Methane oxidation in anoxic lake waters

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

Dissimilatory perchlorate reduction linked to aerobic methane oxidation via chlorite dismutase

NASA Astrophysics Data System (ADS)

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

2013-12-01

The presence of methane (CH4) in the atmosphere of Mars is controversial yet the evidence has aroused scientific interest, as CH4 could be a harbinger of extant or extinct microbial life. There are various oxidized compounds present on the surface of Mars that could serve as electron acceptors for the anaerobic oxidation of CH4, including perchlorate (ClO4-). We examined the role of perchlorate, chlorate (ClO3-) and chlorite (ClO2-) as oxidants linked to CH4 oxidation. Dissimilatory perchlorate reduction begins with reduction of ClO4- to ClO2- and ends with dismutation of chlorite to yield chloride (Cl-) and molecular oxygen (O2). We explored the potential for aerobic CH4 oxidizing bacteria to couple with oxygen derived from chlorite dismutation during dissimilatory perchlorate reduction. Methane (0.2 kPa) was completely removed within several days from the N2-flushed headspace above cell suspensions of methanotrophs (Methylobacter albus strain BG8) and perchlorate reducing bacteria (Dechloromonas agitata strain CKB) in the presence of 5 mM ClO2-. Similar rates of CH4 consumption were observed for these mixed cultures whether they were co-mingled or segregated under a common headspace, indicating that direct contact of cells was not required for methane consumption to occur. We also observed complete removal of 0.2 kPa CH4 in bottles containing dried soil (enriched in methanotrophs by CH4 additions over several weeks) and D. agitata CKB and in the presence of 10 mM ClO2-. This soil (seasonally exposed sediment) collected from the shoreline of a freshwater lake (Searsville Lake, CA) demonstrated endogenous CH4 uptake as well as perchlorate, chlorate and chlorite reduction/dismutation. However, these experiments required physical separation of soil from the aqueous bacterial culture to allow for the partitioning of O2 liberated from chlorite dismutation into the shared headspace. Although dissimilatory reduction of ClO4- and ClO3- could be inferred from the accumulation of chloride ions either in spent media or in slurries prepared from Searsville Lake soil, neither of these oxyanions evoked methane oxidation when added to either anaerobic mixed cultures or soils enriched in methanotrophs. This result leads us to surmise that the release of O2 during enzymatic perchlorate reduction was low, and that the oxygen produced was unavailable to the aerobic methanotrophs. This was borne out by patterns of O2 and CO2 production during experiments with lake soil, growth media, and pure cultures of dissimilatory perchlorate reducing bacteria. We observed that O2 release during incubation of D. agitata CKB with 10 mM ClO4- or ClO3- was decoupled from metabolism. More O2 was released during incubations without added acetate than with 10 mM acetate and an even greater amount of O2 was released during incubation with heat-killed cells. This suggests a chemical mechanism of O2 production during reaction with ClO4- and ClO3-. Hence, perchlorate reducing bacteria need not be present to facilitate O2 release from the surface of Mars, in support of recent interpretations of Viking LR and GEx experiments.

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

PubMed

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

2018-03-29

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

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

PubMed

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

2017-02-01

We sampled the water column of the Dendre stone pit lake (Belgium) in spring, summer, autumn and winter. Depth profiles of several physico-chemical variables, nutrients, dissolved gases (CO 2 , CH 4 , N 2 O), sulfate, sulfide, iron and manganese concentrations and δ 13 C-CH4 were determined. We performed incubation experiments to quantify CH 4 oxidation rates, with a focus on anaerobic CH 4 oxidation (AOM), without and with an inhibitor of sulfate reduction (molybdate). The evolution of nitrate and sulfate concentrations during the incubations was monitored. The water column was anoxic below 20 m throughout the year, and was thermally stratified in summer and autumn. High partial pressure of CO 2 and CH 4 and high concentrations of ammonium and phosphate were observed in anoxic waters. Important nitrous oxide and nitrate concentration maxima were also observed (up to 440 nmol L -1 and 80 μmol L -1 , respectively). Vertical profiles of δ 13 C-CH 4 unambiguously showed the occurrence of AOM. Important AOM rates (up to 14 μmol L -1  d -1 ) were observed and often co-occurred with nitrate consumption peaks, suggesting the occurrence of AOM coupled with nitrate reduction. AOM coupled with sulfate reduction also occurred, since AOM rates tended to be lower when molybdate was added. CH 4 oxidation was mostly aerobic (∼80% of total oxidation) in spring and winter, and almost exclusively anaerobic in summer and autumn. Despite important CH 4 oxidation rates, the estimated CH 4 fluxes from the water surface to the atmosphere were high (mean of 732 μmol m -2  d -1 in spring, summer and autumn, and up to 12,482 μmol m -2  d -1 in winter). Copyright © 2016 Elsevier Ltd. All rights reserved.

Bioinspired organocatalytic aerobic C-H oxidation of amines with an ortho-quinone catalyst.

PubMed

Qin, Yan; Zhang, Long; Lv, Jian; Luo, Sanzhong; Cheng, Jin-Pei

2015-03-20

A simple bioinspired ortho-quinone catalyst for the aerobic oxidative dehydrogenation of amines to imines is reported. Without any metal cocatalysts, the identified optimal ortho-quinone catalyst enables the oxidations of α-branched primary amines and cyclic secondary amines. Mechanistic studies have disclosed the origins of different performances of ortho-quinone vs para-quinone in biomimetic amine oxidations.

A record of aerobic methane oxidation in tropical Africa over the last 2.5 Ma

NASA Astrophysics Data System (ADS)

Spencer-Jones, Charlotte L.; Wagner, Thomas; Talbot, Helen M.

2017-12-01

Methane and CO2 are climatically active greenhouse gases (GHG) and are powerful drivers of rapid global warming. Comparable to the Arctic, the tropics store large volumes of labile sedimentary carbon that is vulnerable to climate change. However, little is known about this labile carbon reservoir, in particular the behaviour of high methane-producing environments (e.g. wetlands), and their role in driving or responding to past periods of global climate change. In this study, we use a microbial biomarker approach that traces continental aerobic methane oxidation (AMO) from sedimentary organic matter in deep-sea fan sediments off the Congo River to reconstruct the link between central African methane cycling and continental export during key periods of global Pleistocene warmth. We use 35-amino bacteriohopanepolyols (BHPs), specifically aminobacteriohopane-31,32,33,34-tetrol (aminotetrol) and 35-aminobacteriohopane-30,31,32,33,34-pentol (aminopentol) as diagnostic molecular markers for AMO (CH4 oxidation markers) and the prevalence of continental wetland environments. BHPs were analysed in sediments from the Congo fan (ODP 1075) dated to 2.5 Ma. High resolution studies of key warm marine isotope stages (MIS) 5, 11 and 13 are included to test the relationship between CH4 oxidation markers in sediments at different levels of elevated global atmospheric GHG. This study presents the oldest reported occurrence, to date, of 35-amino BHPs up to 200 m below sea floor (∼2.5 Ma) with no strong degradation signature observed. Low concentrations of CH4 oxidation markers identified between 1.7 Ma and 1 Ma suggest a reduction in wetland extent in tropical Africa in response to more arid environmental conditions. Correlation of high resolution CH4 oxidation marker signatures with global atmospheric GHG concentrations during MIS 5, 11 and 13 further emphasize periods of enhanced tropical C cycling. However, subsequent analysis would be required to further extrapolate the relative importance of tropical methane sources as a driver of global methane concentrations during the Pleistocene.

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

NASA Astrophysics Data System (ADS)

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

2016-04-01

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

Nutrient Controls on Methane Emissions in a Permafrost Thaw Subarctic Peatland

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Hydrogen Isotope Fractionation during the Biodegradation of 1,2-Dichloroethane: Potential for Pathway Identification Using a Multi-element (C, Cl, and H) Isotope Approach.

PubMed

Palau, Jordi; Shouakar-Stash, Orfan; Hatijah Mortan, Siti; Yu, Rong; Rosell, Monica; Marco-Urrea, Ernest; Freedman, David L; Aravena, Ramon; Soler, Albert; Hunkeler, Daniel

2017-09-19

Even though multi-element isotope fractionation patterns provide crucial information with which to identify contaminant degradation pathways in the field, those involving hydrogen are still lacking for many halogenated groundwater contaminants and degradation pathways. This study investigates for the first time hydrogen isotope fractionation during both aerobic and anaerobic biodegradation of 1,2-dichloroethane (1,2-DCA) using five microbial cultures. Transformation-associated isotope fractionation values (ε bulk H ) were -115 ± 18‰ (aerobic C-H bond oxidation), -34 ± 4‰ and -38 ± 4‰ (aerobic C-Cl bond cleavage via hydrolytic dehalogenation), and -57 ± 3‰ and -77 ± 9‰ (anaerobic C-Cl bond cleavage via reductive dihaloelimination). The dual-element C-H isotope approach (Λ C-H = Δδ 2 H/Δδ 13 C ≈ ε bulk H /ε bulk C , where Δδ 2 H and Δδ 13 C are changes in isotope ratios during degradation) resulted in clearly different Λ C-H values: 28 ± 4 (oxidation), 0.7 ± 0.1 and 0.9 ± 0.1 (hydrolytic dehalogenation), and 1.76 ± 0.05 and 3.5 ± 0.1 (dihaloelimination). This result highlights the potential of this approach to identify 1,2-DCA degradation pathways in the field. In addition, distinct trends were also observed in a multi- (i.e., Δδ 2 H versus Δδ 37 Cl versus Δδ 13 C) isotope plot, which opens further possibilities for pathway identification in future field studies. This is crucial information to understand the mechanisms controlling natural attenuation of 1,2-DCA and to design appropriate strategies to enhance biodegradation.

Oxidation of ammonia and methane in an alkaline, saline lake

USGS Publications Warehouse

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

1999-01-01

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

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

PubMed

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

2016-11-01

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

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

PubMed

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

1994-05-01

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

Field assessment of semi-aerobic condition and the methane correction factor for the semi-aerobic landfills provided by IPCC guidelines

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

Jeong, Sangjae; Nam, Anwoo; Yi, Seung-Muk

Highlights: • CH{sub 4}/CO{sub 2} and CH{sub 4} + CO{sub 2}% are proposed as indices to evaluate semi-aerobic landfills. • A landfill which CH{sub 4}/CO{sub 2} > 1.0 is difficult to be categorized as semi-aerobic landfill. • Field conditions should be carefully investigated to determine landfill types. • The MCF default value for semi-aerobic landfills underestimates the methane emissions. - Abstract: According to IPCC guidelines, a semi-aerobic landfill site produces one-half of the amount of CH{sub 4} produced by an equally-sized anaerobic landfill site. Therefore categorizing the landfill type is important on greenhouse gas inventories. In order to assess semi-aerobicmore » condition in the sites and the MCF value for semi-aerobic landfill, landfill gas has been measured from vent pipes in five semi-aerobically designed landfills in South Korea. All of the five sites satisfied requirements of semi-aerobic landfills in 2006 IPCC guidelines. However, the ends of leachate collection pipes which are main entrance of air in the semi-aerobic landfill were closed in all five sites. The CH{sub 4}/CO{sub 2} ratio in landfill gas, indicator of aerobic and anaerobic decomposition, ranged from 1.08 to 1.46 which is higher than the values (0.3–1.0) reported for semi-aerobic landfill sites and is rather close to those (1.0–2.0) for anaerobic landfill sites. The low CH{sub 4} + CO{sub 2}% in landfill gas implied air intrusion into the landfill. However, there was no evidence that air intrusion has caused by semi-aerobic design and operation. Therefore, the landfills investigated in this study are difficult to be classified as semi-aerobic landfills. Also MCF of 0.5 may significantly underestimate methane emissions compared to other researches. According to the carbon mass balance analyses, the higher MCF needs to be proposed for semi-aerobic landfills. Consequently, methane emission estimate should be based on field evaluation for the semi-aerobically designed landfills.« less

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

NASA Astrophysics Data System (ADS)

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

2003-12-01

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

Spatio-temporal variation of landfill gas in pilot-scale semi-aerobic and anaerobic landfills over 5years.

PubMed

Wu, Xiaohui; Yue, Bo; Huang, Qifei; Wang, Qi; Lin, Ye; Zhang, Wei; Yan, Zhuoyi

2017-04-01

Variation of CH 4 , CO 2 , and O 2 concentrations in layers of different depths in semi-aerobic and anaerobic landfills was analyzed over a period of 5years. The results showed that most of the municipal solid waste became basically stable after 5years of landfill disposal. In the upper and middle layer, the concentration of CH 4 in the semi-aerobic landfill was significantly lower than that in the anaerobic landfill in different landfill periods, while in the lower layer, there was little difference in the CH 4 concentration between the semi-aerobic and anaerobic landfills. The average concentration of CH 4 and CO 2 in the anaerobic landfill was always higher than that in the semi-aerobic landfill, while the O 2 concentration showed an opposite variation in different landfill periods. This was related to the aerobic reaction of landfill waste around the perforated pipe in the semi-aerobic landfill, which inhibited effective landfill gas generation. Copyright © 2016. Published by Elsevier B.V.

Diversity of active aerobic methanotrophs along depth profiles of arctic and subarctic lake water column and sediments

PubMed Central

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

2012-01-01

Methane (CH4) emitted from high-latitude lakes accounts for 2–6% of the global atmospheric CH4 budget. Methanotrophs in lake sediments and water columns mitigate the amount of CH4 that enters the atmosphere, yet their identity and activity in arctic and subarctic lakes are poorly understood. We used stable isotope probing (SIP), quantitative PCR (Q-PCR), pyrosequencing and enrichment cultures to determine the identity and diversity of active aerobic methanotrophs in the water columns and sediments (0–25 cm) from an arctic tundra lake (Lake Qalluuraq) on the north slope of Alaska and a subarctic taiga lake (Lake Killarney) in Alaska's interior. The water column CH4 oxidation potential for these shallow (∼2 m deep) lakes was greatest in hypoxic bottom water from the subarctic lake. The type II methanotroph, Methylocystis, was prevalent in enrichment cultures of planktonic methanotrophs from the water columns. In the sediments, type I methanotrophs (Methylobacter, Methylosoma and Methylomonas) at the sediment-water interface (0–1 cm) were most active in assimilating CH4, whereas the type I methanotroph Methylobacter and/or type II methanotroph Methylocystis contributed substantially to carbon acquisition in the deeper (15–20 cm) sediments. In addition to methanotrophs, an unexpectedly high abundance of methylotrophs also actively utilized CH4-derived carbon. This study provides new insight into the identity and activity of methanotrophs in the sediments and water from high-latitude lakes. PMID:22592821

Diversity of active aerobic methanotrophs along depth profiles of arctic and subarctic lake water column and sediments

USGS Publications Warehouse

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

2012-01-01

Methane (CH4) emitted from high-latitude lakes accounts for 2–6% of the global atmospheric CH4 budget. Methanotrophs in lake sediments and water columns mitigate the amount of CH4 that enters the atmosphere, yet their identity and activity in arctic and subarctic lakes are poorly understood. We used stable isotope probing (SIP), quantitative PCR (Q-PCR), pyrosequencing and enrichment cultures to determine the identity and diversity of active aerobic methanotrophs in the water columns and sediments (0–25 cm) from an arctic tundra lake (Lake Qalluuraq) on the north slope of Alaska and a subarctic taiga lake (Lake Killarney) in Alaska's interior. The water column CH4 oxidation potential for these shallow (~2m deep) lakes was greatest in hypoxic bottom water from the subarctic lake. The type II methanotroph, Methylocystis, was prevalent in enrichment cultures of planktonic methanotrophs from the water columns. In the sediments, type I methanotrophs (Methylobacter, Methylosoma and Methylomonas) at the sediment-water interface (0–1 cm) were most active in assimilating CH4, whereas the type I methanotroph Methylobacter and/or type II methanotroph Methylocystis contributed substantially to carbon acquisition in the deeper (15–20 cm) sediments. In addition to methanotrophs, an unexpectedly high abundance of methylotrophs also actively utilized CH4-derived carbon. This study provides new insight into the identity and activity of methanotrophs in the sediments and water from high-latitude lakes.

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

PubMed

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

2012-07-01

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

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

PubMed

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

2018-06-03

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

Aerobic and Electrochemical Oxidations with N-Oxyl Reagents

NASA Astrophysics Data System (ADS)

Miles, Kelsey C.

Selective oxidation of organic compounds represents a significant challenge for chemical transformations. Oxidation methods that utilize nitroxyl catalysts have become increasingly attractive and include Cu/nitroxyl and nitroxyl/NO x co-catalyst systems. Electrochemical activation of nitroxyls is also well known and offers an appealing alternative to the use of chemical co-oxidants. However, academic and industrial organic synthetic communities have not widely adopted electrochemical methods. Nitroxyl catalysts facilitate effective and selective oxidation of alcohols and aldehydes to ketones and carboxylic acids. Selective benzylic, allylic, and alpha-heteroatom C-H abstraction can also be achieved with nitroxyls and provides access to oxygenated products when used in combination with molecular oxygen as a radical trap. This thesis reports various chemical and electrochemical oxidation methods that were developed using nitroxyl mediators. Chapter 1 provides a short review on practical aerobic alcohol oxidation with Cu/nitroxyl and nitroxyl/NO x systems and emphasizes the utility of bicyclic nitroxyls as co-catalysts. In Chapter 2, the combination of these bicyclic nitroxyls with NOx is explored for development of a mild oxidation of alpha-chiral aryl aldehydes and showcases a sequential asymmetric hydroformylation/oxidation method. Chapter 3 reports the synthesis and characterization of two novel Cu/bicyclic nitroxyl complexes and the electronic structure analysis of these complexes. Chapter 4 highlights the electrochemical activation of various nitroxyls and reports an in-depth study on electrochemical alcohol oxidation and compares the reactivity of nitroxyls under electrochemical or chemical activation. N-oxyls can also participate in selective C-H abstraction, and Chapter 5 reports the chemical and electrochemical activation of N-oxyls for radical-mediated C-H oxygenation of (hetero)arylmethanes. For these electrochemical transformations, the development of user-friendly methods and analysis techniques is emphasized.

Effects of permafrost thaw on carbon emissions under aerobic and anaerobic environments in the Great Hing'an Mountains, China.

PubMed

Song, Changchun; Wang, Xianwei; Miao, Yuqing; Wang, Jiaoyue; Mao, Rong; Song, Yanyu

2014-07-15

The carbon (C) pool of permafrost peatland is very important for the global C cycle. Little is known about how permafrost thaw could influence C emissions in the Great Hing'an Mountains of China. Through aerobic and anaerobic incubation experiments, we studied the effects of permafrost thaw on CH4 and CO2 emissions. The rates of CH4 and CO2 emissions were measured at -10, 0 and 10°C. Although there were still C emissions below 0°C, rates of CH4 and CO2 emissions significantly increased with permafrost thaw under aerobic and anaerobic conditions. The C release under aerobic conditions was greater than under anaerobic conditions, suggesting that permafrost thaw and resulting soil environment change should be important influences on C emissions. However, CH4 stored in permafrost soils could affect accurate estimation of CH4 emissions from microbial degradation. Calculated Q10 values in the permafrost soils were significantly higher than values in active-layer soils under aerobic conditions. Our results highlight that permafrost soils have greater potential decomposability than soils of the active layer, and such carbon decomposition would be more responsive to the aerobic environment. © 2013 Elsevier B.V. All rights reserved.

Trace Metal Requirements for Microbial Enzymes Involved in the Production and Consumption of Methane and Nitrous Oxide

PubMed Central

Glass, Jennifer B.; Orphan, Victoria J.

2011-01-01

Fluxes of greenhouse gases to the atmosphere are heavily influenced by microbiological activity. Microbial enzymes involved in the production and consumption of greenhouse gases often contain metal cofactors. While extensive research has examined the influence of Fe bioavailability on microbial CO2 cycling, fewer studies have explored metal requirements for microbial production and consumption of the second- and third-most abundant greenhouse gases, methane (CH4), and nitrous oxide (N2O). Here we review the current state of biochemical, physiological, and environmental research on transition metal requirements for microbial CH4 and N2O cycling. Methanogenic archaea require large amounts of Fe, Ni, and Co (and some Mo/W and Zn). Low bioavailability of Fe, Ni, and Co limits methanogenesis in pure and mixed cultures and environmental studies. Anaerobic methane oxidation by anaerobic methanotrophic archaea (ANME) likely occurs via reverse methanogenesis since ANME possess most of the enzymes in the methanogenic pathway. Aerobic CH4 oxidation uses Cu or Fe for the first step depending on Cu availability, and additional Fe, Cu, and Mo for later steps. N2O production via classical anaerobic denitrification is primarily Fe-based, whereas aerobic pathways (nitrifier denitrification and archaeal ammonia oxidation) require Cu in addition to, or possibly in place of, Fe. Genes encoding the Cu-containing N2O reductase, the only known enzyme capable of microbial N2O conversion to N2, have only been found in classical denitrifiers. Accumulation of N2O due to low Cu has been observed in pure cultures and a lake ecosystem, but not in marine systems. Future research is needed on metalloenzymes involved in the production of N2O by enrichment cultures of ammonia oxidizing archaea, biological mechanisms for scavenging scarce metals, and possible links between metal bioavailability and greenhouse gas fluxes in anaerobic environments where metals may be limiting due to sulfide-metal scavenging. PMID:22363333

Geochemical constraints on sources of metabolic energy for chemolithoautotrophy in ultramafic-hosted deep-sea hydrothermal systems.

PubMed

McCollom, Thomas M

2007-12-01

Numerical models are employed to investigate sources of chemical energy for autotrophic microbial metabolism that develop during mixing of oxidized seawater with strongly reduced fluids discharged from ultramafic-hosted hydrothermal systems on the seafloor. Hydrothermal fluids in these systems are highly enriched in H(2) and CH(4) as a result of alteration of ultramafic rocks (serpentinization) in the subsurface. Based on the availability of chemical energy sources, inferences are made about the likely metabolic diversity, relative abundance, and spatial distribution of microorganisms within ultramafic-hosted systems. Metabolic reactions involving H(2) and CH(4), particularly hydrogen oxidation, methanotrophy, sulfate reduction, and methanogenesis, represent the predominant sources of chemical energy during fluid mixing. Owing to chemical gradients that develop from fluid mixing, aerobic metabolisms are likely to predominate in low-temperature environments (<20-30 degrees C), while anaerobes will dominate higher-temperature environments. Overall, aerobic metabolic reactions can supply up to approximately 7 kJ of energy per kilogram of hydrothermal fluid, while anaerobic metabolic reactions can supply about 1 kJ, which is sufficient to support a maximum of approximately 120 mg (dry weight) of primary biomass production by aerobic organisms and approximately 20-30 mg biomass by anaerobes. The results indicate that ultramafic-hosted systems are capable of supplying about twice as much chemical energy as analogous deep-sea hydrothermal systems hosted in basaltic rocks.

Dynamics of Gross Methane Production and Oxidation in a Peatland Soil

NASA Astrophysics Data System (ADS)

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

2012-12-01

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

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

PubMed

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

2011-06-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-08-01

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

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

PubMed

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

2009-11-01

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

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

NASA Astrophysics Data System (ADS)

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

2006-12-01

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

Light-driven, proton-controlled, catalytic aerobic C-H oxidation mediated by a Mn(III) porphyrinoid complex.

PubMed

Neu, Heather M; Jung, Jieun; Baglia, Regina A; Siegler, Maxime A; Ohkubo, Kei; Fukuzumi, Shunichi; Goldberg, David P

2015-04-15

The visible light-driven, catalytic aerobic oxidation of benzylic C-H bonds was mediated by a Mn(III) corrolazine complex. To achieve catalytic turnovers, a strict selective requirement for the addition of protons was established. The resting state of the catalyst was unambiguously characterized by X-ray diffraction as [Mn(III)(H2O)(TBP8Cz(H))](+), in which a single, remote site on the ligand is protonated. If two remote sites are protonated, however, reactivity with O2 is shut down. Spectroscopic methods revealed that the related Mn(V)(O) complex is also protonated at the same remote site at -60 °C, but undergoes valence tautomerization upon warming.

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

PubMed

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

2009-01-01

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

Eosin Y-catalyzed visible-light-mediated aerobic oxidative cyclization of N,N-dimethylanilines with maleimides.

PubMed

Liang, Zhongwei; Xu, Song; Tian, Wenyan; Zhang, Ronghua

2015-01-01

A novel and simple strategy for the efficient synthesis of the corresponding tetrahydroquinolines from N,N-dimethylanilines and maleimides using visible light in an air atmosphere in the presence of Eosin Y as a photocatalyst has been developed. The metal-free protocol involves aerobic oxidative cyclization via sp(3) C-H bond functionalization process to afford good yields in a one-pot procedure under mild conditions.

Complementation of biotransformations with chemical C-H oxidation: copper-catalyzed oxidation of tertiary amines in complex pharmaceuticals.

PubMed

Genovino, Julien; Lütz, Stephan; Sames, Dalibor; Touré, B Barry

2013-08-21

The isolation, quantitation, and characterization of drug metabolites in biological fluids remain challenging. Rapid access to oxidized drugs could facilitate metabolite identification and enable early pharmacology and toxicity studies. Herein, we compared biotransformations to classical and new chemical C-H oxidation methods using oxcarbazepine, naproxen, and an early compound hit (phthalazine 1). These studies illustrated the low preparative efficacy of biotransformations and the inability of chemical methods to oxidize complex pharmaceuticals. We also disclose an aerobic catalytic protocole (CuI/air) to oxidize tertiary amines and benzylic CH's in drugs. The reaction tolerates a broad range of functionalities and displays a high level of chemoselectivity, which is not generally explained by the strength of the C-H bonds but by the individual structural chemotype. This study represents a first step toward establishing a chemical toolkit (chemotransformations) that can selectively oxidize C-H bonds in complex pharmaceuticals and rapidly deliver drug metabolites.

Combined chitosan-thyme treatments with modified atmosphere packaging on a ready-to-cook poultry product.

PubMed

Giatrakou, V; Ntzimani, A; Savvaidis, I N

2010-04-01

In the present study, natural antimicrobials chitosan and thyme, and their combination, were evaluated for their effect on the shelf life of a ready-to-cook (RTC) chicken-pepper kebab (skewer) stored under modified atmosphere packaging (MAP) conditions at 4 +/- 0.5 degrees C for 14 days. The following treatments were examined: control samples stored under aerobic packaging (A), samples stored under MAP (M), samples treated with 1.5% chitosan (vol/wt) and stored under MAP (M-CH), samples treated with 0.2% thyme essential oil (vol/wt) (M-T), and samples treated with 1.5% chitosan (vol/wt) and 0.2% thyme essential oil (vol/wt) and stored under MAP (M-CH-T). Treatment M-CH-T significantly affected aerobic plate counts and counts of lactic acid bacteria, Pseudomonas spp., Brochothrix thermosphacta, Enterobacteriaceae, and yeasts and molds during the entire storage period. Similarly, lipid oxidation of the RTC product was retarded (M-CH-T treatment) during storage, whereas redness was maintained in M-T, M-CH, and M-CH-T samples. Based primarily on sensory data (taste attribute), M-CH and M-T treatments extended RTC product shelf life by 6 days, whereas M-CH-T treatment resulted in a product with a shelf life of 14 days that maintained acceptable sensory characteristics (shelf life of the control was 6 days).

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

NASA Astrophysics Data System (ADS)

D'Imperio, Ludovica

2014-05-01

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

Selective C(sp3 )-H Aerobic Oxidation Enabled by Decatungstate Photocatalysis in Flow.

PubMed

Laudadio, Gabriele; Govaerts, Sebastian; Wang, Ying; Ravelli, Davide; Koolman, Hannes F; Fagnoni, Maurizio; Djuric, Stevan W; Noël, Timothy

2018-04-03

A mild and selective C(sp 3 )-H aerobic oxidation enabled by decatungstate photocatalysis has been developed. The reaction can be significantly improved in a microflow reactor enabling the safe use of oxygen and enhanced irradiation of the reaction mixture. Our method allows for the oxidation of both activated and unactivated C-H bonds (30 examples). The ability to selectively oxidize natural scaffolds, such as (-)-ambroxide, pregnenolone acetate, (+)-sclareolide, and artemisinin, exemplifies the utility of this new method. © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

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 and hydrocarbon exploitation. Nonetheless, quantifying methane metabolism typically involves logistically challenging methods and/or specialized equipment; these impediments have limited our understanding of methane fluxes and reservoirs in natural systems, making effective management difficult. Here, we offer an easily implementable, precise method using monodeuterated methane (CH3D) that advances three specific aims. First, it allows users to directly compare methane consumption rates between different experimental treatments of the same inoculum. Second, by empirically linking the CH3D procedure with the well-established 14C radiocarbon approach, we determine absolute scaling factors that facilitate rate measurements for several aerobic and anaerobic systems of interest. Third, CH3D represents a helpful tool in evaluating the relationship between methane activation and full oxidation in methanotrophic metabolisms. The procedural advantages, consistency, and novel research questions enabled by the CH3D method should prove useful in a wide range of culture-based and environmental microbial systems to further elucidate methane metabolism dynamics. PMID:28861523

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 and hydrocarbon exploitation. Nonetheless, quantifying methane metabolism typically involves logistically challenging methods and/or specialized equipment; these impediments have limited our understanding of methane fluxes and reservoirs in natural systems, making effective management difficult. Here, we offer an easily implementable, precise method using monodeuterated methane (CH 3 D) that advances three specific aims. First, it allows users to directly compare methane consumption rates between different experimental treatments of the same inoculum. Second, by empirically linking the CH 3 D procedure with the well-established 14 C radiocarbon approach, we determine absolute scaling factors that facilitate rate measurements for several aerobic and anaerobic systems of interest. Third, CH 3 D represents a helpful tool in evaluating the relationship between methane activation and full oxidation in methanotrophic metabolisms. The procedural advantages, consistency, and novel research questions enabled by the CH 3 D method should prove useful in a wide range of culture-based and environmental microbial systems to further elucidate methane metabolism dynamics.

Nitrous-acid-mediated synthesis of iron-nitrosyl-porphyrin: pH-dependent release of nitric oxide.

PubMed

Bhuyan, Jagannath; Sarkar, Sabyasachi

2012-11-01

Two iron-nitrosyl-porphyrins, nitrosyl[meso-tetrakis(3,4,5-trimethoxyphenylporphyrin]iron(II) acetic acid solvate (3) and nitrosyl[meso-tetrakis(4-methoxyphenylporphyrin]iron(II) CH(2)Cl(2) solvate (4), were synthesized in quantitative yield by using a modified procedure with nitrous acid, followed by oxygen-atom abstraction by triphenylphosphine under an argon atmosphere. These nitrosyl porphyrins are in the {FeNO}(7) class. Under an argon atmosphere, these compounds are relatively stable over a broad range of pH values (4-8) but, under aerobic conditions, they release nitric oxide faster at high pH values than that at low pH values. The generated nitric-oxide-free iron(III)-porphyrin can be re-nitrosylated by using nitrous acid and triphenylphosphine. The rapid release of NO from these Fe(II) complexes at high pH values seems to be similar to that in nitrophorin, a nitric-oxide-transport protein, which formally possesses Fe(III). However, because the release of NO occurs from ferrous-nitrosyl-porphyrin under aerobic conditions, these compounds are more closely related to nitrobindin, a recently discovered heme protein. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Regioselective oxyalkylation of vinylarenes catalyzed by diatomite-supported manganese oxide nanoparticles.

PubMed

Sun, Huayin; Zhang, Yonghui; Guo, Fengfeng; Zha, Zhenggen; Wang, Zhiyong

2012-04-06

A regioselective oxyalkylation reaction of vinylarenes with cyclic ethers was developed under the catalysis of a new heterogeneous catalyst, the diatomite-supported Mn(3)O(4) nanoparticles (SMONP-1). The use of this heterogeneous catalyst provided a novel approach for the synthesis of α-carbonyled β-alkylated aryl derivatives via a sp(3) C-H bond functionalization under mild aerobic conditions.

High resolution and comprehensive techniques to analyze aerobic methane oxidation in mesocosm experiments

NASA Astrophysics Data System (ADS)

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

2015-12-01

Many studies of microbially mediated aerobic methane oxidation in oceanic environments have examined the many different factors that control the rates of oxidation. However, there is debate on how quickly methane is oxidized once a microbial population is established and what factor(s) are limiting in these types of environments. These factors include the availability of CH4, O2, trace metals, nutrients, and the density of cell population. Limits to these factors can also control the temporal aspects of a methane oxidation event. In order to look at this process in its entirety and with higher temporal resolution, a mesocosm incubation system was developed with a Dissolved Gas Analyzer System (DGAS) coupled with a set of analytical tools to monitor aerobic methane oxidation in real time. With the addition of newer laser spectroscopy techniques (cavity ringdown spectroscopy), stable isotope fractionation caused by microbial processes can also be examined on a real time and automated basis. Cell counting, trace metal, nutrient, and DNA community analyses have also been carried out in conjunction with these mesocosm samples to provide a clear understanding of the biology in methane oxidation dynamics. This poster will detail the techniques involved to provide insights into the chemical and isotopic kinetics controlling aerobic methane oxidation. Proof of concept applications will be presented from seep sites in the Hudson Canyon and the Sleeping Dragon seep field, Mississippi Canyon 118 (MC 118). This system was used to conduct mesocosm experiments to examine methane consumption, O2 consumption, nutrient consumption, and biomass production.

Carbon isotope fractionation during microbial methane oxidation

NASA Astrophysics Data System (ADS)

Barker, James F.; Fritz, Peter

1981-09-01

Methane, a common trace constituent of groundwaters, occasionally makes up more than 20% of the total carbon in groundwaters1,2. In aerobic environments CH4-rich waters can enable microbial food chain supporting a mixed culture of bacteria with methane oxidation as the primary energy source to develop3. Such processes may influence the isotopic composition of the residual methane and because 13C/12C analyses have been used to characterize the genesis of methanes found in different environments, an understanding of the magnitude of such effects is necessary. In addition, carbon dioxide produced by the methane-utilizing bacteria can be added to the inorganic carbon pool of affected groundwaters. We found carbon dioxide experimentally produced by methane-utilizing bacteria to be enriched in 12C by 5.0-29.6‰, relative to the residual methane. Where methane-bearing groundwaters discharged into aerobic environments microbial methane oxidation occurred, with the residual methane becoming progressively enriched in 13C. Various models have been proposed to explain the 13C/12C and 14C content of the dissolved inorganic carbon (DIC) of groundwaters in terms of additions or losses during flow in the subsurface4,5. The knowledge of both stable carbon isotope ratios in various pools and the magnitude of carbon isotope fractionation during various processes allows geochemists to use the 13C/12C ratio of the DIC along with water chemistry to estimate corrected 14C groundwater ages4,5. We show here that a knowledge of the carbon isotope fractionation between CH4 and CO2 during microbial methane-utilization could modify such models for application to groundwaters affected by microbial methane oxidation.

Microbial Removal of Atmospheric Carbon Tetrachloride in Bulk Aerobic Soils▿

PubMed Central

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

2011-01-01

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

Portable Cavity Ringdown Spectrometer for Methane Isotope Ratio Measurements

NASA Astrophysics Data System (ADS)

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

2008-12-01

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

New evidence for Cu-decorated binary-oxides mediating bacterial inactivation/mineralization in aerobic media.

PubMed

Rtimi, S; Pulgarin, C; Bensimon, M; Kiwi, J

2016-08-01

Binary oxide semiconductors TiO2-ZrO2 and Cu-decorated TiO2-ZrO2 (TiO2-ZrO2-Cu) uniform films were sputtered on polyester (PES). These films were irradiated under low intensity solar simulated light and led to bacterial inactivation in aerobic and anaerobic media as evaluated by CFU-plate counting. But bacterial mineralization was only induced by TiO2-ZrO2-Cu in aerobic media. The highly oxidative radicals generated on the films surface under light were identified by the use of appropriate scavengers. The hole generated on the TiO2-ZrO2 films is shown to be the main specie leading to bacterial inactivation. TiO2-ZrO2 and Cu-decorated TiO2-ZrO2 films release Zr and Ti <1ppb and Cu 4.6ppb/cm(2) as determined by inductively coupled plasma mass spectrometry (ICP-MS) This level is far below the citotoxicity permitted level allowed for mammalian cells suggesting that bacterial disinfection proceeds through an oligodynamic effect. By Fourier transform attenuated infrared spectroscopy (ATR-FTIR) the systematic shift of the predominating νs(CH2) vibrational-rotational peak making up most of the bacterial cell-wall content in C was monitored. Based on this evidence a mechanism suggested leading to CH bond stretching followed by cell lysis and cell death. Bacterial inactivation cycling was observed on TiO2-ZrO2-Cu showing the stability of these films leading to bacterial inactivation. Copyright © 2016 Elsevier B.V. All rights reserved.

Compositional and functional stability of aerobic methane consuming communities in drained and rewetted peat meadows.

PubMed

Krause, Sascha; Niklaus, Pascal A; Badwan Morcillo, Sara; Meima Franke, Marion; Lüke, Claudia; Reim, Andreas; Bodelier, Paul L E

2015-11-01

The restoration of peatlands is an important strategy to counteract subsidence and loss of biodiversity. However, responses of important microbial soil processes are poorly understood. We assessed functioning, diversity and spatial organization of methanotrophic communities in drained and rewetted peat meadows with different water table management and agricultural practice. Results show that the methanotrophic diversity was similar between drained and rewetted sites with a remarkable dominance of the genus Methylocystis. Enzyme kinetics depicted no major differences, indicating flexibility in the methane (CH4) concentrations that can be used by the methanotrophic community. Short-term flooding led to temporary elevated CH4 emission but to neither major changes in abundances of methane-oxidizing bacteria (MOB) nor major changes in CH4 consumption kinetics in drained agriculturally used peat meadows. Radiolabeling and autoradiographic imaging of intact soil cores revealed a markedly different spatial arrangement of the CH4 consuming zone in cores exposed to near-atmospheric and elevated CH4. The observed spatial patterns of CH4 consumption in drained peat meadows with and without short-term flooding highlighted the spatial complexity and responsiveness of the CH4 consuming zone upon environmental change. The methanotrophic microbial community is not generally altered and harbors MOB that can cover a large range of CH4 concentrations offered due to water-table fluctuations, effectively mitigating CH4 emissions. © FEMS 2015. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

A cool-temperate young larch plantation as a net methane source - A 4-year continuous hyperbolic relaxed eddy accumulation and chamber measurements

NASA Astrophysics Data System (ADS)

Ueyama, Masahito; Yoshikawa, Kota; Takagi, Kentaro

2018-07-01

Upland forests are thought to be methane (CH4) sinks due to oxidation by methanotrophs in aerobic soils. However, CH4 budget for upland forests are not well quantified at the ecosystem scale, when possible CH4 sources, such as small wet areas, exists in the ecosystem. Here, we quantified CH4 fluxes in a cool-temperate larch plantation based on four-year continuous measurements using the hyperbolic relaxed eddy accumulation (HREA) method and dynamic closed chambers with a laser-based analyzer. After filling data gaps for half-hourly data using machine-learning-based regressions, we found that the forest acted as a net CH4 source at the canopy scale: 30 ± 11 mg CH4 m-2 yr-1 in 2014, 56 ± 8 mg CH4 m-2 yr-1 in 2015, 154 ± 5 mg CH4 m-2 yr-1 in 2016, and 132 ± 6 mg CH4 m-2 yr-1 in 2017. Hotspot emissions from the edge of the pond could strongly contribute to the canopy-scale emissions. The magnitude of the hotspot emissions was 10-100 times greater than the order of the canopy-scale and chamber-based CH4 fluxes at the dry soils. The high temperatures with wet conditions stimulated the hotspot emissions, and thus induced canopy-scale CH4 emissions in the summer. Understanding and modeling the dynamics of hotspot emissions are important for quantifying CH4 budgets of upland forests. Micrometeorological measurements at various forests are required for revisiting CH4 budget of upland forests.

Field assessment of semi-aerobic condition and the methane correction factor for the semi-aerobic landfills provided by IPCC guidelines.

PubMed

Jeong, Sangjae; Nam, Anwoo; Yi, Seung-Muk; Kim, Jae Young

2015-02-01

According to IPCC guidelines, a semi-aerobic landfill site produces one-half of the amount of CH4 produced by an equally-sized anaerobic landfill site. Therefore categorizing the landfill type is important on greenhouse gas inventories. In order to assess semi-aerobic condition in the sites and the MCF value for semi-aerobic landfill, landfill gas has been measured from vent pipes in five semi-aerobically designed landfills in South Korea. All of the five sites satisfied requirements of semi-aerobic landfills in 2006 IPCC guidelines. However, the ends of leachate collection pipes which are main entrance of air in the semi-aerobic landfill were closed in all five sites. The CH4/CO2 ratio in landfill gas, indicator of aerobic and anaerobic decomposition, ranged from 1.08 to 1.46 which is higher than the values (0.3-1.0) reported for semi-aerobic landfill sites and is rather close to those (1.0-2.0) for anaerobic landfill sites. The low CH4+CO2% in landfill gas implied air intrusion into the landfill. However, there was no evidence that air intrusion has caused by semi-aerobic design and operation. Therefore, the landfills investigated in this study are difficult to be classified as semi-aerobic landfills. Also MCF of 0.5 may significantly underestimate methane emissions compared to other researches. According to the carbon mass balance analyses, the higher MCF needs to be proposed for semi-aerobic landfills. Consequently, methane emission estimate should be based on field evaluation for the semi-aerobically designed landfills. Copyright © 2015. Published by Elsevier Ltd.

Cu-catalyzed esterification reaction via aerobic oxygenation and C-C bond cleavage: an approach to α-ketoesters.

PubMed

Zhang, Chun; Feng, Peng; Jiao, Ning

2013-10-09

The Cu-catalyzed novel aerobic oxidative esterification reaction of 1,3-diones for the synthesis of α-ketoesters has been developed. This method combines C-C σ-bond cleavage, dioxygen activation and oxidative C-H bond functionalization, as well as provides a practical, neutral, and mild synthetic approach to α-ketoesters which are important units in many biologically active compounds and useful precursors in a variety of functional group transformations. A plausible radical process is proposed on the basis of mechanistic studies.

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

NASA Astrophysics Data System (ADS)

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

2012-12-01

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

Methane correction factors for estimating emissions from aerobic wastewater treatment facilities based on field data in Mexico and on literature review.

PubMed

Noyola, A; Paredes, M G; Güereca, L P; Molina, L T; Zavala, M

2018-10-15

Wastewater treatment (WWT) may be an important source of methane (CH 4 ), a greenhouse gas with significant global warming potential. Sources of CH 4 emissions from WWT facilities can be found in the water and in the sludge process lines. Among the methodologies for estimating CH 4 emissions inventories from WWT, the more adopted are the guidelines of the Intergovernmental Panel on Climate Change (IPCC), which recommends default emission factors (Tier 1) depending on WWT systems. Recent published results show that well managed treatment facilities may emit CH 4 , due to dissolved CH 4 in the influent wastewater; in addition, biological nutrient removal also will produce this gas in the anaerobic (or anoxic) steps. However, none of these elements is considered in the current IPCC guidelines. The aim of this work is to propose modified (and new) methane correction factors (MCF) regarding the current Tier 1 IPCC guidelines for CH 4 emissions from aerobic treatment systems, with and without anaerobic sludge digesters, focusing on intertropical countries. The modifications are supported on in situ assessment of fugitive CH 4 emissions in two facilities in Mexico and on relevant literature data. In the case of well-managed centralized aerobic treatment plant, a MCF of 0.06 (instead of the current 0.0) is proposed, considering that the assumption of a CH 4 -neutral treatment facility, as established in the IPCC methodology, is not supported. Similarly, a MCF of 0.08 is proposed for biological nutrient removal processes, being a new entry in the guidelines. Finally, a one-step straightforward calculation is proposed for centralized aerobic treatment plants with anaerobic digesters that avoids confusion when selecting the appropriate default MCF based on the Tier 1 IPCC guidelines. Copyright © 2018 The Authors. Published by Elsevier B.V. All rights reserved.

Microbial CH4 and N2O Consumption in Acidic Wetlands

PubMed Central

Kolb, Steffen; Horn, Marcus A.

