive methane flux previously documented at the same scale. Organic-rich stream sediments had the highest rates of bubble release and higher enrichment of methane in bubbles, but glacial sand sediments also exhibited high bubble emissions relative to other studied environments. Our results from a database of groundwater chemistry support the hypothesis that methane in bubbles is produced in anoxic near-stream sediment porewaters, and not in deeper, oxygenated groundwaters. Methane interacts with other key elemental cycles such as nitrogen, oxygen, and sulfur, which has implications for ecosystem changes such as drought and increased nutrient loading. Our results support the contention that streams, particularly those draining wetland landscapes of the northern hemisphere, are an important component of the global methane cycle.

Highly vibrationally excited CO generated in a low-temperature chemical reaction between carbon vapor and molecular oxygen

NASA Astrophysics Data System (ADS)

Jans, E.; Frederickson, K.; Yurkovich, M.; Musci, B.; Rich, J. W.; Adamovich, I. V.

2016-08-01

A chemical flow reactor is used to study the vibrational population distribution of CO produced by a reaction between carbon vapor generated in an arc discharge and molecular oxygen. The results demonstrate formation of highly vibrationally excited CO, up to vibrational level v = 14, at low temperatures, T = 400-450 K, with population inversion at v = 4-7, in a collision-dominated environment, 15-20 Torr. The average vibrational energy per CO molecule formed by the reaction is 0.6-1.2 eV/molecule, which corresponds to 10-20% of reaction enthalpy. The results show feasibility of development of a new CO chemical laser using carbon vapor and oxygen as reactants.

A comparative study of carbon plasma emission in methane and argon atmospheres

NASA Astrophysics Data System (ADS)

Yousfi, H.; Abdelli-Messaci, S.; Ouamerali, O.; Dekhira, A.

2018-04-01

The interaction between laser produced plasma (LPP) and an ambient gas is largely investigated by Optical Emission Spectroscopy (OES). The analysis of carbon plasma produced by an excimer KrF laser was performed under controlled atmospheres of methane and argon. For each ambient gas, the features of produced species have been highlighted. Using the time of flight (TOF) analysis, we have observed that the C and C2 exhibit a triple and a double peaks respectively in argon atmosphere in contrast to the methane atmosphere. The evolution of the first peaks of C and C2 follows the plasma expansion, whereas the second peaks move backward, undergoing reflected shocks. It was found that the translational temperature, obtained by Shifted Maxwell Boltzmann distribution function is strongly affected by the nature of ambient gas. The dissociation of CH4 by electronic impact presents the principal approach for explaining the emission of CH radical in reactive plasma. Some chemical reactions have been proposed in order to explain the formation process of molecular species.

Analysis of field measurements of carbon dioxide and water vapor fluxes

NASA Technical Reports Server (NTRS)

Verma, Shashi B.

1991-01-01

Analysis of the field measurements of carbon dioxide and water vapor fluxes is discussed. These data were examined in conjunction with reflectance obtained from helicopter mounted Modular Multiband Radiometer. These measurements are representative of the canopy scale (10 to 100 m)(exp 2) and provide a good basis for investigating the hypotheses/relationship potentially useful in remote sensing applications. All the micrometeorological data collected during FIFE-89 were processed and fluxes of CO2, water vapor, and sensible heat were calculated. Soil CO2 fluxes were also estimated. Employing these soil CO2 flux values, in conjunction with micrometeorological measurements, canopy photosynthesis is being estimated. A biochemical model of leaf photosynthesis was adapted to the prairie vegetation. The modeled leaf photosynthesis rates were scaled up to the canopy level. This model and a multiplicative stomatal conductance model are also used to calculate canopy conductance.

Method for generating methane from a carbonaceous feedstock

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

Snyder, Seth W.; Urgun-Demirtas, Meltem; Shen, Yanwen

The present invention provides a method for generating methane from a carbonaceous feedstock with simultaneous in situ sequestration of carbon dioxide to afford a biogas comprising at least 85 percent by volume methane, the method comprising anaerobically incubating a particulate additive in contact with a carbonaceous feedstock in a neutral or alkaline aqueous culture medium containing a culture of methanogenic consortia and collecting methane generated therefrom. The additive comprises at least one material selected from a biochar, an ash produced by gasification or combustion of a carbonaceous material, a black carbon soil, and a Terra Preta soil.

Limited contribution of ancient methane to surface waters of the U.S. Beaufort Sea shelf

NASA Astrophysics Data System (ADS)

Sparrow, K. J.; Kessler, J. D.

2017-12-01

In response to climate change, methane can be released to ocean sediments and waters from thawing subsea permafrost and decomposing methane hydrates. However, it is unknown if methane derived from these massive stores of frozen, ancient carbon reaches the atmosphere. We quantified the fraction of methane sourced from ancient carbon in shelf waters of the U.S. Beaufort Sea, a region that has both permafrost and methane hydrates and is experiencing significant warming. While the radiocarbon-methane analyses indicate that ancient carbon is being mobilized and emitted as methane into shelf bottom waters, surprisingly, we find that modern sources of methane predominate in surface waters of relatively shallow mid-outer shelf stations. These results suggest that even if there is a heightened liberation of ancient methane as climate change proceeds, oceanic dispersion and oxidation processes can strongly limit its emission to the atmosphere.

Ozone treatment of coal- and coffee grounds-based active carbons: Water vapor adsorption and surface fractal micropores

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

Tsunoda, Ryoichi; Ozawa, Takayoshi; Ando, Junichi

1998-09-15

Characteristics of the adsorption iostherms of water vapor on active carbons from coal and coffee grounds and those ozonized ones from the surface fractal dimension analysis are discussed. The upswing of the adsorption isotherms in the low relative pressure of coffee grounds-based active carbon, of which isotherms were not scarcely affected on ozonization, was attributed to the adsorption of water molecules on the metallic oxides playing the role of oxygen-surface complexes, which formed the corrugated surfaces on the basal planes of micropore walls with the surface fractal dimension D{sub s} > 2. On the other hand, coal-based active carbon withmore » D{sub s} < 2, which indicated the flat surfaces of micropore walls, showed little effect on the upswing even on ozonization, even though the adsorption amounts of water vapor were increased in the low relative pressure.« less

Development of a carbon formation reactor for carbon dioxide reduction

NASA Technical Reports Server (NTRS)

Noyes, G.

1985-01-01

Applied research, engineering development, and performance evaluation were conducted on a process for formation of dense carbon by pyrolysis of methane. Experimental research showed that dense (0.7 to 1.6 g/cc bulk density and 1.6 to 2.2 g/cc solid density) carbon can be produced by methane pyrolysis in quartzwool-packed quartz tubes at temperatrues of 1100 to 1300 C. This result supports the condensation theory of pyrolytic carbon formation from gaseous hydrocarbons. A full-scale Breadboard Carbon Formation Reactor (CFR) was designed, fabricated, and tested at 1100 to 1200 C with 380 to 2280 sccm input flows of methane. Single-pass conversion of methane to carbon ranged from 60 to 100 percent, with 89 percent average conversion. Performance was projected for an Advanced Carbon Reactor Subsystem (ACRS) which indicated that the ACRS is a viable option for management of metabolic carbon on long-duration space missions.

Deposition of hard and adherent diamond-like carbon films inside steel tubes using a pulsed-DC discharge.

PubMed

Trava-Airoldi, Vladimir Jesus; Capote, Gil; Bonetti, Luís Francisco; Fernandes, Jesum; Blando, Eduardo; Hübler, Roberto; Radi, Polyana Alves; Santos, Lúcia Vieira; Corat, Evaldo José

2009-06-01

A new, low cost, pulsed-DC plasma-enhanced chemical vapor deposition system that uses a bipolar, pulsed power supply was designed and tested to evaluate its capacity to produce quality diamond-like carbon films on the inner surface of steel tubes. The main focus of the study was to attain films with low friction coefficients, low total stress, a high degree of hardness, and very good adherence to the inner surface of long metallic tubes at a reasonable growth rate. In order to enhance the diamond-like carbon coating adhesion to metallic surfaces, four steps were used: (1) argon ion sputtering; (2) plasma nitriding; (3) a thin amorphous silicon interlayer deposition, using silane as the precursor gas; and (4) diamond-like carbon film deposition using methane atmosphere. This paper presents various test results as functions of the methane gas pressure and of the coaxial metal anode diameter, where the pulsed-DC voltage constant is kept constant. The influence of the coaxial metal anode diameter and of the methane gas pressure is also demonstrated. The results obtained showed the possibilities of using these DLC coatings for reduced friction and to harden inner surface of the steel tubes.

Vapor sensing using polymer/carbon black composites in the percolative conduction regime.

PubMed

Sisk, Brian C; Lewis, Nathan S

2006-08-29

To investigate the behavior of chemiresistive vapor sensors operating below or around the percolation threshold, chemiresistors have been formed from composites of insulating organic polymers and low mass fractions of conductive carbon black (CB, 1-12% w/w). Such sensors produced extremely large relative differential resistance changes above certain threshold vapor concentrations. At high analyte partial pressures, these sensors exhibited better signal/noise characteristics and were typically less mutually correlated in their vapor response properties than composites formed using higher mass fractions of CB in the same set of polymer sorption layers. The responses of the low-mass-fraction CB sensors were, however, less repeatable, and their nonlinear response as a function of analyte concentration required more complicated calibration schemes to identify and quantify analyte vapors to compensate for drift of a sensor array and to compensate for variability in response between sensor arrays. Because of their much larger response signals, the low-mass-fraction CB sensors might be especially well suited for use with low-precision analog-to-digital signal readout electronics. These sensors serve well as a complement to composites formed from higher mass fractions of CB and have yielded insight into the tradeoffs of signal-to-noise improvements vs complexity of signal processing algorithms necessitated by the use of nonlinearly responding detectors in array-based sensing schemes.

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.

Effect of deposition pressure on the morphology and structural properties of carbon nanotubes synthesized by hot-filament chemical vapor deposition.

PubMed

Arendse, C J; Malgas, G F; Scriba, M R; Cummings, F R; Knoesen, D

2007-10-01

Hot-filament chemical vapor deposition has developed into an attractive method for the synthesis of various carbon nanostructures, including carbon nanotubes. This is primarily due to its versatility, low cost, repeatability, up-scalability, and ease of production. The resulting nano-material synthesized by this technique is dependent on the deposition conditions which can be easily controlled. In this paper we report on the effect of the deposition pressure on the structural properties and morphology of carbon nanotubes synthesized by hot-filament chemical vapor deposition, using Raman spectroscopy and high-resolution scanning electron microscopy, respectively. A 10 nm-thick Ni layer, deposited on a SiO2/Si substrate, was used as catalyst for carbon nanotube growth. Multi-walled carbon nanotubes with diameters ranging from 20-100 nm were synthesized at 500 degrees C with high structural perfection at deposition pressures between 150 and 200 Torr. Raman spectroscopy measurements confirm that the carbon nanotube deposit is homogeneous across the entire substrate area.

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.

Making Carbon Emissions Remotely Sensible: Flux Observations of Carbon from an Airborne Laboratory (FOCAL), its Near-Surface Survey of Carbon Gases and Isotopologues on Alaska's North Slope

NASA Astrophysics Data System (ADS)

Dobosy, R.; Dumas, E. J.; Sayres, D. S.; Healy, C. E.; Munster, J. B.; Baker, B.; Anderson, J. G.

2014-12-01

Detailed process-oriented study of the mechanisms of conversion in the Arctic of fossil carbon to atmospheric gas is progressing, but necessarily limited to a few point locations and requiring detailed subsurface measurements inaccessible to remote sensing. Airborne measurements of concentration, transport and flux of these carbon gases at sufficiently low altitude to reflect surface variations can tie such local measurements to remotely observable features of the landscape. Carbon dioxide and water vapor have been observable for over 20 years from low-altitude small aircraft in the Arctic and elsewhere. Methane has been more difficult, requiring large powerful aircraft or limited flask samples. Recent developments in spectroscopy, however, have reduced the power and weight required to measure methane at rates suitable for eddy-covariance flux estimates. The Flux Observations of Carbon from an Airborne Laboratory (FOCAL) takes advantage of Integrated Cavity-Output Spectroscopy (ICOS) to measure CH4, CO2, and water vapor in a new airborne system. The system, moreover, measures these gases' stable isotopologues every two seconds or faster helping to separate thermogenic from biogenic emissions. Paired with the Best Airborne Turbulence (BAT) probe developed for small aircraft by NOAA's Air Resources Laboratory and a light twin-engine aircraft adapted by Aurora Flight Sciences Inc., the FOCAL measures at 6 m spacing, covering 100 km in less than 30 minutes. It flies between 10 m and 50 m above ground interspersed with profiles to the top of the boundary layer and beyond. This presentation gives an overview of the magnitude and variation in fluxes and concentrations of CH4, CO2, and H2O with space, time, and time of day in a spatially extensive survey, more than 7500 km total in 15 flights over roughly a 100 km square during the month of August 2013. An extensive data set such as this at low altitude with high-rate sampling addresses features that repeat on 1 km scale

Biodiversity on the Rocks: Macrofauna Inhabiting Authigenic Carbonate at Costa Rica Methane Seeps

PubMed Central

Levin, Lisa A.; Mendoza, Guillermo F.; Grupe, Benjamin M.; Gonzalez, Jennifer P.; Jellison, Brittany; Rouse, Greg; Thurber, Andrew R.; Waren, Anders

2015-01-01

Carbonate communities: The activity of anaerobic methane oxidizing microbes facilitates precipitation of vast quantities of authigenic carbonate at methane seeps. Here we demonstrate the significant role of carbonate rocks in promoting diversity by providing unique habitat and food resources for macrofaunal assemblages at seeps on the Costa Rica margin (400–1850 m). The attendant fauna is surprisingly similar to that in rocky intertidal shores, with numerous grazing gastropods (limpets and snails) as dominant taxa. However, the community feeds upon seep-associated microbes. Macrofaunal density, composition, and diversity on carbonates vary as a function of seepage activity, biogenic habitat and location. The macrofaunal community of carbonates at non-seeping (inactive) sites is strongly related to the hydrography (depth, temperature, O2) of overlying water, whereas the fauna at sites of active seepage is not. Densities are highest on active rocks from tubeworm bushes and mussel beds, particularly at the Mound 12 location (1000 m). Species diversity is higher on rocks exposed to active seepage, with multiple species of gastropods and polychaetes dominant, while crustaceans, cnidarians, and ophiuroids were better represented on rocks at inactive sites. Macro-infauna (larger than 0.3 mm) from tube cores taken in nearby seep sediments at comparable depths exhibited densities similar to those on carbonate rocks, but had lower diversity and different taxonomic composition. Seep sediments had higher densities of ampharetid, dorvilleid, hesionid, cirratulid and lacydoniid polychaetes, whereas carbonates had more gastropods, as well as syllid, chrysopetalid and polynoid polychaetes. Stable isotope signatures and metrics: The stable isotope signatures of carbonates were heterogeneous, as were the food sources and nutrition used by the animals. Carbonate δ13Cinorg values (mean = -26.98‰) ranged from -53.3‰ to +10.0‰, and were significantly heavier than carbonate δ13

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Inhibition of methane consumption in forest soils by monoterpenes

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

Amaral, J.A.; Knowles, R.

1998-04-01

Selected monoterpenes were tested for their ability to inhibit atmospheric methane consumption by three forest soils from different vegetation types and by the cultured methanotrophic strain, Methylosinus trichosporium OB3b. Subsurface soil from coniferous (Pinus banksiana), deciduous (Populus tremuloides), and mixed hardwood (Tsuga canadensis and Prunus pensylvanica) stands was used under field-moist and slurry conditions. Most of the hydrocarbon monoterpenes tested significantly inhibited methane consumption by soils at environmentally relevant levels, with ({minus})-{alpha}-pinene being the most effective. With the exception of {beta}-myrcene, monoterpenes also strongly inhibited methane oxidation by Methylosinus trichosporium OB3b. Carbon dioxide production was stimulated in all of themore » soils by the monoterpenes tested. In one case, methane production was stimulated by ({minus})-{alpha}-pinene in an intact, aerobic core. Oxide and alcohol monoterpenoids stimulated methane production. Thus, monoterpenes appear to be potentially important regulators of methane consumption and carbon metabolism in forest soils.« less

A system to investigate the remediation of organic vapors using microwave-induced plasma with fluidized carbon granules

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

Dawson, Elizabeth A.; Parkes, Gareth M. B.; Bond, Gary

This article describes a system to investigate the parameters for the remediation of organic vapors using microwave-induced plasma on fluidized carbon granules. The system is based on a single mode microwave apparatus with a variable power (2.45 GHz) generator. Carbon granules are fluidized in a silica tube situated in the sample section of a waveguide incorporating two additional ports to allow plasma intensity monitoring using a light sensor and imaging with a digital camera. A fluoroptic probe is used for in situ measurement of the carbon granule temperature, while the effluent gas temperature is measured with a thermocouple situated inmore » the silica tube outside the cavity. Data acquisition and control software allow experiments using a variety of microwave power regimes while simultaneously recording the light intensity of any plasma generated within the carbon bed, together with its temperature. Evaluation using two different granular activated carbons and ethyl acetate, introduced as a vapor into the fluidizing air stream at a concentration of 1 ppm, yielded results which indicated that significant destruction of ethyl acetate, as monitored using a mass spectrometer, was achieved only with the carbon granules showing high plasma activity under pulsed microwave conditions. The system is therefore suitable for comparison of the relative microwave activities of various activated carbon granules and their performance in microwave remediation and regeneration.« less

Anaerobic Methane Oxidation in Soils - revealed using 13C-labelled methane tracers

NASA Astrophysics Data System (ADS)

Riekie, G. J.; Baggs, E. M.; Killham, K. S.; Smith, J. U.

2008-12-01

In marine sediments, anaerobic methane oxidation is a significant biogeochemical process limiting methane flux from ocean to atmosphere. To date, evidence for anaerobic methane oxidation in terrestrial environments has proved elusive, and its significance is uncertain. In this study, an isotope dilution method specifically designed to detect the process of anaerobic methane oxidation in methanogenic wetland soils is applied. Methane emissions of soils from three contrasting permanently waterlogged sites in Scotland are investigated in strictly anoxic microcosms to which 13C- labelled methane is added, and changes in the concentration and 12C/13C isotope ratios of methane and carbon dioxide are subsequently measured and used to calculate separate the separate components of the methane flux. The method used takes into account the 13C-methane associated with methanogenesis, and the amount of methane dissolved in the soil. The calculations make no prior assumptions about the kinetics of methane production or oxidation. The results indicate that methane oxidation can take place in anoxic soil environments. The clearest evidence for anaerobic methane oxidation is provided by soils from a minerotrophic fen site (pH 6.0) in Bin Forest underlain by ultra-basic and serpentine till. In the fresh soil anoxic microcosms, net consumption methane was observed, and the amount of headspace 13C-CO2 increased at a greater rate than the 12+13C-CO2, further proof of methane oxidation. A net increase in methane was measured in microcosms of soil from Murder Moss, an alkaline site, pH 6.5, with a strong calcareous influence. However, the 13C-CH4 data provided evidence of methane oxidation, both in the disappearance of C- CH4 and appearance of smaller quantities of 13C-CO2. The least alkaline (pH 5.5) microcosms, of Gateside Farm soil - a granitic till - exhibited net methanogenesis and the changes in 13C-CH4 and 13C-CO2 here followed the pattern expected if no methane is consumed

Methane eddy covariance flux measurements from a low flying aircraft: Bridging the scale gap between local and regional emissions estimates

NASA Astrophysics Data System (ADS)

Sayres, D. S.; Dobosy, R.; Dumas, E. J.; Kochendorfer, J.; Wilkerson, J.; Anderson, J. G.

2017-12-01

The Arctic contains a large reservoir of organic matter stored in permafrost and clathrates. Varying geology and hydrology across the Arctic, even on small scales, can cause large variability in surface carbon fluxes and partitioning between methane and carbon dioxide. This makes upscaling from point source measurements such as small flux towers or chambers difficult. Ground based measurements can yield high temporal resolution and detailed information about a specific location, but due to the inaccessibility of most of the Arctic to date have only made measurements at very few sites. In August 2013, a small aircraft, flying low over the surface (5-30 m), and carrying an air turbulence probe and spectroscopic instruments to measure methane, carbon dioxide, nitrous oxide, water vapor and their isotopologues, flew over the North Slope of Alaska. During the six flights multiple comparisons were made with a ground based Eddy Covariance tower as well as three region surveys flights of fluxes over three areas each approximately 2500 km2. We present analysis using the Flux Fragment Method and surface landscape classification maps to relate the fluxes to different surface land types. We show examples of how we use the aircraft data to upscale from a eddy covariance tower and map spatial variability across different ecotopes.

Impacts of updated spectroscopy on thermal infrared retrievals of methane evaluated with HIPPO data

NASA Astrophysics Data System (ADS)

Alvarado, M. J.; Payne, V. H.; Cady-Pereira, K. E.; Hegarty, J. D.; Kulawik, S. S.; Wecht, K. J.; Worden, J. R.; Pittman, J. V.; Wofsy, S. C.

2015-02-01

Errors in the spectroscopic parameters used in the forward radiative transfer model can introduce spatially, temporally, and altitude-dependent biases in trace gas retrievals. For well-mixed trace gases such as methane, where the variability of tropospheric mixing ratios is relatively small, reducing such biases is particularly important. We use aircraft observations from all five missions of the HIAPER Pole-to-Pole Observations (HIPPO) of the Carbon Cycle and Greenhouse Gases Study to evaluate the impact of updates to spectroscopic parameters for methane (CH4), water vapor (H2O), and nitrous oxide (N2O) on thermal infrared retrievals of methane from the NASA Aura Tropospheric Emission Spectrometer (TES). We find that updates to the spectroscopic parameters for CH4 result in a substantially smaller mean bias in the retrieved CH4 when compared with HIPPO observations. After an N2O-based correction, the bias in TES methane upper tropospheric representative values for measurements between 50° S and 50° N decreases from 56.9 to 25.7 ppbv, while the bias in the lower tropospheric representative value increases only slightly (from 27.3 to 28.4 ppbv). For retrievals with less than 1.6 degrees of freedom for signal (DOFS), the bias is reduced from 26.8 to 4.8 ppbv. We also find that updates to the spectroscopic parameters for N2O reduce the errors in the retrieved N2O profile.

Impacts of updated spectroscopy on thermal infrared retrievals of methane evaluated with HIPPO data

NASA Astrophysics Data System (ADS)

Alvarado, M. J.; Payne, V. H.; Cady-Pereira, K. E.; Hegarty, J. D.; Kulawik, S. S.; Wecht, K. J.; Worden, J. R.; Pittman, J. V.; Wofsy, S. C.