2012-01-01

Acidic wetlands are global sources of the atmospheric greenhouse gases methane (CH4), and nitrous oxide (N2O). Consumption of both atmospheric gases has been observed in various acidic wetlands, but information on the microbial mechanisms underlying these phenomena is scarce. A substantial amount of CH4 is consumed in sub soil by aerobic methanotrophs at anoxic–oxic interfaces (e.g., tissues of Sphagnum mosses, rhizosphere of vascular plant roots). Methylocystis-related species are likely candidates that are involved in the consumption of atmospheric CH4 in acidic wetlands. Oxygen availability regulates the activity of methanotrophs of acidic wetlands. Other parameters impacting on the methanotroph-mediated CH4 consumption have not been systematically evaluated. N2O is produced and consumed by microbial denitrification, thus rendering acidic wetlands as temporary sources or sinks for N2O. Denitrifier communities in such ecosystems are diverse, and largely uncultured and/or new, and environmental factors that control their consumption activity are unresolved. Analyses of the composition of N2O reductase genes in acidic wetlands suggest that acid-tolerant Proteobacteria have the potential to mediate N2O consumption in such soils. Thus, the fragmented current state of knowledge raises open questions concerning methanotrophs and denitrifiers that consume atmospheric CH4 and N2O in acidic wetlands. PMID:22403579

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

USGS Publications Warehouse

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

1993-01-01

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

Oxidation and reduction rates for organic carbon in the Amazon mainstream tributary and floodplain, inferred from distributions of dissolved gases

NASA Technical Reports Server (NTRS)

Richey, Jeffrey E.; Devol, Allan H.; Wofsy, Steven C.; Victoria, Reynaldo; Riberio, Maria N. G.

1986-01-01

Concentrations of CO2, O2, CH4, and N2O in the Amazon River system reflect an oxidation-reduction sequence in combination with physical mixing between the floodplain and the mainstem. Concentrations of CO2 ranged from 150 microM in the Amazon mainstem to 200 to 300 microM in aerobic waters of the floodplain, and up to 1000 microM in oxygen-depleted environments. Apparent oxygen utilization (AOU) ranged from 80 to 250 microM. Methane was highly supersaturated, with concentrations ranging from 0.06 microM in the mainstem to 100 microM on the floodplain. Concentrations of N2O were slightly supersaturated in the mainstem, but were undersaturated on the floodplain. Fluxes calculated from these concentrations indicated decomposition of 1600 g C sq m y(-1) of organic carbon in Amazon floodplain waters. Analysis of relationships between CH4, O2, and CO2 concentrations indicated that approximately 50 percent of carbon mineralization on the floodplain is anaerobic, with 20 percent lost to the atmoshphere as CH4. The predominance of anaerobic metabolism leads to consumption of N2O on the flood plane. Elevated concentrations of CH4 in the mainstem probably reflect imput from the floodplain, while high levels of CO2 in the mainstem are derived from a combination of varzea drainage and in situ respiration.

Methanotrophic communities in aerobic soils with different stages of natural reforestation

NASA Astrophysics Data System (ADS)

Kravchenko, Irina; Sukhacheva, Marina; Kuznetsova, Tatyana

2017-04-01

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

Treatment of an actual slaughterhouse wastewater by integration of biological and advanced oxidation processes: Modeling, optimization, and cost-effectiveness analysis.

PubMed

Bustillo-Lecompte, Ciro Fernando; Mehrvar, Mehrab

2016-11-01

Biological and advanced oxidation processes are combined to treat an actual slaughterhouse wastewater (SWW) by a sequence of an anaerobic baffled reactor, an aerobic activated sludge reactor, and a UV/H2O2 photoreactor with recycle in continuous mode at laboratory scale. In the first part of this study, quadratic modeling along with response surface methodology are used for the statistical analysis and optimization of the combined process. The effects of the influent total organic carbon (TOC) concentration, the flow rate, the pH, the inlet H2O2 concentration, and their interaction on the overall treatment efficiency, CH4 yield, and H2O2 residual in the effluent of the photoreactor are investigated. The models are validated at different operating conditions using experimental data. Maximum TOC and total nitrogen (TN) removals of 91.29 and 86.05%, respectively, maximum CH4 yield of 55.72%, and minimum H2O2 residual of 1.45% in the photoreactor effluent were found at optimal operating conditions. In the second part of this study, continuous distribution kinetics is applied to establish a mathematical model for the degradation of SWW as a function of time. The agreement between model predictions and experimental values indicates that the proposed model could describe the performance of the combined anaerobic-aerobic-UV/H2O2 processes for the treatment of SWW. In the final part of the study, the optimized combined anaerobic-aerobic-UV/H2O2 processes with recycle were evaluated using a cost-effectiveness analysis to minimize the retention time, the electrical energy consumption, and the overall incurred treatment costs required for the efficient treatment of slaughterhouse wastewater effluents. Copyright © 2016 Elsevier Ltd. All rights reserved.

Methanotrophic bacteria in oilsands tailings ponds of northern Alberta

PubMed Central

Saidi-Mehrabad, Alireza; He, Zhiguo; Tamas, Ivica; Sharp, Christine E; Brady, Allyson L; Rochman, Fauziah F; Bodrossy, Levente; Abell, Guy CJ; Penner, Tara; Dong, Xiaoli; Sensen, Christoph W; Dunfield, Peter F

2013-01-01

We investigated methanotrophic bacteria in slightly alkaline surface water (pH 7.4–8.7) of oilsands tailings ponds in Fort McMurray, Canada. These large lakes (up to 10 km2) contain water, silt, clay and residual hydrocarbons that are not recovered in oilsands mining. They are primarily anoxic and produce methane but have an aerobic surface layer. Aerobic methane oxidation was measured in the surface water at rates up to 152 nmol CH4 ml−1 water d−1. Microbial diversity was investigated via pyrotag sequencing of amplified 16S rRNA genes, as well as by analysis of methanotroph-specific pmoA genes using both pyrosequencing and microarray analysis. The predominantly detected methanotroph in surface waters at all sampling times was an uncultured species related to the gammaproteobacterial genus Methylocaldum, although a few other methanotrophs were also detected, including Methylomonas spp. Active species were identified via 13CH4 stable isotope probing (SIP) of DNA, combined with pyrotag sequencing and shotgun metagenomic sequencing of heavy 13C-DNA. The SIP-PCR results demonstrated that the Methylocaldum and Methylomonas spp. actively consumed methane in fresh tailings pond water. Metagenomic analysis of DNA from the heavy SIP fraction verified the PCR-based results and identified additional pmoA genes not detected via PCR. The metagenome indicated that the overall methylotrophic community possessed known pathways for formaldehyde oxidation, carbon fixation and detoxification of nitrogenous compounds but appeared to possess only particulate methane monooxygenase not soluble methane monooxygenase. PMID:23254511

Methane oxidation linked to chlorite dismutation

USGS Publications Warehouse

Miller, Laurence G.; Baesman, Shaun M.; Carlström, Charlotte I.; Coates, John D.; Oremland, Ronald S.

2014-01-01

We examined the potential for CH4 oxidation to be coupled with oxygen derived from the dissimilatory reduction of perchlorate, chlorate, or via chlorite (ClO−2) dismutation. Although dissimilatory reduction of ClO−4 and ClO−3 could be inferred from the accumulation of chloride ions either in spent media or in soil slurries prepared from exposed freshwater lake sediment, neither of these oxyanions evoked methane oxidation when added to either anaerobic mixed cultures or soil enriched in methanotrophs. In contrast, ClO−2 amendment elicited such activity. Methane (0.2 kPa) was completely removed within several days from the headspace of cell suspensions of Dechloromonas agitata CKB incubated with either Methylococcus capsulatus Bath or Methylomicrobium album BG8 in the presence of 5 mM ClO−2. We also observed complete removal of 0.2 kPa CH4 in bottles containing soil enriched in methanotrophs when co-incubated with D. agitata CKB and 10 mM ClO−2. However, to be effective these experiments required physical separation of soil from D. agitata CKB to allow for the partitioning of O2 liberated from chlorite dismutation into the shared headspace. Although a link between ClO−2 and CH4 consumption was established in soils and cultures, no upstream connection with either ClO−4 or ClO−3 was discerned. This result suggests that the release of O2 during enzymatic perchlorate reduction was negligible, and that the oxygen produced was unavailable to the aerobic methanotrophs.

A microbial functional group-based module for simulating methane production and consumption: Application to an incubated permafrost soil

DOE PAGES

Xu, Xiaofeng; Elias, Dwayne A.; Graham, David E.; ...

2015-07-23

In this study, accurately estimating methane (CH 4) flux is critically important for investigating and predicting the biogeochemistry-climate feedback. Better simulating CH 4 flux requires explicit representations of microbial processes on CH 4 dynamics because all processes for CH 4 production and consumption are actually carried out by microbes. A microbial functional group based module was developed and tested against an incubation experiment. The module considers four key mechanisms for CH 4 production and consumption: methanogenesis from acetate or single-carbon compounds and CH 4 oxidation using molecular oxygen or other inorganic electron acceptors. These four processes were carried out bymore » four microbial functional groups: acetoclastic methanogens, hydrogenotrophic methanogens, aerobic methanotrophs, and anaerobic methanotrophs. This module was then linked with the decomposition subroutine of the Community Land Model, and was further used to simulate dynamics of carbon dioxide (CO 2) and CH 4 concentrations from an incubation experiment with permafrost soils. The results show that the model could capture the dynamics of CO 2 and CH 4 concentrations in microcosms with top soils, mineral layer soils and permafrost soils under natural and saturated moisture conditions and a temperature gradient of -2°C, 3°C, and 5°C. Sensitivity analysis confirmed the importance of acetic acid's direct contribution as substrate and indirect effects through pH feedback on CO 2 and CH 4 production and consumption. This study suggests that representing the microbial mechanisms is critical for modeling CH 4 production and consumption; it is urgent to incorporate microbial mechanisms into Earth system models for better predicting the behavior of the climate system.« less

Anaerobic methane oxidation in two tropical freshwater systems

NASA Astrophysics Data System (ADS)

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

2014-05-01

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

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

PubMed Central

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

2016-01-01

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

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

PubMed

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

2016-02-28

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

Effects of Methane-Rich Saline on the Capability of One-Time Exhaustive Exercise in Male SD Rats

PubMed Central

Xin, Lei; Sun, Xuejun; Lou, Shujie

2016-01-01

Purpose To explore the effects of methane-rich saline (CH4 saline) on the capability of one-time exhaustive exercise in male SD rats. Methods Thirty rats were equally divided into to three groups at random: control group (C), placebo group (P) and methane saline group (M). Rats in M group underwent intraperitoneal injection of CH4 saline, and the other two groups simultaneously underwent intraperitoneal injection of normal saline. Then, the exercise capability of rats was tested through one-time exhaustive treadmill exercise except C group. Exercise time and body weight were recorded before and after one-time exhaustive exercise. After exhaustive exercise, the blood and gastrocnemius samples were collected from all rats to detect biochemical parameters in different methods. Results It was found that the treadmill running time was significantly longer in rats treated with CH4 saline. At the same time, CH4 saline reduced the elevation of LD and UN in blood caused by one-time exhaustive exercise. The low level of blood glucose induced by exhaustive exercise was also normalized by CH4 saline. Also CH4 saline lowered the level of CK in plasma. Furthermore, this research indicated that CH4 saline markedly increased the volume of T-AOC in plasma and alleviated the peak of TNF-α in both plasma and gastrocnemius. From H&E staining, CH4 saline effectively improved exercise-induced structural damage in gastrocnemius. Conclusions CH4 saline could enhance exercise capacity in male SD rats through increase of glucose aerobic oxidation, improvement of metabolic clearance and decrease of exhaustive exercise-induced gastrocnemius injury. PMID:26942576

Production of Nitrous Oxide from Nitrite in Stable Type II Methanotrophic Enrichments.

PubMed

Myung, Jaewook; Wang, Zhiyue; Yuan, Tong; Zhang, Ping; Van Nostrand, Joy D; Zhou, Jizhong; Criddle, Craig S

2015-09-15

The coupled aerobic-anoxic nitrous decomposition operation is a new process for wastewater treatment that removes nitrogen from wastewater and recovers energy from the nitrogen in three steps: (1) NH4(+) oxidation to NO2(-), (2) NO2(-) reduction to N2O, and (3) N2O conversion to N2 with energy production. Here, we demonstrate that type II methanotrophic enrichments can mediate step two by coupling oxidation of poly(3-hydroxybutyrate) (P3HB) to NO2(-) reduction. Enrichments grown with NH4(+) and NO2(-) were subject to alternating 48-h aerobic and anoxic periods, in which CH4 and NO2(-) were added together in a "coupled" mode of operation or separately in a "decoupled mode". Community structure was stable in both modes and dominated by Methylocystis. In the coupled mode, production of P3HB and N2O was low. In the decoupled mode, significant P3HB was produced, and oxidation of P3HB drove reduction of NO2(-) to N2O with ∼ 70% conversion for >30 cycles (120 d). In batch tests of wasted cells from the decoupled mode, N2O production rates increased at low O2 or high NO2(-) levels. The results are significant for the development of engineered processes that remove nitrogen from wastewater and for understanding of conditions that favor environmental production of N2O.

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

NASA Astrophysics Data System (ADS)

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

2016-04-01

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

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

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

NASA Astrophysics Data System (ADS)

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

2010-05-01

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

Emission of methane, carbon monoxide, carbon dioxide and short‐chain hydrocarbons from vegetation foliage under ultraviolet irradiation

PubMed Central

FRASER, WESLEY T.; BLEI, EMANUEL; FRY, STEPHEN C.; NEWMAN, MARK F.; REAY, DAVID S.; SMITH, KEITH A.

2015-01-01

Abstract The original report that plants emit methane (CH 4) under aerobic conditions caused much debate and controversy. Critics questioned experimental techniques, possible mechanisms for CH 4 production and the nature of estimating global emissions. Several studies have now confirmed that aerobic CH 4 emissions can be detected from plant foliage but the extent of the phenomenon in plants and the precise mechanisms and precursors involved remain uncertain. In this study, we investigated the role of environmentally realistic levels of ultraviolet (UV) radiation in causing the emission of CH 4 and other gases from foliage obtained from a wide variety of plant types. We related our measured emissions to the foliar content of methyl esters and lignin and to the epidermal UV absorbance of the species investigated. Our data demonstrate that the terrestrial vegetation foliage sampled did emit CH 4, with a range in emissions of 0.6–31.8 ng CH 4 g−1 leaf DW h−1, which compares favourably with the original reports of experimental work. In addition to CH 4 emissions, our data show that carbon monoxide, ethene and propane are also emitted under UV stress but we detected no significant emissions of carbon dioxide or ethane. PMID:25443986

Observations on the methane oxidation capacity of landfill soils.

PubMed

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

2011-05-01

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

Screening biological methods for laboratory scale stabilization of fine fraction from landfill mining.

PubMed

Mönkäre, Tiina J; Palmroth, Marja R T; Rintala, Jukka A

2017-02-01

Increasing interest for the landfill mining and the amount of fine fraction (FF) in landfills (40-70% (w/w) of landfill content) mean that sustainable treatment and utilization methods for FF are needed. For this study FF (<20mm) was mined from a municipal solid waste (MSW) landfill operated from 1967 to 1989. FF, which resembles soil, was stabilized in laboratory scale reactors in two phases: first, anaerobically for 101days and second, for 72days using four different methods: anaerobic with the addition of moisture (water) or inoculum (sewage sludge) and aerobic with continuous water washing, with, or without, bulking material. The aim was to evaluate the effect on the stability of mined FF, which has been rarely reported, and to study the quality and quantity of gas and leachate produced during the stabilization experiment. The study showed that aerobic treatment reduced respiration activity (final values 0.9-1.1mgO 2 /gTS) and residual methane potential (1.1LCH 4 /kgTS) better than anaerobic methods (1.8-2.3mg O 2 /g TS and 1.3-2.4L CH 4 /kg TS, respectively). Bulking material mixed in FF in one aerobic reactor had no effect on the stability of FF. The benefit of anaerobic treatment was the production of methane, which could be utilized as energy. Even though the inoculum addition increased methane production from FF about 30%, but the methane production was still relatively low (in total 1.5-1.7L CH 4 /kg TS). Continuous water washing was essential to remove leachable organic matter and soluble nutrients from FF, while increasing the volume of leachate collected. In the aerobic treatment, nitrogen was oxidized into nitrite and nitrate and then washed out in the leachate. Both anaerobic and aerobic methods could be used for FF stabilization. The use of FF, in landscaping for example, is possible because its nutrient content (4gN/kg TS and 1g P/kg TS) can increase the nutrient content of soil, but this may have limitations due to the possible presence of heavy metal and other contaminants. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

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

NASA Astrophysics Data System (ADS)

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

2012-12-01

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

Uncoupling of the Pathway of Methanogenesis in Northern Wetlands: Connection to Vegetation, and Implications for Variability and Predictability.

NASA Astrophysics Data System (ADS)

Hines, M. E.; Duddleston, K. N.; Chanton, J. P.

2006-12-01

Typical methanogenic decomposition pathways include near terminal carbon intermediates that turn over rapidly with small pool sizes. However, incubation and field experiments demonstrated that these organic intermediates accumulate in northern wetlands due to the lack of consumption by methanogenic bacteria. Acetate is the major organic end product of decomposition rather than CH4, and methanogenesis can be insignificant. The ratio of CO2:acetate:CH4 varied with vegetation type, and habitats dominated by non-vascular plants (Sphagnum) produced more acetate-C than CO2 or CH4. This ratio correlated well with stable C isotope alpha values used to delineate the path of CH4 formation. We suggest that methanogenesis in general is inhibited in oligotrophic wetlands, but that the conversion of acetate to CH4 is more sensitive, which increases the importance of the conversion of H2/CO2 to CH4. The relative importance of CH4 as an end product increased greatly in sites containing even small populations of Carex compared to sites inhabited only by Sphagnum, suggesting that subtle vegetation changes expected to occur during warming could lead to changes in the path of methanogenesis, increasing production. In addition, depth profiles revealed an active surficial (0-7 cm) C cycle that is sensitive to hydrology that may also greatly affect variability of CH4 formation. Acetate production represented a terminal process and was a sink for a large portion of metabolized C whose ultimate fate was aerobic oxidation to CO2. C destined for CH4 is thus bypassed to CO2 and does not contribute to atmospheric CH4. However, the connection and sensitivity of the pathway of methanogenesis to even small vegetation changes suggests that pathways can be mapped, they vary greatly over small distances, and they can change drastically with relatively small temperature increases.

Potential carbon emissions dominated by carbon dioxide from thawed permafrost soils

DOE PAGES

Schadel, Christina; Bader, Martin K. F.; Schuur, Edward; ...

2016-01-01

Increasing temperatures in northern high latitudes are causing permafrost to thaw, making large amounts of previously frozen organic matter vulnerable to microbial decomposition. Permafrost thaw also creates a fragmented landscape of drier and wetter soil conditions that determine the amount and form (carbon dioxide (CO2), or methane (CH4)) of carbon (C) released to the atmosphere. The rate and form of C release control the magnitude of the permafrost C feedback, so their relative contribution with a warming climate remains unclear. We quantified the effect of increasing temperature and changes from aerobic to anaerobic soil conditions using 25 soil incubation studiesmore » from the permafrost zone. Here we show, using two separate meta-analyses, that a 10 C increase in incubation temperature increased C release by a factor of 2.0 (95% confidence interval (CI), 1.8 to 2.2). Under aerobic incubation conditions, soils released 3.4 (95% CI, 2.2 to 5.2) times more C than under anaerobic conditions. Even when accounting for the higher heat trapping capacity of CH4, soils released 2.3 (95% CI, 1.5 to 3.4) times more C under aerobic conditions. These results imply that permafrost ecosystems thawing under aerobic conditions and releasing CO2 will strengthen the permafrost C feedback more than waterlogged systemsreleasingCO2 andCH4 for a given amount of C.« less

Potential carbon emissions dominated by carbon dioxide from thawed permafrost soils

USGS Publications Warehouse

Schädel, Christina; Bader, Martin K.-F.; Schuur, Edward A.G.; Biasi, Christina; Bracho, Rosvel; Čapek, Petr; De Baets, Sarah; Diáková, Kateřina; Ernakovich, Jessica; Estop-Aragones, Cristian; Graham, David E.; Hartley, Iain P.; Iversen, Colleen M.; Kane, Evan S.; Knoblauch, Christian; Lupascu, Massimo; Martikainen, Pertti J.; Natali, Susan M.; Norby, Richard J.; O'Donnell, Jonathan A.; Roy Chowdhury, Taniya; Šantrůčková, Hana; Shaver, Gaius; Sloan, Victoria L.; Treat, Claire C.; Turetsky, Merritt R.; Waldrop, Mark P.; Wickland, Kimberly P.

2016-01-01

Increasing temperatures in northern high latitudes are causing permafrost to thaw, making large amounts of previously frozen organic matter vulnerable to microbial decomposition. Permafrost thaw also creates a fragmented landscape of drier and wetter soil conditions that determine the amount and form (carbon dioxide (CO2), or methane (CH4)) of carbon (C) released to the atmosphere. The rate and form of C release control the magnitude of the permafrost C feedback, so their relative contribution with a warming climate remains unclear. We quantified the effect of increasing temperature and changes from aerobic to anaerobic soil conditions using 25 soil incubation studies from the permafrost zone. Here we show, using two separate meta-analyses, that a 10 °C increase in incubation temperature increased C release by a factor of 2.0 (95% confidence interval (CI), 1.8 to 2.2). Under aerobic incubation conditions, soils released 3.4 (95% CI, 2.2 to 5.2) times more C than under anaerobic conditions. Even when accounting for the higher heat trapping capacity of CH4, soils released 2.3 (95% CI, 1.5 to 3.4) times more C under aerobic conditions. These results imply that permafrost ecosystems thawing under aerobic conditions and releasing CO2 will strengthen the permafrost C feedback more than waterlogged systems releasing CO2 and CH4 for a given amount of C.

A bioinspired catalytic aerobic oxidative C-H functionalization of primary aliphatic amines: synthesis of 1,2-disubstituted benzimidazoles.

PubMed

Nguyen, Khac Minh Huy; Largeron, Martine

2015-09-01

Aerobic oxidative CH functionalization of primary aliphatic amines has been accomplished with a biomimetic cooperative catalytic system to furnish 1,2-disubstituted benzimidazoles that play an important role as drug discovery targets. This one-pot atom-economical multistep process, which proceeds under mild conditions, with ambient air and equimolar amounts of each coupling partner, constitutes a convenient environmentally friendly strategy to functionalize non-activated aliphatic amines that remain challenging substrates for non-enzymatic catalytic aerobic systems. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of Creative Commons Attribution NonCommercial-NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.

Pd-Catalyzed Aerobic Oxidative Biaryl Coupling: Non-Redox Cocatalysis by Cu(OTf)2 and Discovery of Fe(OTf)3 as a Highly Effective Cocatalyst.

PubMed

Wang, Dian; Stahl, Shannon S

2017-04-26

Copper salts find widespread use in Pd-catalyzed oxidation reactions, and they are typically used as oxidants or redox-active cocatalysts. Here, we probe the origin of a dramatic acceleration effect of Cu(OTf) 2 in the C-H/C-H aerobic oxidative coupling of o-xylene. NMR spectroscopic analysis of the Pd II catalyst in the presence of Cu(OTf) 2 , together with other experimental and DFT computational studies of the catalytic reaction, show that Cu(OTf) 2 activates the Pd II catalyst for C-H activation via a non-redox pathway and has negligible impact on catalyst reoxidation. These observations led to the testing of other metal triflate salts as cocatalysts, the results of which show that Fe(OTf) 3 is even more effective than Cu(OTf) 2 .

Copper-promoted methylene C-H oxidation to a ketone derivative by O2.

PubMed

Deville, Claire; McKee, Vickie; McKenzie, Christine J

2017-01-17

The methylene group of the ligand 1,2-di(pyridin-2-yl)-ethanone oxime (dpeo) is slowly oxygenated by the O 2 in air under ambient conditions when [Cu(dpeo) 2 ](ClO 4 ) 2 is dissolved in ethanol or acetonitrile. An initial transient ketone product, 2-(hydroxyimino)-1,2-di(pyridine-2-yl)ethanone, (hidpe) was characterized in the heteroleptic copper(ii) complex [Cu(bpca)(hidpe)](ClO 4 ). The co-ligand in this complex, N-(2'-pyridylcarbonyl)pyridine-2-carboximidate (bpca - ), is derived from a copper-promoted Beckmann rearrangement of hidpe. In the presence of bromide only [Cu(bpca)Br] is isolated. When significant water is present in reaction mixtures copper complexes of dpeo, hidpe and bpca - are not recovered and [Cu(pic) 2 H 2 O] is isolated. This occurs since two equivalents of picolinate are ultimately generated from one equivalent of oxidized and hydrolysed dpeo. The copper-dependent O 2 activation and consequent stoichiometric dpeo C-H oxidation is reminiscent of the previously observed catalysis of dpeo oxidation by Mn(ii) [C. Deville, S. K. Padamati, J. Sundberg, V. McKee, W. R. Browne, C. J. McKenzie, Angew. Chem., Int. Ed., 2016, 55, 545-549]. By contrast dpeo oxidation is not observed during complexation reactions with other late transition metal(ii) ions (M = Fe, Co, Ni, Zn) under aerobic conditions. In these cases bis and tris complexes of bidentate dpeo are isolated in good yields. It is interesting to note that dpeo is not oxidised by H 2 O 2 in the absence of Cu or Mn, suggesting that metal-based oxidants capable of C-H activation are produced from the dpeo-Cu/Mn systems and specifically O 2 . The metastable copper complexes [Cu(dpeo) 2 ](ClO 4 ) 2 and [Cu(bpca)(hidpe)](ClO 4 ), along with [NiX 2 (dpeo) 2 ] (X = Cl, Br), [Ni(dpeo) 3 ](ClO 4 ) 2 , [Co(dpeo) 3 ](ClO 4 ) 3 and the mixed valence complex [Fe III Fe(dpeo-H) 3 (dpeo) 3 ](PF 6 ) 4 , have been structurally characterized.

Calculation of total free energy yield as an alternative approach for predicting the importance of potential chemolithotrophic reactions in geothermal springs.

PubMed

Dodsworth, Jeremy A; McDonald, Austin I; Hedlund, Brian P

2012-08-01

To inform hypotheses regarding the relative importance of chemolithotrophic metabolisms in geothermal environments, we calculated free energy yields of 26 chemical reactions potentially supporting chemolithotrophy in two US Great Basin hot springs, taking into account the effects of changing reactant and product activities on the Gibbs free energy as each reaction progressed. Results ranged from 1.2 × 10(-5) to 3.6 J kg(-1) spring water, or 3.7 × 10(-5) to 11.5 J s(-1) based on measured flow rates, with aerobic oxidation of CH(4) or NH4 + giving the highest average yields. Energy yields calculated without constraining pH were similar to those at constant pH except for reactions where H(+) was consumed, which often had significantly lower yields when pH was unconstrained. In contrast to the commonly used normalization of reaction chemical affinities per mole of electrons transferred, reaction energy yields for a given oxidant varied by several orders of magnitude and were more sensitive to differences in the activities of products and reactants. The high energy yield of aerobic ammonia oxidation is consistent with previous observations of significant ammonia oxidation rates and abundant ammonia-oxidizing archaea in sediments of these springs. This approach offers an additional lens through which to view the thermodynamic landscape of geothermal springs. © 2012 Federation of European Microbiological Societies. Published by Blackwell Publishing Ltd. All rights reserved.

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

USGS Publications Warehouse

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

2015-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-04-01

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

The variations of Oxidation-Reduction Potential in paddy soil and effects on the methane emission from a periodically irrigated paddy field.

NASA Astrophysics Data System (ADS)

Yagi, K.; Iwata, T.; Wakikuromaru, N.

2014-12-01

Paddy fields are one of the most important eco-system in monsoon Asia and one of the largest source of CH4 emission. CH4 has significant contribution to the global warming next to CO2 and its greenhouse effect is about 21 times as large as same amount of CO2. CH4 is generated by decomposition of organic matter in soil under anaerobic condition. Oxidation-Reduction Potential (ORP) is the most suitable index representing soil aerobic condition. Or, CH4 is more generated under lower ORP conditions. In this study, ORP in paddy soil was measured during rice cultivated season at a periodically irrigated paddy field, and some effects on the methane flux from the paddy soil was investigated. 3-days flood and 4-days drained condition were regularly repeated at the site from late-June to early October. ORP under flooded condition was measured during irrigated term in 2013 at two mode; regular interval measurement every 2 weeks and intensive measurements during two flooded periods. Methane flux was also measured by the aerodynamic gradient technique. ORP showed rapid decrease when irrigation water was introduced in the paddy field, and lower ORP was shown under the longer flooded condition. From the seasonal-term point of view, lower ORP was shown in later rice season. ORP was suitably modeled as a function of irrigation time. During an irrigation period for four days, higher methane emissions were shown under lower OPR conditions as shown in Fig.1. From the seasonal-term point of view, however, no significant relationship between ORP and methane fluxes. Rapid rise of CH4 flux in early August and gradual decrease between late August and September were shown. It is suggested that seasonal change of methane flux is affected by seasonal changes of soil temperature or the growth level of rice plants.

A mass balance model to estimate the rate of composting, methane oxidation and anaerobic digestion in soil covers and shallow waste layers.

PubMed

Rafiee, Reza; Obersky, Lizanne; Xie, Sihuang; Clarke, William P

2017-05-01

Although CH 4 oxidation in landfill soil covers is widely studied, the extent of composting and CH 4 oxidation in underlying waste layers has been speculated but not measured. The objective of this study was to develop and validate a mass balance model to estimate the simultaneous rates of anaerobic digestion (r AD ), CH 4 oxidation (r OX ) and composting (r COM ) in environments where O 2 penetration is variable and zones of aerobic and anaerobic activity are intermingled. The modelled domain could include, as an example, a soil cover and the underlying shallow waste to a nominated depth. The proposed model was demonstrated on a blend of biogas from three separate known sources of gas representing the three reaction processes: (i) a bottle of laboratory grade 50:50% CH 4 :CO 2 gas representing anaerobic digestion biogas; (ii) an aerated 250mL bottle containing food waste that represented composting activity; and (iii) an aerated 250mL bottle containing non-degradable graphite granules inoculated with methanotrophs and incubated with CH 4 and O 2 to represent methanotrophic activity. CO 2 , CH 4 , O 2 and the stable isotope 13 C-CO 2 were chosen as the components for the mass balance model. The three reaction rates, r (=r AD , r OX , r COM ) were calculated as fitting parameters to the overdetermined set of 4mass balance equations with the net flux of these components from the bottles q (= [Formula: see text] , [Formula: see text] , [Formula: see text] and [Formula: see text] ) as inputs to the model. The coefficient of determination (r 2 ) for observed versus modelled values of r were 1.00, 0.97, 0.98 when the stoichiometry of each reaction was based on gas yields measured in the individual bottles and q was calculated by summing yields from the three bottles. r 2 deteriorated to 0.95, 0.96, 0.87 when using an average stoichiometry from 11 incubations of each of the composting and methane oxidation processes. The significant deterioration in the estimation of r COM showed that this output is highly sensitive to the evaluated stoichiometry coefficients for the reactions. r 2 deteriorated further to 0.86, 0.77, 0.74 when using the average stoichiometry and experimental measurement of the composition and volume of the blended biogas to determine q. This was primarily attributed to average errors of 8%, 7%, 11% and 14% in the measurement of [Formula: see text] , [Formula: see text] , [Formula: see text] and [Formula: see text] relative to the measurement of the same quantities from the individual bottles. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effects of screenhouse cultivation and organic materials incorporation on global warming potential in rice fields.

PubMed

Xu, Guochun; Liu, Xin; Wang, Qiangsheng; Xiong, Ruiheng; Hang, Yuhao

2017-03-01

Global rice production will be increasingly challenged by providing healthy food for a growing population at minimal environmental cost. In this study, a 2-year field experiment was conducted to investigate the effects of a novel rice cultivation mode (screenhouse cultivation, SHC) and organic material (OM) incorporation (wheat straw and wheat straw-based biogas residue) on methane (CH 4 ) and nitrous oxide (N 2 O) emissions and rice yields. In addition, the environmental factors and soil properties were also determined. Relative to the traditional open-field cultivation (OFC), SHC decreased the CH 4 and N 2 O emissions by 6.58-18.73 and 2.51-21.35%, respectively, and the global warming potential (GWP) was reduced by 6.49-18.65%. This trend was mainly because of lower soil temperature and higher soil redox potential in SHC. Although the rice grain yield for SHC were reduced by 2.51-4.98% compared to the OFC, the CH 4 emissions and GWP per unit of grain yield (yield-scaled CH 4 emissions and GWP) under SHC were declined. Compared to use of inorganic fertilizer only (IN), combining inorganic fertilizer with wheat straw (WS) or wheat straw-based biogas residue (BR) improved rice grain yield by 2.12-4.10 and 4.68-5.89%, respectively. However, OM incorporation enhanced CH 4 emissions and GWP, leading to higher yield-scaled CH 4 emissions and GWP in WS treatment. Due to rice yield that is relatively high, there was no obvious effect of BR treatment on them. These findings suggest that apparent environmental benefit can be realized by applying SHC and fermenting straw aerobically before its incorporation.

Biotransformation potential of 6:2 fluorotelomer sulfonate (6:2 FTSA) in aerobic and anaerobic sediment.

PubMed

Zhang, Shu; Lu, Xiaoxia; Wang, Ning; Buck, Robert C

2016-07-01

Aqueous film-forming foam (AFFF) products are used in industrial and military firefighting around the globe. These products contain fluoroalkylthioamido sulfonates, fluoroalkylthiobetaine, and other related substances as the major ingredients, which can be biotransformed in the environment to form 6:2 fluorotelomer sulfonate (6:2 FTSA, F(CF2)6CH2CH2SO3-) as one of the major initial biotransformation products. Limited information is available on 6:2 FTSA aerobic biotransformation in activated sludge and pure microbial culture. This is the first study to report 6:2 FTSA biotransformation in aerobic and anaerobic sediment. 6:2 FTSA was rapidly biotransformed in aerobic river sediment with a half-life less than 5 d. Major stable transformation products observed after 90 d included 5:3 Acid [F(CF2)5CH2CH2COOH), 16 mol%), PFPeA [F(CF2)4COOH, 21 mol%] and PFHxA (F(CF2)5COOH, 20 mol%). 6:2 fluorotelomer alcohol [6:2 FTOH, F(CF2)6CH2CH2OH] was readily biotransfomed whereas 6:2 FTSA biotransformation did not occur in anaerobic sediment over 100 d, indicating that the enzymatic desulfonation step limited 6:2 FTSA biotransformation in anaerobic sediment. These results suggest that 6:2 FTSA related products, after release to the aerobic environment, is likely to biodegrade forming 5:3 Acid, PFPeA and PFHxA. This study also indicates that 6:2 FTSA formed from its aforementioned precursors may be persistent in the anaerobic environment after their potential release. This work provides insight to understanding the fate and environmental loading of AFFF-related products and their major transformation products in the environment. Copyright © 2016 Elsevier Ltd. All rights reserved.

WETTING STIMULATES ATMOSPHERIC CH4 OXIDATION BY ALPINE SOIL (R823442)

EPA Science Inventory

Studies were done to assess the effects of soil moisture manipulations on CH₄ oxidation in soils from a dry alpine tundra site. When water was added to these soils there was a stimulation of CH₄ oxidation. This stimulation of CH₄ oxidation took ti...

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

PubMed

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

2015-03-01

Mitigation of nitrous oxide (N2 O) emission from swine wastewater treatment was demonstrated in an aerobic bioreactor packed with carbon fibers (CF reactor). The CF reactor had a demonstrated advantage in mitigating N2 O emission and avoiding NOx (NO3  + NO2 ) accumulation. The N2 O emission factor was 0.0003 g N2 O-N/gTN-load in the CF bioreactor compared to 0.03 gN2 O-N/gTN-load in an activated sludge reactor (AS reactor). N2 O and CH4 emissions from the CF reactor were 42 g-CO2 eq/m(3) /day, while those from the AS reactor were 725 g-CO2 eq/m(3) /day. The dissolved inorganic nitrogen (DIN) in the CF reactor removed an average of 156 mg/L of the NH4 -N, and accumulated an average of 14 mg/L of the NO3 -N. In contrast, the DIN in the AS reactor removed an average 144 mg/L of the NH4 -N and accumulated an average 183 mg/L of the NO3 -N. NO2 -N was almost undetectable in both reactors. © 2014 Japanese Society of Animal Science.

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

PubMed

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

2007-01-01

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

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

PubMed

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

2012-10-01

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

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

NASA Astrophysics Data System (ADS)

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

2000-03-01

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

Non-microbial methane emissions from soils

NASA Astrophysics Data System (ADS)

Wang, Bin; Hou, Longyu; Liu, Wei; Wang, Zhiping

2013-12-01

Traditionally, methane (CH4) is anaerobically formed by methanogenic archaea. However, non-microbial CH4 can also be produced from geologic processes, biomass burning, animals, plants, and recently identified soils. Recognition of non-microbial CH4 emissions from soils remains inadequate. To better understand this phenomenon, a series of laboratory incubations were conducted to examine effects of temperature, water, and hydrogen peroxide (H2O2) on CH4 emissions under both aerobic and anaerobic conditions using autoclaved (30 min, 121 °C) soils and aggregates (>2000 μm, A1; 2000-250 μm, A2; 250-53 μm, M1; and <53 μm, M2). Results show that applying autoclaving to pre-treat soils is effective to inhibit methanogenic activity, ensuring the CH4 emitted being non-microbial. Responses of non-microbial CH4 emissions to temperature, water, and H2O2 were almost identical between aerobic and anaerobic conditions. Increasing temperature, water of proper amount, and H2O2 could significantly enhance CH4 emissions. However, the emission rates were inhibited and enhanced by anaerobic conditions without and with the existence of H2O2, respectively. As regards the aggregates, aggregate-based emission presented an order of M1 > A2 > A1 > M2 and C-based emission an order of M2 > M1 > A1 > A2, demonstrating that both organic carbon quantity and property are responsible for CH4 emissions from soils at the scale of aggregate. Whole soil-based order of A2 > A1 > M1 > M2 suggests that non-microbial CH4 release from forest soils is majorly contributed by macro-aggregates (i.e., >250 μm). The underlying mechanism is that organic matter through thermal treatment, photolysis, or reactions with free radicals produce CH4, which, in essence, is identical with mechanisms of other non-microbial sources, indicating that non-microbial CH4 production may be a widespread phenomenon in nature. This work further elucidates the importance of non-microbial CH4 formation which should be distinguished from the well-known microbial CH4 formation in order to define both roles in the atmospheric CH4 global budget.

The Methane to Carbon Dioxide Ratio Produced during Peatland Decomposition and a Simple Approach for Distinguishing This Ratio

NASA Astrophysics Data System (ADS)

Chanton, J.; Hodgkins, S. B.; Cooper, W. T.; Glaser, P. H.; Corbett, J. E.; Crill, P. M.; Saleska, S. R.; Rich, V. I.; Holmes, B.; Hines, M. E.; Tfaily, M.; Kostka, J. E.

2014-12-01

Peatland organic matter is cellulose-like with an oxidation state of approximately zero. When this material decomposes by fermentation, stoichiometry dictates that CH4 and CO2 should be produced in a ratio approaching one. While this is generally the case in temperate zones, this production ratio is often departed from in boreal peatlands, where the ratio of belowground CH4/CO2 production varies between 0.1 and 1, indicating CO2 production by a mechanism in addition to fermentation. The in situ CO2/CH4 production ratio may be ascertained by analysis of the 13C isotopic composition of these products, because CO2 production unaccompanied by methane production produces CO2 with an isotopic composition similar to the parent organic matter while methanogenesis produces 13C depleted methane and 13C enriched CO2. The 13C enrichment in the subsurface CO2 pool is directly related to the amount of if formed from methane production and the isotopic composition of the methane itself. Excess CO2 production is associated with more acidic conditions, Sphagnum vegetation, high and low latitudes, methane production dominated by hydrogenotrophic methane production, 13C depleted methane, and generally, more nutrient depleted conditions. Three theories have been offered to explain these observations— 1) inhibition of acetate utilization, acetate build-up and diffusion to the surface and eventual aerobic oxidation, 2) the use of humic acids as electron acceptors, and the 3) utilization of organic oxygen to produce CO2. In support of #3, we find that 13C-NMR, Fourier transform infrared (FT IR) spectroscopy, and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) clearly show the evolution of polysaccharides and cellulose towards more decomposed humified alkyl compounds stripped of organic oxygen utilized to form CO2. Such decomposition results in more negative carbon oxidation states varying from -1 to -2. Coincident with this reduction in oxidation state, is the greater production of methane. Changing climatic conditions may alter the balance of the factors which affect the CO2/CH4 ratio by changing the water balance of the peatland, nutrient status, or temperature.

Laboratory chalcopyrite oxidation by Acidithiobacillus ferrooxidans: Oxygen and sulfur isotope fractionation

USGS Publications Warehouse

Thurston, R.S.; Mandernack, K.W.; Shanks, Wayne C.

2010-01-01

Laboratory experiments were conducted to simulate chalcopyrite oxidation under anaerobic and aerobic conditions in the absence or presence of the bacterium Acidithiobacillus ferrooxidans. Experiments were carried out with 3 different oxygen isotope values of water (??18OH2O) so that approach to equilibrium or steady-state isotope fractionation for different starting conditions could be evaluated. The contribution of dissolved O2 and water-derived oxygen to dissolved sulfate formed by chalcopyrite oxidation was unambiguously resolved during the aerobic experiments. Aerobic oxidation of chalcopyrite showed 93 ?? 1% incorporation of water oxygen into the resulting sulfate during the biological experiments. Anaerobic experiments showed similar percentages of water oxygen incorporation into sulfate, but were more variable. The experiments also allowed determination of sulfate-water oxygen isotope fractionation, ??18OSO4-H2O, of ~ 3.8??? for the anaerobic experiments. Aerobic oxidation produced apparent ??SO4-H2O values (6.4???) higher than the anaerobic experiments, possibly due to additional incorporation of dissolved O2 into sulfate. ??34SSO4 values are ~ 4??? lower than the parent sulfide mineral during anaerobic oxidation of chalcopyrite, with no significant difference between abiotic and biological processes. For the aerobic experiments, a small depletion in ??34SSO4 of ~- 1.5 ?? 0.2??? was observed for the biological experiments. Fewer solids precipitated during oxidation under aerobic conditions than under anaerobic conditions, which may account for the observed differences in sulfur isotope fractionation under these contrasting conditions. ?? 2009 Elsevier B.V.

Resonance Raman study on photoreduction of cytochrome c oxidase: distinction of cytochromes a and a3 in the intermediate oxidation states.

PubMed

Ogura, T; Yoshikawa, S; Kitagawa, T

1985-12-17

Occurrence of photoreduction of bovine cytochrome c oxidase was confirmed with the difference absorption spectra and oxygen consumption measurements for the enzyme irradiated with laser light at 406.7, 441.6, and 590 nm. The resonance Raman spectra were obtained under the same experimental conditions as those adopted for the measurements of oxygen consumption and difference absorption spectra. The photoreduction was more effective upon irradiation at shorter wavelengths and was irreversible under anaerobic conditions. However, upon aeration into the cell, the original oxidized form was restored. It was found that aerobic laser irradiation produces a photo steady state of the catalytic dioxygen reduction and that the Raman scattering from this photo steady state probes cytochrome a2+ and cytochrome a3(3)+ separately upon excitations at 441.6 and 406.7 nm, respectively. The enzyme was apparently protected from the photoreduction in the spinning cell with the spinning speed between 1 and 1500 rpm. These results were explained satisfactorily with the reported rate constant for the electron transfer from cytochrome a to cytochrome a3 (0.58 s-1) and a comparable photoreduction rate of cytochrome a. The anaerobic photoreduction did give Raman lines at 1666 and 214 cm-1, which are characteristic of the ferrous high-spin cytochrome a3(2)+, but they were absent under aerobic photoreduction. The formyl CH = O stretching mode of the a3 heme was observed at 1671 cm-1 for a2+a3(2)+CO but at 1664 cm-1 for a2+a3(2)+CN-, indicating that the CH = O stretching frequency reflects the pi back-donation to the axial ligand similar to the oxidation state marker line (v4).

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

PubMed

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

2017-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-04-01

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

Flux measurements of benzene and toluene from landfill cover soils.

PubMed

Tassi, Franco; Montegrossi, Giordano; Vaselli, Orlando; Morandi, Andrea; Capecchiacci, Francesco; Nisi, Barbara

2011-01-01

Carbon dioxide and CH(4), C(6)H(6) and C(7)H(8) fluxes from the soil cover of Case Passerini landfill site (Florence, Italy) were measured using the accumulation and static closed chamber methods, respectively. Results show that the CH(4)/CO(2), CH(4)/C(6)H(6) and CH(4)/C(7)H(8) ratios of the flux values are relatively low when compared with those of the 'pristine' biogas produced by degradation processes acting on the solid waste material disposed in the landfill. This suggests that when biogas transits through the cover soil, CH(4) is affected by degradation processes activated by oxidizing bacteria at higher extent than both CO(2) and mono-aromatics. Among the investigated hydrocarbons, C(6)H(6) has shown the highest stability in a wide range of redox conditions. Toluene behaviour only partially resembles that of C(6)H(6), possibly because de-methylation processes require less energy than that necessary for the degradation of C(6)H(6), the latter likely occurring via benzoate at anaerobic conditions and/or through various aerobic metabolic pathways at relatively shallow depth in the cover soil where free oxygen is present. According to these considerations, aromatics are likely to play an important role in the environmental impact of biogas released into the atmosphere from such anthropogenic emission sites, usually only ascribed to CO(2) and CH(4). In this regard, flux measurements using accumulation and static closed chamber methods coupled with gas chromatography and gas chromatography-mass spectrometry analysis may properly be used to obtain a dataset for the estimation of the amount of volatile organic compounds dispersed from landfills.