2014-09-01

Errors in the spectroscopic parameters used in the forward radiative transfer model can introduce altitude-, spatially-, and temporally-dependent biases in trace gas retrievals. For well-mixed trace gases such as methane, where the variability of tropospheric mixing ratios is relatively small, reducing such biases is particularly important. We use aircraft observations from all five missions of the HIAPER Pole-to-Pole Observations (HIPPO) of the Carbon Cycle and Greenhouse Gases Study to evaluate the impact of updates to spectroscopic parameters for methane (CH4), water vapor (H2O), and nitrous oxide (N2O) on thermal infrared retrievals of methane from the NASA Aura Tropospheric Emission Spectrometer (TES). We find that updates to the spectroscopic parameters for CH4 result in a substantially smaller mean bias in the retrieved CH4 when compared with HIPPO observations. After an N2O-based correction, the bias in TES methane upper tropospheric representative values for measurements between 50° S and 50° N decreases from 56.9 to 25.7 ppbv, while the bias in the lower tropospheric representative value increases only slightly (from 27.3 to 28.4 ppbv). For retrievals with less than 1.6 DOFS, the bias is reduced from 26.8 to 4.8 ppbv. We also find that updates to the spectroscopic parameters for N2O reduce the errors in the retrieved N2O profile.

Stable Isotope Measurements of Carbon Dioxide, Methane, and Hydrogen Sulfide Gas Using Frequency Modulation Spectroscopy

NASA Astrophysics Data System (ADS)

Nowak-Lovato, K.

2014-12-01

Seepage from enhanced oil recovery, carbon storage, and natural gas sites can emit trace gases such as carbon dioxide, methane, and hydrogen sulfide. Trace gas emission at these locations demonstrate unique light stable isotope signatures that provide information to enable source identification of the material. Light stable isotope detection through surface monitoring, offers the ability to distinguish between trace gases emitted from sources such as, biological (fertilizers and wastes), mineral (coal or seams), or liquid organic systems (oil and gas reservoirs). To make light stable isotope measurements, we employ the ultra-sensitive technique, frequency modulation spectroscopy (FMS). FMS is an absorption technique with sensitivity enhancements approximately 100-1000x more than standard absorption spectroscopy with the advantage of providing stable isotope signature information. We have developed an integrated in situ (point source) system that measures carbon dioxide, methane and hydrogen sulfide with isotopic resolution and enhanced sensitivity. The in situ instrument involves the continuous collection of air and records the stable isotope ratio for the gas being detected. We have included in-line flask collection points to obtain gas samples for validation of isotopic concentrations using our in-house isotope ratio mass spectroscopy (IRMS). We present calibration curves for each species addressed above to demonstrate the sensitivity and accuracy of the system. We also show field deployment data demonstrating the capabilities of the system in making live dynamic measurements from an active source.

Ethane's 12C/13C Ratio in Titan: Implications for Methane Replenishment

NASA Technical Reports Server (NTRS)

Jennings, Donald E.; Nixon, C. A.; Romani, P. N.; Bjoraker, G. L.; Sada, P. V.; Lunsford, A. W.; Boyle, R. J.; Hesman, B. E.; McCabe, G. H.

2009-01-01

As the .main destination of carbon in the destruction of methane in the atmosphere of Titan, ethane provides information about the carbon isotopic composition of the reservoir from which methane is replenished. If the amount of methane entering the atmosphere is presently equal to the amount converted to ethane, the 12C/13C ratio in ethane should be close to the ratio in the reservoir. We have measured the 12C/13C ratio in ethane both with Cassini CIRS(exp 1) and from the ground and find that it is very close to the telluric standard and outer planet values (89), consistent with a primordial origin for the methane reservoir. The lower 12C/13C ratio measured for methane by Huygens GCMS (82.3) can be explained if the conversion of CH4 to CH3 (and C2H6) favors 12C over 13C with a carbon kinetic isotope effect of 1.08. The time required for the atmospheric methane to reach equilibrium, i.e., for replenishment to equal destruction, is approximately 5 methane atmospheric lifetimes.

Effects of Environmental Conditions on an Urban Wetland's Methane Fluxes

NASA Astrophysics Data System (ADS)

Naor Azrieli, L.; Morin, T. H.; Bohrer, G.; Schafer, K. V.; Brooker, M.; Mitsch, W. J.

2013-12-01

Methane emissions from wetlands are the largest natural source of uncertainty in the global methane (CH4) budget. Wetlands are highly productive ecosystems with a large carbon sequestration potential. While wetlands are a net sink for carbon dioxide, they also release methane, a potent greenhouse gas. To effectively develop wetland management techniques, it is important to properly calculate the carbon budget of wetlands by understand the driving factors of methane fluxes. We constructed an eddy flux covariance system in the Olentangy River Wetland Research Park, a series of created and restored wetland in Columbus Ohio. Through the use of high frequency open path infrared gas analyzer (IRGA) sensors, we have continuously monitored the methane fluxes associated with the wetland since May 2011. To account for the heterogeneous landscape surrounding the tower, a footprint analysis was used to isolate data originating from within the wetland. Continuous measurements of the meteorological and environmental conditions at the wetlands coinciding with the flux measurements allow the interactions between methane fluxes and the climate and ecological forcing to be studied. The wintertime daily cycle of methane peaks around midday indicating a typical diurnal pattern in cold months. In the summer, the peak shifts to earlier in the day and also includes a daily peak occurring at approximately 10 AM. We believe this peak is associated with the onset of photosynthesis in Typha latifolia flushing methane from the plant's air filled tissue. Correlations with methane fluxes include latent heat flux, soil temperature, and incoming radiation. The connection to radiation may be further evidence of plant activity as a driver of methane fluxes. Higher methane fluxes corresponding with higher soil temperature indicates that warmer days stimulate the methanogenic consortium. Further analysis will focus on separating the methane fluxes into emissions from different terrain types within

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

Simultaneous infrared and UV-visible absorption spectra of matrix-isolated carbon vapor

NASA Technical Reports Server (NTRS)

Kurtz, Joe; Huffman, Donald R.

1989-01-01

Carbon molecules were suggested as possible carriers of the diffuse interstellar bands. In particular, it was proposed that the 443 nm diffuse interstellar band is due to the same molecule which gives rise to the 447 nm absorption feature in argon matrix-isolated carbon vapor. If so, then an associated C-C stretching mode should be seen in the IR. By doing spectroscopy in both the IR and UV-visible regions on the same sample, the present work provides evidence for correlating UV-visible absorption features with those found in the IR. Early data indicates no correlation between the strongest IR feature (1997/cm) and the 447 nm band. Correlation with weaker IR features is being investigated.

Methane Fingerprinting: Isotopic Methane and Ethane-to-Methane Ratio Analysis Using a Cavity Ring-Down Spectrometer

NASA Astrophysics Data System (ADS)

Saad, Nabil; Fleck, Derek; Hoffnagle, John

2016-04-01

Emissions of Natural gas, and methane (CH4) specifically, have come under increased scrutiny by virtue of methane's 28-36x greenhouse warming potential compared to carbon dioxide (CO2) while accounting for 10% of the total greenhouse gas emissions in the US. Large uncontrolled leaks, such as the recent Aliso Canyon leak, originating from uncapped wells, coal mines and storage facilities have increased the total global contribution of methane missions even further. Determining the specific fingerprint of methane sources, by quantifying δ13C values and C2:C1 ratios, provides the means to understand methane producing processes and allows for sources of methane to be mapped and classified through these processes; i.e. biogenic vs. thermogenic, wet vs dry. In this study we present a fully developed Cavity Ring-Down Spectrometer (CRDS) that precisely measures 12CH4 concentration and its 13CH4 isotope concentration, yielding δ13C measurements, C2H6 concentration, along with CO2 and H2O. This provides real-time continuous measurements without an upfront separation requirement or multiple analyses to derive the origin of the gas samples. The highly sensitive analyzer allows for measurements of scarce molecules down to sub-ppb 1-σ precision in 5 minutes of measurement: with CH4 <0.1ppb, δ13C <1‰ C2H6 <1ppb and CO2 <1ppm. To complement this work, we provide the analysis of different methane sources providing a 2-dimensional mapping of methane sources as functions of δ13C and C2:C1 ratios, which can be thought of as a modified Bernard Plot. This dual ratio mapping can be used to discriminate between naturally occurring biogenic methane sources, naturally occurring enriched thermogenic sources, and natural gas distribution sources. This also shows future promise in aiding gas and oil exploration, in distinguishing oil vs coal gases, as well as a valuable tool in the development of methane sequestration.

Methane release from the southern Brazilian margin during the last glacial.

PubMed

Portilho-Ramos, R C; Cruz, A P S; Barbosa, C F; Rathburn, A E; Mulitza, S; Venancio, I M; Schwenk, T; Rühlemann, C; Vidal, L; Chiessi, C M; Silveira, C S

2018-04-13

Seafloor methane release can significantly affect the global carbon cycle and climate. Appreciable quantities of methane are stored in continental margin sediments as shallow gas and hydrate deposits, and changes in pressure, temperature and/or bottom-currents can liberate significant amounts of this greenhouse gas. Understanding the spatial and temporal dynamics of marine methane deposits and their relationships to environmental change are critical for assessing past and future carbon cycle and climate change. Here we present foraminiferal stable carbon isotope and sediment mineralogy records suggesting for the first time that seafloor methane release occurred along the southern Brazilian margin during the last glacial period (40-20 cal ka BP). Our results show that shallow gas deposits on the southern Brazilian margin responded to glacial-interglacial paleoceanographic changes releasing methane due to the synergy of sea level lowstand, warmer bottom waters and vigorous bottom currents during the last glacial period. High sea level during the Holocene resulted in an upslope shift of the Brazil Current, cooling the bottom waters and reducing bottom current strength, reducing methane emissions from the southern Brazilian margin.

Net ecosystem methane and carbon dioxide exchanges in a Lake Erie coastal marsh and a nearby cropland

NASA Astrophysics Data System (ADS)

Chu, Housen; Chen, Jiquan; Gottgens, Johan F.; Ouyang, Zutao; John, Ranjeet; Czajkowski, Kevin; Becker, Richard

2014-05-01

Net ecosystem carbon dioxide (FCO2) and methane (FCH4) exchanges were measured by using the eddy covariance method to quantify the atmospheric carbon budget at a Typha- and Nymphaea-dominated freshwater marsh (March 2011 to March 2013) and a soybean cropland (May 2011 to May 2012) in northwestern Ohio, USA. Two year average annual FCH4 (49.7 g C-CH4 m-2 yr-1) from the marsh was high and compatible with its net annual CO2 uptake (FCO2: -21.0 g C-CO2 m-2 yr-1). In contrast, FCH4 was small (2.3 g C-CH4 m-2 yr-1) and accounted for a minor portion of the atmospheric carbon budget (FCO2: -151.8 g C-CO2 m-2 yr-1) at the cropland. At the seasonal scale, soil temperature associated with methane (CH4) production provided the dominant regulator of FCH4 at the marsh (R2 = 0.86). At the diurnal scale, plant-modulated gas flow was the major pathway for CH4 outgassing in the growing season at the marsh. Diffusion and ebullition became the major pathways in the nongrowing season and were regulated by friction velocity. Our findings highlight the importance of freshwater marshes for their efficiency in turning over and releasing newly fixed carbon as CH4. Despite marshes accounting for only 4% of area in the agriculture-dominated landscape, their high FCH4 should be carefully addressed in the regional carbon budget.