Anaerobic methane oxidation coupled to denitrification is the dominant methane sink in a deep lake.

PubMed

Deutzmann, Joerg S; Stief, Peter; Brandes, Josephin; Schink, Bernhard

2014-12-23

Anaerobic methane oxidation coupled to denitrification, also known as "nitrate/nitrite-dependent anaerobic methane oxidation" (n-damo), was discovered in 2006. Since then, only a few studies have identified this process and the associated microorganisms in natural environments. In aquatic sediments, the close proximity of oxygen- and nitrate-consumption zones can mask n-damo as aerobic methane oxidation. We therefore investigated the vertical distribution and the abundance of denitrifying methanotrophs related to Candidatus Methylomirabilis oxyfera with cultivation-independent molecular techniques in the sediments of Lake Constance. Additionally, the vertical distribution of methane oxidation and nitrate consumption zones was inferred from high-resolution microsensor profiles in undisturbed sediment cores. M. oxyfera-like bacteria were virtually absent at shallow-water sites (littoral sediment) and were very abundant at deep-water sites (profundal sediment). In profundal sediment, the vertical distribution of M. oxyfera-like bacteria showed a distinct peak in anoxic layers that coincided with the zone of methane oxidation and nitrate consumption, a strong indication for n-damo carried out by M. oxyfera-like bacteria. Both potential n-damo rates calculated from cell densities (660-4,890 µmol CH4⋅m(-2)⋅d(-1)) and actual rates calculated from microsensor profiles (31-437 µmol CH4⋅m(-2)⋅d(-1)) were sufficiently high to prevent methane release from profundal sediment solely by this process. Additionally, when nitrate was added to sediment cores exposed to anoxic conditions, the n-damo zone reestablished well below the sediment surface, completely preventing methane release from the sediment. We conclude that the previously overlooked n-damo process can be the major methane sink in stable freshwater environments if nitrate is available in anoxic zones.

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

PubMed

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

2011-01-01

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

Microbial processes and communities in sediment samples along a transect across the Lusi mud volcano, Indonesia

NASA Astrophysics Data System (ADS)

Krueger, Martin; Straaten, Nontje; Mazzini, Adriano

2015-04-01

The Lusi eruption represents one of the largest ongoing sedimentary hosted geothermal systems. This eruption started in 2006 following to a 6.3 M earthquake that stroke Java Island. Since then it has been spewing boiling mud from a central crater with peaks reaching 180.000 m3 per day. Today an area of about 8 km2 is covered by locally dried mud breccia where a network of hundreds of satellite seeping pools is active. Numerous investigations focused on the study of offshore microbial colonies that commonly thrive at offshore methane seeps and mud volcanoes, however very little has been done for onshore seeping structures. Lusi represents a unique opportunity to complete a comprehensive study of onshore microbial communities fed by the seepage of CH4 and CO2 as well as of heavier liquid hydrocarbons originating from several km below the surface. We conducted a sampling campaign at the Lusi site collecting samples of fresh mud close to the erupting crater using a remote controlled drone. In addition we completed a transect towards outer parts of the crater to collect older, weathered samples for comparison. In all samples active microorganisms were present. The highest activities for CO2 and CH4 production as well as for CH4 oxidation and hydrocarbon degradation were observed in medium-age mud samples collected roughly in the middle of the transect. Rates for aerobic methane oxidation were high, as was the potential of the microbial communities to degrade hydrocarbons (oils, alkanes, BTEX tested). The data suggests a transition of microbial populations from an anaerobic, hydrocarbon-driven metabolism in fresher samples from center or from small seeps to more generalistic, aerobic microbial communities in older, more consolidated sediments. Currently, the microbial communities in the different sediment samples are analyzed using quantitative PCR and T-RFLP combined with MiSeq sequencing. This study represents an initial step to better understand onshore seepage systems and provides an ideal analogue for comparison with the better investigated offshore structures.

Release and fate of fluorocarbons in a shredder residue landfill cell: 1. Laboratory experiments.

PubMed

Scheutz, Charlotte; Fredenslund, Anders M; Nedenskov, Jonas; Kjeldsen, Peter

2010-11-01

The shredder residues from automobiles, home appliances and other metal-containing products are often disposed in landfills, as recycling technologies for these materials are not common in many countries. Shredder waste contains rigid and soft foams from cushions and insulation panels blown with fluorocarbons. The objective of this study was to use laboratory experiments to estimate fluorocarbon release and attenuation processes in a monofill shredder residue (SR) landfill cell. Waste from the open SR landfill cell at the AV Miljø landfill in Denmark was sampled at three locations. The waste contained 1-3% metal and a relatively low fraction of rigid polyurethane (PUR) foam particles. The PUR waste contained less blowing agent (CFC-11) than predicted from a release model. However, CFC-11 was steadily released in an aerobic bench scale experiment. Anaerobic waste incubation bench tests showed that SRSR produced significant methane (CH(4)), but at rates that were in the low end of the range observed for municipal solid waste. Aerobic and anaerobic batch experiments showed that processes in SRSR potentially can attenuate the fluorocarbons released from the SRSR itself: CFC-11 is degraded under anaerobic conditions with the formation of degradation products, which are being degraded under CH(4) oxidation conditions prevailing in the upper layers of the SR. Copyright © 2010 Elsevier Ltd. All rights reserved.

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

PubMed

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

2013-01-02

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

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Geochemistry of carbon and sulfur in the 2.7 Ga stromatolitic carbonate and shale (ABDP#10 core) from Meentheena, Western Australia

NASA Astrophysics Data System (ADS)

Tomiuka, T.; Yamaguchi, K. E.

2014-12-01

Earth's surface environments about 2.7 Ga ago likely experienced drastic changes such as rapid continental growth, negative excursion of organic carbon isotopes, and positive excursion of mass-independently fractionated sulfur isotopes. Discovery of biomarkers indicating cyanobacteria, although questionable, was also claimed. The coeval shallow ocean could have contained appreciable amount of molecular O2 produced by cyanobacteria, but it has been unknown whether deep sea was oxygenated by ocean circulation. In order to unravel the shallow water environment, we obtained modern-weathering-free 2.7 Ga drilcore samples of stromatolitic carbonate and shale by Archean Biosphere Drilling Project (ABDP#10 core) in Meentheena, NE Western Australia. The purpose of this study is to extract information regarding the surface ocean chemistry by abundance (of various species) and corresponding stable isotope compositions of carbon and sulfur. Based on mass balance calculation, we obtained a much reduced fraction of organic carbon to total carbon (forg) to be 0.11 (c.f., Phanerozoic average is 0.2), suggesting that aerobic and/or anaerobic decomposition of organic matter was vigorous. The very low δ13Corg values suggest carbon recycling involving methanogenesis by methanogen (e.g., 2CH2O → CH4 + CO2) accompanied by large isotope fractionation. Generated CH4 was oxidized by methylotroph to CO2, which was reused to form organic matter by biochemical processes such as photosynthesis. Either O2 or SO42- was required to facilitate CH4 oxidation, suggesting availability of oxidized species in the 2.7 Ga shallow sea environment. Abundance of Spy with near zero δ34Spy values suggest syndepositional and/or diagenetic formation of bacteriogenic pyrite utilizing sulfate formed by oxidation of mantle-derived sulfur (δ34S ≈ 0‰). A plot of Spy vs. Corg abundance shows a trend falling between a Phanerozoic normal marine trend (Spy/Corg = 0.36) and a freshwater trend (Spy << Corg), suggesting formation of Spy in environments fluctuating between near normal marine and fresh water conditions with low SO42- concentration. We suggest that the 2.7 Ga shallow water near Meentheena was slightly oxic in lacustrine setting.

Methane cycling in alpine wetlands - an interplay of microbial communities and vascular plants

NASA Astrophysics Data System (ADS)

Henneberger, Ruth; Cheema, Simrita; Zeyer, Josef

2014-05-01

Wetland environments play an important role for the global climate, as they represent a major terrestrial carbon store. These environments are potential sinks for atmospheric carbon due to reduced decomposition rates of plant material in the waterlogged, anoxic subsurface. In contrast, wetlands are also a major source of the highly potent greenhouse gas methane (CH4), which is produced in the anoxic zones through methanogenic archaea (methanogens) degrading organic matter. The CH4 emitted into the pore water diffuses upwards towards the surface, and is partially oxidized in the oxic zones by aerobic methanotrophic bacteria (methanotrophs) before reaching the atmosphere. Nonetheless, global emissions of atmospheric CH4 from natural wetlands are estimated to range from 100 to 230 Tg a-1. Natural wetlands can be found around the globe, and are also common in temperate-cold climates in the Northern hemisphere. Methane release from these environments is influenced by many factors (e.g., vegetation, water table, temperature, pH) and shows high seasonal and spatial variability. To comprehend these variations and further predict potential responses to climate change, the biotic and abiotic processes involved in CH4 turnover need to be understood in detail. Many research projects focus on (sub-)arctic wetland areas, while studies on CH4 emissions from alpine wetlands are scarce, despite similar processes occurring in these different regions. Recently, we conducted a survey of 14 wetlands (i.e., fens vegetated with vascular plants) located in the Swiss Alps, showing CH4 emissions between 74 ± 43 and 711 ± 212 mg CH4 m-2 d-1 (Franchini et al., in press). A detailed study of one fen also revealed that CH4 emission was highest immediately after snowmelt, followed by a decrease in CH4 emission throughout the snow-free period (Liebner et al., 2012). Even though the CH4 cycle is largely driven by microbially mediated processes, vascular plants also play a crucial role in CH4 emissions from wetlands, as CH4 generated in the deeper layers can bypass the oxic, methanotrophic zones through the plant aerenchyma. In addition, O2 transported to the root system facilitates CH4 oxidation in the rhizosphere. To further comprehend these complex processes, the present study focused on selected fens dominated by different plants (i.e., Carex spp. or Eriophorum spp.). We combined field-measurements of overall CH4 emissions, CH4 and O2 pore water concentrations and plant-mediated bypass with molecular biological analyses of methanogenic and methanotrophic subpopulations at different soil depths. Methane emissions and pore water concentrations varied with location and dominating plant species. Nevertheless, in all fens we observed the presence of active methanogens and methanotrophs throughout the depth profile, independently of O2 and CH4 concentrations, with active methanogens being highly abundant even in the oxic layers indicating the presence of microniches. The often described spatial separation of methanogenic activity in anoxic zones and methanotrophic activity in oxic zones and oxic-anoxic interfaces could not be observed. The composition of the methanogenic and methanotrophic subpopulations that are active at different depths is currently analyzed in detail, providing new insights into the complex processes involved in CH4 turnover in alpine regions.

Biosolid stockpiles are a significant point source for greenhouse gas emissions.

PubMed

Majumder, Ramaprasad; Livesley, Stephen J; Gregory, David; Arndt, Stefan K

2014-10-01

The wastewater treatment process generates large amounts of sewage sludge that are dried and then often stored in biosolid stockpiles in treatment plants. Because the biosolids are rich in decomposable organic matter they could be a significant source for greenhouse gas (GHG) emissions, yet there are no direct measurements of GHG from stockpiles. We therefore measured the direct emissions of methane (CH4), nitrous oxide (N2O) and carbon dioxide (CO2) on a monthly basis from three different age classes of biosolid stockpiles at the Western Treatment Plant (WTP), Melbourne, Australia, from December 2009 to November 2011 using manual static chambers. All biosolid stockpiles were a significant point source for CH4 and N2O emissions. The youngest biosolids (<1 year old) had the greatest CH4 and N2O emissions of 60.2 kg of CO2-e per Mg of biosolid per year. Stockpiles that were between 1 and 3 years old emitted less overall GHG (∼29 kg CO2-e Mg(-1) yr(-1)) and the oldest stockpiles emitted the least GHG (∼10 kg CO2-e Mg(-1) yr(-1)). Methane emissions were negligible in all stockpiles but the relative contribution of N2O and CO2 changed with stockpile age. The youngest stockpile emitted two thirds of the GHG emission as N2O, while the 1-3 year old stockpile emitted an equal amount of N2O and CO2 and in the oldest stockpile CO2 emissions dominated. We did not detect any seasonal variability of GHG emissions and did not observe a correlation between GHG flux and environmental variables such as biosolid temperature, moisture content or nitrate and ammonium concentration. We also modeled CH4 emissions based on a first order decay model and the model based estimated annual CH4 emissions were higher as compared to the direct field based estimated annual CH4 emissions. Our results indicate that labile organic material in stockpiles is decomposed over time and that nitrogen decomposition processes lead to significant N2O emissions. Carbon decomposition favors CO2 over CH4 production probably because of aerobic stockpile conditions or CH4 oxidation in the outer stockpile layers. Although the GHG emission rate decreased with biosolid age, managers of biosolid stockpiles should assess alternate storage or uses for biosolids to avoid nutrient losses and GHG emissions. Copyright © 2014 Elsevier Ltd. All rights reserved.

Anaerobic methane oxidation coupled to denitrification is the dominant methane sink in a deep lake

PubMed Central

Deutzmann, Joerg S.; Stief, Peter; Brandes, Josephin; Schink, Bernhard

2014-01-01

Anaerobic methane oxidation coupled to denitrification, also known as “nitrate/nitrite-dependent anaerobic methane oxidation” (n-damo), was discovered in 2006. Since then, only a few studies have identified this process and the associated microorganisms in natural environments. In aquatic sediments, the close proximity of oxygen- and nitrate-consumption zones can mask n-damo as aerobic methane oxidation. We therefore investigated the vertical distribution and the abundance of denitrifying methanotrophs related to Candidatus Methylomirabilis oxyfera with cultivation-independent molecular techniques in the sediments of Lake Constance. Additionally, the vertical distribution of methane oxidation and nitrate consumption zones was inferred from high-resolution microsensor profiles in undisturbed sediment cores. M. oxyfera-like bacteria were virtually absent at shallow-water sites (littoral sediment) and were very abundant at deep-water sites (profundal sediment). In profundal sediment, the vertical distribution of M. oxyfera-like bacteria showed a distinct peak in anoxic layers that coincided with the zone of methane oxidation and nitrate consumption, a strong indication for n-damo carried out by M. oxyfera-like bacteria. Both potential n-damo rates calculated from cell densities (660–4,890 µmol CH4⋅m−2⋅d−1) and actual rates calculated from microsensor profiles (31–437 µmol CH4⋅m−2⋅d−1) were sufficiently high to prevent methane release from profundal sediment solely by this process. Additionally, when nitrate was added to sediment cores exposed to anoxic conditions, the n-damo zone reestablished well below the sediment surface, completely preventing methane release from the sediment. We conclude that the previously overlooked n-damo process can be the major methane sink in stable freshwater environments if nitrate is available in anoxic zones. PMID:25472842

Vadose zone attenuation of organic compounds at a crude oil spill site - interactions between biogeochemical reactions and multicomponent gas transport.

PubMed

Molins, S; Mayer, K U; Amos, R T; Bekins, B A

2010-03-01

Contaminant attenuation processes in the vadose zone of a crude oil spill site near Bemidji, MN have been simulated with a reactive transport model that includes multicomponent gas transport, solute transport, and the most relevant biogeochemical reactions. Dissolution and volatilization of oil components, their aerobic and anaerobic degradation coupled with sequential electron acceptor consumption, ingress of atmospheric O(2), and the release of CH(4) and CO(2) from the smear zone generated by the floating oil were considered. The focus of the simulations was to assess the dynamics between biodegradation and gas transport processes in the vadose zone, to evaluate the rates and contributions of different electron accepting processes towards vadose zone natural attenuation, and to provide an estimate of the historical mass loss. Concentration distributions of reactive (O(2), CH(4), and CO(2)) and non-reactive (Ar and N(2)) gases served as key constraints for the model calibration. Simulation results confirm that as of 2007, the main degradation pathway can be attributed to methanogenic degradation of organic compounds in the smear zone and the vadose zone resulting in a contaminant plume dominated by high CH(4) concentrations. In accordance with field observations, zones of volatilization and CH(4) generation are correlated to slightly elevated total gas pressures and low partial pressures of N(2) and Ar, while zones of aerobic CH(4) oxidation are characterized by slightly reduced gas pressures and elevated concentrations of N(2) and Ar. Diffusion is the most significant transport mechanism for gases in the vadose zone; however, the simulations also indicate that, despite very small pressure gradients, advection contributes up to 15% towards the net flux of CH(4), and to a more limited extent to O(2) ingress. Model calibration strongly suggests that transfer of biogenically generated gases from the smear zone provides a major control on vadose zone gas distributions and vadose zone carbon balance. Overall, the model was successful in capturing the complex interactions between biogeochemical reactions and multicomponent gas transport processes. However, despite employing a process-based modeling approach, honoring observed parameter ranges, and generally obtaining good agreement between field observations and model simulations, accurate quantification of natural attenuation rates remains difficult. The modeling results are affected by uncertainties regarding gas phase saturations, tortuosities, and the magnitude of CH(4) and CO(2) flux from the smear zone. These findings highlight the need to better delineate gas fluxes at the model boundaries, which will help constrain contaminant degradation rates, and ultimately source zone longevity. Copyright 2009 Elsevier B.V. All rights reserved.

Vadose zone attenuation of organic compounds at a crude oil spill site - Interactions between biogeochemical reactions and multicomponent gas transport

USGS Publications Warehouse

Molins, S.; Mayer, K.U.; Amos, R.T.; Bekins, B.A.

2010-01-01

Contaminant attenuation processes in the vadose zone of a crude oil spill site near Bemidji, MN have been simulated with a reactive transport model that includes multicomponent gas transport, solute transport, and the most relevant biogeochemical reactions. Dissolution and volatilization of oil components, their aerobic and anaerobic degradation coupled with sequential electron acceptor consumption, ingress of atmospheric O2, and the release of CH4 and CO2 from the smear zone generated by the floating oil were considered. The focus of the simulations was to assess the dynamics between biodegradation and gas transport processes in the vadose zone, to evaluate the rates and contributions of different electron accepting processes towards vadose zone natural attenuation, and to provide an estimate of the historical mass loss. Concentration distributions of reactive (O2, CH4, and CO2) and non-reactive (Ar and N2) gases served as key constraints for the model calibration. Simulation results confirm that as of 2007, the main degradation pathway can be attributed to methanogenic degradation of organic compounds in the smear zone and the vadose zone resulting in a contaminant plume dominated by high CH4 concentrations. In accordance with field observations, zones of volatilization and CH4 generation are correlated to slightly elevated total gas pressures and low partial pressures of N2 and Ar, while zones of aerobic CH4 oxidation are characterized by slightly reduced gas pressures and elevated concentrations of N2 and Ar. Diffusion is the most significant transport mechanism for gases in the vadose zone; however, the simulations also indicate that, despite very small pressure gradients, advection contributes up to 15% towards the net flux of CH4, and to a more limited extent to O2 ingress. Model calibration strongly suggests that transfer of biogenically generated gases from the smear zone provides a major control on vadose zone gas distributions and vadose zone carbon balance. Overall, the model was successful in capturing the complex interactions between biogeochemical reactions and multicomponent gas transport processes. However, despite employing a process-based modeling approach, honoring observed parameter ranges, and generally obtaining good agreement between field observations and model simulations, accurate quantification of natural attenuation rates remains difficult. The modeling results are affected by uncertainties regarding gas phase saturations, tortuosities, and the magnitude of CH4 and CO2 flux from the smear zone. These findings highlight the need to better delineate gas fluxes at the model boundaries, which will help constrain contaminant degradation rates, and ultimately source zone longevity. ?? 2009 Elsevier B.V.

Landscape patterns of CH4 fluxes in an alpine tundra ecosystem

USGS Publications Warehouse

West, A.E.; Brooks, P.D.; Fisk, M.C.; Smith, Lesley K.; Holland, E.A.; Jaeger, C. H.; Babcock, S.; Lai, R.S.; Schmidt, S.K.

1999-01-01

We measured CH4 fluxes from three major plant communities characteristic of alpine tundra in the Colorado Front Range. Plant communities in this ecosystem are determined by soil moisture regimes induced by winter snowpack distribution. Spatial patterns of CH4 flux during the snow-free season corresponded roughly with these plant communities. In Carex-dominated meadows, which receive the most moisture from snowmelt, net CH4 production occurred. However, CH4 production in one Carex site (seasonal mean = +8.45 mg CH4 m-2 d-1) was significantly larger than in the other Carex sites (seasonal means = -0.06 and +0.05 mg CH4 m-2 d-1). This high CH4 flux may have resulted from shallower snowpack during the winter. In Acomastylis meadows, which have an intermediate moisture regime, CH4 oxidation dominated (seasonal mean = -0.43 mg CH4 m-2 d-1). In the windswept Kobresia meadow plant community, which receive the least amount of moisture from snowmelt, only CH4 oxidation was observed (seasonal mean = -0.77 mg CH4 m-2 d-1). Methane fluxes correlated with a different set of environmental factors within each plant community. In the Carex plant community, CH4 emission was limited by soil temperature. In the Acomastylis meadows, CH4 oxidation rates correlated positively with soil temperature and negatively with soil moisture. In the Kobresia community, CH4 oxidation was stimulated by precipitation. Thus, both snow-free season CH4 fluxes and the controls on those CH4 fluxes were related to the plant communities determined by winter snowpack.

Degradation of ethylene glycol and polyethylene glycols by methanogenic consortia.

PubMed Central

Dwyer, D F; Tiedje, J M

1983-01-01

Methanogenic enrichments capable of degrading polyethylene glycol and ethylene glycol were obtained from sewage sludge. Ethanol, acetate, methane, and (in the case of polyethylene glycols) ethylene glycol were detected as products. The sequence of product formation suggested that the ethylene oxide unit [HO-(CH2-CH2-O-)xH] was dismutated to acetate and ethanol; ethanol was subsequently oxidized to acetate by a syntrophic association that produced methane. The rates of degradation for ethylene, diethylene, and polyethylene glycol with molecular weights of 400, 1,000, and 20,000, respectively, were inversely related to the number of ethylene oxide monomers per molecule and ranged from 0.84 to 0.13 mM ethylene oxide units degraded per h. The enrichments were shown to best metabolize glycols close to the molecular weight of the substrate on which they were enriched. The anaerobic degradation of polyethylene glycol (molecular weight, 20,000) may be important in the light of the general resistance of polyethylene glycols to aerobic degradation. PMID:6614903

Inside Story of Gas Processes within Stormwater Biofilters: Does Greenhouse Gas Production Tarnish the Benefits of Nitrogen Removal?

PubMed

Payne, Emily G I; Pham, Tracey; Cook, Perran L M; Deletic, Ana; Hatt, Belinda E; Fletcher, Tim D

2017-04-04

Stormwater biofilters are dynamic environments, supporting diverse processes that act to capture and transform incoming pollutants. However, beneficial water treatment processes can be accompanied by undesirable greenhouse gas production. This study investigated the potential for nitrous oxide (N 2 O) and methane (CH 4 ) generation in dissolved form at the base of laboratory-scale stormwater biofilter columns. The influence of plant presence, species, inflow frequency, and inclusion of a saturated zone and carbon source were studied. Free-draining biofilters remained aerobic with negligible greenhouse gas production during storm events. Designs with a saturated zone were oxygenated at their base by incoming stormwater before anaerobic conditions rapidly re-established, although extended dry periods allowed the reintroduction of oxygen by evapotranspiration. Production of CH 4 and N 2 O in the saturated zone varied significantly in response to plant presence, species, and wetting and drying. Concentrations of N 2 O typically peaked rapidly following stormwater inundation, associated with limited plant root systems and poorer nitrogen removal from biofilter effluent. Production of CH 4 also commenced quickly but continued throughout the anaerobic interevent period and lacked clear relationships with plant characteristics or nitrogen removal performance. Dissolved greenhouse gas concentrations were highly variable, but peak concentrations of N 2 O accounted for <1.5% of the incoming total nitrogen load. While further work is required to measure surface emissions, the potential for substantial release of N 2 O or CH 4 in biofilter effluent appears relatively low.

Evaluation of oxidative stress in hunting dogs during exercise.

PubMed

Pasquini, A; Luchetti, E; Cardini, G

2010-08-01

Exercise has been shown to increase the production of reactive oxygen species (ROS) to a point that can exceed antioxidant defenses, to cause oxidative stress. The aim of our trials was to evaluate oxidative stress and recovery times in trained dogs during two different hunting exercises, with reactive oxygen metabolites-derivatives (d-ROMs) and biological antioxidant potential (BAP) tests. A group of nine privately owned Italian hounds were included. A 20-min aerobic exercise and a 4-h aerobic exercise, after 30 days of rest, were performed by the dogs. Our results show an oxidative stress after exercise due to both the high concentration of oxidants (d-ROMs) and the low level of antioxidant power (BAP). Besides, the recovery time is faster after the 4-h aerobic exercise than the 20-min aerobic exercise. Oxidative stress monitoring during dogs exercise could become an interesting aid to establish ideal adaptation to training. Copyright 2010 Elsevier Ltd. All rights reserved.

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

PubMed

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

2017-10-01

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

Initiation Decision Report: Nonpoint Source Discharge

DTIC Science & Technology

1989-08-01

1. Suspended and mixed media growth 2. Anaerobic and aerobic digestion 3. Enzyme treatment 4. In-situ assimilation 5. Composting 6. Land treatment...either anoxic (metabolic reduction) or an aerobic (metabolic oxidation) environment (Ref. 4.2, 4.4, 4.5). Aerobic digestion is one of the most widely used

Response of Carbon Fluxes to Soil Moisture Variability across an Alaskan Tundra Landscape

NASA Astrophysics Data System (ADS)

Melton, S.; Natali, S.; Schade, J. D.; Holmes, R. M.; Mann, P. J.; Fiske, G. J.

2017-12-01

Soils in arctic and sub-arctic permafrost regions store large amounts of carbon (C), which is becoming more biologically available as soils warm and permafrost thaws. Microbial decay of organic forms of C can result in the production and emission of carbon dioxide (CO2) and methane (CH4), and the amount and form of C released into the atmosphere depend on organic matter composition and soil conditions. Soil moisture, which is a strong driver of microbial processes, varies spatially and temporally across tundra landscapes and may change dramatically as a result of permafrost thaw. The Yukon-Kuskokwim Delta (YKD) of Alaska is underlain by discontinuous permafrost and is particularly vulnerable to permafrost thaw and soil moisture changes associated with thaw. As permafrost thaws, some areas may dry as drainage increases with increasing thaw depth. Alternatively, permafrost thaw may lead to ground subsidence and saturation of previously dry soils. Our objective was to investigate patterns in C storage and processing across the landscape and in response to changes in soil moisture in the YKD. We analyzed soil C pools (0-30 cm) and CO2 and CH4 concentrations in soils from sites of different land cover and landscape position, including moist and dry peat plateaus, high and low intensity burned plateaus, fens, and drained lakes. We also conducted aerobic and anaerobic soil incubations to determine changes in CO2 and CH4 production under a range of soil moisture conditions. Soils from burned plateaus, which were drier and had lower C content than unburned soils, had higher CO2 production (per g soil) than unburned soils during aerobic incubations. Both increased and decreased moisture reduced CO2 production from soils. Soil drying increased net CH4 uptake in all aerobically-incubated burned soils, and wetting resulted in CH4 emissions from low intensity burn soils. CO2 and CH4 production from fen soils were higher than from the other landscape positions analyzed here. Our results suggest that soil drying could lead to decreased microbial respiration, whereas subsidence may result in increased methanogenesis. Additionally, amplified CH4 release from burned soils after rainfall events or subsidence may accompany the increased fire frequency projected in tundra regions.

Cu/Nitroxyl Catalyzed Aerobic Oxidation of Primary Amines into Nitriles at Room Temperature

PubMed Central

Kim, Jinho; Stahl, Shannon S.

2013-01-01

An efficient catalytic method has been developed for aerobic oxidation of primary amines to the corresponding nitriles. The reactions proceed at room temperature and employ a catalyst consisting of (4,4′-tBu2bpy)CuI/ABNO (ABNO = 9-azabicyclo[3.3.1]nonan-3-one N-oxyl). The reactions exhibit excellent functional group compatibility and substrate scope, and are effective with benzylic, allylic and aliphatic amines. Preliminary mechanistic studies suggest that aerobic oxidation of the Cu catalyst is the turnover-limiting step of the reaction. PMID:24015373

Cu/Nitroxyl Catalyzed Aerobic Oxidation of Primary Amines into Nitriles at Room Temperature.

PubMed

Kim, Jinho; Stahl, Shannon S

2013-07-05

An efficient catalytic method has been developed for aerobic oxidation of primary amines to the corresponding nitriles. The reactions proceed at room temperature and employ a catalyst consisting of (4,4'- t Bu 2 bpy)CuI/ABNO (ABNO = 9-azabicyclo[3.3.1]nonan-3-one N -oxyl). The reactions exhibit excellent functional group compatibility and substrate scope, and are effective with benzylic, allylic and aliphatic amines. Preliminary mechanistic studies suggest that aerobic oxidation of the Cu catalyst is the turnover-limiting step of the reaction.

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

NASA Astrophysics Data System (ADS)

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

2005-12-01

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

Physiology, biochemistry, and specific inhibitors of CH4, NH4+, and CO oxidation by methanotrophs and nitrifiers.

PubMed Central

Bédard, C; Knowles, R

1989-01-01

Ammonia oxidizers (family Nitrobacteraceae) and methanotrophs (family Methylococcaceae) oxidize CO and CH4 to CO2 and NH4+ to NO2-. However, the relative contributions of the two groups of organisms to the metabolism of CO, CH4, and NH4+ in various environments are not known. In the ammonia oxidizers, ammonia monooxygenase, the enzyme responsible for the conversion of NH4+ to NH2OH, also catalyzes the oxidation of CH4 to CH3OH. Ammonia monooxygenase also mediates the transformation of CH3OH to CO2 and cell carbon, but the pathway by which this is done is not known. At least one species of ammonia oxidizer, Nitrosococcus oceanus, exhibits a Km for CH4 oxidation similar to that of methanotrophs. However, the highest rate of CH4 oxidation recorded in an ammonia oxidizer is still five times lower than rates in methanotrophs, and ammonia oxidizers are apparently unable to grow on CH4. Methanotrophs oxidize NH4+ to NH2OH via methane monooxygenase and NH4+ to NH2OH via methane monooxygenase and NH2OH to NO2- via an NH2OH oxidase which may resemble the enzyme found in ammonia oxidizers. Maximum rates of NH4+ oxidation are considerably lower than in ammonia oxidizers, and the affinity for NH4+ is generally lower than in ammonia oxidizers. NH4+ does not apparently support growth in methanotrophs. Both ammonia monooxygenase and methane monooxygenase oxidize CO to CO2, but CO cannot support growth in either ammonia oxidizers or methanotrophs. These organisms have affinities for CO which are comparable to those for their growth substrates and often higher than those in carboxydobacteria. The methane monooxygenases of methanotrophs exist in two forms: a soluble form and a particulate form. The soluble form is well characterized and appears unrelated to the particulate. Ammonia monooxygenase and the particulate methane monooxygenase share a number of similarities. Both enzymes contain copper and are membrane bound. They oxidize a variety of inorganic and organic compounds, and their inhibitor profiles are similar. Inhibitors thought to be specific to ammonia oxidizers have been used in environmental studies of nitrification. However, almost all of the numerous compounds found to inhibit ammonia oxidizers also inhibit methanotrophs, and most of the inhibitors act upon the monooxygenases. Many probably exert their effect by chelating copper, which is essential to the proper functioning of some monooxygenases. The lack of inhibitors specific for one or the other of the two groups of bacteria hampers the determination of their relative roles in nature. PMID:2496288

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

NASA Astrophysics Data System (ADS)

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

2008-06-01

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

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

NASA Astrophysics Data System (ADS)

Lenhart, Katharina; Keppler, Frank

2017-04-01

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

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

PubMed

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

2017-07-01

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

Teaching Old Compounds New Tricks: DDQ-Photocatalyzed C-H Amination of Arenes with Carbamates, Urea, and N-Heterocycles.

PubMed

Das, Somnath; Natarajan, Palani; König, Burkhard

2017-12-22

The C-H amination of benzene derivatives was achieved using DDQ as photocatalyst and BocNH 2 as the amine source under aerobic conditions and visible light irradiation. Electron-deficient and electron-rich benzenes react as substrates with moderate to good product yields. The amine scope of the reaction comprises Boc-amine, carbamates, pyrazoles, sulfonimides and urea. Preliminary mechanistic investigations indicate arene oxidation by the triplet of DDQ to radical cations with different electrophilicity and a charge transfer complex between the amine and DDQ as intermediate of the reaction. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Origin and fate of methane in the Eastern Tropical North Pacific oxygen minimum zone.

PubMed

Chronopoulou, Panagiota-Myrsini; Shelley, Felicity; Pritchard, William J; Maanoja, Susanna T; Trimmer, Mark

2017-06-01

Oxygen minimum zones (OMZs) contain the largest pools of oceanic methane but its origin and fate are poorly understood. High-resolution (<15 m) water column profiles revealed a 300 m thick layer of elevated methane (20-105 nM) in the anoxic core of the largest OMZ, the Eastern Tropical North Pacific. Sediment core incubations identified a clear benthic methane source where the OMZ meets the continental shelf, between 350 and 650 m, with the flux reflecting the concentration of methane in the overlying anoxic water. Further incubations characterised a methanogenic potential in the presence of both porewater sulphate and nitrate of up to 88 nmol g -1 day -1 in the sediment surface layer. In these methane-producing sediments, the majority (85%) of methyl coenzyme M reductase alpha subunit (mcrA) gene sequences clustered with Methanosarcinaceae (⩾96% similarity to Methanococcoides sp.), a family capable of performing non-competitive methanogenesis. Incubations with 13 C-CH 4 showed potential for both aerobic and anaerobic methane oxidation in the waters within and above the OMZ. Both aerobic and anaerobic methane oxidation is corroborated by the presence of particulate methane monooxygenase (pmoA) gene sequences, related to type I methanotrophs and the lineage of Candidatus Methylomirabilis oxyfera, known to perform nitrite-dependent anaerobic methane oxidation (N-DAMO), respectively.

Origin and fate of methane in the Eastern Tropical North Pacific oxygen minimum zone

PubMed Central

Chronopoulou, Panagiota-Myrsini; Shelley, Felicity; Pritchard, William J; Maanoja, Susanna T; Trimmer, Mark

2017-01-01

Oxygen minimum zones (OMZs) contain the largest pools of oceanic methane but its origin and fate are poorly understood. High-resolution (<15 m) water column profiles revealed a 300 m thick layer of elevated methane (20–105 nM) in the anoxic core of the largest OMZ, the Eastern Tropical North Pacific. Sediment core incubations identified a clear benthic methane source where the OMZ meets the continental shelf, between 350 and 650 m, with the flux reflecting the concentration of methane in the overlying anoxic water. Further incubations characterised a methanogenic potential in the presence of both porewater sulphate and nitrate of up to 88 nmol g−1day−1 in the sediment surface layer. In these methane-producing sediments, the majority (85%) of methyl coenzyme M reductase alpha subunit (mcrA) gene sequences clustered with Methanosarcinaceae (⩾96% similarity to Methanococcoides sp.), a family capable of performing non-competitive methanogenesis. Incubations with 13C-CH4 showed potential for both aerobic and anaerobic methane oxidation in the waters within and above the OMZ. Both aerobic and anaerobic methane oxidation is corroborated by the presence of particulate methane monooxygenase (pmoA) gene sequences, related to type I methanotrophs and the lineage of Candidatus Methylomirabilis oxyfera, known to perform nitrite-dependent anaerobic methane oxidation (N-DAMO), respectively. PMID:28244978

Biodegradable Chitosan Coating Incorporated with Black Pepper Essential Oil for Shelf Life Extension of Common Carp (Cyprinus carpio) during Refrigerated Storage.

PubMed

Moosavi-Nasab, Marzieh; Shad, Ehsan; Ziaee, Esmaeil; Yousefabad, Seyyed Hossein Asadi; Golmakani, Mohammad Taghi; Azizinia, Mehdi

2016-06-01

Chitosan (Ch) coating incorporated with black pepper essential oil (Ch+BPEO) was studied to extend the shelf life of common carp (Cyprinus carpio) during refrigerated storage at 4 ± 1°C. The chemical composition of BPEO was characterized using gas chromatography-mass spectrometry (GC-MS). Antibacterial properties of BPEO were determined by disk diffusion agar, MIC, and MBC. Ch (2% [wt/vol]) and Ch+BPEO (2% [wt/vol] Ch with 1.5% [vol/vol] BPEO) were used for common carp fillet coating. The samples were analyzed periodically for chemical (pH, total volatile basic nitrogen) and microbiological (aerobic plate count, psychrophilic bacteria count, lactic acid bacteria, and Enterobacteriaceae bacterial counts) characteristics during 16 days. The GC-MS results indicated that main components in BPEO were carene, caryophyllene, limonene, β-pinene, and α-pinene. The samples coated with Ch and Ch+BPEO resulted in lower pH and total volatile basic nitrogen values in comparison with the control. The microbiological analysis of fish fillets during refrigerated storage clearly indicated that Ch+BPEO coating significantly reduced the fish fillet microbial load. The aerobic plate count, psychrophilic bacteria count, lactic acid bacteria count, and Enterobacteriaceae bacterial count of samples coated with Ch+BPEO were reduced approximately 4.1, 3.9, 2.3, and 2.8 log CFU/g, respectively, at the end of the storage period. Finally, Ch and Ch+BPEO effectively improved the quality of fish fillet during refrigerated storage and extended the shelf life of fish fillets from 8 to 16 days. Black pepper; Chitosan; Common carp; Essential oil.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Selective CO Production by Photoelectrochemical Methane Oxidation on TiO2.

PubMed

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

2018-05-23

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

Rapid Sediment Accumulation Results in High Methane Effluxes from Coastal Sediments

PubMed Central

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

2016-01-01

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

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

NASA Technical Reports Server (NTRS)

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

1993-01-01

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

Anaerobic Metabolism: Linkages to Trace Gases and Aerobic Processes

NASA Astrophysics Data System (ADS)

Megonigal, J. P.; Hines, M. E.; Visscher, P. T.

2003-12-01

Life evolved and flourished in the absence of molecular oxygen (O2). As the O2 content of the atmosphere rose to the present level of 21% beginning about two billion years ago, anaerobic metabolism was gradually supplanted by aerobic metabolism. Anaerobic environments have persisted on Earth despite the transformation to an oxidized state because of the combined influence of water and organic matter. Molecular oxygen diffuses about 104 times more slowly through water than air, and organic matter supports a large biotic O2 demand that consumes the supply faster than it is replaced by diffusion. Such conditions exist in wetlands, rivers, estuaries, coastal marine sediments, aquifers, anoxic water columns, sewage digesters, landfills, the intestinal tracts of animals, and the rumen of herbivores. Anaerobic microsites are also embedded in oxic environments such as upland soils and marine water columns. Appreciable rates of aerobic respiration are restricted to areas that are in direct contact with air or those inhabited by organisms that produce O2.Rising atmospheric O2 reduced the global area of anaerobic habitat, but enhanced the overall rate of anaerobic metabolism (at least on an area basis) by increasing the supply of electron donors and acceptors. Organic carbon production increased dramatically, as did oxidized forms of nitrogen, manganese, iron, sulfur, and many other elements. In contemporary anaerobic ecosystems, nearly all of the reducing power is derived from photosynthesis, and most of it eventually returns to O2, the most electronegative electron acceptor that is abundant. This photosynthetically driven redox gradient has been thoroughly exploited by aerobic and anaerobic microorganisms for metabolism. The same is true of hydrothermal vents (Tunnicliffe, 1992) and some deep subsurface environments ( Chapelle et al., 2002), where thermal energy is the ultimate source of the reducing power.Although anaerobic habitats are currently a small fraction of Earth's surface area, they have a profound influence on the biogeochemistry of the planet. This is evident from the observation that the O2 and CH4 content of Earth's atmosphere are in extreme disequilibrium (Sagan et al., 1993). The combination of high aerobic primary production and anoxic sediments provided the large deposits of fossil fuels that have become vital and contentious sources of energy for modern industrialized societies. Anaerobic metabolism is responsible for the abundance of N2 in the atmosphere; otherwise N2-fixing bacteria would have consumed most of the N2 pool long ago (Schlesinger, 1997). Anaerobic microorganisms are common symbionts of termites, cattle, and many other animals, where they aid digestion. Nutrient and pollutant chemistry are strongly modified by the reduced conditions that prevail in wetland and aquatic ecosystems.This review of anaerobic metabolism emphasizes aerobic oxidation, because the two processes cannot be separated in a complete treatment of the topic. It is process oriented and highlights the fascinating microorganisms that mediate anaerobic biogeochemistry. We begin this review with a brief discussion of CO2 assimilation by autotrophs, the source of most of the reducing power on Earth, and then consider the biological processes that harness this potential energy. Energy liberation begins with the decomposition of organic macromolecules to relatively simple compounds, which are simplified further by fermentation. Methanogenesis is considered next because CH4 is a product of acetate fermentation, and thus completes the catabolism of organic matter, particularly in the absence of inorganic electron acceptors. Finally, the organisms that use nitrogen, manganese, iron, and sulfur for terminal electron acceptors are considered in order of decreasing free-energy yield of the reactions.

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

PubMed

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

2014-12-01

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

Oxygen and sulfur isotope systematics of sulfate produced during abiotic and bacterial oxidation of sphalerite and elemental sulfur

USGS Publications Warehouse

Balci, N.; Mayer, B.; Shanks, Wayne C.; Mandernack, K.W.

2012-01-01

Studies of metal sulfide oxidation in acid mine drainage (AMD) systems have primarily focused on pyrite oxidation, although acid soluble sulfides (e.g., ZnS) are predominantly responsible for the release of toxic metals. We conducted a series of biological and abiotic laboratory oxidation experiments with pure and Fe-bearing sphalerite (ZnS & Zn 0.88Fe 0.12S), respectively, in order to better understand the effects of sulfide mineralogy and associated biogeochemical controls of oxidation on the resultant ?? 34S and ?? 18O values of the sulfate produced. The minerals were incubated in the presence and absence of Acidithiobacillus ferrooxidans at an initial solution pH of 3 and with water of varying ?? 18O values to determine the relative contributions of H 2O-derived and O 2-derived oxygen in the newly formed sulfate. Experiments were conducted under aerobic and anaerobic conditions using O 2 and Fe(III) aq as the oxidants, respectively. Aerobic incubations with A. ferrooxidans, and S o as the sole energy source were also conducted. The ??34SSO4 values from both the biological and abiotic oxidation of ZnS and ZnS Fe by Fe(III) aq produced sulfur isotope fractionations (??34SSO4-ZnS) of up to -2.6???, suggesting the accumulation of sulfur intermediates during incomplete oxidation of the sulfide. No significant sulfur isotope fractionation was observed from any of the aerobic experiments. Negative sulfur isotope enrichment factors (??34SSO4-ZnS) in AMD systems could reflect anaerobic, rather than aerobic pathways of oxidation. During the biological and abiotic oxidation of ZnS and ZnS Fe by Fe(III) aq all of the sulfate oxygen was derived from water, with measured ?? 18OSO 4-H 2O values of 8.2??0.2??? and 7.5??0.1???, respectively. Also, during the aerobic oxidation of ZnS Fe and S o by A. ferrooxidans, all of the sulfate oxygen was derived from water with similar measured ?? 18OSO 4-H 2O values of 8.1??0.1??? and 8.3??0.3???, respectively. During biological oxidation of ZnS by O 2, an estimated 8% of sulfate-oxygen was derived from O 2, which is enriched in 18O relative to water, thus resulting in a larger apparent ?? 18OSO 4-H 2O value of 9.5???. Based on the data presented we hypothesize that the similar ?? 18OSO 4-H 2O values of ~8??? from all of the aerobic and anaerobic experiments result from a common rate-limiting step that involves oxygen isotopic exchange between a sulfite (SO3-) intermediate and H 2O. Our results indicate that the ??18OSO4 values cannot be used to distinguish biological and abiotic, nor aerobic versus anaerobic, pathways of sphalerite oxidation. However, the ?? 18OSO 4-H 2O values of ~8??? measured here are distinctly higher than ?? 18OSO 4-H 2O values of ~4??? previously reported for pyrite oxidation indicating the influence of sulfide mineralogy on measured ?? 18OSO 4 values. ?? 2011 Elsevier Ltd.

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

PubMed

Yargicoglu, Erin N; Reddy, Krishna R

2017-05-15

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

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

NASA Astrophysics Data System (ADS)

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

2013-10-01

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

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

PubMed

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

2015-01-01

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

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

PubMed Central

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

2015-01-01

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

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

PubMed

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

2016-09-01

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

CH4 and CO2 exchange of a brackish degraded peatland within the drainage-rewetting sequence - Synthesis from an interdisciplinary multi-year approach

NASA Astrophysics Data System (ADS)

Sachs, T.; Koebsch, F.; Boettcher, M. E.; Glatzel, S.; Liebner, S.; Matthias, W.; Koch, M.; Westphal, J.; Jurasinski, G.

2016-12-01

Rewetting is considered as common measure to stop aerobic peat decomposition and to re-establish the net natural C sink function of peatlands. In this long-term study, we accompanied the development of a degraded brackish peatland from drainage to year-round flooding. Based on eddy covariance measurements of CH4 and CO2 fluxes, remote sensing monitoring of vegetation succession and insights into major dissimilatory pathways, we develop a more differentiated perspective on the greenhouse gas (GHG) effect of rewetting measures conducted in brackish peatlands. Contrary to the common assumption that CH4 production is inhibited in coastal ecosystems, CH4 emissions increased remarkably after rewetting. Despite few local exceptions, sulfate - the major electron acceptor in marine environments - was completely converted to stable organic and metal sulfides. Sulfate depletion in concert with high substrate supply derived from a destabilized peat C pool and the extensive die-back of vegetation fuel CH4 emissions especially in the initial rewetting phase. CH4 fluxes are further interpreted in light of climate variables and vegetation data to differentiate between short-term response to climate variation and long-term trends based on ecosystem succession after flooding. High CH4 emissions in the initial rewetting phase are considered to be (at least partially) compensated as CO2 release by aerobic respiration decreases. However, our results indicate that flooding does not only cease CO2 release by ecosystem respiration, but that also CO2 uptake by canopy photosynthesis is affected to the same degree when vegetation cannot cope with the rapid rise in water level. Our study highlights the importance of a multi-year monitoring to cover the dynamic ecosystem development within the drainage-rewetting sequence. We further emphasize the relevance of interdisciplinary approaches to understand the complex interactions between ecosystem compartments as basic controls for GHG exchange.

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

PubMed

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

2017-02-23

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

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

PubMed

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

1997-04-01

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

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

NASA Astrophysics Data System (ADS)

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

1998-12-01

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

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

PubMed

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

2001-08-03

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

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

NASA Astrophysics Data System (ADS)

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

2013-04-01

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

Assessment of farm soil, biochar, compost and weathered pine mulch to mitigate methane emissions.

PubMed

Syed, Rashad; Saggar, Surinder; Tate, Kevin; Rehm, Bernd H A

2016-11-01

Previous studies have demonstrated the effective utility of volcanic pumice soil to mitigate both high and low levels of methane (CH 4 ) emissions through the activity of both γ-proteobacterial (type I) and α-proteobacterial (type II) aerobic methanotrophs. However, the limited availability of volcanic pumice soil necessitates the assessment of other farm soils and potentially suitable, economical and widely available biofilter materials. The potential biofilter materials, viz. farm soil (isolated from a dairy farm effluent pond bank area), pine biochar, garden waste compost and weathered pine bark mulch, were inoculated with a small amount of volcanic pumice soil. Simultaneously, a similar set-up of potential biofilter materials without inoculum was studied to understand the effect of the inoculum on the ability of these materials to oxidise CH 4 and their effect on methanotroph growth and activity. These materials were incubated at 25 °C with periodic feeding of CH 4 , and flasks were aerated with air (O 2 ) to support methanotroph growth and activity by maintaining aerobic conditions. The efficiency of CH 4 removal was monitored over 6 months. All materials supported the growth and activity of methanotrophs. However, the efficiency of CH 4 removal by all the materials tested fluctuated between no or low removal (0-40 %) and high removal phases (>90 %), indicating biological disturbances rather than physico-chemical changes. Among all the treatments, CH 4 removal was consistently high (>80 %) in the inoculated farm soil and inoculated biochar, and these were more resilient to changes in the methanotroph community. The CH 4 removal from inoculated farm soil and inoculated biochar was further enhanced (up to 99 %) by the addition of a nutrient solution. Our results showed that (i) farm soil and biochar can be used as a biofilter material by inoculating with an active methanotroph community, (ii) an abundant population of α-proteobacterial methanotrophs is essential for effective and stable CH 4 removal and (iii) addition of nutrients enhances the growth and activity of methanotrophs in the biofilter materials. Further studies are underway to assess the feasibility of these materials at small plot and field scales.

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

PubMed

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

2008-11-01

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

Performance of green waste biocovers for enhancing methane oxidation.

PubMed

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

2015-05-01

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

Magnetically recoverable magnetite/gold catalyst stabilized by poly(N-vinyl-2-pyrrolidone) for aerobic oxidation of alcohols.

PubMed

Chen, Hsiao Wei; Murugadoss, Arumugam; Hor, T S Andy; Sakurai, Hidehiro

2010-12-29

Fe(3)O(4):PVP/Au nanocomposite synthesized via a two-step procedure was tested as a quasi-homogenous alcohol oxidation catalyst. It was found that the nanocomposite was able to carry out aerobic oxidation of alcohols in water at room temperature. Studies show rapid magnetic recoverability and reusability characteristics.

Arctic tundra and mountain landscapes are persistent sinks of atmospheric CH4

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

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

PubMed

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

2009-05-01

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

Discovery of a metalloenzyme-like cooperative catalytic system of metal nanoclusters and catechol derivatives for the aerobic oxidation of amines.

PubMed

Yuan, Hao; Yoo, Woo-Jin; Miyamura, Hiroyuki; Kobayashi, Shū

2012-08-29

We have discovered a new class of cooperative catalytic system, consisting of heterogeneous polymer-immobilized bimetallic Pt/Ir alloyed nanoclusters (NCs) and 4-tert-butylcatechol, for the aerobic oxidation of amines to imines under ambient conditions. After optimization, the desired imines were obtained in good to excellent yields with broad substrate scope. The reaction rate was determined to be first-order with respect to the substrate and catechol and zero-order for the alloyed Pt/Ir NC catalyst. Control studies revealed that both the heterogeneous NC catalyst and 4-tert-butylcatechol are essential and act cooperatively to facilitate the aerobic oxidation under mild conditions.

Response of greenhouse gas emissions from three types of wetland soils to simulated temperature change on the Qinghai-Tibetan Plateau

NASA Astrophysics Data System (ADS)

Liu, Yi; Liu, Guihua; Xiong, Ziqian; Liu, Wenzhi

2017-12-01

Wetlands emit a large quantity of greenhouse gases into the atmosphere and contribute significantly to global warming. The Qinghai-Tibetan Plateau, known as the ;Third Pole; of the earth, contains abundant and diverse wetlands. Due to increasing human-induced pressures such as reclamation, overgrazing and climate change, many plateau wetlands have been degraded or destroyed. Until now, the response of soil greenhouse gas emissions to extreme summer temperatures in the plateau wetlands remains unknown. In this study, we collected 36 soil samples from riverine, lacustrine and palustrine wetlands on the Qinghai-Tibetan Plateau. We compared the carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O) emissions from soils incubated aerobically at 7, 12, and 19 °C. The results showed that the emissions of CH4 and N2O but not CO2 were significantly affected by the simulated temperature change. The N2O emission rate was considerably higher in palustrine wetlands compared with lacustrine and riverine wetlands. However, the CO2 and CH4 emissions did not differ significantly among the three wetland types. The ratio of CO2 to CH4 production increased with increasing incubation temperatures. The global warming potential of greenhouse gases at 19 °C was approximately 1.18 and 2.12 times greater than that at 12 and 7 °C, respectively. Our findings suggest that temperature change has a strong effect on soil greenhouse gas emissions and global warming potential of wetlands on the Qinghai-Tibetan Plateau, especially palustrine wetlands. Therefore, targeted strategies should be developed to mitigate the potential impacts of climate warming on the plateau.

Influence of acute exercise of varying intensity and duration on postprandial oxidative stress.

PubMed

Canale, Robert E; Farney, Tyler M; McCarthy, Cameron G; Bloomer, Richard J

2014-09-01

Aerobic exercise can reduce postprandial lipemia, and possibly oxidative stress, when performed prior to a lipid-rich meal. To compare the impact of acute exercise on postprandial oxidative stress. We compared aerobic and anaerobic exercise bouts of different intensities and durations on postprandial blood triglycerides (TAG), oxidative stress biomarkers (malondialdehyde, hydrogen peroxide, advanced oxidation protein products), and antioxidant status (trolox equivalent antioxidant capacity, superoxide dismutase, catalase, glutathione peroxidase). Twelve trained men (21-35 years) underwent four conditions: (1) No exercise rest; (2) 60-min aerobic exercise at 70% heart rate reserve; (3) five 60-s sprints at 100% max capacity; and (4) ten 15-s sprints at 200% max capacity. All exercise bouts were performed on a cycle ergometer. A high-fat meal was consumed 1 h after exercise cessation. Blood samples were collected pre-meal and 2 and 4 h post-meal and analyzed for TAG, oxidative stress biomarkers, and antioxidant status. No significant interaction or condition effects were noted for any variable (p > 0.05), with acute exercise having little to no effect on the magnitude of postprandial oxidative stress. In a sample of healthy, well-trained men, neither aerobic nor anaerobic exercise attenuates postprandial oxidative stress in response to a high-fat meal.

Microbial degradation of the brominated flame retardant TBNPA by groundwater bacteria: laboratory and field study.

PubMed

Balaban, Noa; Bernstein, Anat; Gelman, Faina; Ronen, Zeev

2016-08-01

In the present study, the biodegradation of the brominated flame retardant tribromoneopentylalcohol (TBNPA) by a groundwater enrichment culture was investigated using a dual carbon ((13)C/(12)C)- bromine ((81)Br/(79)Br) stable isotope analysis. An indigenous aerobic bacterial consortium was enriched from the polluted groundwater underlying an industrial site in the northern Negev Desert, Israel, where TBNPA is an abundant pollutant. Aerobic biodegradation was shown to be rapid, with complete debromination within a few days, whereas anaerobic biodegradation was not observed. Biodegradation under aerobic conditions was accompanied by a significant carbon isotope effect with an isotopic enrichment factor of ɛCbulk = -8.8‰ ± 1.5‰, without any detectable bromine isotope fractionation. It was found that molecular oxygen is necessary for biodegradation to occur, suggesting an initial oxidative step. Based on these results, it was proposed that H abstraction from the C-H bond is the first step of TBNPA biodegradation under aerobic conditions, and that the C-H bond cleavage results in the formation of unstable intermediates, which are rapidly debrominated. A preliminary isotopic analysis of TBNPA in the groundwater underlying the industrial area revealed that there are no changes in the carbon and bromine isotope ratio values downstream of the contamination source. Considering that anoxic conditions prevail in the groundwater of the contaminated site, the lack of isotope shifts in TBNPA indicates the lack of TBNPA biodegradation in the groundwater, in accordance with our findings. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

PubMed

Bian, Rongxing; Xin, Danhui; Chai, Xiaoli

2018-01-01

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

A novel thermophilic methane-oxidizing bacteria from thermal springs of Uzon volcano caldera, Kamchatka

NASA Astrophysics Data System (ADS)

Dvorianchikova, E.; Kizilova, A.; Kravchenko, I.; Galchenko, V.

2012-04-01

Methane is a radiatively active trace gas, contributing significantly to the greenhouse effect. It is 26 times more efficient in absorbing and re-emitting infrared radiation than carbon dioxide. Methanotrophs play an essential role in the global carbon cycle by oxidizing 50-75% of the biologically produced methane in situ, before it reaches the atmosphere. Methane-oxidizing bacteria are isolated from the various ecosystems and described at present. Their biology, processes of methane oxidation in fresh-water, marsh, soil and marine habitats are investigated quite well. Processes of methane oxidation in places with extreme physical and chemical conditions (high or low , salinity and temperature values) are studied in much smaller degree. Such ecosystems occupy a considerable part of the Earth's surface. The existence of aerobic methanotrophs inhabiting extreme environments has been verified so far by cultivation experiments and direct detection of methane monooxygenase genes specific to almost all aerobic methanotrophs. Thermophilic and thermotolerant methanotrophs have been isolated from such extreme environments and consist of the gammaproteobacterial (type I) genera Methylothermus, Methylocaldum, Methylococcus and the verrucomicrobial genus Methylacidiphilum. Uzon volcano caldera is a unique area, where volcanic processes still happen today. Hydrothermal springs of the area are extreme ecosystems which microbial communities represent considerable scientific interest of fundamental and applied character. A thermophilic aerobic methane-oxidising bacterium was isolated from a sediment sample from a hot spring (56.1; 5.3) of Uzon caldera. Strain S21 was isolated using mineral low salt medium. The headspace gas was composed of CH4, Ar, CO2, and O2 (40:40:15:5). The temperature of cultivation was 50, pH 5.5. Cells of strain S21 in exponential and early-stationary phase were coccoid bacilli, about 1 μm in diameter, and motile with a single polar flagellum. PCR and molecular cloning of a pmoA gene fragment have shown that strain S21 was moderately related to the genus Methylothermus; the closest organism is Methylothermus subterraneus. The further studying of strain S21 will expand our knowledge of this group of organisms, important from the ecological point of view.

Alkalilimnicola ehrlichii sp. nov., a novel, arsenite-oxidizing haloalkaliphilic gammaproteobacterium capable of chemoautotrophic or heterotrophic growth with nitrate or oxygen as the electron acceptor

USGS Publications Warehouse

Hoeft, S.E.; Blum, J.S.; Stolz, J.F.; Tabita, F.R.; Witte, B.; King, G.M.; Santini, J.M.; Oremland, R.S.

2007-01-01

A facultative chemoautotrophic bacterium, strain MLHE-1T, was isolated from Mono Lake, an alkaline hypersaline soda lake in California, USA. Cells of strain MLHE-1T were Gram-negative, short motile rods that grew with inorganic electron donors (arsenite, hydrogen, sulfide or thiosulfate) coupled with the reduction of nitrate to nitrite. No aerobic growth was attained with arsenite or sulfide, but hydrogen sustained both aerobic and anaerobic growth. No growth occurred when nitrite or nitrous oxide was substituted for nitrate. Heterotrophic growth was observed under aerobic and anaerobic (nitrate) conditions. Cells of strain MLHE-1T could oxidize but not grow on CO, while CH4 neither supported growth nor was it oxidized. When grown chemoautotrophically, strain MLHE-1T assimilated inorganic carbon via the Calvin-Benson-Bassham reductive pentose phosphate pathway, with the activity of ribulose 1,5-bisphosphate carboxylase (RuBisCO) functioning optimally at 0.1 M NaCl and at pH 7.3. Strain MLHE-1T grew over broad ranges of pH (7.3-10.0; optimum, 9.3), salinity (115-190 g l-1; optimum 30 g l-1) and temperature (113-40 ??C; optimum, 30 ??C). Phylogenetic analysis of 16S rRNA gene sequences placed strain MLHE-1T in the class Gammaproteobacteria (family Ectothiorhodospiraceae) and most closely related to Alkalispirillum mobile (98.5%) and Alkalilimnicola halodurans (98.6%), although none of these three haloalkaliphilic micro-organisms were capable of photoautotrophic growth and only strain MLHE-1T was able to oxidize As(III). On the basis of physiological characteristics and DNA-DNA hybridization data, it is suggested that strain MLHE-1T represents a novel species within the genus Alkalilimnicola for which the name Alkalilimnicola ehrlichii is proposed. The type strain is MLHE-1T (=DSM 17681T =ATCC BAA-1101T). Aspects of the annotated full genome of Alkalilimnicola ehrlichii are discussed in the light of its physiology. ?? 2007 IUMS.

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

PubMed

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

2017-04-01

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

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

EPA Science Inventory

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

Interannual Variability and Trends of CH4, CO and OH Using the Computationally-Efficient CH4-CO-OH (ECCOH) Module

NASA Technical Reports Server (NTRS)

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

2015-01-01

Methane (CH4) is the second most important anthropogenic greenhouse gas (GHG). Its 100-year global warming potential (GWP) is 34 times larger than that for carbon dioxide. The 100-year integrated GWPof CH4 is sensitive to changes in hydroxyl radical (OH) levels.Oxidation of CH4 and carbon monoxide (CO) by OH is the main loss process, thus affecting the oxidizing capacity of the atmosphere and contributing to the global ozone background. Limitations of using archived, monthly OH fields for studies of methane's and COs evolution are that feedbacks of the CH4-CO-OH system on methane, CO and OH are not captured. In this study, we employ the computationally Efficient CH4-CO-OH (ECCOH) module (Elshorbany et al., 2015) to investigate the nonlinear feedbacks of the CH4-CO-OH system on the interannual variability and trends of the CH4, CO, OH system.

Factors influencing the regioselectivity of the oxidation of asymmetric secondary amines with singlet oxygen.

PubMed

Ushakov, Dmitry B; Plutschack, Matthew B; Gilmore, Kerry; Seeberger, Peter H

2015-04-20

Aerobic amine oxidation is an attractive and elegant process for the α functionalization of amines. However, there are still several mechanistic uncertainties, particularly the factors governing the regioselectivity of the oxidation of asymmetric secondary amines and the oxidation rates of mixed primary amines. Herein, it is reported that singlet-oxygen-mediated oxidation of 1° and 2° amines is sensitive to the strength of the α-C-H bond and steric factors. Estimation of the relative bond dissociation energy by natural bond order analysis or by means of one-bond C-H coupling constants allowed the regioselectivity of secondary amine oxidations to be explained and predicted. In addition, the findings were utilized to synthesize highly regioselective substrates and perform selective amine cross-couplings to produce imines. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

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

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

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

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

DOE PAGES

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

2016-05-17

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

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

PubMed

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

2014-06-01

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

Greenhouse gas emission and microbial community dynamics during simultaneous nitrification and denitrification process.

PubMed

Kong, Qiang; Wang, Zhi-Bin; Niu, Peng-Fei; Miao, Ming-Sheng

2016-06-01

This study evaluates greenhouse gas emission and the microbial community dynamics during simultaneous nitrification and denitrification (SND) process. Based on CO2 equivalents, the SND reactor released 4.28g of greenhouse gases each cycle. 2.91% of the incoming nitrogen load was emitted as N2O. The CO2 and N2O emissions mainly occurred in the aerobic stage and CH4 emissions were consistently near zero. Extracellular polymeric substance (EPS) contents in activated sludge increased during start-up the SND process. High-throughput sequencing showed increases in bacterial species richness, leading to changes in EPS content and composition observed using 3D-EEM fluorescence spectra. For denitrifying bacteria, the relative abundance of Pseudomonas significantly increased during the SND process, while Paracoccus decreased significantly. For phosphorus-accumulating bacteria, the relative abundance of Rhodocyclaceae also significantly increased. The relative abundance of other functional microbes, such as Nitrosomonadaceae (ammonia oxidizer), Nitrospirales (nitrite oxidizer) and Planctomyces (anammox) decreased significantly during the SND process. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effect of aerobic pre-treatment on hydrogen and methane production in a two-stage anaerobic digestion process using food waste with different compositions.

PubMed

Rafieenia, Razieh; Girotto, Francesca; Peng, Wei; Cossu, Raffaello; Pivato, Alberto; Raga, Roberto; Lavagnolo, Maria Cristina

2017-01-01

Aerobic pre-treatment was applied prior to two-stage anaerobic digestion process. Three different food wastes samples, namely carbohydrate rich, protein rich and lipid rich, were prepared as substrates. Effect of aerobic pre-treatment on hydrogen and methane production was studied. Pre-aeration of substrates showed no positive impact on hydrogen production in the first stage. All three categories of pre-aerated food wastes produced less hydrogen compared to samples without pre-aeration. In the second stage, methane production increased for aerated protein rich and carbohydrate rich samples. In addition, the lag phase for carbohydrate rich substrate was shorter for aerated samples. Aerated protein rich substrate yielded the best results among substrates for methane production, with a cumulative production of approximately 351ml/gVS. With regard to non-aerated substrates, lipid rich was the best substrate for CH 4 production (263ml/gVS). Pre-aerated P substrate was the best in terms of total energy generation which amounted to 9.64kJ/gVS. This study revealed aerobic pre-treatment to be a promising option for use in achieving enhanced substrate conversion efficiencies and CH 4 production in a two-stage AD process, particularly when the substrate contains high amounts of proteins. Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

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

PubMed

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

2017-02-01

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

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

PubMed Central

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

2008-01-01

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

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

PubMed

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

2016-08-01

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

Effects of N and P fertilisation on greenhouse gas (GHG) production in floodplain fen peat: A microcosm fertilisation experiment.

NASA Astrophysics Data System (ADS)

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

2016-04-01

Biogeochemical and hydrological cycles are being significantly perturbed by anthropic activities altering atmospheric mole fractions of greenhouse gases (GHG) and increasing global temperatures. With the intensification of the hydrological cycle, lowland areas, such as floodplain fens, may be inundated more frequently. Rivers in agricultural catchments have the potential to pollute floodplain fens with significant amounts of nitrogen (N) and phosphorus (P); however, the effects of short-term (< 15 days) N and P fertilisation via fluvial inundation on GHG emissions from floodplain fens are poorly understood. The aim of this research was to determine how N (51 mg L-1 NO3-N) and P (1.4 mg L-1 PO43--P) additions may alter GHG (CO2, CH4, and N2O) production in floodplain fens of contrasting nutrient status under anaerobic conditions. A five-level (control, glucose (G), N+G, P+G, and N+P+G), fully-factorial microcosm experiment was designed and undertaken in Spring 2013 with peat from two floodplain fens under conservation management with similar vegetation (from Norfolk, United Kingdom). One site receives a higher nutrient load than the other and has a historical legacy of higher N and P contents within the peat. Results from the experiment showed no significant difference in CO2 production between the control and fertilised treatments from 0 to 96 hours, but a significant difference between treatments (ANCOVA, between factors: treatment and site; covariate: time; F4,419 = 11.844, p < 0.001) and site (F1,149 = 5.721, p = 0.017) from 96 hours to in the end of the experiment due to fermentation. N2O production only occurred in samples fertilised with N (N+G and N+P+G) due to denitrification. Rates of N2O production were significantly greater in samples from the lower-nutrient site in comparison to the nutrient-rich site (t12= 6.539, p < 0.001 and t12= 7.273, p < 0.001 for N+G and N+P+G fertilised samples, respectively). Fertilisation with N and P had different effects on CH4 production. Samples fertilised with P+G had the highest CH4 production (ANCOVA, between factors: treatment and site; covariate: time; F4,120= 15.026, p < 0.001). Samples fertilised with N (N+G and N+P+G) showed CH4 inhibition in comparison to G and P+G additions. CH4 production was significantly greater from the nutrient-rich peat than from the lower-nutrient peat (ANCOVA, between factors: treatment and site; covariate: time; F1,120= 38.646, p < 0.01). However, a decline in CH4 concentration in the microcosms suggests that CH4 oxidation occurred after 150 hours at the lower-nutrient site. Owing to the anaerobic conditions within the microcosms, aerobic methanotrophy cannot occur, suggesting anaerobic CH4 oxidation occurred along with denitrification. However, NO and N2 concentrations were not measured in this study, so this suggestion requires examination in future work.

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

NASA Astrophysics Data System (ADS)

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

2017-09-01

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

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

PubMed

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

2016-10-01

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

Oxidative mitigation of aquatic methane emissions in large Amazonian rivers.

PubMed

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

2016-03-01

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

Production and consumption of nitric oxide by three methanotrophic bacteria.

PubMed

Ren, T; Roy, R; Knowles, R

2000-09-01

We studied nitrogen oxide production and consumption by methanotrophs Methylobacter luteus (group I), Methylosinus trichosporium OB3b (group II), and an isolate from a hardwood swamp soil, here identified by 16S ribosomal DNA sequencing as Methylobacter sp. strain T20 (group I). All could consume nitric oxide (nitrogen monoxide, NO), and produce small amounts of nitrous oxide (N(2)O). Only Methylobacter strain T20 produced large amounts of NO (>250 parts per million by volume [ppmv] in the headspace) at specific activities of up to 2.0 x 10(-17) mol of NO cell(-1) day(-1), mostly after a culture became O(2) limited. Production of NO by strain T20 occurred mostly in nitrate-containing medium under anaerobic or nearly anaerobic conditions, was inhibited by chlorate, tungstate, and O(2), and required CH(4). Denitrification (methanol-supported N(2)O production from nitrate in the presence of acetylene) could not be detected and thus did not appear to be involved in the production of NO. Furthermore, cd(1) and Cu nitrite reductases, NO reductase, and N(2)O reductase could not be detected by PCR amplification of the nirS, nirK, norB, and nosZ genes, respectively. M. luteus and M. trichosporium produced some NO in ammonium-containing medium under aerobic conditions, likely as a result of methanotrophic nitrification and chemical decomposition of nitrite. For Methylobacter strain T20, arginine did not stimulate NO production under aerobiosis, suggesting that NO synthase was not involved. We conclude that strain T20 causes assimilatory reduction of nitrate to nitrite, which then decomposes chemically to NO. The production of NO by methanotrophs such as Methylobacter strain T20 could be of ecological significance in habitats near aerobic-anaerobic interfaces where fluctuating O(2) and nitrate availability occur.

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

NASA Astrophysics Data System (ADS)

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

2016-02-01

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

Acetogenic microbial degradation of vinyl chloride

USGS Publications Warehouse

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

2000-01-01

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

Limits and dynamics of methane oxidation in landfill cover soils

USDA-ARS?s Scientific Manuscript database

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

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

DOE PAGES

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

2015-11-08

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

Degradation of municipal solid waste in simulated landfill bioreactors under aerobic conditions.

PubMed

Slezak, Radoslaw; Krzystek, Liliana; Ledakowicz, Stanislaw

2015-09-01

In this study the municipal solid waste degradation processes in simulated landfill bioreactors under aerobic and anaerobic conditions is investigated. The effect of waste aeration on the dynamics of the aerobic degradation processes in lysimeters as well as during anaerobic processes after completion of aeration is presented. The results are compared with the anaerobic degradation process to determine the stabilization stage of waste in both experimental modes. The experiments in aerobic lysimeters were carried out at small aeration rate (4.41⋅10(-3)lmin(-1)kg(-1)) and for two recirculation rates (24.9 and 1.58lm(-3)d(-1)). The change of leachate and formed gases composition showed that the application of even a small aeration rate favored the degradation of organic matter. The amount of CO2 and CH4 released from anaerobic lysimeter was about 5 times lower than that from the aerobic lysimeters. Better stabilization of the waste was obtained in the aerobic lysimeter with small recirculation, from which the amount of CO2 produced was larger by about 19% in comparison with that from the aerobic lysimeter with large leachate recirculation. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

Carbon Mineralization Can Be Sustained or Even Stimulated under Fluctuating Redox Conditions in Tropical and Temperate Soils

NASA Astrophysics Data System (ADS)

Huang, W.; Hall, S. J.

2017-12-01

Soil carbon (C) mineralization is widely thought to be affected by O2 availability, and anaerobiosis represents a significant global mechanism of C stabilization. However, mineral-associated organic C (e.g. Fe-bound organic C) may be vulnerable to redox fluctuations due to release following Fe reduction, which could counteract protective effects of anaerobiosis. Many soils, including temperate Mollisols and tropical Oxisols, experience fluctuating redox conditions following moisture variations that could impact C cycling and stabilization. Here we incubated two soils with C4 leaf litter at different duration and frequencies of anaerobic periods for 128 days to investigate how redox fluctuations affect soil C mineralization. The treatments included static aerobic (control), and 2-, 4-, 8- and 12- day anaerobic followed by 4-day aerobic. We measured CO2, CH4, and their C isotope ratios. Longer durations of anaerobic conditions promoted greater Fe reduction and more DOC released. Notably, in both soils despite their large differences in composition, the production of CO2 and CH4 was stimulated under aerobic conditions following anaerobic conditions (relative to the control), which compensated for the decrease under anaerobic conditions. After 128 days, cumulative C mineralization in the control was similar between the Mollisol (9.7 mg C g-1) and the Oxisol (10.1 mg C g-1). The value in the Mollisol was significantly higher in the 12-day anaerobic treatment (11.2 mg C g-1) than the aerobic control and the 2-day anaerobic treatment (9.7 mg C g-1). In the Oxisol, cumulative C mineralization was not significantly affected by any of the fluctuating redox treatments relative to the control. Our findings challenge theory by showing that redox fluctuations can counteract the suppressive effects of O2 limitation on decomposition.

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

PubMed

Liikanen, Anu; Martikainen, Pertti J

2003-09-01

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

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

NASA Astrophysics Data System (ADS)

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

2015-08-01

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

An anaerobic-aerobic sequential batch process with simultaneous methanogenesis and short-cut denitrification for the treatment of marine biofoulings.

PubMed

Akizuki, S; Toda, T

2018-04-01

Although combination of denitritation and methanogenesis for wastewater treatment has been widely investigated, an application of this technology to solid waste treatment has been rarely studied. This study investigated an anaerobic-aerobic batch system with simultaneous denitritation-methanogenesis as an effective treatment for marine biofoulings, which is a major source of intermittently discharged organic solid wastes. Preliminary NO 2 - -exposed sludge was inoculated to achieve stable methanogenesis process without NO 2 - inhibition. Both high NH 4 + -N removal of 99.5% and high NO 2 - -N accumulation of 96.4% were achieved on average during the nitritation step. Sufficient CH 4 recovery of 101 L-CH 4 kg-COD -1 was achieved, indicating that the use of NO 2 - -exposed sludge is effective to avoid NO 2 - inhibition on methanogenesis. Methanogenesis was the main COD utilization pathway when the substrate solubilization occurred actively, while denitritation was the main when solubilization was limited because of substrate shortage. The results showed a high COD removal efficiency of 96.0% and a relatively low nitrogen removal efficiency of 64.4%. Fitting equations were developed to optimize the effluent exchange ratio. The estimated results showed that the increase of effluent exchange ratio during the active solubilization period increased the nitrogen removal efficiency but decreased CH 4 content in biogas. An appropriate effluent exchange ratio with high anaerobic effluent quality below approximately 120 mg-N L -1 as well as sufficient CH 4 gas quality which can be used as fuel for gas engine generator was achieved by daily effluent exchange of 80% during the first week and 5% during the subsequent 8 days. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

Methane plays a critical role in the radiation balance and chemistry of the atmosphere. Globally, landfill methane emission contributes about 10-19% of the anthropogenic methane burden into the atmosphere. In the United States, 18% of annual anthropogenic methane emissions come from landfills, which represent the third largest source of anthropogenic methane emissions, behind enteric fermentation and natural gas and oil production. One uncertainty in estimating landfill methane emissions is the fraction of methane oxidized when methane produced under anaerobic conditions passes through the cover soil. We developed a simple stoichiometric model to estimate the landfill methane oxidation fraction when the anaerobic CO2/CH4 production ratio is known. The model predicts a linear relationship between CO2 emission rates and CH4 emission rates, where the slope depends on anaerobic CO2/CH4 production ratio and the fraction of methane oxidized, and the intercept depends on non-methane-dependent oxidation processes. The model was tested with eddy covariance CO2 and CH4 emission rates at Bluff Road Landfill in Lincoln Nebraska. It predicted zero oxidation rate in the northern portion of this landfill where a membrane and vents were present. The zero oxidation rate was expected because there would be little opportunity for methane to encounter oxidizing conditions before leaving the vents. We also applied the model at the Turkey Run Landfill in Georgia to estimate the CH4 oxidation rate over a one year period. In contrast to Bluff Road Landfill, the Turkey Run Landfill did not have a membrane or vents. Instead, methane produced in the landfill had to diffuse through a 0.5 m soil cap before release to the atmosphere. We observed evidence for methane oxidation ranging from about 18% to above 60% depending upon the age of deposited waste material. The model will be briefly described, and results from the two contrasting landfills will be discussed in this presentation.

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

PubMed

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

2014-05-28

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

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

NASA Astrophysics Data System (ADS)

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

2013-04-01

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

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

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

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

2010-02-15

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

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

NASA Astrophysics Data System (ADS)

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

2016-04-01

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

Experimental characterization of enhanced SNCR process with carbonaceous gas additives.

PubMed

Yao, Ting; Duan, Yufeng; Yang, Zhizhong; Li, Yuan; Wang, Linwei; Zhu, Chun; Zhou, Qiang; Zhang, Jun; She, Min; Liu, Meng

2017-06-01

Carbonaceous gases such as CO and alkanes are commonly used as additives to enhance the selective non-catalytic reduction (SNCR) performance due to their high reducibility. This study compared the effect of CO and CH 4 on NO reduction in a tubular reactor with simulated flue gas. The enhancement of C 3 H 8 on SNCR process was tested at extremely low temperature, i.e. 650 °C. Experimental results suggested that reactions between NH 3 and SO 2 were favored at low temperatures and the competition for NH 3 between SO 2 and NO was influenced by gas additives. A maximum downward shift of 25 °C and 100 °C in temperature window for 50% NO reduction efficiency was obtained with the addition of CO and CH 4 , respectively. Considerable CO emission was observed with addition of CH 4 . The addition of CH 4 contributed to the formation of a self-accelerating reaction route within NO/O 2 /NH 3 SNCR reaction system. NO 2 produced from NO accelerates the oxidation of CH 4 to CO, while the oxidation of CH 4 returns to enhance the NO reduction globally. Optimal NO reduction of 44% was achieved with addition of C 3 H 8 at 650 °C. Substantial portion of C 3 H 8 was partially oxidized to CO and the remaining was converted into C 2 H 4 and C 3 H 6 during the SNCR process. Oxidative dehydrogenation of C 3 H 8 was involved. High reactivity of C 3 H 6 and C 2 H 4 favored the further oxidation and cracking to produce CO. These differences in oxidation behavior significantly influence the promotion capacities of CO, CH 4 and C 3 H 8 for NO reduction. Copyright © 2017 Elsevier Ltd. All rights reserved.

Comparison of Landfill Methane Oxidation Measured Using Stable Isotope Analysis and CO2/CH4 Fluxes Measured by the Eddy Covariance Method

NASA Astrophysics Data System (ADS)

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

2015-12-01

Methane plays a critical role in the radiation balance and chemistry of the atmosphere. Globally, landfill methane emission contributes about 10-19% of the anthropogenic methane burden into the atmosphere. In the United States, 18% of annual anthropogenic methane emissions come from landfills, which represent the third largest source of anthropogenic methane emissions, behind enteric fermentation and natural gas and oil production. One uncertainty in estimating landfill methane emissions is the fraction of methane oxidized when methane produced under anaerobic conditions passes through the cover soil. We developed a simple stoichiometric model to estimate methane oxidation fraction when the anaerobic CO2 / CH4 production ratio is known, or can be estimated. The model predicts a linear relationship between CO2 emission rates and CH4 emission rates, where the slope depends on anaerobic CO2 / CH4 production ratio and the fraction of methane oxidized, and the intercept depends on non-methane-dependent oxidation processes. The model was tested using carbon dioxide emission rates (fluxes) and methane emission rates (fluxes) measured using the eddy covariance method over a one year period at the Turkey Run landfill in Georgia, USA. The CO2 / CH4 production ratio was estimated by measuring CO2 and CH4 concentrations in air sampled under anaerobic conditions deep inside the landfill. We also used a mass balance approach to independently estimate fractional oxidation based on stable isotope measurements (δ13C of methane) of gas samples taken from deep inside the landfill and just above the landfill surface. Results from the two independent methods agree well. The model will be described and methane oxidation will be discussed in relation to wind direction, location at the landfill, and age of the deposited refuse.

Diversity and Function of Methanotrophic Bacteria in Caves

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

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

PubMed

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

2013-04-18

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

Catalyzed and Electrocatalyzed Oxidation of l-Tyrosine and l-Phenylalanine to Dopachrome by Nanozymes.

PubMed

Hou, Jianwen; Vázquez-González, Margarita; Fadeev, Michael; Liu, Xia; Lavi, Ronit; Willner, Itamar

2018-06-13

Catalyzed oxygen insertion into C-H bonds represents a continuous challenge in chemistry. Particularly, driving this process at ambient temperature and aqueous media represents a "holy grail" in catalysis. We report on the catalyzed cascade transformations of l-tyrosine or l-phenylalanine to dopachrome in the presence of l-ascorbic acid/H 2 O 2 as oxidizing mixture and CuFe-Prussian Blue-like nanoparticles, Fe 3 O 4 nanoparticles or Au nanoparticles as catalysts. The process involves the primary transformation of l-tyrosine to l-DOPA that is further oxidized to dopachrome. The transformation of l-phenylalanine to dopachrome in the presence of CuFe-Prussian Blue-like nanoparticles and l-ascorbic acid/H 2 O 2 involves in the first step the formation of l-tyrosine and, subsequently, the operation of the catalytic oxidation cascade of l-tyrosine to l-DOPA and dopachrome. Electron spin resonance experiments demonstrate that ascorbate radicals and hydroxyl radicals play cooperative functions in driving the different oxygen-insertion processes. In addition, the aerobic elecrocatalyzed oxidation of l-tyrosine to dopachrome in the presence of naphthoquinone-modified Fe 3 O 4 nanoparticles and l-ascorbic acid is demonstrated. In this system, magnetic-field attraction of the naphthoquinone-modified Fe 3 O 4 nanoparticles onto the electrode allows the quinone-mediated electrocatalyzed reduction of O 2 to H 2 O 2 (bias potential -0.5 V vs SCE). The electrogenerated H 2 O 2 is then utilized to promote the transformation of l-tyrosine to dopachrome in the presence of l-ascorbic acid and Fe 3 O 4 catalyst.

Graphite-supported gold nanoparticles as efficient catalyst for aerobic oxidation of benzylic amines to imines and N-substituted 1,2,3,4-tetrahydroisoquinolines to amides: synthetic applications and mechanistic study.

PubMed

So, Man-Ho; Liu, Yungen; Ho, Chi-Ming; Che, Chi-Ming

2009-10-05

Selective oxidation of amines using oxygen as terminal oxidant is an important area in green chemistry. In this work, we describe the use of graphite-supported gold nanoparticles (AuNPs/C) to catalyze aerobic oxidation of cyclic and acyclic benzylic amines to the corresponding imines with moderate-to-excellent substrate conversions (43-100%) and product yields (66-99%) (19 examples). Oxidation of N-substituted 1,2,3,4-tetrahydroisoquinolines in the presence of aqueous NaHCO3 solution gave the corresponding amides in good yields (83-93%) with high selectivity (up to amide/enamide=93:4) (6 examples). The same protocol can be applied to the synthesis of benzimidazoles from the reaction of o-phenylenediamines with benzaldehydes under aerobic conditions (8 examples). By simple centrifugation, AuNPs/C can be recovered and reused for ten consecutive runs for the oxidation of dibenzylamine to N-benzylidene(phenyl)methanamine without significant loss of catalytic activity and selectivity. This protocol "AuNPs/C+O2" can be scaled to the gram scale, and 8.9 g (84 % isolated yield) of 3,4-dihydroisoquinoline can be obtained from the oxidation of 10 g 1,2,3,4-tetrahydroisoquinoline in a one-pot reaction. Based on the results of kinetic studies, radical traps experiment, and Hammett plot, a mechanism involving the hydrogen-transfer reaction from amine to metal and oxidation of M-H is proposed.

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

PubMed

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

2015-01-01

Effects of elevated atmospheric CO2 concentrations on plant growth and associated C cycling have intensively been studied, but less is known about effects on the fluxes of radiatively active trace gases other than CO2. Net soil-atmosphere CH4 fluxes are determined by the balance of soil microbially-driven methane (CH4) oxidation and methanogenesis, and both might change under elevated CO2. Here, we studied CH4 dynamics in a permanent grassland exposed to elevated CO2 for 14 years. Soil-atmosphere fluxes of CH4 were measured using large static chambers, over a period of four years. The ecosystem was a net sink for atmospheric CH4 for most of the time except summer to fall when net CH4 emissions occurred. We did not detect any elevated CO2 effects on CH4 fluxes, but emissions were difficult to quantify due to their discontinuous nature, most likely because of ebullition from the saturated zone. Potential methanotrophic activity, determined by incubation of fresh sieved soil under standardized conditions, also did not reveal any effect of the CO2 treatment. Finally, we determined the spatial micro-distribution of methanotrophic activity at less than 5× atmospheric (10 ppm) and elevated (10000 ppm) CH4 concentrations, using a novel auto-radiographic technique. These analyses indicated that domains of net CH4 assimilation were distributed throughout the analyzed top 15 cm of soils, with no dependence on CH4 concentration or CO2 treatment. Our investigations suggest that elevated CO2 exerts no or only minor effects on CH4 fluxes in the type of ecosystem we studied, at least as long as soil moisture differences are small or absent as was the case here. The autoradiographic analyses further indicate that the spatial niche of CH4 oxidation does not shift in response to CO2 enrichment or CH4 concentration, and that the same type of methanotrophs may oxidize CH4 from atmospheric and soil-internal sources.

Response of anaerobic carbon cycling to water table manipulation in an Alaskan rich fen

USGS Publications Warehouse

Kane, E.S.; Chivers, M.R.; Turetsky, M.R.; Treat, C.C.; Petersen, D.G.; Waldrop, M.; Harden, J.W.; McGuire, A.D.

2013-01-01

To test the effects of altered hydrology on organic soil decomposition, we investigated CO2 and CH4 production potential of rich-fen peat (mean surface pH = 6.3) collected from a field water table manipulation experiment including control, raised and lowered water table treatments. Mean anaerobic CO2 production potential at 10 cm depth (14.1 ± 0.9 μmol C g−1 d−1) was as high as aerobic CO2 production potential (10.6 ± 1.5 μmol C g−1 d−1), while CH4 production was low (mean of 7.8 ± 1.5 nmol C g−1 d−1). Denitrification enzyme activity indicated a very high denitrification potential (197 ± 23 μg N g−1 d−1), but net NO-3 reduction suggested this was a relatively minor pathway for anaerobic CO2 production. Abundances of denitrifier genes (nirK and nosZ) did not change across water table treatments. SO2-4 reduction also did not appear to be an important pathway for anaerobic CO2 production. The net accumulation of acetate and formate as decomposition end products in the raised water table treatment suggested that fermentation was a significant pathway for carbon mineralization, even in the presence of NO-3. Dissolved organic carbon (DOC) concentrations were the strongest predictors of potential anaerobic and aerobic CO2 production. Across all water table treatments, the CO2:CH4 ratio increased with initial DOC leachate concentrations. While the field water table treatment did not have a significant effect on mean CO2 or CH4 production potential, the CO2:CH4 ratio was highest in shallow peat incubations from the drained treatment. These data suggest that with continued drying or with a more variable water table, anaerobic CO2 production may be favored over CH4 production in this rich fen. Future research examining the potential for dissolved organic substances to facilitate anaerobic respiration, or alternative redox processes that limit the effectiveness of organic acids as substrates in anaerobic metabolism, would help explain additional uncertainty concerning carbon mineralization in this system.

Effects of aerobic training on exercise-related oxidative stress in mitochondrial myopathies.

PubMed

Siciliano, Gabriele; Simoncini, Costanza; Lo Gerfo, Annalisa; Orsucci, Daniele; Ricci, Giulia; Mancuso, Michelangelo

2012-12-01

In mitochondrial myopathies with respiratory chain deficiency impairment of energy cell production may lead to in excess reactive oxygen species generation with consequent oxidative stress and cell damage. Aerobic training has been showed to increase muscle performance in patients with mitochondrial myopathies. Aim of this study has been to evaluate, in 7 patients (6 F e 1M, mean age 44.9 ± 12.1 years) affected by mitochondrial disease, concomitantly to lactate exercise curve, the occurrence of oxidative stress, as indicated by circulating levels of lipoperoxides, in rest condition and as effect of exercise, and also, to verify if an aerobic training program is able to modify, in these patients, ox-redox balance efficiency. At rest and before training blood level of lipoperoxides was 382.4 ± 37.8 AU, compared to controls (318.7 ± 63.8; P<0.05), this corresponding to a moderate oxidative stress degree according to the adopted scale. During incremental exercise blood level of lipoperoxides did not increase, but maintained significantly higher compared to controls. After an aerobic training of 10 weeks the blood level of lipoperoxides decreased by 13.7% at rest (P<0.01) and 10.4%, 8.6% and 8.5% respectively at the corresponding times during the exercise test (P=0.06). These data indicate that, in mitochondrial patients, oxidative stress occurs and that an aerobic training is useful in partially reverting this condition. Copyright © 2012 Elsevier B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2012-01-01

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

Extensive processing of sediment pore water dissolved organic matter during anoxic incubation as observed by high-field mass spectrometry (FTICR-MS).