High spatial variability of carbon dioxide and methane emission in three tropical reservoirs

NASA Astrophysics Data System (ADS)

Reinaldo Paranaiba, José; Barros, Nathan O.; Mendonça, Raquel F.; Linkhorst, Annika; Isidorova, Anastasija; Roland, Fabio; Sobek, Sebastian

2017-04-01

In the tropics, many new large hydropower dams are being built, in order to produce renewable energy for economic growth. Most inland waters, such as rivers, lakes and reservoirs, emit greenhouse gases to the atmosphere, and especially tropical reservoirs have been pointed out as strong sources of methane. However, present estimates of greenhouse gas emission from reservoirs are limited by the amount of available data. In particular, the spatial variability of greenhouse gas emission from reservoirs is insufficiently understood. In order to test the hypothesis that the diffusive emission of carbon dioxide (CO2) and methane (CH4) from tropical reservoirs is characterized by strong spatial variability and incorrectly represented by measurements at one site only, we studied three reservoirs situated in different tropical climates, during the dry period. We conducted spatially resolved measurements of surface water concentrations of dissolved carbon dioxide and methane using an on-line equilibration system, as well as of the gas exchange velocity using floating chambers. We found pronounced spatial variability of diffusive CO2 and CH4 emission in all three reservoirs. River inflow areas were more likely to have high concentrations of particularly CH4, but also CO2, than other areas in the reservoirs. Close to the dam, CH4 concentrations were comparatively low in each reservoir. The variability of CH4 concentration was linked to geographical position, which we ascribe to hot spots of methanogenesis at sites of high sediment deposition, such as river inflow areas. The variability of CO2 concentration seemed instead rather to be linked to in-situ metabolism. Also the gas exchange velocity varied pronouncedly in each reservoir, but without any detectable systematic patterns, calling for further studies. We conclude that accurate upscaling of reservoir greenhouse gas emissions requires accounting for within-reservoir spatial variability, and that the anthropogenic increase

The effect of vapor polarity and boiling point on breakthrough for binary mixtures on respirator carbon.

PubMed

Robbins, C A; Breysse, P N

1996-08-01

This research evaluated the effect of the polarity of a second vapor on the adsorption of a polar and a nonpolar vapor using the Wheeler model. To examine the effect of polarity, it was also necessary to observe the effect of component boiling point. The 1% breakthrough time (1% tb), kinetic adsorption capacity (W(e)), and rate constant (kv) of the Wheeler model were determined for vapor challenges on carbon beds for both p-xylene and pyrrole (referred to as test vapors) individually, and in equimolar binary mixtures with the polar and nonpolar vapors toluene, p-fluorotoluene, o-dichlorobenzene, and p-dichlorobenzene (referred to as probe vapors). Probe vapor polarity (0 to 2.5 Debye) did not systematically alter the 1% tb, W(e), or kv of the test vapors. The 1% tb and W(e) for test vapors in binary mixtures can be estimated reasonably well, using the Wheeler model, from single-vapor data (1% tb +/- 30%, W(e) +/- 20%). The test vapor 1% tb depended mainly on total vapor concentration in both single and binary systems. W(e) was proportional to test vapor fractional molar concentration (mole fraction) in mixtures. The kv for p-xylene was significantly different (p < or = 0.001) when compared according to probe boiling point; however, these differences were apparently of limited importance in estimating 1% tb for the range of boiling points tested (111 to 180 degrees C). Although the polarity and boiling point of chemicals in the range tested are not practically important in predicting 1% tb with the Wheeler model, an effect due to probe boiling point is suggested, and tests with chemicals of more widely ranging boiling point are warranted. Since the 1% tb, and thus, respirator service life, depends mainly on total vapor concentration, these data underscore the importance of taking into account the presence of other vapors when estimating respirator service life for a vapor in a mixture.

The exposure history of the Apollo 16 site: An assessment based on methane and hydrolysable carbon

NASA Technical Reports Server (NTRS)

Pillinger, C. T.; Eglinton, G.; Gowar, A. P.; Jull, A. J. T.; Maxwell, J. R.

1977-01-01

Nineteen soils from eight stations at the Apollo 16 landing site have been analyzed for methane and hydrolysable carbon. These results, in conjunction with published data from photogeology, bulk chemistry, rare gases, primordial and cosmogenic radionuclides, and agglutinate abundances have been interpreted in terms of differing contributions from three components-North and South Ray Crater ejecta and Cayley Plains material.

Relation of Hydrogen and Methane to Carbon Monoxide in Exhaust Gases from Internal-Combustion Engines

NASA Technical Reports Server (NTRS)

Gerrish, Harold C; Tessmann, Arthur M

1935-01-01

The relation of hydrogen and methane to carbon monoxide in the exhaust gases from internal-combustion engines operating on standard-grade aviation gasoline, fighting-grade aviation gasoline, hydrogenated safety fuel, laboratory diesel fuel, and auto diesel fuel was determined by analysis of the exhaust gases. Two liquid-cooled single-cylinder spark-ignition, one 9-cylinder radial air-cooled spark-ignition, and two liquid-cooled single-cylinder compression-ignition engines were used.

A flow-system comparison of the reactivities of calcium superoxide and potassium superoxide with carbon dioxide and water vapor

NASA Technical Reports Server (NTRS)

Wood, P. C.; Ballou, E. V.; Spitze, L. A.; Wydeven, T.

1982-01-01

A single pass flow system was used to test the reactivity of calcium superoxide with respiratory gases and the performance was compared to that of potassium superoxide. The KO2 system is used by coal miners as a self-contained unit in rescue operations. Particular attention was given to the reactivity with carbon dioxide and water vapor at different temperatures and partial pressures of oxygen, carbon dioxide, and water vapor. The calcium superoxide beds were found to absorb CO2 and H2O vapor, releasing O2. The KO2 bed, however, released O2 at twice the rate of CO2 absorption at 37 C. It is concluded that the calcium superoxide material is not a suitable replacement for the KO2 bed, although Ca(O2)2 may be added to the KO2 bed to enhance the CO2 absorption.

Microbial methane in the shallow Paleozoic sediments and glacial deposits of Illinois, U.S.A.

USGS Publications Warehouse

Coleman, D.D.; Liu, Chao-Li; Riley, K.M.

1988-01-01

Methane formed by the microbial decomposition of buried organic matter is virtually ubiquitous in the groundwaters of Illinois. Chemical and carbon isotopic compositions are reported for gas samples collected from over 200 private and municipal water wells and from 39 small gas wells completed in glacial deposits (drift-gas wells). Carbon and hydrogen isotopic data for methane, carbon dioxide and water show that these gases were formed by the carbon dioxide reduction pathway, the same mechanism which has been previously shown to be responsible for microbial methane formation in the marine environment. The isotopic composition of methane in these samples can be closely correlated with the chemical composition of the gas and with water chemistry. The data are interpreted as indicating that isotopically very light methane is found in waters where the residence time of groundwater in the methanogenesis zone was very short relative to the methane production rate. ?? 1988.

Producing Hydrogen by Plasma Pyrolysis of Methane

NASA Technical Reports Server (NTRS)

Atwater, James; Akse, James; Wheeler, Richard

2010-01-01

Plasma pyrolysis of methane has been investigated for utility as a process for producing hydrogen. This process was conceived as a means of recovering hydrogen from methane produced as a byproduct of operation of a life-support system aboard a spacecraft. On Earth, this process, when fully developed, could be a means of producing hydrogen (for use as a fuel) from methane in natural gas. The most closely related prior competing process - catalytic pyrolysis of methane - has several disadvantages: a) The reactor used in the process is highly susceptible to fouling and deactivation of the catalyst by carbon deposits, necessitating frequent regeneration or replacement of the catalyst. b) The reactor is highly susceptible to plugging by deposition of carbon within fixed beds, with consequent channeling of flow, high pressure drops, and severe limitations on mass transfer, all contributing to reductions in reactor efficiency. c) Reaction rates are intrinsically low. d) The energy demand of the process is high.

The regulation of methane oxidation in soil

NASA Technical Reports Server (NTRS)

Mancinelli, R. L.

1995-01-01

The atmospheric concentration of methane, a greenhouse gas, has more than doubled during the past 200 years. Consequently, identifying the factors influencing the flux of methane into the atmosphere is becoming increasingly important. Methanotrophs, microaerophilic organisms widespread in aerobic soils and sediments, oxidize methane to derive energy and carbon for biomass. In so doing, they play an important role in mitigating the flux of methane into the atmosphere. Several physico-chemical factors influence rates of methane oxidation in soil, including soil diffusivity; water potential; and levels of oxygen, methane, ammonium, nitrate, nitrite, and copper. Most of these factors exert their influence through interactions with methane monooxygenase (MMO), the enzyme that catalyzes the reaction converting methane to methanol, the first step in methane oxidation. Although biological factors such as competition and predation undoubtedly play a role in regulating the methanotroph population in soils, and thereby limit the amount of methane consumed by methanotrophs, the significance of these factors is unknown. Obtaining a better understanding of the ecology of methanotrophs will help elucidate the mechanisms that regulate soil methane oxidation.

Simultaneous atmospheric nitrous oxide, methane and water vapor detection with a single continuous wave quantum cascade laser.

PubMed

Cao, Yingchun; Sanchez, Nancy P; Jiang, Wenzhe; Griffin, Robert J; Xie, Feng; Hughes, Lawrence C; Zah, Chung-en; Tittel, Frank K

2015-02-09

A continuous wave (CW) quantum cascade laser (QCL) based absorption sensor system was demonstrated and developed for simultaneous detection of atmospheric nitrous oxide (N(2)O), methane (CH(4)), and water vapor (H(2)O). A 7.73-µm CW QCL with its wavelength scanned over a spectral range of 1296.9-1297.6 cm(-1) was used to simultaneously target three neighboring strong absorption lines, N(2)O at 1297.05 cm(-1), CH(4) at 1297.486 cm(-1), and H(2)O at 1297.184 cm(-1). An astigmatic multipass Herriott cell with a 76-m path length was utilized for laser based gas absorption spectroscopy at an optimum pressure of 100 Torr. Wavelength modulation and second harmonic detection was employed for data processing. Minimum detection limits (MDLs) of 1.7 ppb for N(2)O, 8.5 ppb for CH(4), and 11 ppm for H(2)O were achieved with a 2-s integration time for individual gas detection. This single QCL based multi-gas detection system possesses applications in environmental monitoring and breath analysis.

Methane production and isotopic fingerprinting in ethanol fuel contaminated sites.

PubMed

Freitas, Juliana G; Fletcher, Barbara; Aravena, Ramon; Barker, James F

2010-01-01

Biodegradation of organic compounds in groundwater can be a significant source of methane in contaminated sites. Methane might accumulate in indoor spaces posing a hazard. The increasing use of ethanol as a gasoline additive is a concern with respect to methane production since it is easily biodegraded and has a high oxygen demand, favoring the development of anaerobic conditions. This study evaluated the use of stable carbon isotopes to distinguish the methane origin between gasoline and ethanol biodegradation, and assessed the occurrence of methane in ethanol fuel contaminated sites. Two microcosm tests were performed under anaerobic conditions: one test using ethanol and the other using toluene as the sole carbon source. The isotopic tool was then applied to seven field sites known to be impacted by ethanol fuels. In the microcosm tests, it was verified that methane from ethanol (δ¹³C = -11.1‰) is more enriched in ¹³C, with δ¹³C values ranging from -20‰ to -30‰, while the methane from toluene (δ¹³C = -28.5‰) had a carbon isotopic signature of -55‰. The field samples had δ¹³C values varying over a wide range (-10‰ to -80‰), and the δ¹³C values allowed the methane source to be clearly identified in five of the seven ethanol/gasoline sites. In the other two sites, methane appears to have been produced from both sources. Both gasoline and ethanol were sources of methane in potentially hazardous concentrations and methane could be produced from organic acids originating from ethanol along the groundwater flow system even after all the ethanol has been completed biodegraded. Copyright © 2010 The Author(s). Journal compilation © 2010 National Ground Water Association.

Understanding the Phase Behavior of Tetrahydrofuran + Carbon Dioxide, + Methane, and + Water Binary Mixtures from the SAFT-VR Approach.