PubMed

Valle, Juliana; Gonsior, Michael; Harir, Mourad; Enrich-Prast, Alex; Schmitt-Kopplin, Philippe; Bastviken, David; Conrad, Ralf; Hertkorn, Norbert

2018-02-01

Dissolved organic matter (DOM) contained in lake sediments is a carbon source for many microbial degradation processes, including aerobic and anaerobic mineralization. During anaerobic degradation, DOM is partially consumed and transformed into new molecules while the greenhouse gases methane (CH 4 ) and carbon dioxide (CO 2 ) are produced. In this study, we used ultrahigh resolution mass spectrometry to trace differences in the composition of solid-phase extractable (PPL resin) pore water DOM (SPE-DOM) isolated from surface sediments of three boreal lakes before and after 40 days of anoxic incubation, with concomitant determination of CH 4 and CO 2 evolution. CH 4 and CO 2 production detected by gas chromatography varied considerably among replicates and accounted for fractions of ∼2-4 × 10 -4 of sedimentary organic carbon for CO 2 and ∼0.8-2.4 × 10 -5 for CH 4 . In contrast, the relative changes of key bulk parameters during incubation, such as relative proportions of molecular series, elemental ratios, average mass and unsaturation, were regularly in the percent range (1-3% for compounds decreasing and 4-10% for compounds increasing), i.e. several orders of magnitude higher than mineralization alone. Computation of the average carbon oxidation state in CHO molecules of lake pore water DOM revealed rather non-selective large scale transformations of organic matter during incubation, with depletion of highly oxidized and highly reduced CHO molecules, and formation of rather non-labile fulvic acid type molecules. In general, proportions of CHO compounds slightly decreased. Nearly saturated CHO and CHOS lipid-like substances declined during incubation: these rather commonplace molecules were less specific indicators of lake sediment alteration than the particular compounds, such as certain oxygenated aromatics and carboxyl-rich alicyclic acids (CRAM) found more abundant after incubation. There was a remarkable general increase in many CHNO compounds during incubation across all lakes. Differences in DOM transformation between lakes corresponded with lake size and water residence time. While in the small lake Svarttjärn, CRAM increased during incubation, lignin-and tannin-like compounds were enriched in the large lake Bisen, suggesting selective preservation of these rather non-labile aromatic compounds rather than recent synthesis. SPE-DOM after incubation may represent freshly synthesized compounds, leftover bulk DOM which is primarily composed of intrinsically refractory molecules and/or microbial metabolites which were not consumed in our experiments. In spite of a low fraction of the total DOM being mineralized to CO 2 and CH 4 , the more pronounced change in molecular DOM composition during the incubation indicates that diagenetic modification of organic matter can be substantial compared to complete mineralization. Copyright © 2017 Elsevier Ltd. All rights reserved.

Oxidation of methane in biotrickling filters inoculated with methanotrophic bacteria.

PubMed

Cáceres, Manuel; Dorado, Antonio D; Gentina, Juan C; Aroca, Germán

2017-11-01

The oxidation of methane (CH 4 ) using biofilters has been proposed as an alternative to mitigate anthropogenic greenhouse gas emissions with a low concentration of CH 4 that cannot be used as a source of energy. However, conventional biofilters utilize organic packing materials that have a short lifespan, clogging problems, and are commonly inoculated with non-specific microorganisms leading to unpredictable CH 4 elimination capacities (EC) and removal efficiencies (RE). The main objective of this work was to characterize the oxidation of CH 4 in two biotrickling filters (BTFs) packed with polyethylene rings and inoculated with two methanotrophic bacteria, Methylomicrobium album and Methylocystis sp., in order to determine EC and CO 2 production (pCO 2 ) when using a specific inoculum. The repeatability of the results in both BTFs was determined when they operated at the same inlet load of CH 4 . A dynamic mathematical model that describes the CH 4 abatement in the BTFs was developed and validated using mass transfer and kinetic parameters estimated independently. The results showed that EC and pCO 2 of the BTFs are not identical but very similar for all the conditions tested. The use of specific inoculum has shown a faster startup and higher EC per unit area (0.019 gCH 4  m -2  h -1 ) in comparison to most of the previous studies at the same CH 4 load rate (23.2 gCH 4  m -3  h -1 ). Global mass balance showed that the maximum reduction of CO 2 equivalents was 98.5 gCO 2eq  m -3  h -1 . The developed model satisfactorily described CH 4 abatement in BTFs for a wide range of conditions.

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

NASA Astrophysics Data System (ADS)

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

2011-04-01

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

Modeling the impediment of methane ebullition bubbles by seasonal lake ice

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

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

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

Modeling the impediment of methane ebullition bubbles by seasonal lake ice

DOE PAGES

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

2014-12-08

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

Global Methane Biogeochemistry

NASA Astrophysics Data System (ADS)

Reeburgh, W. S.

2003-12-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-08-01

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

Greenhouse gas emissions and global warming potential of traditional and diversified tropical rice rotation systems.

PubMed

Weller, Sebastian; Janz, Baldur; Jörg, Lena; Kraus, David; Racela, Heathcliff S U; Wassmann, Reiner; Butterbach-Bahl, Klaus; Kiese, Ralf

2016-01-01

Global rice agriculture will be increasingly challenged by water scarcity, while at the same time changes in demand (e.g. changes in diets or increasing demand for biofuels) will feed back on agricultural practices. These factors are changing traditional cropping patterns from double-rice cropping to the introduction of upland crops in the dry season. For a comprehensive assessment of greenhouse gas (GHG) balances, we measured methane (CH4 )/nitrous oxide (N2 O) emissions and agronomic parameters over 2.5 years in double-rice cropping (R-R) and paddy rice rotations diversified with either maize (R-M) or aerobic rice (R-A) in upland cultivation. Introduction of upland crops in the dry season reduced irrigation water use and CH4 emissions by 66-81% and 95-99%, respectively. Moreover, for practices including upland crops, CH4 emissions in the subsequent wet season with paddy rice were reduced by 54-60%. Although annual N2 O emissions increased two- to threefold in the diversified systems, the strong reduction in CH4 led to a significantly lower (P < 0.05) annual GWP (CH4  + N2 O) as compared to the traditional double-rice cropping system. Measurements of soil organic carbon (SOC) contents before and 3 years after the introduction of upland crop rotations indicated a SOC loss for the R-M system, while for the other systems SOC stocks were unaffected. This trend for R-M systems needs to be followed as it has significant consequences not only for the GWP balance but also with regard to soil fertility. Economic assessment showed a similar gross profit span for R-M and R-R, while gross profits for R-A were reduced as a consequence of lower productivity. Nevertheless, regarding a future increase in water scarcity, it can be expected that mixed lowland-upland systems will expand in SE Asia as water requirements were cut by more than half in both rotation systems with upland crops. © 2015 John Wiley & Sons Ltd.

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.

Electrochemical Oxidation of Alkylnitro Compounds PP-1345

DTIC Science & Technology

2004-08-17

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

Efficacy of calcium oxide and calcium hydroxide nanoparticles on the elimination of Enterococcus faecalis in human root dentin.

PubMed

Louwakul, Phumisak; Saelo, Attapon; Khemaleelakul, Saengusa

2017-04-01

The objective of this study was to compare the antibacterial effect of calcium oxide nanoparticles (CONPs) and calcium hydroxide nanoparticles (CHNPs) against Enterococcus faecalis in a dentinal block model. E. faecalis strain JCM 7783 was introduced into dentinal tubules of semicylindrical dentin specimens by centrifugation and incubated for 1 week. Fifty microliters of CONPs or CHNPs was placed on the root canal side of the infected dentin specimens. The specimens were then incubated in aerobic condition at 37 °C and 100 % relative humidity for 1 week. The treated dentin specimens were subjected to fluorescent staining and confocal laser scanning microscopy (CLSM) to analyze the proportions of non-vital and vital bacterial cells inside the dentinal tubules. Scanning electron microscopy (SEM) was used to confirm the effect of the medicaments on the bacteria in the dentinal tubules. Calcium oxide (CO) and calcium hydroxide (CH) were used as controls. Based on the CLSM and SEM analyses, CHNPs were more efficient than CONPs in the elimination of the bacteria in the dentinal tubules. CONPs significantly killed more E. faecalis than CO and CH (P < .05). Neither CO nor CH was able to kill the bacteria. CHNPs were more effective than CONPs in the elimination of E. faecalis in dentinal tubules. CHNPs are effective nanoparticles in killing endodontic bacteria present in dentinal tubules. They have potential as an intracanal medicament, which may be beneficial in root canal therapy.

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

NASA Astrophysics Data System (ADS)

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

2007-12-01

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

Impact of Organic Amendments on Global Warming Potential of Diversified Tropical Rice Rotation Systems

NASA Astrophysics Data System (ADS)

Janz, B.; Weller, S.; Kraus, D.; Wassmann, R.; Butterbach-Bahl, K.; Ralf, K.

2017-12-01

Paddy rice cultivation is increasingly challenged by irrigation water scarcity, which is forcing farmers to change traditional rice cultivation from flooded double-rice systems to the introduction of well-aerated upland crops during dry season. Emissions of methane (CH4) are expected to decrease, while there is a risk of increasing emissions of nitrous oxide (N2O) and decreasing soil organic carbon (SOC) stocks through volatilization in the form of carbon dioxide (CO2). We present a unique dataset of long-term continuous greenhouse gas emission measurements (CH4 and N2O) in the Philippines to assess global warming potentials (GWP) of diversified rice crop rotations including different field management practices such as straw residue application and legume intercropping. Since 2012, more than four years of CH4 and N2O emissions in double-rice cropping (R-R) and paddy rice rotations diversified with either maize (R-M) or aerobic rice (R-A) during dry season have been collected. Introduction of upland crops reduced irrigation water use and CH4 emissions by 66-81% and 95-99%, respectively. Although dry season N2O emissions increased twice- to threefold in the diversified systems, the strong reduction of CH4 led to a significantly lower annual GWP (CH4 + N2O) as compared to the traditional R-R system. Diversified crop management practices were first implemented during land-preparation for dry season 2015 where i) 6 t/ha rice straw was returned to the field and ii) mungbean was grown as a cover-crop between dry and wet season in addition to rice straw application. The input of organic material (straw and mungbean) led to higher substrate availability for methanogens during the following season. Therefore, GWP was 9-39% higher following straw incorporation than the control treatment. This increase was mainly driven by additional CH4 emissions. Even more, mungbean intercropping further increased GWPs, whereby the increment was highest in R-R rotation (88%) and lowest in R-M rotation (55%), with annual emissions of 11.8 and 5.6 t CO2 eq. ha-1, respectively. Nevertheless, regarding a future expansion of lowland-upland rotations due to water scarcity in SE Asia it can be expected that input of crop residues can counteract the SOC loss that is likely associated with the shift to more aerated soil conditions under upland crops.

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

PubMed

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

2004-05-21

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

Soil greenhouse gas emissions and carbon budgeting in a short-hydroperiod floodplain wetland

NASA Astrophysics Data System (ADS)

Batson, Jackie; Noe, Gregory B.; Hupp, Cliff R.; Krauss, Ken W.; Rybicki, Nancy B.; Schenk, Edward R.

2015-01-01

Understanding the controls on floodplain carbon (C) cycling is important for assessing greenhouse gas emissions and the potential for C sequestration in river-floodplain ecosystems. We hypothesized that greater hydrologic connectivity would increase C inputs to floodplains that would not only stimulate soil C gas emissions but also sequester more C in soils. In an urban Piedmont river (151 km2 watershed) with a floodplain that is dry most of the year, we quantified soil CO2, CH4, and N2O net emissions along gradients of floodplain hydrologic connectivity, identified controls on soil aerobic and anaerobic respiration, and developed a floodplain soil C budget. Sites were chosen along a longitudinal river gradient and across lateral floodplain geomorphic units (levee, backswamp, and toe slope). CO2 emissions decreased downstream in backswamps and toe slopes and were high on the levees. CH4 and N2O fluxes were near zero; however, CH4 emissions were highest in the backswamp. Annual CO2 emissions correlated negatively with soil water-filled pore space and positively with variables related to drier, coarser soil. Conversely, annual CH4 emissions had the opposite pattern of CO2. Spatial variation in aerobic and anaerobic respiration was thus controlled by oxygen availability but was not related to C inputs from sedimentation or vegetation. The annual mean soil CO2 emission rate was 1091 g C m-2 yr-1, the net sedimentation rate was 111 g C m-2 yr-1, and the vegetation production rate was 240 g C m-2 yr-1, with a soil C balance (loss) of -338 g C m-2 yr-1. This floodplain is losing C likely due to long-term drying from watershed urbanization.

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

EPA Science Inventory

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

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

PubMed

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

2005-07-01

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

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

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

Bataineh, Hajem; Pestovsky, Oleg; Bakac, Andreja

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

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

DOE PAGES

Bataineh, Hajem; Pestovsky, Oleg; Bakac, Andreja

2015-02-11

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

Statistical assessment of dumpsite soil suitability to enhance methane bio-oxidation under interactive influence of substrates and temperature.

PubMed

Bajar, Somvir; Singh, Anita; Kaushik, C P; Kaushik, Anubha

2017-05-01

Biocovers are considered as the most effective and efficient way to treat methane (CH 4 ) emission from dumpsites and landfills. Active methanotrophs in the biocovers play a crucial role in reduction of emissions through microbiological methane oxidation. Several factors affecting methane bio-oxidation (MOX) have been well documented, however, their interactive effect on the oxidation process needs to be explored. Therefore, the present study was undertaken to investigate the suitability of a dumpsite soil to be employed as biocover, under the influence of substrate concentrations (CH 4 and O 2 ) and temperature at variable incubation periods. Statistical design matrix of Response Surface Methodology (RSM) revealed that MOX rate up to 69.58μgCH 4 g -1 dw h -1 could be achieved under optimum conditions. MOX was found to be more dependent on CH 4 concentration at higher level (30-40%, v/v), in comparison to O 2 concentration. However, unlike other studies MOX was found in direct proportionality relationship with temperature within a range of 25-35°C. The results obtained with the dumpsite soil biocover open up a new possibility to provide improved, sustained and environmental friendly systems to control even high CH 4 emissions from the waste sector. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

PubMed

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

2017-11-01

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

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

NASA Astrophysics Data System (ADS)

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

1996-03-01

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

Mitochondria As Sources and Targets of Methane.

PubMed

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

2017-01-01

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

Mitochondria As Sources and Targets of Methane

PubMed Central

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

2017-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2012-06-01

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

Factors Driving Potential Ammonia Oxidation in Canadian Arctic Ecosystems: Does Spatial Scale Matter?

PubMed Central

Banerjee, Samiran

2012-01-01

Ammonia oxidation is a major process in nitrogen cycling, and it plays a key role in nitrogen limited soil ecosystems such as those in the arctic. Although mm-scale spatial dependency of ammonia oxidizers has been investigated, little is known about the field-scale spatial dependency of aerobic ammonia oxidation processes and ammonia-oxidizing archaeal and bacterial communities, particularly in arctic soils. The purpose of this study was to explore the drivers of ammonia oxidation at the field scale in cryosols (soils with permafrost within 1 m of the surface). We measured aerobic ammonia oxidation potential (both autotrophic and heterotrophic) and functional gene abundance (bacterial amoA and archaeal amoA) in 279 soil samples collected from three arctic ecosystems. The variability associated with quantifying genes was substantially less than the spatial variability observed in these soils, suggesting that molecular methods can be used reliably evaluate spatial dependency in arctic ecosystems. Ammonia-oxidizing archaeal and bacterial communities and aerobic ammonia oxidation were spatially autocorrelated. Gene abundances were spatially structured within 4 m, whereas biochemical processes were structured within 40 m. Ammonia oxidation was driven at small scales (<1m) by moisture and total organic carbon, whereas gene abundance and other edaphic factors drove ammonia oxidation at medium (1 to 10 m) and large (10 to 100 m) scales. In these arctic soils heterotrophs contributed between 29 and 47% of total ammonia oxidation potential. The spatial scale for aerobic ammonia oxidation genes differed from potential ammonia oxidation, suggesting that in arctic ecosystems edaphic, rather than genetic, factors are an important control on ammonia oxidation. PMID:22081570

Properties of Multiphase Polyurethane Systems.

DTIC Science & Technology

1981-08-01

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

Limited role for methane in the mid-Proterozoic greenhouse

PubMed Central

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

2016-01-01

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

Oxygen and sulfur isotope systematics of sulfate produced by bacterial and abiotic oxidation of pyrite

USGS Publications Warehouse

Balci, N.; Shanks, Wayne C.; Mayer, B.; Mandernack, K.W.

2007-01-01

To better understand reaction pathways of pyrite oxidation and biogeochemical controls on ??18O and ??34S values of the generated sulfate in acid mine drainage (AMD) and other natural environments, we conducted a series of pyrite oxidation experiments in the laboratory. Our biological and abiotic experiments were conducted under aerobic conditions by using O2 as an oxidizing agent and under anaerobic conditions by using dissolved Fe(III)aq as an oxidant with varying ??18OH2O values in the presence and absence of Acidithiobacillus ferrooxidans. In addition, aerobic biological experiments were designed as short- and long-term experiments where the final pH was controlled at ???2.7 and 2.2, respectively. Due to the slower kinetics of abiotic sulfide oxidation, the aerobic abiotic experiments were only conducted as long term with a final pH of ???2.7. The ??34SSO4 values from both the biological and abiotic anaerobic experiments indicated a small but significant sulfur isotope fractionation (???-0.7???) in contrast to no significant fractionation observed from any of the aerobic experiments. Relative percentages of the incorporation of water-derived oxygen and dissolved oxygen (O2) to sulfate were estimated, in addition to the oxygen isotope fractionation between sulfate and water, and dissolved oxygen. As expected, during the biological and abiotic anaerobic experiments all of the sulfate oxygen was derived from water. The percentage incorporation of water-derived oxygen into sulfate during the oxidation experiments by O2 varied with longer incubation and lower pH, but not due to the presence or absence of bacteria. These percentages were estimated as 85%, 92% and 87% from the short-term biological, long-term biological and abiotic control experiments, respectively. An oxygen isotope fractionation effect between sulfate and water (??18 OSO4 s(-) H2 O) of ???3.5??? was determined for the anaerobic (biological and abiotic) experiments. This measured ??18 OSO42 - s(-) H2 O value was then used to estimate the oxygen isotope fractionation effects (??18 OSO42 - s(-) O2) between sulfate and dissolved oxygen in the aerobic experiments which were -10.0???, -10.8???, and -9.8??? for the short-term biological, long-term biological and abiotic control experiments, respectively. Based on the similarity between ??18OSO4 values in the biological and abiotic experiments, it is suggested that ??18OSO4 values cannot be used to distinguish biological and abiotic mechanisms of pyrite oxidation. The results presented here suggest that Fe(III)aq is the primary oxidant for pyrite at pH < 3, even in the presence of dissolved oxygen, and that the main oxygen source of sulfate is water-oxygen under both aerobic and anaerobic conditions. ?? 2007 Elsevier Ltd. All rights reserved.

Testing climate-smart irrigation strategies to reduce methane emissions from rice fields

NASA Astrophysics Data System (ADS)

Runkle, B.; Suvocarev, K.; Reba, M. L.

2017-12-01

Approximately 11% of the global 308 Tg CH4 anthropogenic emissions are currently attributed to rice cultivation. In this study, the impact of water conservation practices on rice field CH4 emissions was evaluated in Arkansas, the leading state in US rice cultivation. While conserving water, the Alternate Wetting and Drying (AWD) irrigation practice can also reduce CH4 emissions through the deliberate, periodic introduction of aerobic conditions. Seasonal CH4emissions from a pair of adjacent, production-sized rice fields were estimated and compared during the 2015 to 2017 growing seasons using the eddy covariance method on each field. The fields were alternately treated with continuous flood (CF) and AWD irrigation. In 2015, the seasonal cumulative carbon losses by CH4 emission were 30.3 ± 6.3 and 141.9 ± 8.6 kg CH4-C ha-1 for the AWD and CF treatments, respectively. Data from 2016 and 2017 will be analyzed and shown within this presentation; an initial view demonstrates consistent findings to 2015. When accounting for differences in field conditions and soils, the AWD practice is attributable to a 36-51% reduction in seasonal emissions. The substantial decrease in CH4 emissions by AWD supports previous chamber-based research and offers strong evidence for the efficacy of AWD in reducing CH4 emissions in Arkansas rice production. The AWD practice has enabled the sale of credits for carbon offsets trading and this new market could encourage CH4 emissions reductions on a national scale. These eddy covariance towers are being placed into a regional perspective including crop and forest land in the three states comprising the Mississippi Delta: Arkansas, Mississippi, and Louisiana.

Production of Manganese Oxide Nanoparticles by Shewanella Species

PubMed Central

Farooqui, Saad M.; White, Alan R.

2016-01-01

ABSTRACT Several species of the bacterial genus Shewanella are well-known dissimilatory reducers of manganese under anaerobic conditions. In fact, Shewanella oneidensis is one of the most well studied of all metal-reducing bacteria. In the current study, a number of Shewanella strains were tested for manganese-oxidizing capacity under aerobic conditions. All were able to oxidize Mn(II) and to produce solid dark brown manganese oxides. Shewanella loihica strain PV-4 was the strongest oxidizer, producing oxides at a rate of 20.3 mg/liter/day and oxidizing Mn(II) concentrations of up to 9 mM. In contrast, S. oneidensis MR-1 was the weakest oxidizer tested, producing oxides at 4.4 mg/liter/day and oxidizing up to 4 mM Mn(II). Analysis of products from the strongest oxidizers, i.e., S. loihica PV-4 and Shewanella putrefaciens CN-32, revealed finely grained, nanosize, poorly crystalline oxide particles with identical Mn oxidation states of 3.86. The biogenic manganese oxide products could be subsequently reduced within 2 days by all of the Shewanella strains when culture conditions were made anoxic and an appropriate nutrient (lactate) was added. While Shewanella species were detected previously as part of manganese-oxidizing consortia in natural environments, the current study has clearly shown manganese-reducing Shewanella species bacteria that are able to oxidize manganese in aerobic cultures. IMPORTANCE Members of the genus Shewanella are well known as dissimilatory manganese-reducing bacteria. This study shows that a number of species from Shewanella are also capable of manganese oxidation under aerobic conditions. Characterization of the products of the two most efficient oxidizers, S. loihica and S. putrefaciens, revealed finely grained, nanosize oxide particles. With a change in culture conditions, the manganese oxide products could be subsequently reduced by the same bacteria. The ability of Shewanella species both to oxidize and to reduce manganese indicates that the genus plays a significant role in the geochemical cycling of manganese. Due to the high affinity of manganese oxides for binding other metals, these bacteria may also contribute to the immobilization and release of other metals in the environment. PMID:27342559

Alternate wetting and drying practice for reducing greenhouse gas emissions in flooded rice agroecosystems

NASA Astrophysics Data System (ADS)

Adviento-Borbe, A.; Anders, M. M.; Runkle, B.; Reba, M. L.; Suvocarev, K.; Massey, J. H.; Linquist, B.

2017-12-01

Alternate wetting and drying management (AWD) practices which minimize flooding times have been shown to reduce both CH4 emissions and water use but effects on N2O emissions and grain yields are variable. Grain yield and seasonal CH4 and N2O emissions were measured from AWD treatments with various soil water thresholds and conventionally flooded water treatment in two commercial farms in Arkansas and in an experimental field in Biggs, CA during 2015 and 2016 crop seasons. Methane and N2O emissions were measured using vented flux chamber and gas chromatography methods. Grain yields ( 10 Mg ha-1) were similar in AWD and conventional water treatments. Total CH4 emissions ranged from 21 to 338 kg CH4-C ha-1 season-1. The AWD practice reduced growing season CH4 emissions by 44-73% while N2O emissions remained low and represented only <2% of the total seasonal global warming potential in all treatments. The long aerobic periods and proper implementation of AWD drain events showed greatest CH4 reduction. However, N2O emissions can increase if soil inorganic N levels are potentially high prior to initiating the dry cycle. Our results showed that AWD can reduce CH4 and N2O emissions while maintaining optimal grain yields. However, adoption of AWD to mitigate greenhouse gas emissions (GHG) in commercial farms requires proper implementation of AWD to avoid risk of yield loss and high GHG emissions.

Oxidative esterification via photocatalytic C-H activation

EPA Science Inventory

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

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

PubMed

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

2013-05-14

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

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

PubMed

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

2016-03-07

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

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

PubMed

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

2011-01-01

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

Wet air oxidation induced enhanced biodegradability of distillery effluent.

PubMed

Malik, S N; Saratchandra, T; Tembhekar, P D; Padoley, K V; Mudliar, S L; Mudliar, S N

2014-04-01

The present study reports the feasibility of Wet Air Oxidation (WAO) as a pretreatment option for enhanced biodegradation of complex distillery effluent. Initially, the distillery effluent was pretreated by WAO at different process conditions (pressure, temperature and time) to facilitate enhancement in the biodegradability index (BI = BOD5: COD ratio). The biodegradability of WAO pretreated effluent was evaluated by subjecting it to aerobic biodegradation and anaerobic followed by aerobic biodegradation. Aerobic biodegradation of pretreated effluent with enhanced biodegradability index (BI = 0.4-0.8) showed enhanced COD reduction of up to 67.7%, whereas the untreated effluent (BI = 0.17) indicated poor COD reduction of only 22.5%. Anaerobic followed by aerobic biodegradation of pretreated effluent has shown up to 87.9% COD reduction, while the untreated effluent has shown only 43.1% COD reduction. Bio-kinetic parameters also confirmed the increased rate of bio-oxidation at enhanced BIs. The results indicate that the WAO pretreatment facilitates enhanced bio-oxidation/bio-degradation of complex effluents like the distillery spent wash. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

PubMed Central

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

2015-01-01

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

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

NASA Astrophysics Data System (ADS)

Madronich, S.

2017-12-01

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

Biodegradability and biodegradation rate of poly(caprolactone)-starch blend and poly(butylene succinate) biodegradable polymer under aerobic and anaerobic environment.

PubMed

Cho, H S; Moon, H S; Kim, M; Nam, K; Kim, J Y

2011-03-01

The biodegradability and the biodegradation rate of two kinds biodegradable polymers; poly(caprolactone) (PCL)-starch blend and poly(butylene succinate) (PBS), were investigated under both aerobic and anaerobic conditions. PCL-starch blend was easily degraded, with 88% biodegradability in 44 days under aerobic conditions, and showed a biodegradation rate of 0.07 day(-1), whereas the biodegradability of PBS was only 31% in 80 days under the same conditions, with a biodegradation rate of 0.01 day(-1). Anaerobic bacteria degraded well PCL-starch blend (i.e., 83% biodegradability for 139 days); however, its biodegradation rate was relatively slow (6.1 mL CH(4)/g-VS day) compared to that of cellulose (13.5 mL CH(4)/g-VS day), which was used as a reference material. The PBS was barely degraded under anaerobic conditions, with only 2% biodegradability in 100 days. These results were consistent with the visual changes and FE-SEM images of the two biodegradable polymers after the landfill burial test, showing that only PCL-starch blend had various sized pinholes on the surface due to attack by microorganisms. This result may be use in deciding suitable final disposal approaches of different types of biodegradable polymers in the future. Copyright © 2010 Elsevier Ltd. All rights reserved.

Arsenic redox transformation by Pseudomonas sp. HN-2 isolated from arsenic-contaminated soil in Hunan, China.

PubMed

Zhang, Zhennan; Yin, Naiyi; Cai, Xiaolin; Wang, Zhenzhou; Cui, Yanshan

2016-09-01

A mesophilic, Gram-negative, arsenite[As(III)]-oxidizing and arsenate[As(V)]-reducing bacterial strain, Pseudomonas sp. HN-2, was isolated from an As-contaminated soil. Phylogenetic analysis based on 16S rRNA gene sequencing indicated that the strain was closely related to Pseudomonas stutzeri. Under aerobic conditions, this strain oxidized 92.0% (61.4μmol/L) of arsenite to arsenate within 3hr of incubation. Reduction of As(V) to As(III) occurred in anoxic conditions. Pseudomonas sp. HN-2 is among the first soil bacteria shown to be capable of both aerobic As(III) oxidation and anoxic As(V) reduction. The strain, as an efficient As(III) oxidizer and As(V) reducer in Pseudomonas, has the potential to impact arsenic mobility in both anoxic and aerobic environments, and has potential application in As remediation processes. Copyright © 2016. Published by Elsevier B.V.

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

NASA Astrophysics Data System (ADS)

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

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

High-pressure oxidation of ethane

DOE PAGES

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

2017-05-02

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

Gas-geochemical condition and ecological functions of urban soils in areas with gas generating grounds

NASA Astrophysics Data System (ADS)

Mozharova, Nadezhda; Lebed-Sharlevich, Iana; Kulachkova, Svetlana

2014-05-01

Rapid urbanization and expansion of city borders lead to development of new areas, often following with relief changes, covering of gully-ravine systems and river beds with technogenic grounds containing construction and municipal waste. Decomposition of organic matter in these grounds is a source of methane and carbon dioxide. Intensive generation and accumulation of CO2 and CH4 into grounds may cause a fire and explosion risk for constructed objects. Gases emission to the atmosphere changes the global balance of GHGs and negatively influences on human health. The aim of this investigation is to study gas-geochemical condition and ecological functions of urban soils in areas with gas generating grounds. Studied areas are the gully-ravine systems or river beds, covered with technogenic grounds during land development. Stratigraphic columns of these grounds are 5-17 meters of man-made loamy material with inclusion of construction waste. Gas generating layer with increased content of organic matter, reductive conditions and high methanogenic activity (up to 1.0 ng*g-1*h-1) is situated at the certain depth. Maximum CH4 and CO2 concentrations in this layer reach dangerous values (2-10% and 11%, respectively) in the current standards. In case of disturbance of ground layer (e.g. well-drilling) methane is rapidly transferred by convective flux to atmosphere. The rate of CH4 emission reaches 100 mg*m-2*h-1 resulting in its atmospheric concentration growth by an order of magnitude compared with background. In normal occurrence of grounds methane gradually diffuses into the upper layers by pore space, consuming on different processes (e.g. formation of organic matter, nitrogen compounds or specific particles of magnetite), and emits to atmosphere. CH4 emission rate varies from 1 to 40 mg*m-2*h-1 increasing with depth of grounds. Carbon dioxide emission is about 100 mg*m-2*h-1. During soil formation on gas generating grounds bacterial oxidation of methane, one of the most important ecological functions of such soils, is initiated. Due to high rate of this process (25-30 ng*g-1*h-1) accumulation of methane in the profile does not observed, its content in soil averages 2-5 ppm. Methane emission from soils is low (0.01-0.03 mg*m-2*h-1) or there is a weak consumption of atmospheric CH4, whereby its concentration in the air corresponds to the average content of this gas. Active methane oxidation and decomposition of organic matter under aerobic conditions result to intensive formation of carbon dioxide and, thus, increase its emission (600 mg*m-2*h-1), concentration in soils (0.2-0.9%) and in atmosphere (up to 0.5%). Fixed concentration of CO2 in the air is dangerous for human health. Thus, presence of gas generating grounds with high content of organic matter leads to methane formation, causing its intensive emission to atmosphere. At upper layers of soils and grounds bacterial oxidation of methane occurs and results in complete CH4 utilization. During this process significant amounts of carbon dioxide are released and accumulated in the atmosphere up to concentration dangerous for people. Carbon dioxide emission increases current level of this gas in the urban atmosphere.

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

NASA Technical Reports Server (NTRS)

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

2014-01-01

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

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

PubMed Central

Gulledge, Jay; Schimel, Joshua P.

1998-01-01

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

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

NASA Astrophysics Data System (ADS)

Watanabe, Akira; Kimura, Makoto

1998-08-01

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

Production and Consumption of Nitric Oxide by Three Methanotrophic Bacteria

PubMed Central

Ren, Tie; Roy, Réal; Knowles, Roger

2000-01-01

We studied nitrogen oxide production and consumption by methanotrophs Methylobacter luteus (group I), Methylosinus trichosporium OB3b (group II), and an isolate from a hardwood swamp soil, here identified by 16S ribosomal DNA sequencing as Methylobacter sp. strain T20 (group I). All could consume nitric oxide (nitrogen monoxide, NO), and produce small amounts of nitrous oxide (N2O). Only Methylobacter strain T20 produced large amounts of NO (>250 parts per million by volume [ppmv] in the headspace) at specific activities of up to 2.0 × 10−17 mol of NO cell−1 day−1, mostly after a culture became O2 limited. Production of NO by strain T20 occurred mostly in nitrate-containing medium under anaerobic or nearly anaerobic conditions, was inhibited by chlorate, tungstate, and O2, and required CH4. Denitrification (methanol-supported N2O production from nitrate in the presence of acetylene) could not be detected and thus did not appear to be involved in the production of NO. Furthermore, cd1 and Cu nitrite reductases, NO reductase, and N2O reductase could not be detected by PCR amplification of the nirS, nirK, norB, and nosZ genes, respectively. M. luteus and M. trichosporium produced some NO in ammonium-containing medium under aerobic conditions, likely as a result of methanotrophic nitrification and chemical decomposition of nitrite. For Methylobacter strain T20, arginine did not stimulate NO production under aerobiosis, suggesting that NO synthase was not involved. We conclude that strain T20 causes assimilatory reduction of nitrate to nitrite, which then decomposes chemically to NO. The production of NO by methanotrophs such as Methylobacter strain T20 could be of ecological significance in habitats near aerobic-anaerobic interfaces where fluctuating O2 and nitrate availability occur. PMID:10966405

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

PubMed

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

2011-03-21

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

Uniform distributions of glucose oxidation and oxygen extraction in gray matter of normal human brain: No evidence of regional differences of aerobic glycolysis.

PubMed

Hyder, Fahmeed; Herman, Peter; Bailey, Christopher J; Møller, Arne; Globinsky, Ronen; Fulbright, Robert K; Rothman, Douglas L; Gjedde, Albert

2016-05-01

Regionally variable rates of aerobic glycolysis in brain networks identified by resting-state functional magnetic resonance imaging (R-fMRI) imply regionally variable adenosine triphosphate (ATP) regeneration. When regional glucose utilization is not matched to oxygen delivery, affected regions have correspondingly variable rates of ATP and lactate production. We tested the extent to which aerobic glycolysis and oxidative phosphorylation power R-fMRI networks by measuring quantitative differences between the oxygen to glucose index (OGI) and the oxygen extraction fraction (OEF) as measured by positron emission tomography (PET) in normal human brain (resting awake, eyes closed). Regionally uniform and correlated OEF and OGI estimates prevailed, with network values that matched the gray matter means, regardless of size, location, and origin. The spatial agreement between oxygen delivery (OEF≈0.4) and glucose oxidation (OGI ≈ 5.3) suggests that no specific regions have preferentially high aerobic glycolysis and low oxidative phosphorylation rates, with globally optimal maximum ATP turnover rates (VATP ≈ 9.4 µmol/g/min), in good agreement with (31)P and (13)C magnetic resonance spectroscopy measurements. These results imply that the intrinsic network activity in healthy human brain powers the entire gray matter with ubiquitously high rates of glucose oxidation. Reports of departures from normal brain-wide homogeny of oxygen extraction fraction and oxygen to glucose index may be due to normalization artefacts from relative PET measurements. © The Author(s) 2016.

Diffusion of 99-technetium in compacted bentonite under aerobic and anaerobic conditions

NASA Astrophysics Data System (ADS)

Večerník, P.; Jedináková-Křížová, V.

2006-01-01

The main aim of this study was to investigate diffusion of technetium 99Tc under different conditions. Because technetium represents one of the most dangerous fission products due to its very long halftime and high mobility in aerobic conditions diffusion experiments of technetium (as 99TcO 4 - anion) in Czech bentonite from Rokle locality have been carried out. For performance and evaluation of experiments the through-diffusion method was chosen and apparent (Da) and effective (De) diffusion coefficients were evaluated. The effects of particle mesh-size, dry bulk density and aerobic or anaerobic conditions on diffusion were studied. In the presence of oxygen, technetium occurs in oxidation state VII, as an anion, soluble and mobile in the environment. However, under reducing conditions it occurs in a lower oxidation states, mainly as insoluble oxides or hydroxides. Aerobic experiments were carried out under laboratory conditions and anaerobic experiments were performed in a nitrogen atmosphere in a glove box, to simulate the real underground conditions.

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

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

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

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

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Potential for cometabolic biodegradation of 1,4-dioxane in aquifers with methane or ethane as primary substrates.

PubMed

Hatzinger, Paul B; Banerjee, Rahul; Rezes, Rachael; Streger, Sheryl H; McClay, Kevin; Schaefer, Charles E

2017-12-01

The objective of this research was to evaluate the potential for two gases, methane and ethane, to stimulate the biological degradation of 1,4-dioxane (1,4-D) in groundwater aquifers via aerobic cometabolism. Experiments with aquifer microcosms, enrichment cultures from aquifers, mesophilic pure cultures, and purified enzyme (soluble methane monooxygenase; sMMO) were conducted. During an aquifer microcosm study, ethane was observed to stimulate the aerobic biodegradation of 1,4-D. An ethane-oxidizing enrichment culture from these samples, and a pure culture capable of growing on ethane (Mycobacterium sphagni ENV482) that was isolated from a different aquifer also biodegraded 1,4-D. Unlike ethane, methane was not observed to appreciably stimulate the biodegradation of 1,4-D in aquifer microcosms or in methane-oxidizing mixed cultures enriched from two different aquifers. Three different pure cultures of mesophilic methanotrophs also did not degrade 1,4-D, although each rapidly oxidized 1,1,2-trichloroethene (TCE). Subsequent studies showed that 1,4-D is not a substrate for purified sMMO enzyme from Methylosinus trichosporium OB3b, at least not at the concentrations evaluated, which significantly exceeded those typically observed at contaminated sites. Thus, our data indicate that ethane, which is a common daughter product of the biotic or abiotic reductive dechlorination of chlorinated ethanes and ethenes, may serve as a substrate to enhance 1,4-D degradation in aquifers, particularly in zones where these products mix with aerobic groundwater. It may also be possible to stimulate 1,4-D biodegradation in an aerobic aquifer through addition of ethane gas. Conversely, our results suggest that methane may have limited importance in natural attenuation or for enhancing biodegradation of 1,4-D in groundwater environments.

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

NASA Astrophysics Data System (ADS)

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

1995-06-01

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

Enrichment culture and identification of endophytic methanotrophs isolated from peatland plants.

PubMed

Stępniewska, Zofia; Goraj, Weronika; Kuźniar, Agnieszka; Łopacka, Natalia; Małysza, Magdalena

2017-09-01

Aerobic methane-oxidizing bacteria (MOB) are an environmentally significant group of microorganisms due to their role in the global carbon cycle. Research conducted over the past few decades has increased the interest in discovering novel genera of methane-degrading bacteria, which efficiently utilize methane and decrease the global warming effect. Moreover, methanotrophs have more promising applications in environmental bioengineering, biotechnology, and pharmacy. The investigations were undertaken to recognize the variety of endophytic methanotrophic bacteria associated with Carex nigra, Vaccinium oxycoccus, and Eriophorum vaginatum originating from Moszne peatland (East Poland). Methanotrophic bacteria were isolated from plants by adding sterile fragments of different parts of plants (roots and stems) to agar mineral medium (nitrate mineral salts (NMS)) and incubated at different methane values (1-20% CH4). Single colonies were streaked on new NMS agar media and, after incubation, transferred to liquid NMS medium. Bacterial growth dynamics in the culture solution was studied by optical density-OD600 and methane consumption. Changes in the methane concentration during incubation were controlled by the gas chromatography technique. Characterization of methanotrophs was made by fluorescence in situ hybridization (FISH) with Mg705 and Mg84 for type I methanotrophs and Ma450 for type II methanotrophs. Identification of endophytes was performed after 16S ribosomal RNA (rRNA) and mmoX gene amplification. Our study confirmed the presence of both types of methanotrophic bacteria (types I and II) with the predominance of type I methanotrophs. Among cultivable methanotrophs, there were different strains of the genus Methylomonas and Methylosinus. Furthermore, we determined the potential of the examined bacteria for methane oxidation, which ranged from 0.463 ± 0.067 to 5.928 ± 0.169 μmol/L CH4/mL/day.

Atmospheric nitrous oxide uptake in boreal spruce forest soil

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

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

NASA Astrophysics Data System (ADS)

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

2009-04-01

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

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

PubMed

Sadasivam, Bala Yamini; Reddy, Krishna R

2015-09-01

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

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

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

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

2012-09-15

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

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

PubMed Central

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

2016-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2011-12-01

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

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

USGS Publications Warehouse

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

2012-01-01

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

Ecosystem Level Methane Dynamics in a Southern Forest Wetland

NASA Astrophysics Data System (ADS)

Mitra, B.; Minick, K.; Miao, G.; Furst, J.; Domec, J. C.; Sun, G.; McNulty, S.; King, J. S.; Noormets, A.

2017-12-01

Methane (CH4) budgets of most ecosystems remain poorly defined, particularly for the forested wetlands of the Southeastern United States.These once abundant ecosystems are unique in the amount of sequestered soil carbon they hold, and because of their interaction with climate through their contribution to both CO2 and CH4 exchange. The stability of the large C stocks in the vegetation and soil of these ecosystems is largest in submerged anoxic conditions, even though methanogenic processes still occur. However, the pressure from land development and drainage, more variable hydrology, and salt-water intrusion can alter the magnitude and balance of aerobic and anaerobic decomposition processes. Here we report five years of CH4 and CO2 fluxes from a forested wetland in the Alligator River National Wildlife Refuge (ARNWR) on the Albemarle-Pamlico Peninsula of North Carolina, USA. Time series of eddy covariance based estimates of CH4 fluxes from 2012 to 2016 show large temporal variation, with seasonal progression in daily mean fluxes from June through October. The peak methane emission coincided with the peak of gross primary production and ecosystem level respiration. The combined responses of these fluxes increases the uncertainty in whether wetlands will be sources or sinks of carbon. CH4 fluxes demonstrated strong variability and different environmental regulation across years and seasons. Water table depth and atmospheric pressure regulated synoptic and seasonal patterns of CH4 emissions. Across all years, the forested wetland emitted CH4 at rates far exceeding those reported for mid-latitude wetlands and rice paddy systems.

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

EPA Science Inventory

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

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

PubMed

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

2017-12-01

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

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

PubMed

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

2013-01-01

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

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

PubMed

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

2011-10-12

Kinetic and isotopic data and density functional theory treatments provide evidence for the elementary steps and the active site requirements involved in the four distinct kinetic regimes observed during CH(4) oxidation reactions using O(2), H(2)O, or CO(2) as oxidants on Pt clusters. These four regimes exhibit distinct rate equations because of the involvement of different kinetically relevant steps, predominant adsorbed species, and rate and equilibrium constants for different elementary steps. Transitions among regimes occur as chemisorbed oxygen (O*) coverages change on Pt clusters. O* coverages are given, in turn, by a virtual O(2) pressure, which represents the pressure that would give the prevalent steady-state O* coverages if their adsorption-desorption equilibrium was maintained. The virtual O(2) pressure acts as a surrogate for oxygen chemical potentials at catalytic surfaces and reflects the kinetic coupling between C-H and O═O activation steps. O* coverages and virtual pressures depend on O(2) pressure when O(2) activation is equilibrated and on O(2)/CH(4) ratios when this step becomes irreversible as a result of fast scavenging of O* by CH(4)-derived intermediates. In three of these kinetic regimes, C-H bond activation is the sole kinetically relevant step, but occurs on different active sites, which evolve from oxygen-oxygen (O*-O*), to oxygen-oxygen vacancy (O*-*), and to vacancy-vacancy (*-*) site pairs as O* coverages decrease. On O*-saturated cluster surfaces, O*-O* site pairs activate C-H bonds in CH(4) via homolytic hydrogen abstraction steps that form CH(3) groups with significant radical character and weak interactions with the surface at the transition state. In this regime, rates depend linearly on CH(4) pressure but are independent of O(2) pressure. The observed normal CH(4)/CD(4) kinetic isotope effects are consistent with the kinetic-relevance of C-H bond activation; identical (16)O(2)-(18)O(2) isotopic exchange rates in the presence or absence of CH(4) show that O(2) activation steps are quasi-equilibrated during catalysis. Measured and DFT-derived C-H bond activation barriers are large, because of the weak stabilization of the CH(3) fragments at transition states, but are compensated by the high entropy of these radical-like species. Turnover rates in this regime decrease with increasing Pt dispersion, because low-coordination exposed Pt atoms on small clusters bind O* more strongly than those that reside at low-index facets on large clusters, thus making O* less effective in H-abstraction. As vacancies (*, also exposed Pt atoms) become available on O*-covered surfaces, O*-* site pairs activate C-H bonds via concerted oxidative addition and H-abstraction in transition states effectively stabilized by CH(3) interactions with the vacancies, which lead to much higher turnover rates than on O*-O* pairs. In this regime, O(2) activation becomes irreversible, because fast C-H bond activation steps scavenge O* as it forms. Thus, O* coverages are set by the prevalent O(2)/CH(4) ratios instead of the O(2) pressures. CH(4)/CD(4) kinetic isotope effects are much larger for turnovers mediated by O*-* than by O*-O* site pairs, because C-H (and C-D) activation steps are required to form the * sites involved in C-H bond activation. Turnover rates for CH(4)-O(2) reactions mediated by O*-* pairs decrease with increasing Pt dispersion, as in the case of O*-O* active structures, because stronger O* binding on small clusters leads not only to less reactive O* atoms, but also to lower vacancy concentrations at cluster surfaces. As O(2)/CH(4) ratios and O* coverages become smaller, O(2) activation on bare Pt clusters becomes the sole kinetically relevant step; turnover rates are proportional to O(2) pressures and independent of CH(4) pressure and no CH(4)/CD(4) kinetic isotope effects are observed. In this regime, turnover rates become nearly independent of Pt dispersion, because the O(2) activation step is essentially barrierless. In the absence of O(2), alternate weaker oxidants, such as H(2)O or CO(2), lead to a final kinetic regime in which C-H bond dissociation on *-* pairs at bare cluster surfaces limit CH(4) conversion rates. Rates become first-order in CH(4) and independent of coreactant and normal CH(4)/CD(4) kinetic isotope effects are observed. In this case, turnover rates increase with increasing dispersion, because low-coordination Pt atoms stabilize the C-H bond activation transition states more effectively via stronger binding to CH(3) and H fragments. These findings and their mechanistic interpretations are consistent with all rate and isotopic data and with theoretical estimates of activation barriers and of cluster size effects on transition states. They serve to demonstrate the essential role of the coverage and reactivity of chemisorbed oxygen in determining the type and effectiveness of surface structures in CH(4) oxidation reactions using O(2), H(2)O, or CO(2) as oxidants, as well as the diversity of rate dependencies, activation energies and entropies, and cluster size effects that prevail in these reactions. These results also show how theory and experiments can unravel complex surface chemistries on realistic catalysts under practical conditions and provide through the resulting mechanistic insights specific predictions for the effects of cluster size and surface coordination on turnover rates, the trends and magnitude of which depend sensitively on the nature of the predominant adsorbed intermediates and the kinetically relevant steps.