PubMed

Míguez, J M; Piñeiro, M M; Algaba, J; Mendiboure, B; Torré, J P; Blas, F J

2015-11-05

The high-pressure phase diagrams of the tetrahydrofuran(1) + carbon dioxide(2), + methane(2), and + water(2) mixtures are examined using the SAFT-VR approach. Carbon dioxide molecule is modeled as two spherical segments tangentially bonded, water is modeled as a spherical segment with four associating sites to represent the hydrogen bonding, methane is represented as an isolated sphere, and tetrahydrofuran is represented as a chain of m tangentially bonded spherical segments. Dispersive interactions are modeled using the square-well intermolecular potential. In addition, two different molecular model mixtures are developed to take into account the subtle balance between water-tetrahydrofuran hydrogen-bonding interactions. The polar and quadrupolar interactions present in water, tetrahydrofuran, and carbon dioxide are treated in an effective way via square-well potentials of variable range. The optimized intermolecular parameters are taken from the works of Giner et al. (Fluid Phase Equil. 2007, 255, 200), Galindo and Blas (J. Phys. Chem. B 2002, 106, 4503), Patel et al. (Ind. Eng. Chem. Res. 2003, 42, 3809), and Clark et al. (Mol. Phys. 2006, 104, 3561) for tetrahydrofuran, carbon dioxide, methane, and water, respectively. The phase diagrams of the binary mixtures exhibit different types of phase behavior according to the classification of van Konynenburg and Scott, ranging from types I, III, and VI phase behavior for the tetrahydrofuran(1) + carbon dioxide(2), + methane(2), and + water(2) binary mixtures, respectively. This last type is characterized by the presence of a Bancroft point, positive azeotropy, and the so-called closed-loop curves that represent regions of liquid-liquid immiscibility in the phase diagram. The system exhibits lower critical solution temperatures (LCSTs), which denote the lower limit of immiscibility together with upper critical solution temperatures (UCSTs). This behavior is explained in terms of competition between the incompatibility

Clay enhancement of methane, low molecular weight hydrocarbon and halocarbon conversion by methanotrophic bacteria

DOEpatents

Apel, William A.; Dugan, Patrick R.

1995-01-01

An apparatus and method for increasing the rate of oxidation of toxic vapors by methanotrophic bacteria. The toxic vapors of interest are methane and trichloroethylene. The apparatus includes a gas phase bioreactor within a closed loop pumping system or a single pass system. The methanotrophic bacteria include Methylomonas methanica, Methylosinus trichosporium, and uncharacterized environmental enrichments.

Clay enhancement of methane, low molecular weight hydrocarbon and halocarbon conversion by methanotrophic bacteria

DOEpatents

Apel, William A.; Dugan, Patrick R.

1995-04-04

An apparatus and method for increasing the rate of oxidation of toxic vapors by methanotrophic bacteria. The toxic vapors of interest are methane and trichloroethylene. The apparatus includes a gas phase bioreactor within a closed loop pumping system or a single pass system. The methanotrophic bacteria include Methylomonas methanica, Methylosinus trichosporium, and uncharacterized environmental enrichments.

Limited contribution of ancient methane to surface waters of the U.S. Beaufort Sea shelf

PubMed Central

Sparrow, Katy J.; Kessler, John D.; Southon, John R.; Garcia-Tigreros, Fenix; Schreiner, Kathryn M.; Ruppel, Carolyn D.; Miller, John B.; Lehman, Scott J.; Xu, Xiaomei

2018-01-01

In response to warming climate, methane can be released to Arctic Ocean sediment and waters from thawing subsea permafrost and decomposing methane hydrates. However, it is unknown whether methane derived from this sediment storehouse of frozen ancient carbon reaches the atmosphere. We quantified the fraction of methane derived from ancient sources in shelf waters of the U.S. Beaufort Sea, a region that has both permafrost and methane hydrates and is experiencing significant warming. Although the radiocarbon-methane analyses indicate that ancient carbon is being mobilized and emitted as methane into shelf bottom waters, surprisingly, we find that methane in surface waters is principally derived from modern-aged carbon. We report that at and beyond approximately the 30-m isobath, ancient sources that dominate in deep waters contribute, at most, 10 ± 3% of the surface water methane. These results suggest that even if there is a heightened liberation of ancient carbon–sourced methane as climate change proceeds, oceanic oxidation and dispersion processes can strongly limit its emission to the atmosphere. PMID:29349299

Limited contribution of ancient methane to surface waters of the U.S. Beaufort Sea shelf

USGS Publications Warehouse

Sparrow, Katy J.; Kessler, John D.; Southon, John R.; Garcia-Tigreros, Fenix; Schreiner, Kathryn M.; Ruppel, Carolyn D.; Miller, John B.; Lehman, Scott J.; Xu, Xiaomei

2018-01-01

In response to warming climate, methane can be released to Arctic Ocean sediment and waters from thawing subsea permafrost and decomposing methane hydrates. However, it is unknown whether methane derived from this sediment storehouse of frozen ancient carbon reaches the atmosphere. We quantified the fraction of methane derived from ancient sources in shelf waters of the U.S. Beaufort Sea, a region that has both permafrost and methane hydrates and is experiencing significant warming. Although the radiocarbon-methane analyses indicate that ancient carbon is being mobilized and emitted as methane into shelf bottom waters, surprisingly, we find that methane in surface waters is principally derived from modern-aged carbon. We report that at and beyond approximately the 30-m isobath, ancient sources that dominate in deep waters contribute, at most, 10 ± 3% of the surface water methane. These results suggest that even if there is a heightened liberation of ancient carbon–sourced methane as climate change proceeds, oceanic oxidation and dispersion processes can strongly limit its emission to the atmosphere.

Pathways and regulation of carbon, sulfur and energy transfer in marine sediments overlying methane gas hydrates on the Opouawe Bank (New Zealand)

NASA Astrophysics Data System (ADS)

Dale, A. W.; Sommer, S.; Haeckel, M.; Wallmann, K.; Linke, P.; Wegener, G.; Pfannkuche, O.

2010-10-01

This study combines sediment geochemical analysis, in situ benthic lander deployments and numerical modeling to quantify the biogeochemical cycles of carbon and sulfur and the associated rates of Gibbs energy production at a novel methane seep. The benthic ecosystem is dominated by a dense population of tube-building ampharetid polychaetes and conspicuous microbial mats were unusually absent. A 1D numerical reaction-transport model, which allows for the explicit growth of sulfide and methane oxidizing microorganisms, was tuned to the geochemical data using a fluid advection velocity of 14 cm yr -1. The fluids provide a deep source of dissolved hydrogen sulfide and methane to the sediment with fluxes equal to 4.1 and 18.2 mmol m -2 d -1, respectively. Chemosynthetic biomass production in the subsurface sediment is estimated to be 2.8 mmol m -2 d -1 of C biomass. However, carbon and oxygen budgets indicate that chemosynthetic organisms living directly above or on the surface sediment have the potential to produce 12.3 mmol m -2 d -1 of C biomass. This autochthonous carbon source meets the ampharetid respiratory carbon demand of 23.2 mmol m -2 d -1 to within a factor of 2. By contrast, the contribution of photosynthetically-fixed carbon sources to ampharetid nutrition is minor (3.3 mmol m -2 d -1 of C). The data strongly suggest that mixing of labile autochthonous microbial detritus below the oxic layer sustains high measured rates of sulfate reduction in the uppermost 2 cm of the sulfidic sediment (100-200 nmol cm -3 d -1). Similar rates have been reported in the literature for other seeps, from which we conclude that autochthonous organic matter is an important substrate for sulfate reducing bacteria in these sediment layers. A system-scale energy budget based on the chemosynthetic reaction pathways reveals that up to 8.3 kJ m -2 d -1 or 96 mW m -2 of catabolic (Gibbs) energy is dissipated at the seep through oxidation reactions. The microorganisms mediating sulfide

The interaction of climate change and methane hydrates

USGS Publications Warehouse

Ruppel, Carolyn D.; Kessler, John D.

2017-01-01

Gas hydrate, a frozen, naturally-occurring, and highly-concentrated form of methane, sequesters significant carbon in the global system and is stable only over a range of low-temperature and moderate-pressure conditions. Gas hydrate is widespread in the sediments of marine continental margins and permafrost areas, locations where ocean and atmospheric warming may perturb the hydrate stability field and lead to release of the sequestered methane into the overlying sediments and soils. Methane and methane-derived carbon that escape from sediments and soils and reach the atmosphere could exacerbate greenhouse warming. The synergy between warming climate and gas hydrate dissociation feeds a popular perception that global warming could drive catastrophic methane releases from the contemporary gas hydrate reservoir. Appropriate evaluation of the two sides of the climate-methane hydrate synergy requires assessing direct and indirect observational data related to gas hydrate dissociation phenomena and numerical models that track the interaction of gas hydrates/methane with the ocean and/or atmosphere. Methane hydrate is likely undergoing dissociation now on global upper continental slopes and on continental shelves that ring the Arctic Ocean. Many factors—the depth of the gas hydrates in sediments, strong sediment and water column sinks, and the inability of bubbles emitted at the seafloor to deliver methane to the sea-air interface in most cases—mitigate the impact of gas hydrate dissociation on atmospheric greenhouse gas concentrations though. There is no conclusive proof that hydrate-derived methane is reaching the atmosphere now, but more observational data and improved numerical models will better characterize the climate-hydrate synergy in the future.

The interaction of climate change and methane hydrates

NASA Astrophysics Data System (ADS)

Ruppel, Carolyn D.; Kessler, John D.

2017-03-01

Gas hydrate, a frozen, naturally-occurring, and highly-concentrated form of methane, sequesters significant carbon in the global system and is stable only over a range of low-temperature and moderate-pressure conditions. Gas hydrate is widespread in the sediments of marine continental margins and permafrost areas, locations where ocean and atmospheric warming may perturb the hydrate stability field and lead to release of the sequestered methane into the overlying sediments and soils. Methane and methane-derived carbon that escape from sediments and soils and reach the atmosphere could exacerbate greenhouse warming. The synergy between warming climate and gas hydrate dissociation feeds a popular perception that global warming could drive catastrophic methane releases from the contemporary gas hydrate reservoir. Appropriate evaluation of the two sides of the climate-methane hydrate synergy requires assessing direct and indirect observational data related to gas hydrate dissociation phenomena and numerical models that track the interaction of gas hydrates/methane with the ocean and/or atmosphere. Methane hydrate is likely undergoing dissociation now on global upper continental slopes and on continental shelves that ring the Arctic Ocean. Many factors—the depth of the gas hydrates in sediments, strong sediment and water column sinks, and the inability of bubbles emitted at the seafloor to deliver methane to the sea-air interface in most cases—mitigate the impact of gas hydrate dissociation on atmospheric greenhouse gas concentrations though. There is no conclusive proof that hydrate-derived methane is reaching the atmosphere now, but more observational data and improved numerical models will better characterize the climate-hydrate synergy in the future.

A Compact, Low Resource Instrument to Measure Atmospheric Methane and Carbon Dioxide From Orbit

NASA Astrophysics Data System (ADS)

Rafkin, Scot; Davis, Michael; Varner, Ruth; Basu, Sourish; Bruhwiler, Lori; Luspay-Kuti, Adrienn; Mandt, Kathy; Roming, Pete; Soto, Alejandro; Tapley, Mark

2017-04-01

Methane is the second most important radiatively active trace gas forcing anthropogenic climate change. Methane has ˜28 times more warming potential than carbon dioxide on a 100-year time horizon, and the background atmospheric concentration of methane has increased by more than 150% compared to pre-industrial levels. The increase in methane abundance is driven by a combination of direct human activity, such as fossil fuel extraction and agriculture, and natural feedback processes that respond to human-induced climate change, such as increased wetland production. Accurate accounting of the exchange between the atmosphere and the natural and anthropogenic methane reservoirs is necessary to predict how methane concentration will increase going forward, how that increase will modulate the natural methane cycle, and how effective policy decisions might be at mitigating methane-induced climate change. Monitoring and quantifying methane source intensity and spatial-temporal variability has proven challenging; there are unresolved and scientifically significant discrepancies between flux estimates based on limited surface measurements (the so-called "bottom-up" method) and the values derived from limited, remotely-sensed estimates from orbit and modeling (the so-called "top-down" method). A major source of the discrepancy between bottom-up and top-down estimates is likely a result of insufficient accuracy and resolution of space-based instrumentation. Methane releases, especially anthropogenic sources, are often at kilometer-scale (or less), whereas past remote sensing instruments have at least an order of magnitude greater footprint areas. Natural sources may be larger in areal extent, but the enhancement over background levels can be just a few percent, which demands high spectral resolution and signal-to-noise ratios from monitoring instrumentation. In response to the need for higher performance space-based methane monitoring, we have developed a novel, compact, low

From Fundamental Understanding To Predicting New Nanomaterials For High Capacity Hydrogen/Methane Storage and Carbon Capture

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

Yildirim, Taner

2015-03-03

On-board hydrogen/methane storage in fuel cell-powered vehicles is a major component of the national need to achieve energy independence and protect the environment. The main obstacles in hydrogen storage are slow kinetics, poor reversibility and high dehydrogenation temperatures for the chemical hydrides; and very low desorption temperatures/energies for the physisorption materials (MOF’s, porous carbons). Similarly, the current methane storage technologies are mainly based on physisorption in porous materials but the gravimetric and volumetric storage capacities are below the target values. Finally, carbon capture, a critical component of the mitigation of CO2 emissions from industrial plants, also suffers from similar problems.more » The solid-absorbers such as MOFs are either not stable against real flue-gas conditions and/or do not have large enough CO2 capture capacity to be practical and cost effective. In this project, we addressed these challenges using a unique combination of computational, synthetic and experimental methods. The main scope of our research was to achieve fundamental understanding of the chemical and structural interactions governing the storage and release of hydrogen/methane and carbon capture in a wide spectrum of candidate materials. We studied the effect of scaffolding and doping of the candidate materials on their storage and dynamics properties. We reviewed current progress, challenges and prospect in closely related fields of hydrogen/methane storage and carbon capture.[1-5] For example, for physisorption based storage materials, we show that tap-densities or simply pressing MOFs into pellet forms reduce the uptake capacities by half and therefore packing MOFs is one of the most important challenges going forward. For room temperature hydrogen storage application of MOFs, we argue that MOFs are the most promising scaffold materials for Ammonia-Borane (AB) because of their unique interior active metal-centers for AB binding and

Alloy catalysts with monolith supports for methanation of coal-derived gases. Quarterly technical progress report, September 21-December 20, 1979

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

Bartholomew, C.H.

1980-01-05

Tests for catalyst deactivation by carbon deposition in a Berty reactor showed that CO partial pressure exerted a greater influence on deactivation than H/sub 2/ partial pressure. In kinetic studies in which H/sub 2/O vapor was added to the reactant gases, H/sub 2/O was found to inhibit the methanation reaction. H/sub 2/O inhibition was found to increase with temperature and loss of activity was observed at H/sub 2/O/CO ratios greater than one. The order of methanation with respect to H/sub 2/ and CO varies over the range of temperature from 498 to 598/sup 0/K. Rate data indicate a change inmore » mechanism or rate determining step at higher temperatures. Our experience with a quartz CFSTR has shown that this reactor is very delicate and needs near constant attention to maintain proper working order.« less

The future of methane

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

Howell, D.G.

1995-12-31

Natural gas, mainly methane, produces lower CO{sub 2}, CO, NO{sub x}, SO{sub 2} and particulate emissions than either oil or coal; thus further substitutions of methane for these fuels could help mitigate air pollution. Methane is, however, a potent greenhouse gas and the domestication of ruminants, cultivation of rice, mining of coal, drilling for oil, and transportation of natural gas have all contributed to a doubling of the amount of atmospheric methane since 1800. Today nearly 300,000 wells yearly produce ca. 21 trillion cubic feet of methane. Known reserves suggest about a 10 year supply at the above rates ofmore » recovery; and the potential for undiscovered resources is obscured by uncertainty involving price, new technologies, and environmental restrictions steming from the need to drill an enormous number of wells, many in ecologically sensitive areas. Until all these aspects of methane are better understood, its future role in the world`s energy mix will remain uncertain. The atomic simplicity of methane, composed of one carbon and four hydrogen atoms, may mask the complexity and importance of this, the most basic of organic molecules. Within the Earth, methane is produced through thermochemical alteration of organic materials, and by biochemical reactions mediated by metabolic processes of archaebacteria; some methane may even be primordial, a residue of planetary accretion. Methane also occurs in smaller volumes in landfills, rice paddies, termite complexes, ruminants, and even many humans. As an energy source, its full energy potential is controversial. Methane is touted by some as a viable bridge to future energy systems, fueled by the sun and uranium and carried by electricity and hydrogen.« less

Modeling the formation of methane hydrate-bearing intervals in fine-grained sediments

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

Malinverno, Alberto; Cook, Ann; Daigle, Hugh

Sediment grain size exerts a fundamental control on how methane hydrates are distributed within the pore space. Fine-grained muds are the predominant sediments in continental margins, and hydrates in these sediments have often been observed in semi-vertical veins and fractures. In several instances, these hydrate veins/fractures are found in discrete depth intervals a few tens meters thick within the gas hydrate stability zone (GHSZ) surrounded by hydrate-free sediments above and below. As they are not obviously connected with free gas occurring beneath the base of the GHSZ, these isolated hydrate-bearing intervals have been interpreted as formed by microbial methane generatedmore » in situ. To investigate further the formation of these hydrate deposits, we applied a time-dependent advection-diffusion-reaction model that includes the effects of sedimentation, solute diffusion, and microbial methane generation. The microbial methane generation term depends on the amount of metabolizable organic carbon deposited at the seafloor, which is degraded at a prescribed rate resulting in methane formation beneath the sulfate reduction zone. In the model, methane hydrate precipitates once the dissolved methane concentration is greater than solubility, or hydrate dissolves if concentration goes below solubility. If the deposition of organic carbon at the seafloor is kept constant in time, we found that the predicted amounts of hydrate formed in discrete intervals within the GHSZ are much less than those estimated from observations. We then investigated the effect of temporal variations in the deposition of organic carbon. If greater amounts of organic carbon are deposited during some time interval, methane generation is enhanced during burial in the corresponding sediment interval. With variations in organic carbon deposition that are consistent with observations in continental margin sediments, we were able to reproduce the methane hydrate contents estimated in discrete

Solar Spectrum Photocatalytic Conversion of CO2 and Water Vapor Into Hydrocarbons Using TiO2 Nanoparticle Membranes

NASA Astrophysics Data System (ADS)

Rani, Sanju; Bao, Ningzhong; Roy, Somnath C.

2014-01-01

A viable option for recycling carbon dioxide is through the sunlight-powered photocatalytic conversion of CO2 and water vapor into hydrocarbon fuels over highly active nanocatalysts. With photocatalytic CO2 reduction sunlight, a renewable energy source as durable as the sun, is used to drive the catalytic reaction with the resultant fuel products compatible with the current hydrocarbon-based energy infrastructure. The use of co-catalyst (Cu, Pt)-sensitized TiO2 nanoparticle wafers in the photocatalytic conversion of CO2 and water vapor to hydrocarbon fuels, with optimal humidity levels and exposure times established. We also attempted to increase product formation by sputtering both co-catalysts on the nanoparticle wafer's surface, with the resulting product rates significantly higher than that of either the Cu or Pt coated samples. When the TiO2 nanoparticle wafers are used in a flow-through membrane implementation we find a significant increase in product rates of formation, including methane, hydrogen, and carbon monoxide. We believe that nanocatalyst-based flow-through membranes are a viable route for achieving large-scale and low cost photocatalytic solar fuel production.

Vapor deposition of hardened niobium

DOEpatents

Blocher, Jr., John M.; Veigel, Neil D.; Landrigan, Richard B.

1983-04-19

A method of coating ceramic nuclear fuel particles containing a major amount of an actinide ceramic in which the particles are placed in a fluidized bed maintained at ca. 800.degree. to ca. 900.degree. C., and niobium pentachloride vapor and carbon tetrachloride vapor are led into the bed, whereby niobium metal is deposited on the particles and carbon is deposited interstitially within the niobium. Coating apparatus used in the method is also disclosed.

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.

Interannual Variability of Carbon Dioxide, Methane and Nitrous Oxide Fluxes in Subarctic European Russian Tundra

NASA Astrophysics Data System (ADS)

Marushchak, M. E.; Voigt, C.; Gil, J.; Lamprecht, R. E.; Trubnikova, T.; Virtanen, T.; Kaverin, D.; Martikainen, P. J.; Biasi, C.

2017-12-01

Southern tundra landscapes are particularly vulnerable to climate warming, permafrost thaw and associated landscape rearrangement due to near-zero permafrost temperatures. The large soil C and N stocks of subarctic tundra may create a positive feedback for warming if released to the atmosphere at increased rates. Subarctic tundra in European Russia is a mosaic of land cover types, which all play different roles in the regional greenhouse gas budget. Peat plateaus - massive upheaved permafrost peatlands - are large storehouses of soil carbon and nitrogen, but include also bare peat surfaces that act as hot-spots for both carbon dioxide and nitrous oxide emissions. Tundra wetlands are important for the regional greenhouse gas balance since they show high rates of methane emissions and carbon uptake. The most dominant land-form is upland tundra vegetated by shrubs, lichens and mosses, which displays a close-to-neutral balance with respect to all three greenhouse gases. The study site Seida (67°03'N, 62°56'E), located in the discontinuous permafrost zone of Northeast European Russia, incorporates all these land forms and has been an object for greenhouse gas investigations since 2007. Here, we summarize the growing season fluxes of carbon dioxide, methane and nitrous oxide measured by chamber techniques over the study years. We analyzed the flux time-series together with the local environmental data in order to understand the drivers of interannual variability. Detailed soil profile measurements of greenhouse gas concentrations, soil moisture and temperature provide insights into soil processes underlying the net emissions to the atmosphere. The multiannual time-series allows us to assess the importance of the different greenhouse gases and landforms to the overall climate forcing of the study region.

Cyclic process for producing methane with catalyst regeneration

DOEpatents

Frost, Albert C.; Risch, Alan P.

1980-01-01

Carbon monoxide-containing gas streams are passed over a catalyst capable of catalyzing the disproportionation of carbon monoxide so as to deposit a surface layer of active surface carbon on the catalyst essentially without formation of inactive coke thereon. The surface layer is contacted with steam and is thus converted to methane and CO.sub.2, from which a relatively pure methane product may be obtained. For practical commercial operations utilizing the two-step process of the invention of a cyclic basis, nickel, cobalt, ruthenium, thenium and alloys thereof are especially prepared for use in a metal state, with CO disproportionation being carried out at temperatures up to about 350.degree. C. and with the conversion of active surface carbon to methane being carried out by reaction with steam. The catalyst is employed in such cyclic operations without the necessity for employing a regeneration step as part of each processing cycle. Inactive carbon or coke that tends to form on the catalyst over the course of continuous operations utilizing such cyclic process is effectively and advantageously removed, on a periodic basis, in place of conventional burn off with an inert stream containing a low concentration of oxygen.