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

USDA-ARS?s Scientific Manuscript database

We have developed and field-validated an annual inventory model for California landfill CH4 emissions that incorporates both site-specific soil properties and soil microclimate modeling coupled to 0.5o scale global climatic models. Based on 1-D diffusion, CALMIM (California Landfill Methane Inventor...

Mesoscale Laboratory Models of the Biodegradation of Municipal Landfill Materials

NASA Astrophysics Data System (ADS)

Borglin, S. E.; Hazen, T. C.; Oldenburg, C. M.; Zawislanski, P. T.

2001-12-01

Stabilization of municipal landfills is a critical issue involving land reuse, leachate treatment, and odor control. In an effort to increase landfill stabilization rates and decrease leachate treatment costs, municipal landfills can be operated as active aerobic or anaerobic bioreactors. Rates of settling and biodegradation were compared in three different treatments of municipal landfill materials in laboratory-scale bioreactors. Each of the three fifty-five-gallon clear acrylic tanks was fitted with pressure transducers, thermistors, neutron probe access tubes, a leachate recirculation system, gas vents, and air injection ports. The treatments applied to the tanks were (a) aerobic (air injection with leachate recirculation and venting from the top), (b) anaerobic (leachate recirculation with passive venting from the top), and (c) a control tank (passive venting from the top and no leachate recirculation). All tanks contained a 10-cm-thick layer of pea gravel at the bottom, overlain by a mixture of fresh waste materials on the order of 5-10 cm in size to an initial height of 0.55 m. Concentrations of O2, CO2 and CH4 were measured at the gas vent, and leachate was collected at the bottom drain. The water saturation in the aerobic and anaerobic tanks averaged 17 % and the control tank averaged 1 %. Relative degradation rates between the tanks were monitored by CO2 and CH4 production rates and O2 respiration rates. Respiration tests on the aerobic tank show a decrease in oxygen consumption rates from 1.3 mol/day at 20 days to 0.1 mol/day at 300 days, indicating usable organics are being depleted. The anaerobic tank produced measurable methane after 300 days that increased to 41% by volume after 370 days. Over the test period, the aerobic tank settled 30 %, the anaerobic tank 18.5 %, and the control tank 11.1 %. The concentrations of metals, nitrate, phosphate, and total organic carbon in the aerobic tank leachate are an order of magnitude lower than in the anaerobic tank leachate. This work was supported by Laboratory Directed Research and Development Funds at Lawrence Berkeley National Laboratory under Department of Energy Contract No. DE-AC03-76SF00098.

RETRACTED: Aerobic degradation of 4-nitroaniline (4-NA) via novel degradation intermediates by Rhodococcus sp. strain FK48.

PubMed

Khan, Fazlurrahman; Pandey, Janmejay; Vikram, Surendra; Pal, Deepika; Cameotra, Swaranjit Singh

2013-06-15

An aerobic strain, Rhodococcus sp. strain FK48, capable of growing on 4-nitroaniline (4-NA) as the sole source of carbon, nitrogen, and energy has been isolated from enrichment cultures originating from contaminated soil samples. During growth studies with non- induced cells of FK48 catalyzed sequential denitrification (release of NO₂ substituent) and deamination (release of NH₂ substituent) of 4-NA. However, none of the degradation intermediates could be identified with growth studies. During resting cell studies, 4-NA-induced cells of strain FK48 transformed 4-NA via a previously unknown pathway which involved oxidative hydroxylation leading to formation of 4-aminophenol (4-AP). Subsequent degradation involved oxidated deamination of 4-AP and formation of 1,2,4-benzenetriol (BT) as the major identified terminal aromatic intermediate. Identification of these intermediates was ascertained by HPLC, and GC-MS analyses of the culture supernatants. 4-NA-induced cells of strain FK48 showed positive activity for 1,2,4-benzenetriol dioxygenase in spectrophotometric assay. This is the first conclusive study on aerobic microbial degradation of 4-NA and elucidation of corresponding metabolic pathway. Copyright © 2013 Elsevier B.V. All rights reserved.

Interactions between Nitrogen Fixation and Methane Cycling in Northern Minnesota Peat Bogs

NASA Astrophysics Data System (ADS)

Warren, M. J.; Gaby, J. C.; Lin, X.; Morton, P. L.; Kostka, J. E.; Glass, J. B.

2014-12-01

Peatlands cover only 3% of the Earth's surface, yet store a third of soil carbon. Increasing global temperatures have the potential to change peatlands from a net sink to a net source of atmospheric carbon. N is a limiting nutrient in oligotrophic Sphagnum-dominated peatlands and biological N2 fixation likely supplies a significant but unknown fraction of N inputs. Moreover, environmental controls on diazotrophic community composition in N-limited peatlands are poorly constrained. Thus, improved understanding of feedbacks between the CH4 and N cycles is critical for predicting future changes to CH4 flux from peat bogs. We coupled measurements of N2 fixation activity measured by the acetylene (C2H2) reduction assay (ARA) with molecular analyses of expression and diversity of nifH genes encoding the molybdenum (Mo)-containing nitrogenase from two peat bogs in the Marcell Experimental Forest, Minnesota, USA. The top 10 cm of peat was sampled from the high CH4 flux S1 bog and the low CH4 flux Zim bog in April and June 2014. Despite similar N concentrations in the top 10 cm of both bogs (0.5-1.0 μM NO2-+NO3- and 2-3 μM NH4+), the S1 bog displayed variable ARA activity (1-100 nmol C2H4 h-1 g-1) whereas the Zim bog had consistently low ARA activity (<1 nmol C2H4 h-1 g-1). Highest ARA activity was measured in June from S1 bog hollows with higher moisture content incubated without O2 in the light (20-100 nmol C2H4 h-1 g-1). Dissolved Fe (1-25 μM) was higher in hollow vs. hummock samples, and at S1 vs. Zim bog, while dissolved V (4-14 nM) was consistently higher than Mo (1-4 nM), suggesting that alternative V or Fe-containing nitrogenases might be present in these bogs. In contrast, Cu, an essential micronutrient for aerobic methanotrophs, was higher in hummocks (25-48 nM) than hollows (6-17 nM). The facultative methanotroph Methylocella was the dominant diazotroph in the S1 bog based on high throughput next generation sequencing of nifH cDNA amplicons. Given previous reports of C2H2 inhibition of methanotrophy, we measured CH4 consumption in the presence or absence of 1% C2H2. Preliminary results suggest minimal effect of C2H2 on CH4 oxidation. Future measurements of 15N2 incorporation coupled to molecular analysis will elucidate whether methanotroph diazotrophy was suppressed by C2H2 in ARA incubations.

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

The Arctic CH4 sink and its implications for the permafrost carbon feedbacks to the global climate system

NASA Astrophysics Data System (ADS)

Juncher Jørgensen, Christian; Christiansen, Jesper; Mariager, Tue; Hugelius, Gustaf

2016-04-01

Using atmospheric methane (CH4), certain soil microbes are able to sustain their metabolism, and in turn remove this powerful greenhouse gas from the atmosphere. While the process of CH4 oxidation is a common feature in most natural and unmanaged ecosystems in temperate and boreal ecosystems, the interactions between soil physical properties and abiotic process drivers, net landscape exchange and spatial patterns across Arctic drylands remains highly uncertain. Recent works show consistent CH4 comsumption in upland dry tundra soils in Arctic and High Arctic environments (Christiansen et al., 2014, Biogeochemistry 122; Jørgensen et al., 2015, Nature Geoscience 8; Lau et al., 2015, The ISME Journal 9). In these dominantly dry or barren soil ecosystems, CH4 consumption has been observed to significantly exceed the amounts of CH4 emitted from adjacent wetlands. These observations point to a potentially important but largely overlooked component of the global soil-climate system interaction and a counterperspective to the conceptual understanding of the Arctic being a only a source of CH4. However, due to our limited knowledge of spatiotemporal occurrence of CH4 consumption across a wider range of the Arctic landscape we are left with substantial uncertainites and an overall unconstrained range estimate of this terrestrial CH4 sink and its potential effects on permafrost carbon feedback to the atmospheric CH4 concentration. To address this important knowledge gap and identify the most relevant spatial scaling parameters, we studied in situ CH4 net exchange across a large landscape transect on West Greenland. The transect representated soils formed from the dominant geological parent materials of dry upland tundra soils found in the ice-free land areas of Western Greenland, i.e. 1) granitic/gneissic parent material, 2) basaltic parent material and 3) sedimentary deposits. Results show that the dynamic variations in soil physical properties and soil hydrology exerts an overriding control on the net CH4 consumption both within and across these well-aerated soil systems. Quite surprisingly, we found high CH4 sink rates in conditions when soils were both extremely thin (< 10 cm to bedrock), very dry (< 5-10 % soil moisture), weakly developed and exposed to harsh environmental conditions such as mountain tops, alpine tundra and abrasion plateaus, which are historically overlooked "extreme soils" regarding CH4 exchange. The results show that the physical areas and landforms where CH4 oxidation and net CH4 deposition occurs has not been delimited for the Arctic. This calls for a revised understanding of the role of CH4 consumption in natural drylands and extreme environments for the net CH4 budget at the circumpolar scale. In these sensitive regions, changes towards warmer and drier soil conditions in some areas as a consequence of a warming Arctic could favor the activity of the CH4 oxidizing bacteria, leading to future increase in net atmospheric CH4 consumption in dry and barren land areas. This could have far-reaching implications for the permafrost carbon feedback to the global climate system and how we integrate the soil CH4 consumption feedback in Earth Systems Model simulating the Artic CH4 budget.

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

PubMed

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

2016-03-21

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

Isotopomer analysis of production and consumption mechanisms of N2O and CH4 in an advanced wastewater treatment system.

PubMed

Toyoda, Sakae; Suzuki, Yuuri; Hattori, Shohei; Yamada, Keita; Fujii, Ayako; Yoshida, Naohiro; Kouno, Rina; Murayama, Kouki; Shiomi, Hiroshi

2011-02-01

Wastewater treatment processes are believed to be anthropogenic sources of nitrous oxide (N(2)O) and methane (CH(4)). However, few studies have examined the mechanisms and controlling factors in production of these greenhouse gases in complex bacterial systems. To elucidate production and consumption mechanisms of N(2)O and CH(4) in microbial consortia during wastewater treatment and to characterize human waste sources, we measured their concentrations and isotopomer ratios (elemental isotope ratios and site-specific N isotope ratios in asymmetric molecules of NNO) in water and gas samples collected by an advanced treatment system in Tokyo. Although the estimated emissions of N(2)O and CH(4) from the system were found to be lower than those from the typical treatment systems reported before, water in biological reaction tanks was supersaturated with both gases. The concentration of N(2)O, produced mainly by nitrifier-denitrification as indicated by isotopomer ratios, was highest in the oxic tank (ca. 4000% saturation). The dissolved CH(4) concentration was highest in in-flow water (ca. 3000% saturation). It decreased gradually during treatment. Its carbon isotope ratio indicated that the decrease resulted from bacterial CH(4) oxidation and that microbial CH(4) production can occur in anaerobic and settling tanks.

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

PubMed

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

2012-10-15

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

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

PubMed

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

2004-01-05

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

Emission of greenhouse gases from home aerobic composting, anaerobic digestion and vermicomposting of household wastes in Brisbane (Australia).

PubMed

Chan, Yiu C; Sinha, Rajiv K; Weijin Wang

2011-05-01

This study investigated greenhouse gas (GHG) emissions from three different home waste treatment methods in Brisbane, Australia. Gas samples were taken monthly from 34 backyard composting bins from January to April 2009. Averaged over the study period, the aerobic composting bins released lower amounts of CH(4) (2.2 mg m(- 2) h(-1)) than the anaerobic digestion bins (9.5 mg m(-2) h(-1)) and the vermicomposting bins (4.8 mg m(-2) h( -1)). The vermicomposting bins had lower N(2)O emission rates (1.2 mg m(-2) h(- 1)) than the others (1.5-1.6 mg m(-2) h( -1)). Total GHG emissions including both N(2)O and CH(4) were 463, 504 and 694 mg CO(2)-e m(- 2) h(-1) for vermicomposting, aerobic composting and anaerobic digestion, respectively, with N(2)O contributing >80% in the total budget. The GHG emissions varied substantially with time and were regulated by temperature, moisture content and the waste properties, indicating the potential to mitigate GHG emission through proper management of the composting systems. In comparison with other mainstream municipal waste management options including centralized composting and anaerobic digestion facilities, landfilling and incineration, home composting has the potential to reduce GHG emissions through both lower on-site emissions and the minimal need for transportation and processing. On account of the lower cost, the present results suggest that home composting provides an effective and feasible supplementary waste management method to a centralized facility in particular for cities with lower population density such as the Australian cities.

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

NASA Astrophysics Data System (ADS)

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

2013-04-01

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

Regimes of an atmospheric pressure nanosecond repetitively pulsed discharge for methane partial oxidation

NASA Astrophysics Data System (ADS)

Maqueo, P. D. G.; Maier, M.; Evans, M. D. G.; Coulombe, S.; Bergthorson, J. M.

2018-04-01

The operation of a nanosecond repetitively pulsed discharge for partial oxidation of CH4 is characterized at atmospheric pressure and room temperature. Two regimes are observed: diffuse and filamentary. The first is a low power regime, characterized by low rotational temperatures around 400 K. The second is much more energetic with rotational temperatures close to 600 K. Both have vibrational temperatures of at least 10 times their rotational temperatures. The average electron number density was determined to be 8.9×1015 and 4.0×1017 cm-3, respectively, showing an increase in the ionization fraction in the more powerful filamentary regime. Results of CH4 conversion to H2, CO, CO2 and C2H6 are presented for the filamentary regime, while the diffuse regime shows no measurable conversion ability. As expected, oxidative mixtures show higher conversion ability than pure CH4. A maximum conversion efficiency of 26.3% and a maximum energy efficiency of 19.7% were reached for the oxidative mixtures.

Methodology to determine the extent of anaerobic digestion, composting and CH4 oxidation in a landfill environment.

PubMed

Obersky, Lizanne; Rafiee, Reza; Cabral, Alexandre R; Golding, Suzanne D; Clarke, William P

2018-06-01

An examination of the processes contributing to the production of landfill greenhouse gas (GHG) emissions is required, as the actual level to which waste degrades anaerobically and aerobically beneath covers has not been differentiated. This paper presents a methodology to distinguish between the rate of anaerobic digestion (r AD ), composting (r COM ) and CH 4 oxidation (r OX ) in a landfill environment, by means of a system of mass balances developed for molecular species (CH 4 , CO 2 ) and stable carbon isotopes (δ 13 C-CO 2 and δ 13 C-CH 4 ). The technique was applied at two sampling locations on a sloped area of landfill. Four sampling rounds were performed over an 18 month period after a 1.0 m layer of fresh waste and 30-50 cm of silty clay loam had been placed over the area. Static chambers were used to measure the flux of the molecular and isotope species at the surface and soil gas probes were used to collect gas samples at depths of approximately 0.5, 1.0 and 1.5 m. Mass balances were based on the surface flux and the concentration of the molecular and isotopic species at the deepest sampling depth. The sensitivity of calculated rates was considered by randomly varying stoichiometric and isotopic parameters by ±5% to generate at least 500 calculations of r OX , r AD and r COM for each location in each sampling round. The resulting average value of r AD and r COM indicated anaerobic digestion and composting were equally dominant at both locations. Average values of r COM : ranged from 9.8 to 44.5 g CO 2 m -2  d -1 over the four sampling rounds, declining monotonically at one site and rising then falling at the other. Average values of r AD: ranged from 10.6 to 45.3 g CO 2 m -2  d -1 . Although the highest average r AD value occurred in the initial sampling round, all subsequent r AD values fell between 10 and 20 g CO 2 m -2  d -1 . r OX had the smallest activity contribution at both sites, with averages ranging from 1.6 to 8.6 g CO 2 m -2  d -1 . This study has demonstrated that for an interim cover, composting and anaerobic digestion of shallow landfill waste can occur simultaneously. Copyright © 2018 Elsevier Ltd. All rights reserved.

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

PubMed

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

2009-06-25

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

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

NASA Astrophysics Data System (ADS)

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

2018-06-01

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

Biofouling of contaminated ground-water recovery wells: Characterization of microorganisms

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

Taylor, S.W.; Lange, C.R.; Lesold, E.A.

1997-11-01

The taxonomy and physiology of microorganisms isolated from contaminated ground-water recovery wells prone to biofouling are characterized for an industrial site in Rochester, New York. Principal aquifer contaminants include acetone, cyclohexane, dichloroethane, dichloromethane, 1,4-dioxane, isopropanol, methanol, and toluene. These contaminants represent a significant fraction (up to 95%) of the total organic carbon in the ground water. Ground-water samples from 12 recovery wells were used to isolate, quantify, and identify aerobic and anaerobic bacterial populations. Samples from selected wells were also characterized geochemically to assess redox conditions and availability of essential and trace nutrients. Dominant bacteria, listed in order of descendingmore » numbers, including sulfate-reducers (Desulfovibrio desulfuricans), anaerobic heterotrophs (Actinomyces, Bacteriodes, Bacillus, Agrobacterium), aerobic heterotrophs (Pseudomonas, Flavobacterium, Nocardia, Citrobacter), iron-oxidizers (Gallionella ferruginea, Crenothrix polyspora), iron-reducers (Shewanella), and sulfur-oxidizers (Thiobacillus ferrooxidans). Fungi were also recovered in low numbers. Both aerobic and anaerobic heterotrophs were able to utilize all principal contaminants as sole carbon and energy sources except 1,4-dioxane. The prevalence of heterotrophic bacteria and their ability to use the available anthropogenic carbon suggests that aerobic and anaerobic heterotrophs contribute to the biofouling of wells at this site, in addition to the often cited fouling due to iron-oxidizing bacteria and sulfate-reducing bacteria.« less

Aerobic methanol-oxidizing bacteria in soil.

PubMed

Kolb, Steffen

2009-11-01

Methanol is an atmospheric compound that is primarily released from plant polymers and impacts ozone formation. The global methanol emission rate from terrestrial ecosystems is of the same order of magnitude (4.9 x 10(12) mol year(-1)) as that of methane (10 x 10(12) mol year(-1)). The major proportion of the annual plant-released methanol does not enter the atmosphere, but may be reoxidized by biological methanol oxidation, which is catalyzed by methanol-oxidizing prokaryotes. Fifty-six aerobic methanol-oxidizing species have been isolated from soils. These methylotrophs belong to the Alpha-, Beta-, and Gammaproteobacteria, Verrucomicrobia, Firmicutes, and Actinobacteria. Their ecological niches are determined by oxygen and methanol concentration, temperature, pH, the capability to utilize nitrate as an electron acceptor, and the spectrum of nitrogen sources and utilizable multicarbon substrates. Recently discovered interactions with eukaryotes indicate that their ecological niches may not solely be defined by physicochemical parameters. Nonetheless, there are still gaps in knowledge; based on global methanol budgets, methanol oxidation in soil is important, but has not been addressed adequately by biogeochemical studies. Ratios of above-ground and soil-internal methanol oxidation are not known. The contribution to methanol-oxidation by aerobic and anaerobic methylotrophs in situ also needs further research.

GC-MS and /sup 17/O NMR tracer studies of Et/sub 3/PO formation from auranofin and H/sub 2//sup 17/O in the presence of bovine serum albumin: an in vitro model for auranofin metabolism

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

Isab, A.A.; Shaw, C.F. III; Locke, J.

1988-09-21

/sup 17/O NMR spectroscopy and gas chromatographic-mass spectral analysis have been used to monitor the source of oxygen in the triethylphosphine oxide formed by the reaction of the antiarthritic drug auranofin ((2,3,4,6-tetra-O-acetyl-..beta..-D-1-glucopyranosato)(triethylphosphine)gold(I)) and bovine serum albumin (BSA) in the presence of reduced glutathione (GtSH). A procedure to extract Et/sub 3/PO from aqueous solutions and concentrate it for subsequent analyses was developed. When the in vitro reaction is carried out aerobically in /sup 17/O-enriched water, Et/sub 3/P/sup 17/O is generated. The chemical ionization (CH/sub 4/) mass measurement, (m + 1)/z = 135, and the /sup 17/O NMR parameters (delta/sub O/ =more » 40.6 and /sup 1/J/sub PO/ = 156 /plus minus/ 5 Hz) unambiguously establish its identity. The SH titer of the albumin (mole ratio of protein SH groups to BSA) increases during the reaction, confirming that albumin disulfide bonds are reduced in the reaction. Under aerobic conditions, the enriched Et/sub 3/PO accounts for at least 60% of the Et/sub 3/PO formed. The significance of these results for the in vivo formation of Et/sub 3/PO, an auranofin metabolite, is discussed. 25 references, 2 figures.« less

Visible-Light-Promoted Metal-Free Aerobic Oxidation of Primary Amines to Acids and Lactones.

PubMed

Cheng, Xiaokai; Yang, Bo; Hu, Xingen; Xu, Qing; Lu, Zhan

2016-12-05

A unique metal-free aerobic oxidation of primary amines via visible light photocatalytic double carbon-carbon bonds cleavage and multi carbon-hydrogen bonds oxidation was observed. Aerobic oxidation of primary amines could be controlled to afford acids by using dioxane with 18 W CFL, and lactones by using DMF with 8 W green LEDs, respectively. A plausible mechanism was proposed based on control experiments. This observation showed direct evidences for the fragmentation in the aerobic oxidation of aliphatic primary amines. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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

2016-12-01

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

CO2, CH4, and DOC Flux During Long Term Thaw of High Arctic Tundra

NASA Astrophysics Data System (ADS)

Stackhouse, B. T.; Vishnivetskaya, T. A.; Layton, A.; Bennett, P.; Mykytczuk, N.; Lau, C. M.; Whyte, L.; Onstott, T. C.

2013-12-01

Arctic regions are expected to experience temperature increases of >4° C by the end of this century. This warming is projected to cause a drastic reduction in the extent of permafrost at high northern latitudes, affecting an estimated 1000 Pg of SOC in the top 3 m. Determining the effects of this temperature change on CO2 and CH4 emissions is critical for defining source constraints to global climate models. To investigate this problem, 18 cores of 1 m length were collected in late spring 2011 before the thawing of the seasonal active layer from an ice-wedge polygon near the McGill Arctic Research Station (MARS) on Axel Heiberg Island, Nunavut, Canada (N79°24, W90°45). Cores were collected from acidic soil (pH 5.5) with low SOC (~1%), summertime active layer depth between 40-70 cm (2010-2013), and sparse vegetation consisting primarily of small shrubs and sedges. Cores were progressively thawed from the surface over the course of 14 weeks to a final temperature of 4.5° C and held at that temperature for 15 months under the following conditions: in situ water saturation conditions versus fully water saturated conditions using artificial rain fall, surface light versus no surface light, cores from the polygon edge, and control cores with a permafrost table maintained at 70 cm depth. Core headspaces were measured weekly for CO2, CH4, H2, CO, and O2 flux during the 18 month thaw experiment. After ~20 weeks of thawing maximum, CO2 flux for the polygon edge and dark treatment cores were 3.0×0.7 and 1.7×0.4 mmol CO2 m-2 hr-1, respectively. The CO2 flux for the control, saturated, and in situ saturation cores reached maximums of 0.6×0.2, 0.9×0.5, and 0.9×0.1 mmol CO2 m-2 hr-1, respectively. Field measurements of CO2 flux from an adjacent polygon during the mid-summer of 2011 to 2013 ranged from 0.3 to 3.7 mmol CO2 m-2 hr-1. Cores from all treatments except water saturated were found to consistently oxidize CH4 at ~atmospheric concentrations (2 ppmv) with a maximum rate of -196×12 (dark) nmol CH4 m-2 hr-1. Saturated cores occasionally acted as slight CH4 sources (17×17 nmol CH4 m-2 hr-1) but were generally found to still behave as CH4 sinks (maximum rate -93×56 nmol CH4 m-2 hr-1). Dissolved CH4 in the permafrost pore water immediately upon thaw was ~0.5 μM in all treatments, and remained at this concentration in the saturated cores. In in situ water saturation treatments, however, pore water CH4 concentrations decreased from 0.6×0.3 μM to 0.2×0.1 μM over the course of three weeks without release into the core headspace. This is likely due to aerobic methanotrophy, as the concentration of genomic sequences associated with methanotrophic bacteria was found to be 30 times greater in the upper 60 cm than in the permafrost. Sustained concentrations of CH4 in the deeper portion of saturated cores indicated that methanogenesis is occurring at depths near and below the permafrost table. Measurements of in situ DOC were 0.22×0.05 mmol L-1, whereas core DOC values increased to a maximum of >1.7 mmol L-1 (primarily acetate) during the course of the thawing experiment. These findings indicate that in a warming Arctic, even under various hydrological regimes, these soil types will be able to act as a sink of atmospheric CH4, a moderate source of CO2 and a potential source for DOC.

Effective oxidation of benzylic and alkane C-H bonds catalyzed by sodium o-iodobenzenesulfonate with Oxone as a terminal oxidant under phase-transfer conditions.

PubMed

Cui, Li-Qian; Liu, Kai; Zhang, Chi

2011-04-07

Catalytic oxidation of benzylic C-H bonds could be efficiently realized using IBS as a catalyst which was generated in situ from the oxidation of sodium 2-iodobenzenesulfonate (1b) by Oxone in the presence of a phase-transfer catalyst, tetra-n-butylammonium hydrogen sulfate, in anhydrous acetonitrile at 60 °C. Various alkylbenzenes, including toluenes and ethylbenzenes, several oxygen-containing functionalities substituted alkylbenzenes, and a cyclic benzyl ether could be efficiently oxidized. And, the same reagent system of cat. 1b/Oxone/cat. n-Bu(4)NHSO(4) could be applied to the effective oxidation of alkanes as well.

Soil Redox Conditions Are a Strong Determinant of Microbial Community Composition and the Fate of Carbon Following Permafrost Thaw.

NASA Astrophysics Data System (ADS)

Bottos, E. M.; Bramer, L.; Kim, Y. M.; Fansler, S.; Nicora, C.; Zink, E.; Chu, R. K.; Tfaily, M. M.; Metz, T. O.; Jansson, J.; Stegen, J.

2016-12-01

Permafrost-affected soils contain enormous stocks of carbon, which are becoming increasingly available to microbial transformation as permafrost regions warm; however, how this warming will influence the permafrost microbiome and the transformation of soil carbon remains unclear. We hypothesize that the redox conditions that arise following permafrost thaw will dictate the structure and function of the microbial community, and strongly influence the nature of carbon transformations. To examine this, permafrost-affected soils from Caribou Poker Creek Research Watershed, Alaska were incubated at 4 °C under aerobic and anaerobic conditions for periods of 9 and 94 days. Over the incubation period, rates of CO2 and CH4 production were measured by gas chromatography, shifts in microbial community structure were characterized by 16S rRNA gene sequencing, and changes in metabolite and organic matter composition were analyzed by GC-MS and ESI-FTICR MS, respectively. CO2 production rates were significantly higher in aerobic treatments in 9-day and 94-day incubations, by 3-times and 12-times, respectively. Rates of CH4 production were not significantly different between treatments in 9-day incubations, but were 1.6-times higher in anaerobic treatments in 94-day incubations. The community composition remained largely unchanged in the incubated samples, with the exception of the 94-day aerobic incubations, which shifted strongly to become dominated by a single OTU, Rhodoferax ferrireducens. Metabolite profiles also shifted most strongly in the 94-day aerobic incubations, with the abundance of phosphorylated carbon compounds overrepresented in these samples. This work suggests that the redox conditions that arise following permafrost thaw will be a strong determinant of community composition and will govern the ultimate fate of carbon stocks in permafrost-affected soils. Our results are currently being integrated with numerical models aimed at predicting the coupled microbiome-ecosystem response to thaw.

Soil greenhouse gas emissions and carbon budgeting in a short-hydroperiod floodplain wetland

USGS Publications Warehouse

Batson, Jackie; Noe, Gregory B.; Hupp, Cliff R.; Krauss, Ken W.; Rybicki, Nancy B.; Schenk, Edward R.

2015-01-01

Understanding the controls on floodplain carbon (C) cycling is important for assessing greenhouse gas emissions and the potential for C sequestration in river-floodplain ecosystems. We hypothesized that greater hydrologic connectivity would increase C inputs to floodplains that would not only stimulate soil C gas emissions but also sequester more C in soils. In an urban Piedmont river (151 km2 watershed) with a floodplain that is dry most of the year, we quantified soil CO2, CH4, and N2O net emissions along gradients of floodplain hydrologic connectivity, identified controls on soil aerobic and anaerobic respiration, and developed a floodplain soil C budget. Sites were chosen along a longitudinal river gradient and across lateral floodplain geomorphic units (levee, backswamp, and toe slope). CO2 emissions decreased downstream in backswamps and toe slopes and were high on the levees. CH4 and N2O fluxes were near zero; however, CH4emissions were highest in the backswamp. Annual CO2 emissions correlated negatively with soil water-filled pore space and positively with variables related to drier, coarser soil. Conversely, annual CH4 emissions had the opposite pattern of CO2. Spatial variation in aerobic and anaerobic respiration was thus controlled by oxygen availability but was not related to C inputs from sedimentation or vegetation. The annual mean soil CO2 emission rate was 1091 g C m−2 yr−1, the net sedimentation rate was 111 g C m−2 yr−1, and the vegetation production rate was 240 g C m−2 yr−1, with a soil C balance (loss) of −338 g C m−2 yr−1. This floodplain is losing C likely due to long-term drying from watershed urbanization.

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

NASA Astrophysics Data System (ADS)

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

2017-01-01

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

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

PubMed

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

2005-12-28

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

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

C3N4-H5PMo10V2O40: a dual-catalysis system for reductant-free aerobic oxidation of benzene to phenol

NASA Astrophysics Data System (ADS)

Long, Zhouyang; Zhou, Yu; Chen, Guojian; Ge, Weilin; Wang, Jun

2014-01-01

Hydroxylation of benzene is a widely studied atom economical and environmental benign reaction for producing phenol, aiming to replace the existing three-step cumene process. Aerobic oxidation of benzene with O2 is an ideal and dream process, but benzene and O2 are so inert that current systems either require expensive noble metal catalysts or wasteful sacrificial reducing agents; otherwise, phenol yields are extremely low. Here we report a dual-catalysis non-noble metal system by simultaneously using graphitic carbon nitride (C3N4) and Keggin-type polyoxometalate H5PMo10V2O40 (PMoV2) as catalysts, showing an exceptional activity for reductant-free aerobic oxidation of benzene to phenol. The dual-catalysis mechanism results in an unusual route to create phenol, in which benzene is activated on the melem unit of C3N4 and O2 by the V-O-V structure of PMoV2. This system is simple, highly efficient and thus may lead the one-step production of phenol from benzene to a more practical pathway.

C3N4-H5PMo10V2O40: a dual-catalysis system for reductant-free aerobic oxidation of benzene to phenol

PubMed Central

Long, Zhouyang; Zhou, Yu; Chen, Guojian; Ge, Weilin; Wang, Jun

2014-01-01

Hydroxylation of benzene is a widely studied atom economical and environmental benign reaction for producing phenol, aiming to replace the existing three-step cumene process. Aerobic oxidation of benzene with O2 is an ideal and dream process, but benzene and O2 are so inert that current systems either require expensive noble metal catalysts or wasteful sacrificial reducing agents; otherwise, phenol yields are extremely low. Here we report a dual-catalysis non-noble metal system by simultaneously using graphitic carbon nitride (C3N4) and Keggin-type polyoxometalate H5PMo10V2O40 (PMoV2) as catalysts, showing an exceptional activity for reductant-free aerobic oxidation of benzene to phenol. The dual-catalysis mechanism results in an unusual route to create phenol, in which benzene is activated on the melem unit of C3N4 and O2 by the V-O-V structure of PMoV2. This system is simple, highly efficient and thus may lead the one-step production of phenol from benzene to a more practical pathway. PMID:24413448

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

PubMed

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

2014-05-01

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

Synthesis of Formate Esters and Formamides Using an Au/TiO2-Catalyzed Aerobic Oxidative Coupling of Paraformaldehyde

PubMed Central

Metaxas, Ioannis; Vasilikogiannaki, Eleni

2017-01-01

A simple method for the synthesis of formate esters and formamides is presented based on the Au/TiO2-catalyzed aerobic oxidative coupling between alcohols or amines and formaldehyde. The suitable form of formaldehyde is paraformaldehyde, as cyclic trimeric 1,3,5-trioxane is inactive. The reaction proceeds via the formation of an intermediate hemiacetal or hemiaminal, respectively, followed by the Au nanoparticle-catalyzed aerobic oxidation of the intermediate. Typically, the oxidative coupling between formaldehyde (2 equiv) and amines occurs quantitatively at room temperature within 4 h, and there is no need to add a base as in analogous coupling reactions. The oxidative coupling between formaldehyde (typically 3 equiv) and alcohols is unprecedented and occurs more slowly, yet in good to excellent yields and selectivity. Minor side-products (2–12%) from the acetalization of formaldehyde by the alcohol are also formed. The catalyst is recyclable and can be reused after a simple filtration in five consecutive runs with a small loss of activity. PMID:29231853

Moisture effects on greenhouse gases generation in nitrifying gas-phase compost biofilters.

PubMed

Maia, Guilherme D N; Day, George B; Gates, Richard S; Taraba, Joseph L; Coyne, Mark S

2012-06-01

Gas-phase compost biofilters are extensively used in concentrated animal feeding operations to remove odors and, in some cases, ammonia from air sources. The expected biochemical pathway for these predominantly aerobic systems is nitrification. However, non-uniform media with low oxygen levels can shift biofilter microbial pathways to denitrification, a source of greenhouse gases. Several factors contribute to the formation of anoxic/anaerobic zones: media aging, media and particle structure, air velocity distribution, compaction, biofilm thickness, and moisture content (MC) distribution. The present work studies the effects of media moisture conditions on ammonia (NH(3)) removal and greenhouse gas generation (nitrous oxide, N(2)O and methane, CH(4)) for gas-phase compost biofilters subject to a 100-day controlled drying process. Continuous recordings were made for the three gases and water vapor (2.21-h sampling cycle, each cycle consisted of three gas species, and water vapor, for a total of 10,050 data points). Media moisture conditions were classified into three corresponding media drying rate (DR) stages: Constant DR (wetter media), falling DR, and stable-dry system. The first-half of the constant DR period (0-750 h; MC=65-52%, w.b.) facilitated high NH(3) removal rates, but higher N(2)O generation and no CH(4) generation. At the drier stages of the constant DR (750-950 h; MC=52-48%, w.b.) NH(3) removal remained high but N(2)O net generation decreased to near zero. In the falling DR stage (1200-1480 h; MC=44-13%) N(2)O generation decreased, CH(4) increased, and NH(3) was no longer removed. No ammonia removal or greenhouse gas generation was observed in the stable-dry system (1500-2500 h; MC=13%). These results indicate that media should remain toward the drier region of the constant DR (in close proximity to the falling DR stage; MC=50%, approx.), to maintain high levels of NH(3) removal, reduced levels of N(2)O generation, and nullify levels of CH(4) generation. Copyright © 2012 Elsevier Ltd. All rights reserved.

Oxidase catalysis via aerobically generated hypervalent iodine intermediates

NASA Astrophysics Data System (ADS)

Maity, Asim; Hyun, Sung-Min; Powers, David C.

2018-02-01

The development of sustainable oxidation chemistry demands strategies to harness O2 as a terminal oxidant. Oxidase catalysis, in which O2 serves as a chemical oxidant without necessitating incorporation of oxygen into reaction products, would allow diverse substrate functionalization chemistry to be coupled to O2 reduction. Direct O2 utilization suffers from intrinsic challenges imposed by the triplet ground state of O2 and the disparate electron inventories of four-electron O2 reduction and two-electron substrate oxidation. Here, we generate hypervalent iodine reagents—a broadly useful class of selective two-electron oxidants—from O2. This is achieved by intercepting reactive intermediates of aldehyde autoxidation to aerobically generate hypervalent iodine reagents for a broad array of substrate oxidation reactions. The use of aryl iodides as mediators of aerobic oxidation underpins an oxidase catalysis platform that couples substrate oxidation directly to O2 reduction. We anticipate that aerobically generated hypervalent iodine reagents will expand the scope of aerobic oxidation chemistry in chemical synthesis.

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

PubMed

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

2013-08-07

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

Quantitative modeling of the rise in atmospheric oxygen

NASA Astrophysics Data System (ADS)

Claire, Mark W.

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

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

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

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

1992-10-01

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

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

DOE Data Explorer

David E. Graham; Jianqiu Zheng; Taniya RoyChowdhury

2016-08-31

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

Greenhouse gas fluxes and carbon leaching before and after partial harvesting and clearcutting in a drained peatland forest

NASA Astrophysics Data System (ADS)

Korkiakoski, Mika; Tuovinen, Juha-Pekka; Ojanen, Paavo; Penttilä, Timo; Minkkinen, Kari; Rainne, Juuso; Laurila, Tuomas; Lohila, Annalea

2017-04-01

The most common method of forest management in Finland is rotation forestry including clearcutting and forest regeneration. Typical clearcutting involves removing stem wood and leaving logging residues (foliage, branches, stumps, and roots) on the site. After clearcutting of a peatland forest, water table level (WTL) rises due to ceased interception and transpiration of trees. Due to the elevated WTL, the thickness of the oxic peat layer and peat mass susceptible to aerobic decomposition decrease, and consequently, carbon dioxide (CO2) emissions from the 'old' peat are expected to decrease. On the other hand, conditions for methane (CH4) producing microbes will be more favorable and methane oxidation may decrease, which together may increase emissions of CH4 to the atmosphere. Also, nitrogen oxide (N2O) emissions are expected to increase due to the enhancing effect of logging residues on nitrification and denitrification processes. Due to the rising WTL, the leaching of dissolved organic carbon (DOC) may temporarily increase. In our project, we aim to reduce the adverse environmental impacts of peatland forestry by conducting a partial harvesting instead of clearcutting to regenerate our study forest (Lettosuo, Tammela in southern Finland). Ca. 3/4 of the tree biomass was removed in spring 2016. With this, we hope to achieve a moderate (about 20 cm) rise in the WTL from the original -50 cm level. This should eventually decrease CO2 emissions but not significantly increase CH4 emissions nor DOC leaching. The effect of harvest and the moderate WTL rise on greenhouse gas (GHG) fluxes and evapotranspiration are studied using the data collected with the eddy covariance method before (2009-2015) and after (2016-) the harvest. We also retained an uncut control and set up a clear-cut plot at the site to compare the impacts of different management practices on site conditions, soil GHG fluxes and C and N leaching. The impact of logging residues on GHG fluxes are also studied with manual chambers. To have "a calibration year", we started to measure most of these variables already in spring 2015. In this presentation, we will show the GHG and aquatic carbon fluxes before and after the logging and discuss the most important short-term implications of logging on GHG fluxes as well as on meteorology.

Second-Order Biomimicry: In Situ Oxidative Self-Processing Converts Copper(I)/Diamine Precursor into a Highly Active Aerobic Oxidation Catalyst.

PubMed

McCann, Scott D; Lumb, Jean-Philip; Arndtsen, Bruce A; Stahl, Shannon S

2017-04-26

A homogeneous Cu-based catalyst system consisting of [Cu(MeCN) 4 ]PF 6 , N , N '-di- tert -butylethylenediamine (DBED), and p -( N , N -dimethylamino)pyridine (DMAP) mediates efficient aerobic oxidation of alcohols. Mechanistic study of this reaction shows that the catalyst undergoes an in situ oxidative self-processing step, resulting in conversion of DBED into a nitroxyl that serves as an efficient cocatalyst for aerobic alcohol oxidation. Insights into this behavior are gained from kinetic studies, which reveal an induction period at the beginning of the reaction that correlates with the oxidative self-processing step, EPR spectroscopic analysis of the catalytic reaction mixture, which shows the buildup of the organic nitroxyl species during steady state turnover, and independent synthesis of oxygenated DBED derivatives, which are shown to serve as effective cocatalysts and eliminate the induction period in the reaction. The overall mechanism bears considerable resemblance to enzymatic reactivity. Most notable is the "oxygenase"-type self-processing step that mirrors generation of catalytic cofactors in enzymes via post-translational modification of amino acid side chains. This higher-order function within a synthetic catalyst system presents new opportunities for the discovery and development of biomimetic catalysts.

Cu-catalyzed aerobic oxidative cyclizations of 3-N-hydroxyamino-1,2-propadienes with alcohols, thiols, and amines to form α-O-, S-, and N-substituted 4-methylquinoline derivatives.

PubMed

Sharma, Pankaj; Liu, Rai-Shung

2015-03-16

A one-pot, two-step synthesis of α-O-, S-, and N-substituted 4-methylquinoline derivatives through Cu-catalyzed aerobic oxidations of N-hydroxyaminoallenes with alcohols, thiols, and amines is described. This reaction sequence involves an initial oxidation of N-hydroxyaminoallenes with NuH (Nu = OH, OR, NHR, and SR) to form 3-substituted 2-en-1-ones, followed by Brønsted acid catalyzed intramolecular cyclizations of the resulting products. Our mechanistic analysis suggests that the reactions proceed through a radical-type mechanism rather than a typical nitrone-intermediate route. The utility of this new Cu-catalyzed reaction is shown by its applicability to the synthesis of several 2-amino-4-methylquinoline derivatives, which are known to be key precursors to several bioactive molecules. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Anaerobic oxidation of 2-chloroethanol under denitrifying conditions by Pseudomonas stutzeri strain JJ.

PubMed

Dijk, J A; Stams, A J M; Schraa, G; Ballerstedt, H; de Bont, J A M; Gerritse, J

2003-11-01

A bacterium that uses 2-chloroethanol as sole energy and carbon source coupled to denitrification was isolated from 1,2-dichloroethane-contaminated soil. Its 16 S rDNA sequence showed 98% similarity with the type strain of Pseudomonas stutzeri (DSM 5190) and the isolate was tentatively identified as Pseudomonas stutzeri strain JJ. Strain JJ oxidized 2-chloroethanol completely to CO(2) with NO(3)(- )or O(2) as electron acceptor, with a preference for O(2) if supplied in combination. Optimum growth on 2-chloroethanol with nitrate occurred at 30 degrees C with a mu(max) of 0.14 h(-1) and a yield of 4.4 g protein per mol 2-chloroethanol metabolized. Under aerobic conditions, the mu(max) was 0.31 h(-1). NO(2)(-) also served as electron acceptor, but reduction of Fe(OH)(3), MnO(2), SO(4)(2-), fumarate or ClO(3)(-) was not observed. Another chlorinated compound used as sole energy and carbon source under aerobic and denitrifying conditions was chloroacetate. Various different bacterial strains, including some closely related Pseudomonas stutzeri strains, were tested for their ability to grow on 2-chloroethanol as sole energy and carbon source under aerobic and denitrifying conditions, respectively. Only three strains, Pseudomonas stutzeri strain LMD 76.42, Pseudomonas putida US2 and Xanthobacter autotrophicus GJ10, grew aerobically on 2-chloroethanol. This is the first report of oxidation of 2-chloroethanol under denitrifying conditions by a pure bacterial culture.