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

Carbon Doping of Compound Semiconductor Epitaxial Layers Grown by Metalorganic Chemical Vapor Deposition Using Carbon Tetrachloride.

NASA Astrophysics Data System (ADS)

Cunningham, Brian Thomas

1990-01-01

A dilute mixture of CCl_4 in high purity H_2 has been used as a carbon dopant source for rm Al_ {x}Ga_{1-x}As grown by low pressure metalorganic chemical vapor deposition (MOCVD). To understand the mechanism for carbon incorporation from CCl_4 doping and to provide experimental parameters for the growth of carbon doped device structures, the effects of various crystal growth parameters on CCl _4 doping have been studied, including growth temperature, growth rate, V/III ratio, Al composition, and CCl_4 flow rate. Although CCl _4 is an effective p-type dopant for MOCVD rm Al_{x}Ga_ {1-x}As, injection of CCl_4 into the reactor during growth of InP resulted in no change in the carrier concentration or carbon concentration. Abrupt, heavy carbon doping spikes in GaAs have been obtained using CCl_4 without a dopant memory effect. By annealing samples with carbon doping spikes grown within undoped, n-type, and p-type GaAs, the carbon diffusion coefficient in GaAs at 825 ^circC has been estimated and has been found to depend strongly on the GaAs background doping. Heavily carbon doped rm Al_{x}Ga _{1-x}As/GaAs superlattices have been found to be more stable against impurity induced layer disordering (IILD) than Mg or Zn doped superlattices, indicating that the low carbon diffusion coefficient limits the IILD process. Carbon doping has been used in the base region on an Npn AlGaAs/GaAs heterojunction bipolar transistor (HBT). Transistors with 3 x 10 μm self-aligned emitter fingers have been fabricated which exhibit a current gain cutoff frequency of f_ {rm t} = 26 GHz.

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.

Solid-phase extraction using bis(indolyl)methane-modified silica reinforced with multiwalled carbon nanotubes for the simultaneous determination of flavonoids and aromatic organic acid preservatives.

PubMed

Wang, Na; Liao, Yuan; Wang, Jiamin; Tang, Sheng; Shao, Shijun

2015-12-01

A novel bis(indolyl)methane-modified silica reinforced with multiwalled carbon nanotubes sorbent for solid-phase extraction was designed and synthesized by chemical immobilization of nitro-substituted 3,3'-bis(indolyl)methane on silica modified with multiwalled carbon nanotubes. Coupled with high-performance liquid chromatography analysis, the extraction properties of the sorbent were evaluated for flavonoids and aromatic organic acid compounds. Under optimum conditions, the sorbent can simultaneously extract five flavonoids and two aromatic organic acid preservatives in aqueous solutions in a single-step solid-phase extraction procedure. Wide linear ranges were obtained with correlation coefficients (R(2) ) ranging from 0.9843 to 0.9976, and the limits of detection were in the range of 0.5-5 μg/L for the compounds tested. Compared with the silica modified with multiwalled carbon nanotubes sorbent and the nitro-substituted 3,3'-bis(indolyl)methane-modified silica sorbent, the developed sorbent exhibited higher extraction efficiency toward the selected analytes. The synergistic effect of nitro-substituted 3,3'-bis(indolyl)methane and multiwalled carbon nanotubes not only improved the surface-to-volume ratio but also enhanced multiple intermolecular interactions, such as hydrogen bonds, π-π, and hydrophobic interactions, between the new sorbent and the selected analytes. The as-established solid-phase extraction with high-performance liquid chromatography and diode array detection method was successfully applied to the simultaneous determination of flavonoids and aromatic organic acid preservatives in grape juices with recoveries ranging from 83.9 to 112% for all the selected analytes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An analytical solubility model for nitrogen-methane-ethane ternary mixtures

NASA Astrophysics Data System (ADS)

Hartwig, Jason; Meyerhofer, Peter; Lorenz, Ralph; Lemmon, Eric

2018-01-01

Saturn's moon Titan has surface liquids of liquid hydrocarbons and a thick, cold, nitrogen atmosphere, and is a target for future exploration. Critical to the design and operation of vehicles for this environment is knowledge of the amount of dissolved nitrogen gas within the cryogenic liquid methane and ethane seas. This paper rigorously reviews experimental data on the vapor-liquid equilibrium of nitrogen/methane/ethane mixtures, noting the possibility for split liquid phases, and presents simple analytical models for conveniently predicting solubility of nitrogen in pure liquid ethane, pure liquid methane, and a mixture of liquid ethane and methane. Model coefficients are fit to three temperature ranges near the critical point, intermediate range, and near the freezing point to permit accurate predictions across the full range of thermodynamic conditions. The models are validated against the consolidated database of 2356 experimental data points, with mean absolute error between data and model less than 8% for both binary nitrogen/methane and nitrogen/ethane systems, and less than 17% for the ternary nitrogen/methane/ethane system. The model can be used to predict the mole fractions of ethane, methane, and nitrogen as a function of location within the Titan seas.

Liquid hydrogen production via hydrogen sulfide methane reformation

NASA Astrophysics Data System (ADS)

Huang, Cunping; T-Raissi, Ali

Hydrogen sulfide (H 2S) methane (CH 4) reformation (H 2SMR) (2H 2S + CH 4 = CS 2 + 4H 2) is a potentially viable process for the removal of H 2S from sour natural gas resources or other methane containing gases. Unlike steam methane reformation that generates carbon dioxide as a by-product, H 2SMR produces carbon disulfide (CS 2), a liquid under ambient temperature and pressure-a commodity chemical that is also a feedstock for the synthesis of sulfuric acid. Pinch point analyses for H 2SMR were conducted to determine the reaction conditions necessary for no carbon lay down to occur. Calculations showed that to prevent solid carbon formation, low inlet CH 4 to H 2S ratios are needed. In this paper, we analyze H 2SMR with either a cryogenic process or a membrane separation operation for production of either liquid or gaseous hydrogen. Of the three H 2SMR hydrogen production flowsheets analyzed, direct liquid hydrogen generation has higher first and second law efficiencies of exceeding 80% and 50%, respectively.

Age of Sulfate Methane Transition Zone Determined by Modelling Barium Sulfate Growth

NASA Astrophysics Data System (ADS)

Lin, S.; Wang, W. C.; Lien, K. L.; Liu, C. C.; Fan, L. F.

2017-12-01

Methane seep to the sediment/water interface could initiate anaerobic methane oxidation (AOM) with subsequent build up of chemosynthetic community, carbonate, pyrite and a number of other authigenic mineral formation. Determination the duration, sequence and time of methane seeps are keys to understand how methane seep to the environment and degree of alteration to the vicinity area. However, limited method existed in defining time of methane seep since there are some known problems involving typical dating methods, i.e. old carbon on C14 of fossil test or authigenic carbonate, thorium from surrounding matrix on U/Th authigenic carbonate dating. In this study, we have employed barium determination method (Dickens, 2001) to model timing of methane seep at two locations in the South China Sea. Our objective is to compare timing of the barium accumulation near the sulfate methane transition zone (SMTZ) on these two different locations and to seek if a similar mechanism driving the methane seep at two locations far apart. Dissolved barium, total sediment barium and aluminum were measured as well as pore water sulfate, and sediment pyrite concentrations. Time for the barium sulfate accumulation is calculated by: T = C/F, C= ∫ I x p x (1-Ø) Our results show that SMTZ is stabilized at each site for a duration of about 4000-5000 years. AOM process have been active at both sites at about the same time. In conjunction, pyrite also accumulated at a depth near the SMTZ as a result of methane oxidation. This result show that AOM could stay at the SMTZ for a relatively long period of time, on a scale of thousands of years.

Methane Hydrate Formation from Enhanced Organic Carbon Burial During Glacial Lowstands: Examples from the Gulf of Mexico

NASA Astrophysics Data System (ADS)

Malinverno, A.; Cook, A.; Daigle, H.; Oryan, B.

2017-12-01

Methane hydrates in fine-grained marine sediments are often found within veins and fractures occupying discrete depth intervals that are surrounded by hydrate-free sediments. As they are not connected with gas sources beneath the base of the methane hydrate stability zone (MHSZ), these isolated hydrate-bearing intervals have been interpreted as formed by in situ microbial methane. We investigate here the hypothesis that these hydrate deposits form in sediments that were deposited during glacial lowstands and contain higher amounts of labile particulate organic carbon (POC), leading to enhanced microbial methanogenesis. During Pleistocene lowstands, river loads are deposited near the steep top of the continental slope and turbidity currents transport organic-rich, fine-grained sediments to deep waters. Faster sedimentation rates during glacial periods result in better preservation of POC because of decreased exposure times to oxic conditions. The net result is that more labile POC enters the methanogenic zone and more methane is generated in these sediments. To test this hypothesis, we apply an advection-diffusion-reaction model with a time-dependent deposition of labile POC at the seafloor controlled by glacioeustatic sea level variations in the last 250 kyr. The model is run for parameters estimated at three sites drilled by the 2009 Gulf of Mexico Joint Industry Project: Walker Ridge in the Terrebonne Basin (WR313-G and WR313-H) and Green Canyon near the canyon embayment into the Sigsbee Escarpment (GC955-H). In the model, gas hydrate forms in sediments with higher labile POC content deposited during the glacial cycle between 230 and 130 kyr (marine isotope stages 6 and 7). The corresponding depth intervals in the three sites contain hydrates, as shown by high bulk electrical resistivities and resistive subvertical fracture fills. This match supports the hypothesis that enhanced POC burial during glacial lowstands can result in hydrate formation from in situ

Methane Hydrate Formation from Enhanced Organic Carbon Burial During Glacial Lowstands: Examples from the Gulf of Mexico

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

Malinverno, Alberto; Cook, Ann; Daigle, Hugh

Methane hydrates in fine-grained marine sediments are often found within veins and fractures occupying discrete depth intervals that are surrounded by hydrate-free sediments. As they are not connected with gas sources beneath the base of the methane hydrate stability zone (MHSZ), these isolated hydrate-bearing intervals have been interpreted as formed by in situ microbial methane. We investigate here the hypothesis that these hydrate deposits form in sediments that were deposited during glacial lowstands and contain higher amounts of labile particulate organic carbon (POC), leading to enhanced microbial methanogenesis. During Pleistocene lowstands, river loads are deposited near the steep top ofmore » the continental slope and turbidity currents transport organic-rich, fine-grained sediments to deep waters. Faster sedimentation rates during glacial periods result in better preservation of POC because of decreased exposure times to oxic conditions. The net result is that more labile POC enters the methanogenic zone and more methane is generated in these sediments. To test this hypothesis, we apply an advection-diffusion-reaction model with a time-dependent deposition of labile POC at the seafloor controlled by glacioeustatic sea level variations in the last 250 kyr. The model is run for parameters estimated at three sites drilled by the 2009 Gulf of Mexico Joint Industry Project: Walker Ridge in the Terrebonne Basin (WR313-G and WR313-H) and Green Canyon near the canyon embayment into the Sigsbee Escarpment (GC955-H). In the model, gas hydrate forms in sediments with higher labile POC content deposited during the glacial cycle between 230 and 130 kyr (marine isotope stages 6 and 7). The corresponding depth intervals in the three sites contain hydrates, as shown by high bulk electrical resistivities and resistive subvertical fracture fills. This match supports the hypothesis that enhanced POC burial during glacial lowstands can result in hydrate formation from in

Water Vapor Adsorption on Biomass Based Carbons under Post-Combustion CO2 Capture Conditions: Effect of Post-Treatment

PubMed Central

Querejeta, Nausika; Plaza, Marta G.; Rubiera, Fernando; Pevida, Covadonga

2016-01-01

The effect of post-treatment upon the H2O adsorption performance of biomass-based carbons was studied under post-combustion CO2 capture conditions. Oxygen surface functionalities were partially replaced through heat treatment, acid washing, and wet impregnation with amines. The surface chemistry of the final carbon is strongly affected by the type of post-treatment: acid treatment introduces a greater amount of oxygen whereas it is substantially reduced after thermal treatment. The porous texture of the carbons is also influenced by post-treatment: the wider pore volume is somewhat reduced, while narrow microporosity remains unaltered only after acid treatment. Despite heat treatment leading to a reduction in the number of oxygen surface groups, water vapor adsorption was enhanced in the higher pressure range. On the other hand acid treatment and wet impregnation with amines reduce the total water vapor uptake thus being more suitable for post-combustion CO2 capture applications. PMID:28773488

The isotopic composition of methane in polar ice cores

NASA Technical Reports Server (NTRS)

Craig, H.; Chou, C. C.; Welhan, J. A.; Stevens, C. M.; Engelkemeir, A.