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

NASA Astrophysics Data System (ADS)

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

2016-04-01

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

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

PubMed

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

2018-05-01

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

Clumped isotope effects during OH and Cl oxidation of methane

NASA Astrophysics Data System (ADS)

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

2017-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2014-06-01

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

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

NASA Astrophysics Data System (ADS)

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

2010-12-01

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

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

PubMed

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

2017-06-01

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

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

PubMed

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

2015-11-01

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

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

USGS Publications Warehouse

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

1993-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

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

PubMed

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

1996-06-14

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

From iron coordination compounds to metal oxide nanoparticles.

PubMed

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

2016-01-01

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

From iron coordination compounds to metal oxide nanoparticles

PubMed Central

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

2016-01-01

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

Age-related effect of aerobic exercise training on antioxidant and oxidative markers in the liver challenged by doxorubicin in rats.

PubMed

Ahmadian, Mehdi; Dabidi Roshan, Valiollah; Leicht, Anthony S

2018-05-16

The aims of the current study were to investigate the oxidant and antioxidant status of liver tissue challenged by doxorubicin and to examine the possible protective effects of aerobic exercise on doxorubicin-induced oxidative stress. Seventy-two rats were divided into three age groups (Young, Adult, and Elderly) with three treatment subgroups consisting of eight rats per age group: doxorubicin, aerobic exercise + doxorubicin, and aerobic exercise + saline. The experimental groups performed regular treadmill running for 3 weeks. Doxorubicin was administered by i.p. injection at a dosage of 20 mg kg -1 while the aerobic exercise + saline group received saline of a comparable volume. Heat shock protein 70, malondialdehyde, glutathione peroxidase, and protein carbonyl were determined from the liver homogenates following the intervention period. Treatment with doxorubicin induced hepatotoxicity in all groups with lower values of oxidative stress in young compared with the older groups. The inclusion of aerobic exercise training significantly increased heat shock protein 70 and antioxidant enzyme levels (glutathione peroxidase) whereas it decreased oxidative stress biomarkers (malondialdehyde and protein carbonyl) for all age groups. These results suggest that aerobic exercise training may be a potential, non-drug strategy to modulate doxorubicin-induced hepatotoxicity through its positive impact on antioxidant levels and oxidative stress biomarkers.

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

PubMed Central

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

2011-01-01

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

Thermal degradation of (6R,S)-5,10-methenyltetrahydrofolate in aqueous solution at pH 8

NASA Astrophysics Data System (ADS)

Tyagi, A.; Penzkofer, A.; Batschauer, A.; Wolf, E.

2009-03-01

The degradation of the folate (6R,S)-5,10-methenyltetrahydrofolate chloride (MTHF-Cl) in aqueous solution at pH 8 at room temperature is studied by absorption spectra measurements. Samples with and without the reducing agent β-mercaptoethanol (β-ME) both under aerobic and anaerobic conditions are investigated. MTHF-Cl hydrolyses to (6R,S)-10-formyltetrahydrofolate (10-HCO-H4folate) in all four cases. 10-HCO-H4folate oxidizes to 10-formyldihydrofolate (10-HCO-H2folate) under aerobic conditions in the absence of β-ME. The degradation dynamics is analysed theoretically and conversion rate constants of hydrolysis and oxidation are determined.

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

PubMed

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

2011-11-04

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

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

PubMed

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

2011-08-15

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

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

PubMed

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

2009-01-01

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

Redirection of the Respiro-Fermentative Flux Distribution in Saccharomyces cerevisiae by Overexpression of the Transcription Factor Hap4p

PubMed Central

Blom, Jolanda; De Mattos, M. Joost Teixeira; Grivell, Leslie A.

2000-01-01

Reduction of aerobic fermentation on sugars by altering the fermentative/oxidative balance is of significant interest for optimization of industrial production of Saccharomyces cerevisiae. Glucose control of oxidative metabolism in baker's yeast is partly mediated through transcriptional regulation of the Hap4p subunit of the Hap2/3/4/5p transcriptional activator complex. To alleviate glucose repression of oxidative metabolism, we constructed a yeast strain with constitutively elevated levels of Hap4p. Genetic analysis of expression levels of glucose-repressed genes and analysis of respiratory capacity showed that Hap4p overexpression (partly) relieves glucose repression of respiration. Analysis of the physiological properties of the Hap4p overproducer in batch cultures in fermentors (aerobic, glucose excess) has shown that the metabolism of this strain is more oxidative than in the wild-type strain, resulting in a significant reduced ethanol production and improvement of growth rate and a 40% gain in biomass yield. Our results show that modification of one or more transcriptional regulators can be a powerful and a widely applicable tool for redirection of metabolic fluxes in microorganisms. PMID:10788368

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

PubMed

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

2008-03-01

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

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

PubMed

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

2018-03-01

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

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

NASA Astrophysics Data System (ADS)

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

2009-07-01

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

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

PubMed

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

2011-10-07

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

Design of top covers supporting aerobic in situ stabilization of old landfills--an experimental simulation in lysimeters.

PubMed

Hrad, Marlies; Huber-Humer, Marion; Wimmer, Bernhard; Reichenauer, Thomas G

2012-12-01

Landfill aeration by means of low pressure air injection is a promising tool to reduce long term emissions from organic waste fractions through accelerated biological stabilization. Top covers that enhance methane oxidation could provide a simple and economic way to mitigate residual greenhouse gas emissions from in situ aerated landfills, and may replace off-gas extraction and treatment, particularly at smaller and older sites. In this respect the installation of a landfill cover system adjusted to the forced-aerated landfill body is of great significance. Investigations into large scale lysimeters (2 × 2 × 3m) under field conditions have been carried out using different top covers including compost materials and natural soils as a surrogate to gas extraction during active low pressure aeration. In the present study, the emission behaviour as well as the water balance performance of the lysimeters has been investigated, both prior to and during the first months of in situ aeration. Results reveal that mature sewage sludge compost (SSC) placed in one lysimeter exhibits in principle optimal ambient conditions for methanotrophic bacteria to enhance methane oxidation. Under laboratory conditions the mature compost mitigated CH(4) loadings up to 300 lCH(4)/m(2)d. In addition, the compost material provided high air permeability even at 100% water holding capacity (WHC). In contrast, the more cohesive, mineral soil cover was expected to cause a notably uniform distribution of the injected air within the waste layer. Laboratory results also revealed sufficient air permeability of the soil materials (TS-F and SS-Z) placed in lysimeter C. However, at higher compaction density SS-Z became impermeable at 100% WHC. Methane emissions from the reference lysimeter with the smaller substrate cover (12-52 g CH(4)/m(2)d) were significantly higher than fluxes from the other lysimeters (0-19 g CH(4)/m(2)d) during in situ aeration. Regarding water balance, lysimeters covered with compost and compost-sand mixture, showed the lowest leachate rate (18-26% of the precipitation) due to the high water holding capacity and more favourable plant growth conditions compared to the lysimeters with mineral, more cohesive, soil covers (27-45% of the precipitation). On the basis of these results, the authors suggest a layered top cover system using both compost material as well as mineral soil in order to support active low-pressure aeration. Conventional soil materials with lower permeability may be used on top of the landfill body for a more uniform aeration of the waste due to an increased resistance to vertical gas flow. A compost cover may be built on top of the soil cover underlain by a gas distribution layer to improve methane oxidation rates and minimise water infiltration. By planting vegetation with a high transpiration rate, the leachate amount emanating from the landfill could be further minimised. The suggested design may be particularly suitable in combination with intermittent in situ aeration, in the later stage of an aeration measure, or at very small sites and shallow deposits. The top cover system could further regulate water infiltration into the landfill and mitigate residual CH(4) emissions, even beyond the time of active aeration. Copyright © 2012 Elsevier Ltd. All rights reserved.

The impact of anaerobic microorganisms activities in ruminant waste and coal

NASA Astrophysics Data System (ADS)

Harlia, Ellin; Hamdani, H.; Winantris, Kurnani, Tb. B. A.; Hidayati, Y. A.; Marlina, E. T.; Rahmah, K. N.; Arief, H.; Ridwan, R.; Joni, I. M.

2018-02-01

Ruminant (dairy cattle, beef cattle and buffalo) waste from intensive farming concentrated in highly populated areas when stacked and accumulated in certain heights and in anaerobic condition, may produce Green House Gases (GHGs) which lead to global warming. This condition is generated through fermentation by microorganism contained in livestock waste and biogenic activities on coal. The GHGs include CH4 (methane), CO2 (carbon dioxide) and N2O (nitrous oxide). The GHG emission should be early monitored to minimize greater problems. In the other hand, methane can be utilized as an environmental friendly energy after stored as biogas on digester. The aim of this research is to detect how much GHGs formed from ruminant waste and biogenic activities on coal, which can be utilized as an alternative energy. This research conducted as an explorative study utilizing dairy cattle feces, beef cattle feces, buffalo feces and three types of coal: lignite, bituminous and sub-bituminous, which is separately added into medium 98-5 made from mixture of agar medium and chemical components in powder and crystal form diluted with distilled water and rumen liquid, with six repetitions. Each sample was stored into 250 mL anaerobic digester, observed weekly for period of 4 weeks, analyzed by Gas Chromatography (GC-A14). The result showed that GHGs: CH4, CO2 and N2O were found in all samples. Anticipation of GHGs formation to avoid air pollution is by utilizing livestock waste and coal in aerobic condition or in anaerobic condition through digester.

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

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

PubMed

Ji, Eun Sook; Park, Kyu-Hyun

2012-12-01

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

Nutrient loading enhances methane flux in an ombrotrophic bog

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

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

PubMed

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

2014-10-01

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

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

PubMed

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

2015-11-01

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

Heterotrophic and Autotrophic Microbial Populations in Cold Perennial Springs of the High Arctic ▿ †

PubMed Central

Perreault, Nancy N.; Greer, Charles W.; Andersen, Dale T.; Tille, Stefanie; Lacrampe-Couloume, Georges; Lollar, Barbara Sherwood; Whyte, Lyle G.

2008-01-01

The saline springs of Gypsum Hill in the Canadian high Arctic are a rare example of cold springs originating from deep groundwater and rising to the surface through thick permafrost. The heterotrophic bacteria and autotrophic sulfur-oxidizing bacteria (up to 40% of the total microbial community) isolated from the spring waters and sediments were classified into four phyla (Actinobacteria, Bacteroidetes, Firmicutes, and Proteobacteria) based on 16S rRNA gene analysis; heterotrophic isolates were primarily psychrotolerant, salt-tolerant, facultative anaerobes. Some of the isolates contained genes for thiosulfate oxidation (soxB) and anoxygenic photosynthesis (pufM), possibly enabling the strains to better compete in these sulfur-rich environments subject to long periods of illumination in the Arctic summer. Although leucine uptake by the spring water microbial community was low, CO2 uptake was relatively high under dark incubation, reinforcing the idea that primary production by chemoautotrophs is an important process in the springs. The small amounts of hydrocarbons in gases exsolving from the springs (0.38 to 0.51% CH4) were compositionally and isotopically consistent with microbial methanogenesis and possible methanotrophy. Anaerobic heterotrophic sulfur oxidation and aerobic autotrophic sulfur oxidation activities were demonstrated in sediment slurries. Overall, our results describe an active microbial community capable of sustainability in an extreme environment that experiences prolonged periods of continuous light or darkness, low temperatures, and moderate salinity, where life seems to rely on chemolithoautotrophy. PMID:18805995

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

USDA-ARS?s Scientific Manuscript database

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

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

USGS Publications Warehouse

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

1995-01-01

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

Integrated measurements and modeling of CO2, CH4, and N2O fluxes using soil microsite frequency distributions

NASA Astrophysics Data System (ADS)

Davidson, Eric; Sihi, Debjani; Savage, Kathleen

2017-04-01

Soil fluxes of greenhouse gases (GHGs) play a significant role as biotic feedbacks to climate change. Production and consumption of carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O) are affected by complex interactions of temperature, moisture, and substrate supply, which are further complicated by spatial heterogeneity of the soil matrix. Models of belowground processes of these GHGs should be internally consistent with respect to the biophysical processes of gaseous production, consumption, and transport within the soil, including the contrasting effects of oxygen (O2) as either substrate or inhibitor. We installed automated chambers to simultaneously measure soil fluxes of CO2 (using LiCor-IRGA), CH4, and N2O (using Aerodyne quantum cascade laser) along soil moisture gradients at the Howland Forest in Maine, USA. Measured fluxes of these GHGs were used to develop and validate a merged model. While originally intended for aerobic respiration, the core structure of the Dual Arrhenius and Michaelis-Menten (DAMM) model was modified by adding M-M and Arrhenius functions for each GHG production and consumption process, and then using the same diffusion functions for each GHG and for O2. The area under a soil chamber was partitioned according to a log-normal probability distribution function, where only a small fraction of microsites had high available-C. The probability distribution of soil C leads to a simulated distribution of heterotrophic respiration, which translates to a distribution of O2 consumption among microsites. Linking microsite consumption of O2 with a diffusion model generates microsite concentrations of O2, which then determine the distribution of microsite production and consumption of CH4 and N2O, and subsequently their microsite concentrations using the same diffusion function. At many moisture values, there are some microsites of production and some of consumption for each gas, and the resulting simulated microsite concentrations of CH4 and N2O range from below ambient to above ambient atmospheric values. As soil moisture or temperature increase, the skewness of the microsite distributions of heterotrophic respiration and CH4 concentrations shifts toward a larger fraction of high values, while the skewness of microsite distributions of O2 and N2O concentrations shifts toward a larger fraction of low values. This approach of probability distribution functions for each gas simulates the importance of microsite hotspots of methanogenesis and N2O reduction at high moisture (and temperature). In addition, the model demonstrates that net consumption of atmospheric CH4 and N2O can occur simultaneously within a chamber due to the distribution of soil microsite conditions, which is consistent with some episodes of measured fluxes. Because soil CO2, N2O and CH4 fluxes are linked through substrate supply and O2 effects, the multiple constraints of simultaneous measurements of all three GHGs proved to be effective when applied to our combined model. Simulating all three GHGs simultaneously in a parsimonious modeling framework provides confidence that the most important mechanisms are skillfully simulated using appropriate parameterization and good process representation.

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

NASA Astrophysics Data System (ADS)

Datta, A.; Adhya, T. K.

2014-08-01

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

Geosphere-Biosphere Interactions in Bio-Activity Volcanic Lakes: Evidences from Hule and Rìo Cuarto (Costa Rica)

PubMed Central

Cabassi, Jacopo; Tassi, Franco; Mapelli, Francesca; Borin, Sara; Calabrese, Sergio; Rouwet, Dmitri; Chiodini, Giovanni; Marasco, Ramona; Chouaia, Bessem; Avino, Rosario; Vaselli, Orlando; Pecoraino, Giovannella; Capecchiacci, Francesco; Bicocchi, Gabriele; Caliro, Stefano; Ramirez, Carlos; Mora-Amador, Raul

2014-01-01

Hule and Río Cuarto are maar lakes located 11 and 18 km N of Poás volcano along a 27 km long fracture zone, in the Central Volcanic Range of Costa Rica. Both lakes are characterized by a stable thermic and chemical stratification and recently they were affected by fish killing events likely related to the uprising of deep anoxic waters to the surface caused by rollover phenomena. The vertical profiles of temperature, pH, redox potential, chemical and isotopic compositions of water and dissolved gases, as well as prokaryotic diversity estimated by DNA fingerprinting and massive 16S rRNA pyrosequencing along the water column of the two lakes, have highlighted that different bio-geochemical processes occur in these meromictic lakes. Although the two lakes host different bacterial and archaeal phylogenetic groups, water and gas chemistry in both lakes is controlled by the same prokaryotic functions, especially regarding the CO2-CH4 cycle. Addition of hydrothermal CO2 through the bottom of the lakes plays a fundamental priming role in developing a stable water stratification and fuelling anoxic bacterial and archaeal populations. Methanogens and methane oxidizers as well as autotrophic and heterotrophic aerobic bacteria responsible of organic carbon recycling resulted to be stratified with depth and strictly related to the chemical-physical conditions and availability of free oxygen, affecting both the CO2 and CH4 chemical concentrations and their isotopic compositions along the water column. Hule and Río Cuarto lakes were demonstrated to contain a CO2 (CH4, N2)-rich gas reservoir mainly controlled by the interactions occurring between geosphere and biosphere. Thus, we introduced the term of bio-activity volcanic lakes to distinguish these lakes, which have analogues worldwide (e.g. Kivu: D.R.C.-Rwanda; Albano, Monticchio and Averno: Italy; Pavin: France) from volcanic lakes only characterized by geogenic CO2 reservoir such as Nyos and Monoun (Cameroon). PMID:25058537

Geosphere-biosphere interactions in bio-activity volcanic lakes: evidences from Hule and Rìo Cuarto (Costa Rica).

PubMed

Cabassi, Jacopo; Tassi, Franco; Mapelli, Francesca; Borin, Sara; Calabrese, Sergio; Rouwet, Dmitri; Chiodini, Giovanni; Marasco, Ramona; Chouaia, Bessem; Avino, Rosario; Vaselli, Orlando; Pecoraino, Giovannella; Capecchiacci, Francesco; Bicocchi, Gabriele; Caliro, Stefano; Ramirez, Carlos; Mora-Amador, Raul

2014-01-01

Hule and Río Cuarto are maar lakes located 11 and 18 km N of Poás volcano along a 27 km long fracture zone, in the Central Volcanic Range of Costa Rica. Both lakes are characterized by a stable thermic and chemical stratification and recently they were affected by fish killing events likely related to the uprising of deep anoxic waters to the surface caused by rollover phenomena. The vertical profiles of temperature, pH, redox potential, chemical and isotopic compositions of water and dissolved gases, as well as prokaryotic diversity estimated by DNA fingerprinting and massive 16S rRNA pyrosequencing along the water column of the two lakes, have highlighted that different bio-geochemical processes occur in these meromictic lakes. Although the two lakes host different bacterial and archaeal phylogenetic groups, water and gas chemistry in both lakes is controlled by the same prokaryotic functions, especially regarding the CO2-CH4 cycle. Addition of hydrothermal CO2 through the bottom of the lakes plays a fundamental priming role in developing a stable water stratification and fuelling anoxic bacterial and archaeal populations. Methanogens and methane oxidizers as well as autotrophic and heterotrophic aerobic bacteria responsible of organic carbon recycling resulted to be stratified with depth and strictly related to the chemical-physical conditions and availability of free oxygen, affecting both the CO2 and CH4 chemical concentrations and their isotopic compositions along the water column. Hule and Río Cuarto lakes were demonstrated to contain a CO2 (CH4, N2)-rich gas reservoir mainly controlled by the interactions occurring between geosphere and biosphere. Thus, we introduced the term of bio-activity volcanic lakes to distinguish these lakes, which have analogues worldwide (e.g. Kivu: D.R.C.-Rwanda; Albano, Monticchio and Averno: Italy; Pavin: France) from volcanic lakes only characterized by geogenic CO2 reservoir such as Nyos and Monoun (Cameroon).

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

NASA Astrophysics Data System (ADS)

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

2015-09-01

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

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

PubMed Central

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

2018-01-01

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

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

PubMed Central

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

2017-01-01

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

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

PubMed

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

2018-06-15

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

Simple Copper Catalysts for the Aerobic Oxidation of Amines: Selectivity Control by the Counterion.

PubMed

Xu, Boran; Hartigan, Elizabeth M; Feula, Giancarlo; Huang, Zheng; Lumb, Jean-Philip; Arndtsen, Bruce A

2016-12-19

We describe the use of simple copper-salt catalysts in the selective aerobic oxidation of amines to nitriles or imines. These catalysts are marked by their exceptional efficiency, operate at ambient temperature and pressure, and allow the oxidation of amines without expensive ligands or additives. This study highlights the significant role counterions can play in controlling selectivity in catalytic aerobic oxidations. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

The transformation from anammox granules to deammonification granules in micro-aerobic system by facilitating indigenous ammonia oxidizing bacteria.

PubMed

Wang, Xiaolong; Gao, Dawen

2018-02-01

Granular deammonification process is a good way to retain aerobic and anaerobic ammonia oxidizing bacteria (AOB and anammox bacteria) and exhaust flocculent nitrite oxidizing bacteria (NOB). In this study, to facilitate indigenous AOB growth on anammox granules, by stepwise reducing influent nitrite, anammox granules were effectively transformed into deammonification granules in a micro-aerobic EGSB in 100 days. Total nitrogen removal efficiency of 90% and nitrogen removal rate of 2.3 g N/L/d were reached at stable deammonification stage. High influent FA and limited oxygen supply contributed suppression for Nitrospira-like NOB. In transition stages, Proteobacteria and Chloroflexi were always dominated. Anammox abundance decreased, while AOB abundance grew fast. Anammox bacteria and AOB were dominated by Brocadia fulgida and Nitrosomonas europaea, respectively. Denitrification activity and bacteria existed although without influent organic. The final AOB abundance was about 4.55-13.8 times more than anammox bacteria abundance, with almost equal potential activities. Copyright © 2017 Elsevier Ltd. All rights reserved.

Microbial Communities in Subpermafrost Saline Fracture Water at the Lupin Au Mine, Nunavut, Canada

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

Onstott, Tullis; McGown, Daniel; Bakermans, Corien

2009-01-01

We report the first investigation of a deep subpermafrost microbial ecosystem, a terrestrial analog for the Martian subsurface. Our multidisciplinary team analyzed fracture water collected at 890 and 1,130 m depths beneath a 540-m-thick permafrost layer at the Lupin Au mine (Nunavut, Canada). 14C, 3H, and noble gas isotope analyses suggest that the Na Ca Cl, suboxic, fracture water represents a mixture of geologically ancient brine, ~25-kyr-old, meteoric water and a minor modern talik-water component. Microbial planktonic concentrations were ~103 cells mL 1. Analysis of the 16S rRNA gene from extracted DNA and enrichment cultures revealed 42 unique operational taxonomicmore » units in 11 genera with Desulfosporosinus, Halothiobacillus, and Pseudomonas representing the most prominent phylotypes and failed to detect Archaea. The abundance of terminally branched and midchain-branched saturated fatty acids (5 to 15 mol%) was consistent with the abundance of Grampositive bacteria in the clone libraries. Geochemical data, the ubiquinone (UQ) abundance (3 to 11 mol%), and the presence of both aerobic and anaerobic bacteria indicated that the environment was suboxic, not anoxic. Stable sulfur isotope analyses of the fracture water detected the presence of microbial sulfate reduction, and analyses of the vein-filling pyrite indicated that it was in isotopic equilibrium with the dissolved sulfide. Free energy calculations revealed that sulfate reduction and sulfide oxidation via denitrification and not methanogenesis were the most thermodynamically viable consistent with the principal metabolisms inferred from the 16S rRNA community composition and with CH4 isotopic compositions. The sulfate-reducing bacteria most likely colonized the subsurface during the Pleistocene or earlier, whereas aerobic bacteria may have entered the fracture water networks either during deglaciation prior to permafrost formation 9,000 years ago or from the nearby talik through the hydrologic gradient created during mine dewatering. Although the absence of methanogens from this subsurface ecosystem is somewhat surprising, it may be attributable to an energy bottleneck that restricts their migration from surface permafrost deposits where they are frequently reported. These results have implications for the biological origin of CH4 on Mars.« less

Second-Order Biomimicry: In Situ Oxidative Self-Processing Converts Copper(I)/Diamine Precursor into a Highly Active Aerobic Oxidation Catalyst

PubMed Central

2017-01-01

A homogeneous Cu-based catalyst system consisting of [Cu(MeCN)4]PF6, N,N′-di-tert-butylethylenediamine (DBED), and p-(N,N-dimethylamino)pyridine (DMAP) mediates efficient aerobic oxidation of alcohols. Mechanistic study of this reaction shows that the catalyst undergoes an in situ oxidative self-processing step, resulting in conversion of DBED into a nitroxyl that serves as an efficient cocatalyst for aerobic alcohol oxidation. Insights into this behavior are gained from kinetic studies, which reveal an induction period at the beginning of the reaction that correlates with the oxidative self-processing step, EPR spectroscopic analysis of the catalytic reaction mixture, which shows the buildup of the organic nitroxyl species during steady state turnover, and independent synthesis of oxygenated DBED derivatives, which are shown to serve as effective cocatalysts and eliminate the induction period in the reaction. The overall mechanism bears considerable resemblance to enzymatic reactivity. Most notable is the “oxygenase”-type self-processing step that mirrors generation of catalytic cofactors in enzymes via post-translational modification of amino acid side chains. This higher-order function within a synthetic catalyst system presents new opportunities for the discovery and development of biomimetic catalysts. PMID:28470049

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

PubMed

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

2013-04-01

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

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

PubMed

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

2016-02-01

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

Dietary citrus pulp reduces lipid oxidation in lamb meat.

PubMed

Inserra, L; Priolo, A; Biondi, L; Lanza, M; Bognanno, M; Gravador, R; Luciano, G

2014-04-01

This study investigated the effect of replacing cereal concentrates with high levels of dried citrus pulp in the diet on lamb meat oxidative stability. Over 56 days, lambs were fed a barley-based concentrate (Control) or concentrates in which 24% and 35% dried citrus pulp were included to partially replace barley (Citrus 24% and Citrus 35%, respectively). Meat was aged under vacuum for 4 days and subsequently stored aerobically at 4 °C. The Control diet increased the redness, yellowness and saturation of meat after blooming (P<0.01). Regardless of the level of supplementation, dietary dried citrus pulp strongly reduced meat lipid oxidation over 6 days of aerobic storage (P<0.001), while colour parameters did not change noticeably over storage and their variation rate was not affected by the diet. In conclusion, replacing cereals with dried citrus pulp in concentrate-based diets might represent a feasible strategy to naturally improve meat oxidative stability and to promote the exploitation of this by-product. Copyright © 2013 Elsevier Ltd. All rights reserved.

Aerobic exercise regulates blood lipid and insulin resistance via the toll‑like receptor 4‑mediated extracellular signal‑regulated kinases/AMP‑activated protein kinases signaling pathway.

PubMed

Wang, Mei; Li, Sen; Wang, Fubaihui; Zou, Jinhui; Zhang, Yanfeng

2018-06-01

Diabetes mellitus is a complicated metabolic disease with symptoms of hyperglycemia, insulin resistance, chronic damage and dysfunction of tissues, and metabolic syndrome for insufficient insulin production. Evidence has indicated that exercise treatments are essential in the progression of type‑ІІ diabetes mellitus, and affect insulin resistance and activity of islet β‑cells. In the present study, the efficacy and signaling mechanism of aerobic exercise on blood lipids and insulin resistance were investigated in the progression of type‑ІІ diabetes mellitus. Body weight, glucose metabolism and insulin serum levels were investigated in mouse models of type‑ІІ diabetes mellitus following experienced aerobic exercise. Expression levels of inflammatory factors, interleukin (IL)‑6, high‑sensitivity C‑reactive protein, tumor necrosis factor‑α and leucocyte differentiation antigens, soluble CD40 ligand in the serum were analyzed in the experimental mice. In addition, expression levels of toll‑like receptor 4 (TLR‑4) were analyzed in the liver cells of experimental mice. Changes of oxidative stress indicators, including reactive oxygen species, superoxide dismutase, glutathione and catalase were examined in the liver cells of experimental mice treated by aerobic exercise. Expression levels and activity of extracellular signal‑regulated kinases (ERK) and AMP‑activated protein kinase (AMPK) signaling pathways were investigated in the liver cells of mouse models of type‑ІІ diabetes mellitus after undergoing aerobic exercise. Aerobic exercise decreased the expression levels of inflammatory factors in the serum of mouse models of type‑ІІ diabetes mellitus. The results indicated that aerobic exercise downregulated oxidative stress indicators in liver cells from mouse models of type‑ІІ diabetes mellitus. In addition, the ERK and AMPK signaling pathways were inactivated by aerobic exercise in liver cells in mouse models of type‑ІІ diabetes mellitus. The activity of ERK and AMPK, and the function of islet β‑cells were observed to be improved in experimental mice treated with aerobic exercise. Furthermore, blood lipid metabolism and insulin resistance were improved by treatment with aerobic exercise. Body weight and glucose concentration of serology was markedly improved in mouse models of type‑ІІ diabetes mellitus. Furthermore, TLR‑4 inhibition markedly promoted ERK and AMPK expression levels and activity. Thus, these results indicate that aerobic exercise may improve blood lipid metabolism, insulin resistance and glucose plasma concentration in mouse models of type‑ІІ diabetes mellitus. Thus indicating aerobic exercise is beneficial for improvement of blood lipid and insulin resistance via the TLR‑4‑mediated ERK/AMPK signaling pathway in the progression of type‑ІІ diabetes mellitus.

Greenhouse-gas exchange of croplands worldwide: a process-based model simulation

NASA Astrophysics Data System (ADS)

Inatomi, M.; Ito, A.

2009-12-01

Croplands cover about 15% of the land surface, and play unique roles in global biogeochemical cycles. Especially, greenhouse gas budget of croplands is important for climate projection in the future and for mitigation toward climate stabilization. Sustainable cropland is carbon-neutral (i.e., neither a sink nor a source of CO2 for a long time), but those in developed countries consume fossil fuels for agricultural operations and releases CO2 as revealed by LCAs. Paddy field is one of the substantial sources of CH4, and cropland may be the largest anthropogenic source of N2O. However, these features have not been evaluated and discussed using a spatial-explicit comprehensive framework at the global scale. This study applies a process-based terrestrial ecosystem model (VISIT) to worldwide croplands. Exchange of CO2 is simulated as a difference between photosynthesis and respiration, each of which is calculated in a biogeochemical carbon cycle scheme. Net carbon budget accounts for carbon flows by planting, compost input, and harvest. Exchange of CH4 is simulated as a difference between oxidation by aerobic soils and production by anaerobic soils, each of which is calculated using mechanistic schemes. Emission of N2O from nitrification and denitrification is simulated with a semi-mechanistic scheme on the basis of leaky-pipe concept. We are also validating the model through comparison with chamber and tower flux measurements. Global simulations were conducted during a period from 1901 to 2100 on the basis of historical and projected climate and land-use conditions, at a spatial resolution of 0.5 x 0.5 degree. Cropland type and distribution was derived from SAGE-HYDE dataset and country-base fertilizer input was obtained from FAOSTAT. Our preliminary simulation for the 1990s estimated that croplands are a net sink of CO2 by 1.1 Gt C/yr; this sink is offset by emission by food consumption. Paddy fields are estimated to release CH4 by 46 Tg CH4/yr, and croplands worldwide release N2O by 5.9 Tg N2O/yr. Because of high Global Warming Potential of CH4 (25 for 100-yr) and N2O (298), these results imply that agriculture is a net source of radiative forcing for the atmosphere. Additionally, recent studies show that N2O is the most important substance for stratospheric ozone depletion. Therefore, further studies are needed to improve quantification of greenhouse gas budget in croplands and to design mitigation strategy.

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

PubMed

Trivedi, Suverna; Prasad, Ram

2018-03-01

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

Anaerobic consumers of monosaccharides in a moderately acidic fen.

PubMed

Hamberger, Alexandra; Horn, Marcus A; Dumont, Marc G; Murrell, J Colin; Drake, Harold L

2008-05-01

16S rRNA-based stable isotope probing identified active xylose- and glucose-fermenting Bacteria and active Archaea, including methanogens, in anoxic slurries of material obtained from a moderately acidic, CH(4)-emitting fen. Xylose and glucose were converted to fatty acids, CO(2), H(2), and CH(4) under moderately acidic, anoxic conditions, indicating that the fen harbors moderately acid-tolerant xylose- and glucose-using fermenters, as well as moderately acid-tolerant methanogens. Organisms of the families Acidaminococcaceae, Aeromonadaceae, Clostridiaceae, Enterobacteriaceae, and Pseudomonadaceae and the order Actinomycetales, including hitherto unknown organisms, utilized xylose- or glucose-derived carbon, suggesting that highly diverse facultative aerobes and obligate anaerobes contribute to the flow of carbon in the fen under anoxic conditions. Uncultured Euryarchaeota (i.e., Methanosarcinaceae and Methanobacteriaceae) and Crenarchaeota species were identified by 16S rRNA analysis of anoxic slurries, demonstrating that the acidic fen harbors novel methanogens and Crenarchaeota organisms capable of anaerobiosis. Fermentation-derived molecules are conceived to be the primary drivers of methanogenesis when electron acceptors other than CO(2) are absent, and the collective findings of this study indicate that fen soils harbor diverse, acid-tolerant, and novel xylose-utilizing as well as glucose-utilizing facultative aerobes and obligate anaerobes that form trophic links to novel moderately acid-tolerant methanogens.

Energy Conservation at the West Dover, Vermont, Water Pollution Control Facility.

DTIC Science & Technology

1982-11-01

chlorination of oxidation ditch effluent ---- 8 Discontinue aerobic digestion --------------------------- 8 Discharge contents of holding pond into...Immediate Discontinue aerobic digestion Instead of aerobically digesting the waste activated sludge, it may be possible to mix it directly with pond...elimi- nated by replacing the oxidation ditches with facultative ponds. Also, this would eliminate the need for aerobic digestion , in-plant process water

Multistage treatment system for raw leachate from sanitary landfill combining biological nitrification-denitrification/solar photo-Fenton/biological processes, at a scale close to industrial--biodegradability enhancement and evolution profile of trace pollutants.

PubMed

Silva, Tânia F C V; Silva, M Elisabete F; Cunha-Queda, A Cristina; Fonseca, Amélia; Saraiva, Isabel; Sousa, M A; Gonçalves, C; Alpendurada, M F; Boaventura, Rui A R; Vilar, Vítor J P

2013-10-15

A multistage treatment system, at a scale close to the industrial, was designed for the treatment of a mature raw landfill leachate, including: a) an activated sludge biological oxidation (ASBO), under aerobic and anoxic conditions; b) a solar photo-Fenton process, enhancing the bio-treated leachate biodegradability, with and without sludge removal after acidification; and c) a final polishing step, with further ASBO. The raw leachate was characterized by a high concentration of humic substances (HS) (1211 mg CHS/L), representing 39% of the dissolved organic carbon (DOC) content, and a high nitrogen content, mainly in the form of ammonium nitrogen (>3.8 g NH4(+)-N/L). In the first biological oxidation step, a 95% removal of total nitrogen and a 39% mineralization in terms of DOC were achieved, remaining only the recalcitrant fraction, mainly attributed to HS (57% of DOC). Under aerobic conditions, the highest nitrification rate obtained was 8.2 mg NH4(+)-N/h/g of volatile suspended solids (VSS), and under anoxic conditions, the maximum denitrification rate obtained was 5.8 mg (NO2(-)-N + NO3(-)-N)/h/g VSS, with a C/N consumption ratio of 2.4 mg CH3OH/mg (NO2(-)-N + NO3(-)-N). The precipitation of humic acids (37% of HS) after acidification of the bio-treated leachate corresponds to a 96% DOC abatement. The amount of UV energy and H2O2 consumption during the photo-Fenton reaction was 30% higher in the experiment without sludge removal and, consequently, the reaction velocity was 30% lower. The phototreatment process led to the depletion of HS >80%, of low-molecular-weight carboxylate anions >70% and other organic micropollutants, thus resulting in a total biodegradability increase of >70%. The second biological oxidation allowed to obtain a final treated leachate in compliance with legal discharge limits regarding water bodies (with the exception of sulfate ions), considering the experiment without sludge. Finally, the high efficiency of the overall treatment process was further reinforced by the total removal percentages attained for the identified organic trace contaminants (>90%). Copyright © 2013 Elsevier Ltd. All rights reserved.

Antibacterial Efficacy of Several Surgical Hand Preparation Products Used by Veterinary Students.

PubMed

Chou, Po-Yen; Doyle, Aimie J; Arai, Shiori; Burke, Pierre J; Bailey, Trina R

2016-05-01

To compare the antibacterial efficacy of different surgical hand antisepsis protocols used by veterinary students. Prospective, randomized, controlled study. Third year veterinary students (n=45). The participants were randomly assigned to 4 of the following 12 hand preparation product/time combinations: nonabrasive hand scrub method with 4% chlorhexidine gluconate (CH); hand rub with a mixture of 30% 1-propanol and 45% 2-propanol solution (MPS), 70% 2-propanol solution (IPS), or 61% ethanol solution with 1% chlorhexidine gluconate (ES/CH), with a contact time of 1.5, 3, or 5 minutes. Antibacterial efficacy was assessed after surgical hand preparation and at the end of surgery. Log reductions of total bacterial colony forming unit (CFU)/mL and positive aerobic culture rates were compared using multivariable analysis of variance and multivariable logistic regression, respectively. After surgical hand preparation, CH and ES/CH provided significantly higher log CFU reduction and lower positive culture rate for Gram-positive and spore-forming bacteria compared to MPS and IPS. Increase in contact time did not provide significant improvement in bacterial reduction. At the end of surgery, ES/CH provided significantly higher log CFU reduction compared to IPS and lower positive culture rate for Gram-positive bacteria compared to CH, MPS, and IPS. Increase in contact time significantly improved log CFU reduction in ES/CH and MPS groups. In our population of veterinary students ES/CH hand rubs or CH scrubs were more effective in reducing bacterial CFU during surgical hand preparation than MPS or IPS. © Copyright 2016 by The American College of Veterinary Surgeons.

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

USGS Publications Warehouse

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

1998-01-01

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

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

NASA Astrophysics Data System (ADS)

Liebner, Susanne; Zeyer, Josef; Knoblauch, Christian

2010-05-01

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

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

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

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

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

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

DOE PAGES

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

2017-07-03

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

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

PubMed

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

2010-08-01

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

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

PubMed

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

2015-10-16

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

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

PubMed

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

2014-05-07

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

Methane Cycling in a Warming Wetland

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Combined effect of cooking (grilling and roasting) and chilling storage (with and without air) on lipid and cholesterol oxidation in chicken breast.

PubMed

Conchillo, Ana; Ansorena, Diana; Astiasarán, Iciar

2003-05-01

The oxidation of the lipid fraction and cholesterol in raw and cooked chicken breast samples stored for 0 and 6 days at 4 degrees C under aerobic conditions and in vacuum packaging was studied. The multivariate statistical analysis showed significant effects of both culinary process and storage conditions on the lipid and cholesterol oxidation process, with a significant interaction between the two variables. Aerobic storage increased thiobarbituric acid reactive substances (TBA) from 0.04 to 0.06 ppm for raw samples, from 0.21 to 1.20 ppm for grilled samples, and from 0.24 to 1.62 ppm for roasted samples. During vacuum storage, only roasted samples showed significant increases in TBA. Levels of total cholesterol oxidation products (COP) remained low (2.88 to 4.35 microg/g of lipid) for all raw samples. Cooking increased COP levels to 12.85 and 11.54 microg/ g of lipid for grilled and roasted samples, respectively. Total COP and all individual COP except for cholestanetriol were significantly correlated with TBA and the peroxide index. However, the most extensive effect was attributable to the aerobic storage of cooked samples, which led to COP levels of 92.35 and 88.60 microg/g of lipid in grilled and roasted samples, respectively. Vacuum packaging did not increase COP levels for cooked samples.

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

PubMed

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

2007-05-17

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

C-11 cyanide production system

DOEpatents

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

2015-01-13

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

C-11 cyanide production system

DOEpatents

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

2017-11-21

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

Effect of biomass concentration on methane oxidation activity using mature compost and graphite granules as substrata.

PubMed

Xie, S; O'Dwyer, T; Freguia, S; Pikaar, I; Clarke, W P

2016-10-01

Reported methane oxidation activity (MOA) varies widely for common landfill cover materials. Variation is expected due to differences in surface area, the composition of the substratum and culturing conditions. MOA per methanotrophic cell has been calculated in the study of natural systems such as lake sediments to examine the inherent conditions for methanotrophic activity. In this study, biomass normalised MOA (i.e., MOA per methanotophic cell) was measured on stabilised compost, a commonly used cover in landfills, and on graphite granules, an inert substratum widely used in microbial electrosynthesis studies. After initially enriching methanotrophs on both substrata, biomass normalised MOA was quantified under excess oxygen and limiting methane conditions in 160ml serum vials on both substrata and blends of the substrata. Biomass concentration was measured using the bicinchoninic acid assay for microbial protein. The biomass normalised MOA was consistent across all compost-to-graphite granules blends, but varied with time, reflecting the growth phase of the microorganisms. The biomass normalised MOA ranged from 0.069±0.006μmol CH4/mg dry biomass/h during active growth, to 0.024±0.001μmol CH4/mg dry biomass/h for established biofilms regardless of the substrata employed, indicating the substrata were equally effective in terms of inherent composition. The correlation of MOA with biomass is consistent with studies on methanotrophic activity in natural systems, but biomass normalised MOA varies by over 5 orders of magnitude between studies. This is partially due to different methods being used to quantify biomass, such as pmoA gene quantification and the culture dependent Most Probable Number method, but also indicates that long term exposure of materials to a supply of methane in an aerobic environment, as can occur in natural systems, leads to the enrichment and adaptation of types suitable for those conditions. Copyright © 2016 Elsevier Ltd. All rights reserved.

Modeling greenhouse gas emissions from dairy farms

USDA-ARS?s Scientific Manuscript database

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

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

PubMed Central

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

2010-01-01

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

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

NASA Astrophysics Data System (ADS)

Berrittella, C.; van Huissteden, J.

2011-10-01

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

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

Observations and modeling of methane flux in northern wetlands

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Abundances of ethylene oxide and acetaldehyde in hot molecular cloud cores

NASA Technical Reports Server (NTRS)

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

1998-01-01

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

Room temperature aerobic oxidation of amines by a nanocrystalline ruthenium oxide pyrochlore nafion composite catalyst.

PubMed

Venkatesan, Shanmuganathan; Kumar, Annamalai Senthil; Lee, Jyh-Fu; Chan, Ting-Shan; Zen, Jyh-Myng

2012-05-14

The aerobic oxidation of primary amines to their respective nitriles has been carried out at room temperature using a highly reusable nanocrystalline ruthenium oxide pyrochlore Nafion composite catalyst (see figure). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

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

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

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

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

DOE PAGES

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

2017-06-13

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

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

NASA Astrophysics Data System (ADS)

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

2015-04-01

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

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

NASA Astrophysics Data System (ADS)

Thompson, Rona; Nisbet, Euan

2017-04-01

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

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

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

Gulledge, J.; Schimel, J.P.

1998-11-01

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

o-Naphthoquinone-Catalyzed Aerobic Oxidation of Amines to (Ket)imines: A Modular Catalyst Approach.

PubMed

Goriya, Yogesh; Kim, Hun Young; Oh, Kyungsoo

2016-10-07

A modular aerobic oxidation of amines to imines has been achieved using an ortho-naphthoquinone (o-NQ) catalyst. The cooperative catalyst system of o-NQ and Cu(OAc) 2 enabled the formation of homocoupled imines from benzylamines, while the presence of TFA helped the formation of cross-coupled imines in excellent yields. The current mild aerobic oxidation protocol could also be applied to the oxidation of secondary amines to imines or ketimines with the help of cocatalyst, Ag 2 CO 3 , with excellent yields.

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

PubMed

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

2012-11-16

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

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

PubMed

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

2018-05-31

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

Community Structure of Active Aerobic Methanotrophs in Red Mangrove (Kandelia obovata) Soils Under Different Frequency of Tides.