1988-01-01

Air bubbles in polar ice cores indicate that about 300 years ago the atmospheric mixing ratio of methane began to increase rapidly. Today the mixing ratio is about 1.7 parts per million by volume, and, having doubled once in the past several hundred years, it will double again in the next 60 years if current rates continue. Carbon isotope ratios in methane up to 350 years in age have been measured with as little as 25 kilograms of polar ice recovered in 4-meter-long ice-core segments. The data show that: (1) in situ microbiology or chemistry has not altered the ice-core methane concentrations, and (2) that the carbon-13 to carbon-12 ratio of atmospheric CH4 in ice from 100 years and 300 years ago was about 2 per mil lower than at present. Atmospheric methane has a rich spectrum of isotopic sources: the ice-core data indicate that anthropogenic burning of the earth's biomass is the principal cause of the recent C-13H4 enrichment, although other factors may also contribute.

Methane-derived authigenic carbonates from the northern Gulf of Mexico - MD02 Cruise

USGS Publications Warehouse

Chen, Y.; Matsumoto, R.; Paull, C.K.; Ussler, W.; Lorenson, T.; Hart, P.; Winters, W.

2007-01-01

Authigenic carbonates were sampled in piston cores collected from both the Tunica Mound and the Mississippi Canyon area on the continental slope of the northern Gulf of Mexico during a Marion Dufresne cruise in July 2002. The carbonates are present as hardgrounds, porous crusts, concretions or nodules and shell fragments with or without carbonate cements. Carbonates occurred at gas venting sites which are likely to overlie gas hydrates bearing sediments. Electron microprobe, X-ray diffraction (XRD) and thinsection investigations show that these carbonates are high-Mg calcite (6-21??mol% MgCO3), with significant presence of framboidal pyrite. All carbonates are depleted in 13C (??13C = - 61.9 to - 31.5??? PDB) indicating that the carbon is derived mainly from anaerobic methane oxidation (AMO). Age estimates based on 14C dating of shell fragments and on regional sedimentation rates indicate that these authigenic carbonates formed within the last 1000??yr in the Mississippi Canyon and within 5500??yr at the Tunica Mound. The oxygen isotopic composition of carbonates ranges from + 3.4 to + 5.9??? PDB. Oxygen isotopic compositions and Mg2+ contents of carbonates, and present in-situ temperatures of bottom seawater/sediments, show that some of these carbonates, especially from a core associated with underlying massive gas hydrates precipitated in or near equilibrium with bottom-water. On the other hand, those carbonates more enriched in 18O are interpreted to have precipitated from 18O-rich fluids which are thought to have been derived from the dissociation of gas hydrates. The dissociation of gas hydrates in the northern Gulf of Mexico within the last 5500??yr may be caused by nearby salt movement and related brines. ?? 2007 Elsevier B.V. All rights reserved.

Ruminant methane delta(/sup 13/C//sup 12/C) values: relation to atmospheric methane

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

Rust, F.

1981-03-06

The delta(/sup 13/C//sup 12/C) - values of methane produced by fistulated steers, dairy cattle, and wethers, and dairy and beef cattle herds show a bimodal distribution that appears to be correlated with the plant type (C/sub 3/ or C/sub 4/, that is, producing either a three- or a four-carbon acid in the first step of photosynthesis) consumed by the animals. These results indicate that cattle and sheep, on a global basis, release methane with an average delta(/sup 13/C//sup 12/C) value of -60 and -63 per mil, respectively. Together they are a source of atmospheric methane whose delta(/sup 13/C//sup 12/C) ismore » similar to published values for marsh gas and cannot explain the 20 per mil higher values for atmospheric methane.« less

Carbon Dioxide and Methane Flux Related to Forest Type and Managed and Unmanaged Conditions in the Great Dismal Swamp, USA

NASA Astrophysics Data System (ADS)

Gutenberg, L. W.; Krauss, K.; Qu, J. J.; Hogan, D. M.; Zhu, Z.; Xu, C.

2017-12-01

The Great Dismal Swamp in Virginia and North Carolina, USA, has been greatly impacted by human use and management for the last few hundred years through logging, ditching, and draining. Today, the once dominant cedar, cypress and pocosin forest types are fragmented due to logging and environmental change. Maple-gum forest has taken over more than half the remaining area of the swamp ecosystem, which is now a National Wildlife Refuge and State Park. The peat soils and biomass store a vast quantity of carbon compared with the size of the refuge, but this store is threatened by fire and drying. This study looks at three of the main forest types in the GDS— maple-sweet gum, tall pine pocosin, and Atlantic white cedar— in terms of their carbon dioxide and methane soil flux. Using static chambers to sample soil gas flux in locally representative sites, we found that cedar sites showed a higher carbon dioxide flux rate as the soil temperature increased than maple sites, and the rate of carbon dioxide flux decreased as soil moisture increased faster in cedar sites than in maple sites. Methane flux increased as temperature increased for pocosin, but decreased with temperature for cedar and maple. All of the methane fluxes increased as soil moisture increased. Cedar average carbon dioxide flux was statistically significantly different from both maple and pocosin. These results show that soil carbon gas flux depends on soil moisture and temperature, which are factors that are changing due to human actions, as well as on forest type, which is also the result of human activity. Some of these variables may be adjustable by the managers of the land. Variables other than forest type, temperature and soil moisture/inundation may also play a role in influencing soil flux, such as stand age, tree height, composition of the peat and nutrient availability, and source of moisture as some sites are more influenced by groundwater from ditches and some more by rainfall depending on the

Quantifying simultaneous fluxes of ozone, carbon dioxide and water vapor above a subalpine forest ecosystem

Treesearch

K. F. Zeller; N. T. Nikolov

2000-01-01

Assessing the long-term exchange of trace gases and energy between terrestrial ecosystems and the atmosphere is an important priority of the current climate change research. In this regard, it is particularly significant to provide valid data on simultaneous fluxes of carbon, water vapor and pollutants over representative ecosystems. Eddy covariance measurements and...

Forest cockchafer larvae as methane production hotspots in soils and their importance for net soil methane fluxes

NASA Astrophysics Data System (ADS)

Görres, Carolyn-Monika; Kammann, Claudia; Murphy, Paul; Müller, Christoph

2016-04-01

Certain groups of soil invertebrates, namely scarab beetles and millipedes, are capable of emitting considerable amounts of methane due to methanogens inhabiting their gut system. It was already pointed out in the early 1990's, that these groups of invertebrates may represent a globally important source of methane. However, apart from termites, the importance of invertebrates for the soil methane budget is still unknown. Here, we present preliminary results of a laboratory soil incubation experiment elucidating the influence of forest cockchafer larvae (Melolontha hippocastani FABRICIUS) on soil methane cycling. In January/February 2016, two soils from two different management systems - one from a pine forest (extensive use) and one from a vegetable field (intensive use) - were incubated for 56 days either with or without beetle larvae. Net soil methane fluxes and larvae methane emissions together with their stable carbon isotope signatures were quantified at regular intervals to estimate gross methane production and gross methane oxidation in the soils. The results of this experiment will contribute to testing the hypothesis of whether methane production hotspots can significantly enhance the methane oxidation capacity of soils. Forest cockchafer larvae are only found in well-aerated sandy soils where one would usually not suspect relevant gross methane production. Thus, besides quantifying their contribution to net soil methane fluxes, they are also ideal organisms to study the effect of methane production hotspots on overall soil methane cycling. Funding support: Reintegration grant of the German Academic Exchange Service (DAAD) (#57185798).

The interaction of climate change and methane hydrates

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

Ruppel, Carolyn D.; Kessler, John D.

Gas hydrate, a frozen, naturally-occurring, and highly-concentrated form of methane, sequesters significant carbon in the global system and is stable only over a range of low-temperature and moderate-pressure conditions. Gas hydrate is widespread in the sediments of marine continental margins and permafrost areas, locations where ocean and atmospheric warming may perturb the hydrate stability field and lead to release of the sequestered methane into the overlying sediments and soils. Methane and methane-derived carbon that escape from sediments and soils and reach the atmosphere could exacerbate greenhouse warming. The synergy between warming climate and gas hydrate dissociation feeds a popular perceptionmore » that global warming could drive catastrophic methane releases from the contemporary gas hydrate reservoir. Appropriate evaluation of the two sides of the climate-methane hydrate synergy requires assessing direct and indirect observational data related to gas hydrate dissociation phenomena and numerical models that track the interaction of gas hydrates/methane with the ocean and/or atmosphere. Methane hydrate is likely undergoing dissociation now on global upper continental slopes and on continental shelves that ring the Arctic Ocean. Many factors—the depth of the gas hydrates in sediments, strong sediment and water column sinks, and the inability of bubbles emitted at the seafloor to deliver methane to the sea-air interface in most cases—mitigate the impact of gas hydrate dissociation on atmospheric greenhouse gas concentrations though. There is no conclusive proof that hydrate-derived methane is reaching the atmosphere now, but more observational data and improved numerical models will better characterize the climate-hydrate synergy in the future.« less

The interaction of climate change and methane hydrates

DOE PAGES

Ruppel, Carolyn D.; Kessler, John D.

2016-12-14

Gas hydrate, a frozen, naturally-occurring, and highly-concentrated form of methane, sequesters significant carbon in the global system and is stable only over a range of low-temperature and moderate-pressure conditions. Gas hydrate is widespread in the sediments of marine continental margins and permafrost areas, locations where ocean and atmospheric warming may perturb the hydrate stability field and lead to release of the sequestered methane into the overlying sediments and soils. Methane and methane-derived carbon that escape from sediments and soils and reach the atmosphere could exacerbate greenhouse warming. The synergy between warming climate and gas hydrate dissociation feeds a popular perceptionmore » that global warming could drive catastrophic methane releases from the contemporary gas hydrate reservoir. Appropriate evaluation of the two sides of the climate-methane hydrate synergy requires assessing direct and indirect observational data related to gas hydrate dissociation phenomena and numerical models that track the interaction of gas hydrates/methane with the ocean and/or atmosphere. Methane hydrate is likely undergoing dissociation now on global upper continental slopes and on continental shelves that ring the Arctic Ocean. Many factors—the depth of the gas hydrates in sediments, strong sediment and water column sinks, and the inability of bubbles emitted at the seafloor to deliver methane to the sea-air interface in most cases—mitigate the impact of gas hydrate dissociation on atmospheric greenhouse gas concentrations though. There is no conclusive proof that hydrate-derived methane is reaching the atmosphere now, but more observational data and improved numerical models will better characterize the climate-hydrate synergy in the future.« less