PubMed

Shiau, Yo-Jin; Cai, Yuanfeng; Lin, Yu-Te; Jia, Zhongjun; Chiu, Chih-Yu

2018-04-01

Methanotrophs are important microbial communities in coastal ecosystems. They reduce CH 4 emission in situ, which is influenced by soil conditions. This study aimed to understand the differences in active aerobic methanotrophic communities in mangrove forest soils experiencing different inundation frequency, i.e., in soils from tidal mangroves, distributed at lower elevations, and from dwarf mangroves, distributed at higher elevations. Labeling of pmoA gene of active methanotrophs using DNA-based stable isotope probing (DNA-SIP) revealed that methanotrophic activity was higher in the dwarf mangrove soils than in the tidal mangrove soils, possibly because of the more aerobic soil conditions. Methanotrophs affiliated with the cluster deep-sea-5 belonging to type Ib methanotrophs were the most dominant methanotrophs in the fresh mangrove soils, whereas type II methanotrophs also appeared in the fresh dwarf mangrove soils. Furthermore, Methylobacter and Methylosarcina were the most important active methanotrophs in the dwarf mangrove soils, whereas Methylomonas and Methylosarcina were more active in the tidal mangrove soils. High-throughput sequencing of the 16S ribosomal RNA (rRNA) gene also confirmed similar differences in methanotrophic communities at the different locations. However, several unclassified methanotrophic bacteria were found by 16S rRNA MiSeq sequencing in both fresh and incubated mangrove soils, implying that methanotrophic communities in mangrove forests may significantly differ from the methanotrophic communities documented in previous studies. Overall, this study showed the feasibility of 13 CH 4 DNA-SIP to study the active methanotrophic communities in mangrove forest soils and revealed differences in the methanotrophic community structure between coastal mangrove forests experiencing different tide frequencies.

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

PubMed

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

2009-02-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

A factorial randomized controlled trial to evaluate the effect of micronutrients supplementation and regular aerobic exercise on maternal endothelium-dependent vasodilatation and oxidative stress of the newborn.

PubMed

Ramírez-Vélez, Robinson; Romero, Miryam; Echeverri, Isabella; Ortega, José Guillermo; Mosquera, Mildrey; Salazar, Blanca; Girón, Sandra Lorena; Saldarriaga, Wilmar; Aguilar de Plata, Ana Cecilia; Mateus, Julio Cesar

2011-02-28

Many studies have suggested a relationship between metabolic abnormalities and impaired fetal growth with the development of non-transmissible chronic diseases in the adulthood. Moreover, it has been proposed that maternal factors such as endothelial function and oxidative stress are key mechanisms of both fetal metabolic alterations and subsequent development of non-transmissible chronic diseases. The objective of this project is to evaluate the effect of micronutrient supplementation and regular aerobic exercise on endothelium-dependent vasodilation maternal and stress oxidative of the newborn. 320 pregnant women attending to usual prenatal care in Cali, Colombia will be included in a factorial randomized controlled trial. Women will be assigned to the following intervention groups: 1. usual prenatal care (PC) and placebo (maltodextrine). 2. Exercise group: PC, placebo and aerobic physical exercise. 3. Micronutrients group: PC and a micronutrients capsule consisting of zinc (30 mg), selenium (70 μg), vitamin A (400 μg), alphatocopherol (30 mg), vitamin C (200 mg), and niacin (100 mg). 4. Combined interventions Group: PC, supplementation of micronutrients, and aerobic physical exercise. Anthropometric measures will be taken at the start and at the end of the interventions. Since in previous studies has been showed that the maternal endothelial function and oxidative stress are related to oxidative stress of the newborn, this study proposes that complementation with micronutrients during pregnancy and/or regular physical exercise can be an early and innovative alternative to strengthen the prevention of chronic diseases in the population. NCT00872365.

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Trp64Arg polymorphism in beta3-adrenergic receptor gene is associated with decreased fat oxidation both in resting and aerobic exercise in the Japanese male.

PubMed

Morita, Emiko; Taniguchi, Hiroshi; Sakaue, Motoyoshi

2009-01-01

The purpose of our study was to investigate whether the Trp64Arg polymorphism in beta3-AR gene and the -3826A/G polymorphism in the UCP1 gene were associated with the reduction in energy expenditure and fat oxidation both in resting and aerobic exercise in Japanese. Eighty-six nonobese young healthy Japanese were recruited. Energy expenditure was measured using indirect calorimetry. The subjects performed an aerobic exercise program at 60% of their maximal heart rate for 30 minutes. The level of fat oxidation at rest and aerobic exercise of the male subjects with Trp/Arg of the beta3-AR gene was significantly lower than that of the Trp/Trp genotype. No difference in FO(0-30) was observed in the female subjects. There was no association between UCP-1 polymorphism and energy expenditure during aerobic exercise. It was revealed that the Trp64Arg polymorphism in beta3-AR gene is associated with reduction of fat oxidation both in resting and aerobic exercise in healthy, young Japanese males.

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

NASA Technical Reports Server (NTRS)

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

2015-01-01

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

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

PubMed

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

2004-12-01

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

Evaluation of biochar powder on oxygen supply efficiency and global warming potential during mainstream large-scale aerobic composting.

PubMed

He, Xueqin; Chen, Longjian; Han, Lujia; Liu, Ning; Cui, Ruxiu; Yin, Hongjie; Huang, Guangqun

2017-12-01

This study investigated the effects of biochar powder on oxygen supply efficiency and global warming potential (GWP) in the large-scale aerobic composting pattern which includes cyclical forced-turning with aeration at the bottom of composting tanks in China. A 55-day large-scale aerobic composting experiment was conducted in two different groups without and with 10% biochar powder addition (by weight). The results show that biochar powder improves the holding ability of oxygen, and the duration time (O 2 >5%) is around 80%. The composting process with above pattern significantly reduce CH 4 and N 2 O emissions compared to the static or turning-only styles. Considering the average GWP of the BC group was 19.82% lower than that of the CK group, it suggests that rational addition of biochar powder has the potential to reduce the energy consumption of turning, improve effectiveness of the oxygen supply, and reduce comprehensive greenhouse effects. Copyright © 2017. Published by Elsevier Ltd.

Enhanced erythrocyte antioxidant status following an 8-week aerobic exercise training program in heavy drinkers.

PubMed

Georgakouli, Kalliopi; Manthou, Eirini; Fatouros, Ioannis G; Georgoulias, Panagiotis; Deli, Chariklia K; Koutedakis, Yiannis; Theodorakis, Yannis; Jamurtas, Athanasios Z

2018-06-01

Alcohol-induced oxidative stress is involved in the development and progression of various pathological conditions and diseases. On the other hand, exercise training has been shown to improve redox status, thus attenuating oxidative stress-associated disease processes. The purpose of the present study was to evaluate the effect of an exercise training program that has been previously reported to decrease alcohol consumption on blood redox status in heavy drinkers. In a non-randomized within-subject design, 11 sedentary, heavily drinking men (age: 30.3 ± 3.5 years; BMI: 28.4 ± 0.86 kg/m 2 ) participated first in a control condition for 4 weeks, and then in an intervention where they completed an 8-week supervised aerobic training program of moderate intensity (50-60% of the heart rate reserve). Blood samples were collected in the control condition (pre-, post-control) as well as before, during (week 4 of the training program), and after intervention (week 8 of the training program). Samples were analyzed for total antioxidant capacity (TAC), thiobarbituric acid reactive substances (TBARS), protein carbonyls (PC), uric acid (UA), bilirubin, reduced glutathione (GSH), and catalase activity. No significant change in indices of redox status in the pre- and post-control was observed. Catalase activity increased (p < 0.05) after 8 weeks of intervention compared to week 4. GSH increased (p < 0.05) after 8 weeks of intervention compared to the control condition and to week 4 of intervention. TAC, UA, bilirubin, TBARS, and PC did not significantly change at any time point. Moreover, concentrations of GSH, TBARS, and catalase activity negatively correlated with alcohol consumption. In conclusion, an 8-week aerobic training program enhanced erythrocyte antioxidant status in heavy drinkers, indicating that aerobic training may attenuate pathological processes caused by alcohol-induced oxidative stress. Copyright © 2017 Elsevier Inc. All rights reserved.

Revealing the halide effect on the kinetics of the aerobic oxidation of Cu(I) to Cu(II)

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

Deng, Yi; Zhang, Guanghui; Qi, Xiaotian

2015-01-01

In situ infrared (IR) and X-ray absorption near-edge structure (XANES) spectroscopic investigations reveal that different halide ligands have distinct effects on the aerobic oxidation of Cu(I) to Cu(II) in the presence of TMEDA (tetramethylethylenediamine). The iodide ligand gives the lowest rate and thus leads to the lowest catalytic reaction rate of aerobic oxidation of hydroquinone to benzoquinone. Further DFT calculations suggest that oxidation of CuI–TMEDA involves a side-on transition state, while oxidation of CuCl–TMEDA involves an end-on transition state which has a lower activation energy.

Effect of aerobic exercise intervention on DDT degradation and oxidative stress in rats.

PubMed

Li, Kefeng; Zhu, Xiaohua; Wang, Yuzhan; Zheng, Shuqian; Dong, Guijun

2017-03-01

Dichlorodiphenyltrichloroethane (DDT) reportedly causes extensively acute or chronic effects to human health. Exercise can generate positive stress. We evaluated the effect of aerobic exercise on DDT degradation and oxidative stress. Male Wistar rats were randomly assigned into control (C), DDT without exercise training (D), and DDT plus exercise training (DE) groups. The rats were treated as follows: DDT exposure to D and DE groups at the first 2 weeks; aerobic exercise treatment only to the DE group from the 1st day until the rats are killed. DDT levels in excrements, muscle, liver, serum, and hearts were analyzed. Superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GSH-Px), and malondialdehyde (MDA) levels were determined. Aerobic exercise accelerated the degradation of DDT primarily to DDE due to better oxygen availability and aerobic condition and promoted the degradation of DDT. Cumulative oxidative damage of DDT and exercise led to significant decrease of SOD level. Exercise resulted in consistent increase in SOD activity. Aerobic exercise enhanced activities of CAT and GSH-Px and promoted MDA scavenging. Results suggested that exercise can accelerate adaptive responses to oxidative stress and activate antioxidant enzymes activities. Exercise can also facilitate the reduction of DDT-induced oxidative damage and promoted DDT degradation. This study strongly implicated the positive effect of exercise training on DDT-induced liver oxidative stress.

Endurance exercise, plasma oxidation and cardiovascular risk.

PubMed

Sharman, James E; Geraghty, Dominic P; Shing, Cecilia M; Fraser, David I; Coombes, Jeff S

2004-12-01

Although physical activity is beneficial to health, people who exercise at high intensities throughout their lifetime may have increased cardiovascular risk. Aerobic exercise increases oxidative stress and may contribute to atherogenesis by augmented oxidation of plasma lipoproteins. The aim of this study was to examine the relationship between aerobic power and markers of oxidative stress, including the susceptibility of plasma to oxidation. Aerobic power was measured in 24 healthy men aged 29+/-9 years (mean+/-SD). Plasma was analysed from subjects of high aerobic power (HAP; VO2max, 64.6+/-6.1 ml/kg/min) and lower aerobic power (LAP;VO2max, 45.1+/-6.3 ml/kg/min) for total antioxidant capacity (TAC), malondialdehyde (MDA) and susceptibility to oxidation. Three measures were used to quantify plasma oxidizability: (1) lag time to conjugated diene formation (lag time); (2) change in absorbance at 234 nm and; (3) slope of the oxidation curve during propagation (slope). The HAP subjects had significantly lower TAC (1.38+/-0.04 versus 1.42+/-0.06 TEAC units; P < 0.05), significantly higher change in absorbance (1.55+/-0.21 versus 1.36+/-0.17 arbitrary units; P < 0.05), but no difference in MDA (P = 0.6), compared to LAP subjects. There was a significant inverse association between TAC and slope (r = -0.49; P < 0.05). Lipoprotein profiles and daily intake of nutrients did not differ between the groups. These findings suggest that people with high aerobic power, due to extreme endurance exercise, have plasma with decreased antioxidant capacity and higher susceptibility to oxidation, which may increase their cardiovascular risk.

The biogeochemical vertical structure renders a meromictic volcanic lake a trap for geogenic CO2 (Lake Averno, Italy)

PubMed Central

Fazi, Stefano; Rossetti, Simona; Pratesi, Paolo; Ceccotti, Marco; Cabassi, Jacopo; Capecchiacci, Francesco; Venturi, Stefania; Vaselli, Orlando

2018-01-01

Volcanic lakes are characterized by physicochemical favorable conditions for the development of reservoirs of C-bearing greenhouse gases that can be dispersed to air during occasional rollover events. By combining a microbiological and geochemical approach, we showed that the chemistry of the CO2- and CH4-rich gas reservoir hosted within the meromictic Lake Averno (Campi Flegrei, southern Italy) are related to the microbial niche differentiation along the vertical water column. The simultaneous occurrence of diverse functional groups of microbes operating under different conditions suggests that these habitats harbor complex microbial consortia that impact on the production and consumption of greenhouse gases. In the epilimnion, the activity of aerobic methanotrophic bacteria and photosynthetic biota, together with CO2 dissolution at relatively high pH, enhanced CO2- and CH4 consumption, which also occurred in the hypolimnion. Moreover, results from computations carried out to evaluate the dependence of the lake stability on the CO2/CH4 ratios, suggested that the water density vertical gradient was mainly controlled by salinity and temperature, whereas the effect of dissolved gases was minor, excepting if extremely high increases of CH4 are admitted. Therefore, biological processes, controlling the composition of CO2 and CH4, contributed to stabilize the lake stratification of the lake. Overall, Lake Averno, and supposedly the numerous worldwide distributed volcanic lakes having similar features (namely bio-activity lakes), acts as a sink for the CO2 supplied from the hydrothermal/magmatic system, displaying a significant influence on the local carbon budget. PMID:29509779

[Physiological and biochemical analysis of the transformants of aerobic methylobacteria expressing the dcm A gene of dichloromethane dehydrogenase].

PubMed

Firsova, Iu E; Doronina, N V; Trotsenko, Iu A

2004-01-01

The transformants of Methylobacterium dichloromethanicum DM4 (DM4-2cr-/pME8220 and DM4-2cr-/pME8221) and of Methylobacterium extorquens AM1 (AM1/pME8220 and AM1/pME8221) that express the dcm A gene of dichloromethane dehalogenase undergo lysis when incubated in the presence of dichloromethane and are sensitive to acidic shock. The lysis of the transformants was found to be related neither to the accumulation of Cl- ions, CH2O, and HCOOH, nor to the impairment of glutathione synthesis or to the maintenance of intracellular pH. The (exo-) Klenow fragment-mediated incorporation of [alpha-32P]dATP into the DNA of the transformants DM4-2cr-/pME8220 and AM1/pME8220 was considerably greater when the transformed cells were incubated with CH2Cl2 than when they were incubated with CH3OH, indicating the occurrence of a significant increase in the total length of gaps. At the same time, the strain AM1 (which lacks dichloromethane dehalogenase) and the dichloromethane-degrading strain DM4 incubated with CH2Cl2 showed an insignificant increase in the total length of the gaps. The transformed cells are likely to lyse due to the relatively inefficient repair of DNA lesions that are induced in response to the alkylating action of S-chloromethylglutathione, an intermediate product of CH2Cl2 degradation. The data obtained suggest that the bacterial mineralization of dichloromethane requires an efficient DNA repair system.

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

PubMed Central

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

2015-01-01

SnO2 has been studied intensely for applications to sensors, Li-ion batteries and solar cells. Despite this, comparatively little attention has been paid to the changes in morphology and crystal phase that occur on the metal oxide surface during chemical reactions. This paper reports anaerobic and aerobic ethanol and CO oxidation reactions over SnO2 nanoparticles (NPs), as well as the subsequent changes in the nature of the NPs. Uniform SnO2@C core-shells (10 nm) were formed by an aerobic ethanol oxidation reaction over SnO2 NPs. On the other hand, metallic Sn spheres were produced by an anaerobic ethanol oxidation reaction at 450 °C, which is significantly lower than that (1200 °C) used in industrial Sn production. Anaerobic and aerobic CO oxidation reactions were also examined. The novelty of the methods for the production of metallic Sn and SnO2@C core-shells including other anaerobic and aerobic reactions will contribute significantly to Sn and SnO2-based applications. PMID:26300041

Azobisisobutyronitrile initiated aerobic oxidative transformation of amines: coupling of primary amines and cyanation of tertiary amines.

PubMed

Liu, Lianghui; Wang, Zikuan; Fu, Xuefeng; Yan, Chun-Hua

2012-11-16

In the presence of a catalytic amount of radical initiator AIBN, primary amines are oxidatively coupled to imines and tertiary amines are cyanated to α-aminonitriles. These "metal-free" aerobic oxidative coupling reactions may find applications in a wide range of "green" oxidation chemistry.

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

USGS Publications Warehouse

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

2014-01-01

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

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

USDA-ARS?s Scientific Manuscript database

Methane (CH4) and nitrous oxide (N2O) are potent greenhouse gases; their concentrations in the atmosphere have increased because of human activity. Soils are important sources and sinks of both gases where their production and consumption are largely regulated by biological processes. Climate change...

Diurnal variation in greenhouse fluxes from a feedyard pen surface

USDA-ARS?s Scientific Manuscript database

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

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

NASA Astrophysics Data System (ADS)

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

2015-04-01

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

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

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

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

1996-03-01

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

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

NASA Astrophysics Data System (ADS)

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

2015-01-01

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

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

PubMed

Asatryan, Rubik; Bozzelli, Joseph W

2008-04-07

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

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

NASA Technical Reports Server (NTRS)

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

1989-01-01

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

Enzymatic properties of the membrane-bound NADH oxidase system in the aerobic respiratory chain of Bacillus cereus.

PubMed

Kim, Man Suk; Kim, Young Jae

2004-11-30

Membranes prepared from Bacillus cereus KCTC 3674, grown aerobically on a complex medium, oxidized NADH exclusively, whereas deamino-NADH was little oxidized. The respiratory chain-linked NADH oxidase exhibited an apparent K(m) value of approximately 65 microM for NADH. The maximum activity of the NADH oxidase was obtained at about pH 8.5 in the presence of 0.1 M KCl (or NaCl). Respiratory chain inhibitor 2-heptyl-4-hydroxyquinoline-N-oxide (HQNO) inhibited the activity of the NADH oxidase by about 90% at a concentration of 40 microM. Interestingly, rotenone and capsaicin inhibited the activity of the NADH oxidase by about 60% at a concentration of 40 microM and the activity was also highly sensitive to Ag(+).

Evolution of stable carbon-isotope compositions for methane and carbon dioxide in freshwater wetlands and other anaerobic environments

NASA Astrophysics Data System (ADS)

Hornibrook, Edward R. C.; Longstaffe, Frederick J.; Fyfe, William S.

2000-03-01

Two types of distribution for α C values are observed in anaerobic environments when δ 13C-ΣCO 2 and δ 13C-CH 4 values are measured across gradients of depth or age of organic debris. The type-I distribution involves a systematic increase in α C values with depth as a result of decreasing δ 13C-CH 4 and increasing δ 13C-ΣCO 2 values. This behavior corresponds to a progressive increase in the prevalence of methanogenesis by the CO 2 reduction pathway relative to acetate fermentation. Utilization of autotrophically formed acetate by methanogens would also cause an increase in α C values. The type-II distribution occurs when both δ 13C-CH 4 and δ 13C-ΣCO 2 values decrease with depth, resulting in approximately constant α C values. This condition corresponds with a strong dependence of methanogens on porewater ΣCO 2 as a carbon source by way of either the CO 2 reduction pathway or utilization of autotrophically formed acetate. Freshwater wetlands possess both types of α C value distribution. Wetlands with type-I distributions exhibit curves with slopes that vary probably as a function of deposition and preservation of labile organic carbon. An abundance of labile substrates in anaerobic soils yields steeper curves because aceticlastic methanogenesis predominates and δ 13C-CH 4 and δ 13C-CO 2 values are high. Diminished transfer of labile carbon to the methanogenic zone results in an increased prevalence of the CO 2 reduction pathway, yielding low δ 13C-CH 4 values and shallowly sloping curves. Aerobic oxidation of organic matter or decay involving sulfate reduction produces CO 2 with low δ 13C values, which also will contribute to shallowly sloping curves. The size of the dissolved CO 2 pool can influence the sensitivity of δ 13C-CO 2 values to change during methanogenesis. Regression curves of δ 13C-CH 4 and δ 13C-ΣCO 2 values from four wetlands with type-I distributions intersect at δ 13C-CH 4 = -40.7 ± 6.1‰ (1σ) and δ 13C-ΣCO 2 = -23.9 ± 4.8‰ (1σ). These values are similar to δ 13C values for methyl and carboxyl moieties within acetate produced by anaerobic degradation of fresh C 3 plant matter. A low abundance of acetate during aceticlastic methanogenesis will result in minimal expression of metabolic kinetic isotope effects (KIEs) and production of CH 4 and CO 2 with δ 13C values similar to the intramolecular distribution of sedimentary acetate. The type-II distribution is prevalent in marine environments, probably because of substrate depletion in the sulfate reduction zone. The type-I distribution does occur in marine settings where deposition rates of organic matter are high. Landfills possess only the type-I distribution of α C values and exhibit unusually steep curves, possibly because methanogenesis occurs predominantly from acetate produced by fermentation at mesophilic temperatures. The high abundance of acetate in landfill leachate may permit varying degrees of expression of the KIE associated with aceticlastic methanogenesis. Outgassing of 12CO 2 may contribute further to the steepening of α C curves in landfills and other anaerobic environments possessing a type-I distribution. Defining the type of α C distributions in different wetlands could reduce uncertainty in estimating the δ 13C value of CH 4 emissions. Hence, the prevalence of type-I vs. type-II α C distributions in wetlands may have practical importance for the refinement of global CH 4 budgets that rely on 13C/ 12C ratios for mass balance.

Consumption of atmospheric methane by desert soils

USGS Publications Warehouse

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

1992-01-01

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

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

PubMed

Castaldi, Simona; Tedesco, Dario

2005-01-01

Methane fluxes were measured, using closed chambers, in the Crater of Solfatara volcano, Campi Flegrei (Southern Italy), along eight transects covering areas of the crater presenting different landscape physiognomies. These included open bare areas, presenting high geothermal fluxes, and areas covered by vegetation, which developed along a gradient from the central open area outwards, in the form of maquis, grassland and woodland. Methane fluxes decreased logarithmically (from 150 to -4.5 mg CH4 m(-2)day(-1)) going from the central part of the crater (fangaia) to the forested edges, similarly to the CO2 fluxes (from 1500 g CO2 m(-2)day(-1) in the centre of the crater to almost zero flux in the woodlands). In areas characterized by high emissions, soil presented elevated temperature (up to 70 degrees C at 0-10 cm depth) and extremely low pH (down to 1.8). Conversely, in woodland areas pH was higher (between 3.7 and 5.1) and soil temperature close to air values. Soil (0-10 cm) was sampled, in two different occasions, along the eight transects, and was tested for methane oxidation capacity in laboratory. Areas covered by vegetation mostly consumed CH4 in the following order woodland>macchia>grassland. Methanotrophic activity was also measured in soil from the open bare area. Oxidation rates were comparable to those measured in the plant covered areas and were significantly correlated with field CH4 emissions. The biological mechanism of uptake was demonstrated by the absence of activity in autoclaved replicates. Thus results suggest the existence of a population of micro-organisms adapted to this extreme environment, which are able to oxidize CH4 and whose activity could be stimulated and supported by elevated concentrations of CH4.

Formaldehyde activation factor, tetrahydromethanopterin, a coenzyme of methanogenesis

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

Escalante-Semerena, J.C.; Leigh, J.A.; Rinehart, K.L. Jr.

1984-04-01

An oxygen-labile formaldehyde activation factor (FAF) was isolated in highly purified form by use of anoxic fractionation procedures. The molecular weight of FAF was determined to be 776 and that of methanopterin (MPT) 772 by fast-atom-bombardment mass spectrometry (FABMS). High-resolution FABMS measurements on MPT and FAF indicated molecular formulas of C/sub 30/H/sub 41/N/sub 6/O/sub 16/P and C/sub 30/H/sub 45/N/sub 6/O/sub 16/P, respectively. The presence of phosphorus was confirmed by 100-MHz /sup 31/P NMR. The 360-MHz /sup 1/H NMR spectrum of FAF in deuterium oxide was similar to that of MPT. A functional relationship between MPT and FAF was documented; bothmore » compounds stimulated the reductive demethylation of 2-(methylthio)ethanesulfonic acid (CH/sub 3/-S-CoM) to CH/sub 4/ when formaldehyde oxidation provided a source of electrons, and FAF replaced MPT in the CH/sub 3/-S-CoM-stimulated conversion of CO/sub 2/ to CH/sub 4/ under H/sub 2/ (the RPG effect). MPT was enzymically converted to FAF during the reduction of CH/sub 3/-S-CoM, and HCHO to CH/sub 4/ under H/sub 2/. Evidence indicates that FAF is tetrahydromethanopterin. 14 references, 8 figures.« less

Cobalt-Catalyzed C(sp(2))-H Borylation: Mechanistic Insights Inspire Catalyst Design.

PubMed

Obligacion, Jennifer V; Semproni, Scott P; Pappas, Iraklis; Chirik, Paul J

2016-08-24

A comprehensive study into the mechanism of bis(phosphino)pyridine (PNP) cobalt-catalyzed C-H borylation of 2,6-lutidine using B2Pin2 (Pin = pinacolate) has been conducted. The experimentally observed rate law, deuterium kinetic isotope effects, and identification of the catalyst resting state support turnover limiting C-H activation from a fully characterized cobalt(I) boryl intermediate. Monitoring the catalytic reaction as a function of time revealed that borylation of the 4-position of the pincer in the cobalt catalyst was faster than arene borylation. Cyclic voltammetry established the electron withdrawing influence of 4-BPin, which slows the rate of C-H oxidative addition and hence overall catalytic turnover. This mechanistic insight inspired the next generation of 4-substituted PNP cobalt catalysts with electron donating and sterically blocking methyl and pyrrolidinyl substituents that exhibited increased activity for the C-H borylation of unactivated arenes. The rationally designed catalysts promote effective turnover with stoichiometric quantities of arene substrate and B2Pin2. Kinetic studies on the improved catalyst, 4-(H)2BPin, established a change in turnover limiting step from C-H oxidative addition to C-B reductive elimination. The iridium congener of the optimized cobalt catalyst, 6-(H)2BPin, was prepared and crystallographically characterized and proved inactive for C-H borylation, a result of the high kinetic barrier for reductive elimination from octahedral Ir(III) complexes.

Beyond benzoin condensation: trimerization of aldehydes via metal-free aerobic oxidative esterification of aldehydes with benzoin products in the presence of cyanide.

PubMed

Kim, Yoo-Jin; Kim, Na Yeun; Cheon, Cheol-Hong

2014-05-02

An unusual trimerization of aldehydes in the presence of cyanide via metal-free aerobic oxidative esterification under ambient conditions is described. Various aromatic aldehydes provided the corresponding oxidative esterification products in good to excellent yields. Mechanistic studies suggested that this reaction would proceed via a two-step sequence: cyanide-catalyzed benzoin condensation of aldehydes and subsequent aerobic oxidative esterification of aldehydes with the resultant benzoin products. The usefulness of this protocol was further demonstrated by converting the resulting trimeric products into other biologically important compounds.

Assessment of tomato and wine processing solid wastes as soil amendments for biosolarization.

PubMed

Achmon, Yigal; Harrold, Duff R; Claypool, Joshua T; Stapleton, James J; VanderGheynst, Jean S; Simmons, Christopher W

2016-02-01

Pomaces from tomato paste and wine production are the most abundant fruit processing residues in California. These residues were examined as soil amendments for solarization to promote conditions conducive to soil disinfestation (biosolarization). Simulated biosolarization studies were performed in both aerobic and anaerobic soil environments and soil temperature elevation, pH, and evolution of CO2, H2 and CH4 gases were measured as metrics of soil microbial activity. Tomato pomace amendment induced conditions associated with soil pest inactivation, including elevation of soil temperature by up to 2°C for a duration of 4days under aerobic conditions and a reduction of soil pH from 6.5 to 4.68 under anaerobic conditions. White wine grape pomace amendment showed similar trends but to a lesser extent. Red wine grape pomace was generally less suitable for biosolarization due to significantly lower soil temperature elevations, reduced acidification relative to the other pomaces and induction of methanogenesis in the soil. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

DOE PAGES

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

2015-08-04

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

Oxidative deterioration of pork during superchilling storage.

PubMed

Pomponio, Luigi; Ruiz-Carrascal, Jorge

2017-12-01

In superchilling (SC), meat is kept at temperatures around 1 °C below its initial freezing point, leading to a significant increase in shelf life. This study aimed to address the oxidative changes taking place in pork loins during prolonged storage at SC temperature. Loins were stored either at chilling (CH) conditions (2-4 °C) for 4 weeks or at SC temperature (around -1 °C) for 12 weeks. Storage at SC temperature diminished the rate of lipid and protein oxidation and discoloration in pork loins, so that final levels of most oxidation products and instrumental color values after 12 weeks of SC storage were similar to those after 4 weeks at CH conditions. However, hexanal content peaked by the end of SC storage, pointing to a potential accumulation of compounds from lipid oxidation during SC storage. SC storage of pork slows down the rate of lipid and protein oxidation. However, accumulation of volatile compounds from lipid oxidation could be a limiting factor for shelf life. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

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

PubMed

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

2015-03-27

The copper-catalyzed aerobic oxidation of primary and secondary alcohols without an external N-oxide co-oxidant is described. The catalyst system is composed of a Cu/diamine complex inspired by the enzyme tyrosinase, along with dimethylaminopyridine (DMAP) or N-methylimidazole (NMI). The Cu catalyst system works without 2,2,6,6-tetramethyl-l-piperidinoxyl (TEMPO) at ambient pressure and temperature, and displays activity for un-activated secondary alcohols, which remain a challenging substrate for catalytic aerobic systems. Our work underscores the importance of finding alternative mechanistic pathways for alcohol oxidation, which complement Cu/TEMPO systems, and demonstrate, in this case, a preference for the oxidation of activated secondary over primary alcohols. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical Feedback From Decreasing Carbon Monoxide Emissions

NASA Astrophysics Data System (ADS)

Gaubert, B.; Worden, H. M.; Arellano, A. F. J.; Emmons, L. K.; Tilmes, S.; Barré, J.; Martinez Alonso, S.; Vitt, F.; Anderson, J. L.; Alkemade, F.; Houweling, S.; Edwards, D. P.

2017-10-01

Understanding changes in the burden and growth rate of atmospheric methane (CH4) has been the focus of several recent studies but still lacks scientific consensus. Here we investigate the role of decreasing anthropogenic carbon monoxide (CO) emissions since 2002 on hydroxyl radical (OH) sinks and tropospheric CH4 loss. We quantify this impact by contrasting two model simulations for 2002-2013: (1) a Measurement of the Pollution in the Troposphere (MOPITT) CO reanalysis and (2) a Control-Run without CO assimilation. These simulations are performed with the Community Atmosphere Model with Chemistry of the Community Earth System Model fully coupled chemistry climate model with prescribed CH4 surface concentrations. The assimilation of MOPITT observations constrains the global CO burden, which significantly decreased over this period by 20%. We find that this decrease results to (a) increase in CO chemical production, (b) higher CH4 oxidation by OH, and (c) 8% shorter CH4 lifetime. We elucidate this coupling by a surrogate mechanism for CO-OH-CH4 that is quantified from the full chemistry simulations.

Processing of catalysts by atomic layer epitaxy: modification of supports

NASA Astrophysics Data System (ADS)

Lindblad, Marina; Haukka, Suvi; Kytökivi, Arla; Lakomaa, Eeva-Liisa; Rautiainen, Aimo; Suntola, Tuomo

1997-11-01

Different supports were modified with titania, zirconia and chromia by the atomic layer epitaxy technique (ALE). In ALE, a metal precursor is bound to the support in saturating gas-solid reactions. Surface oxides are grown by alternating reactions of the metal precursor and an oxidizing agent. Growth mechanisms differ depending on the precursor-support pair and the processing conditions. In this work, the influences of the support, precursor and reaction temperature were investigated by comparing the growth of titania from Ti(OCH(CH 3) 2) 4 on silica and alumina, titania from TiCl 4 and Ti(OCH(CH 3) 2) 4 on silica, and zirconia from ZrCl 4 on silica and alumina. The modification of porous oxides supported on metal substrates (monoliths) was demonstrated for the growth of chromia from Cr(acac) 3.

Top-down control of methane emission and nitrogen cycling by waterfowl.

PubMed

Winton, R Scott; Richardson, Curtis J

2017-01-01

Aquatic herbivores impose top-down control on the structure of wetland ecosystems, but the biogeochemical consequences of herbivory on methane (CH 4 ) and nitrogen (N) are poorly known. To investigate the top-down effects of waterfowl on wetland biogeochemistry, we implemented exclosure experiments in a major waterfowl overwintering wetland in the southeastern United States over two growing seasons. We found that herbivory inhibited the oxidation of CH 4 , leading to a mean increase in emission by 230% over control plots, and prevented nitrification, as indicated by low nitrate availability and undetectable emissions of nitrous oxide. Herbivory reduced belowground biomass of macrophytes, retarding the subsequent spring emergence of aerenchymous stems, effectively starving wetland soils of oxygen necessary for CH 4 oxidation and nitrification. The recognition that important populations of aquatic herbivores may influence the capacity for wetlands to emit greenhouse gases and cycle N is particularly salient in the context of climate change and nutrient pollution mitigation goals. For example, our results suggest that (1) annual emissions of 23 Gg CH 4 /yr from ~57 000 ha of publicly owned waterfowl impoundments in the southeastern United States could be tripled by overgrazing and that (2) waterfowl impoundments may export as much N as agricultural fields. We discuss potential implications for habitat management in the context of historic wetland loss and waterfowl population recovery. © 2016 by the Ecological Society of America.

Annual methane and nitrous oxide emissions from rice paddies and inland fish aquaculture wetlands in southeast China

NASA Astrophysics Data System (ADS)

Wu, Shuang; Hu, Zhiqiang; Hu, Tao; Chen, Jie; Yu, Kai; Zou, Jianwen; Liu, Shuwei

2018-02-01

Inland aquaculture ponds have been documented as important sources of atmospheric methane (CH4) and nitrous oxide (N2O), while their regional or global source strength remains unclear due to lack of direct flux measurements by covering more typical habitat-specific aquaculture environments. In this study, we compared the CH4 and N2O fluxes from rice paddies and nearby inland fish aquaculture wetlands that were converted from rice paddies in southeast China. Both CH4 and N2O fluxes were positively related to water temperature and sediment dissolved organic carbon, but negatively related to water dissolved oxygen concentration. More robust response of N2O fluxes to water mineral N was observed than to sediment mineral N. Annual CH4 and N2O fluxes from inland fish aquaculture averaged 0.51 mg m-2 h-1 and 54.78 μg m-2 h-1, amounting to 42.31 kg CH4 ha-1 and 2.99 kg N2O-N ha-1, respectively. The conversion of rice paddies to conventional fish aquaculture significantly reduced CH4 and N2O emissions by 23% and 66%, respectively. The emission factor for N2O was estimated to be 0.46% of total N input in the feed or 1.23 g N2O-N kg-1 aquaculture production. The estimate of sustained-flux global warming potential of annual CH4 and N2O emissions and the net economic profit suggested that such conversion of rice paddies to inland fish aquaculture would help to reconcile the dilemma for simultaneously achieving both low climatic impacts and high economic benefits in China. More solid direct field measurements from inland aquaculture are in urgent need to direct the overall budget of national or global CH4 and N2O fluxes.

Methane and Nitrous Oxide Emissions Reduced Following Conversion of Rice Paddies to Inland Crab-Fish Aquaculture in Southeast China.

PubMed

Liu, Shuwei; Hu, Zhiqiang; Wu, Shuang; Li, Shuqing; Li, Zhaofu; Zou, Jianwen

2016-01-19

Aquaculture is an important source of atmospheric methane (CH4) and nitrous oxide (N2O), while few direct flux measurements are available for their regional and global source strength estimates. A parallel field experiment was performed to measure annual CH4 and N2O fluxes from rice paddies and rice paddy-converted inland crab-fish aquaculture wetlands in southeast China. Besides N2O fluxes dependent on water/sediment mineral N and CH4 fluxes related to water chemical oxygen demand, both CH4 and N2O fluxes from aquaculture were related to water/sediment temperature, sediment dissolved organic carbon, and water dissolved oxygen concentration. Annual CH4 and N2O fluxes from inland aquaculture averaged 0.37 mg m(-2) h(-1) and 48.1 μg m(-2) h(-1), yielding 32.57 kg ha(-1) and 2.69 kg N2O-N ha(-1), respectively. The conversion of rice paddies to aquaculture significantly reduced CH4 and N2O emissions by 48% and 56%, respectively. The emission factor for N2O was estimated to be 0.66% of total N input in the feed or 1.64 g N2O-N kg(-1) aquaculture production in aquaculture. The conversion of rice paddies to inland aquaculture would benefit for reconciling greenhouse gas mitigation and agricultural income increase as far as global warming potentials and net ecosystem economic profits are of concomitant concern. Some agricultural practices such as better aeration and feeding, and fallow season dredging would help to lower CH4 and N2O emissions from inland aquaculture. More field measurements from inland aquaculture are highly needed to gain an insight into national and global accounting of CH4 and N2O emissions.

The Soil Sink for Nitrous Oxide: Trivial Amount but Challenging Question

NASA Astrophysics Data System (ADS)

Davidson, E. A.; Savage, K. E.; Sihi, D.

2015-12-01

Net uptake of atmospheric nitrous oxide (N2O) has been observed sporadically for many years. Such observations have often been discounted as measurement error or noise, but they were reported frequently enough to gain some acceptance as valid. The advent of fast response field instruments with good sensitivity and precision has permitted confirmation that some soils can be small sinks of N2O. With regards to "closing the global N2O budget" the soil sink is trivial, because it is smaller than the error terms of most other budget components. Although not important from a global budget perspective, the existence of a soil sink for atmospheric N2O presents a fascinating challenge for understanding the physical, chemical, and biological processes that explain the sink. Reduction of N2O by classical biological denitrification requires reducing conditions generally found in wet soil, and yet we have measured the N2O sink in well drained soils, where we also simultaneously measure a sink for atmospheric methane (CH4). Co-occurrence of N2O reduction and CH4 oxidation would require a broad range of microsite conditions within the soil, spanning high and low oxygen concentrations. Abiotic sinks for N2O or other biological processes that consume N2O could exist, but have not yet been identified. We are attempting to simulate processes of diffusion of N2O, CH4, and O2 from the atmosphere and within a soil profile to determine if classical biological N2O reduction and CH4 oxidation at rates consistent with measured fluxes are plausible.

Metaproteomic identification of diazotrophic methanotrophs and their localization in root tissues of field-grown rice plants.

PubMed

Bao, Zhihua; Okubo, Takashi; Kubota, Kengo; Kasahara, Yasuhiro; Tsurumaru, Hirohito; Anda, Mizue; Ikeda, Seishi; Minamisawa, Kiwamu

2014-08-01

In a previous study by our group, CH4 oxidation and N2 fixation were simultaneously activated in the roots of wild-type rice plants in a paddy field with no N input; both processes are likely controlled by a rice gene for microbial symbiosis. The present study examined which microorganisms in rice roots were responsible for CH4 oxidation and N2 fixation under the field conditions. Metaproteomic analysis of root-associated bacteria from field-grown rice (Oryza sativa Nipponbare) revealed that nitrogenase complex-containing nitrogenase reductase (NifH) and the alpha subunit (NifD) and beta subunit (NifK) of dinitrogenase were mainly derived from type II methanotrophic bacteria of the family Methylocystaceae, including Methylosinus spp. Minor nitrogenase proteins such as Methylocella, Bradyrhizobium, Rhodopseudomonas, and Anaeromyxobacter were also detected. Methane monooxygenase proteins (PmoCBA and MmoXYZCBG) were detected in the same bacterial group of the Methylocystaceae. Because these results indicated that Methylocystaceae members mediate both CH4 oxidation and N2 fixation, we examined their localization in rice tissues by using catalyzed reporter deposition-fluorescence in situ hybridization (CARD-FISH). The methanotrophs were localized around the epidermal cells and vascular cylinder in the root tissues of the field-grown rice plants. Our metaproteomics and CARD-FISH results suggest that CH4 oxidation and N2 fixation are performed mainly by type II methanotrophs of the Methylocystaceae, including Methylosinus spp., inhabiting the vascular bundles and epidermal cells of rice roots. Copyright © 2014, American Society for Microbiology. All Rights Reserved.

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

PubMed

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

2017-07-15

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

Seasonal variability in methane and nitrous oxide fluxes from tropical peatlands in the western Amazon basin

NASA Astrophysics Data System (ADS)

Arn Teh, Yit; Murphy, Wayne A.; Berrio, Juan-Carlos; Boom, Arnoud; Page, Susan E.

2017-08-01

The Amazon plays a critical role in global atmospheric budgets of methane (CH4) and nitrous oxide (N2O). However, while we have a relatively good understanding of the continental-scale flux of these greenhouse gases (GHGs), one of the key gaps in knowledge is the specific contribution of peatland ecosystems to the regional budgets of these GHGs. Here we report CH4 and N2O fluxes from lowland tropical peatlands in the Pastaza-Marañón foreland basin (PMFB) in Peru, one of the largest peatland complexes in the Amazon basin. The goal of this research was to quantify the range and magnitude of CH4 and N2O fluxes from this region, assess seasonal trends in trace gas exchange, and determine the role of different environmental variables in driving GHG flux. Trace gas fluxes were determined from the most numerically dominant peatland vegetation types in the region: forested vegetation, forested (short pole) vegetation, Mauritia flexuosa-dominated palm swamp, and mixed palm swamp. Data were collected in both wet and dry seasons over the course of four field campaigns from 2012 to 2014. Diffusive CH4 emissions averaged 36.05 ± 3.09 mg CH4-C m-2 day-1 across the entire dataset, with diffusive CH4 flux varying significantly among vegetation types and between seasons. Net ebullition of CH4 averaged 973.3 ± 161.4 mg CH4-C m-2 day-1 and did not vary significantly among vegetation types or between seasons. Diffusive CH4 flux was greatest for mixed palm swamp (52.0 ± 16.0 mg CH4-C m-2 day-1), followed by M. flexuosa palm swamp (36.7 ± 3.9 mg CH4-C m-2 day-1), forested (short pole) vegetation (31.6 ± 6.6 mg CH4-C m-2 day-1), and forested vegetation (29.8 ± 10.0 mg CH4-C m-2 day-1). Diffusive CH4 flux also showed marked seasonality, with divergent seasonal patterns among ecosystems. Forested vegetation and mixed palm swamp showed significantly higher dry season (47.2 ± 5.4 mg CH4-C m-2 day-1 and 85.5 ± 26.4 mg CH4-C m-2 day-1, respectively) compared to wet season emissions (6.8 ± 1.0 mg CH4-C m-2 day-1 and 5.2 ± 2.7 mg CH4-C m-2 day-1, respectively). In contrast, forested (short pole) vegetation and M. flexuosa palm swamp showed the opposite trend, with dry season flux of 9.6 ± 2.6 and 25.5 ± 2.9 mg CH4-C m-2 day-1, respectively, versus wet season flux of 103.4 ± 13.6 and 53.4 ± 9.8 mg CH4-C m-2 day-1, respectively. These divergent seasonal trends may be linked to very high water tables (> 1 m) in forested vegetation and mixed palm swamp during the wet season, which may have constrained CH4 transport across the soil-atmosphere interface. Diffusive N2O flux was very low (0.70 ± 0.34 µg N2O-N m-2 day-1) and did not vary significantly among ecosystems or between seasons. We conclude that peatlands in the PMFB are large and regionally significant sources of atmospheric CH4 that need to be better accounted for in regional emissions inventories. In contrast, N2O flux was negligible, suggesting that this region does not make a significant contribution to regional atmospheric budgets of N2O. The divergent seasonal pattern in CH4 flux among vegetation types challenges our underlying assumptions of the controls on CH4 flux in tropical peatlands and emphasizes the need for more process-based measurements during periods of high water table.

A Na+-coupled C4-dicarboxylate transporter (Asuc_0304) and aerobic growth of Actinobacillus succinogenes on C4-dicarboxylates.

PubMed

Rhie, Mi Na; Yoon, Hyo Eun; Oh, Hye Yun; Zedler, Sandra; Unden, Gottfried; Kim, Ok Bin

2014-07-01

Actinobacillus succinogenes, which is known to produce large amounts of succinate during fermentation of hexoses, was able to grow on C4-dicarboxylates such as fumarate under aerobic and anaerobic conditions. Anaerobic growth on fumarate was stimulated by glycerol and the major product was succinate, indicating the involvement of fumarate respiration similar to succinate production from glucose. The aerobic growth on C4-dicarboxylates and the transport proteins involved were studied. Fumarate was oxidized to acetate. The genome of A. succinogenes encodes six proteins with similarity to secondary C4-dicarboxylate transporters, including transporters of the Dcu (C4-dicarboxylate uptake), DcuC (C4-dicarboxylate uptake C), DASS (divalent anion : sodium symporter) and TDT (tellurite resistance dicarboxylate transporter) family. From the cloned genes, Asuc_0304 of the DASS family protein was able to restore aerobic growth on C4-dicarboxylates in a C4-dicarboxylate-transport-negative Escherichia coli strain. The strain regained succinate or fumarate uptake, which was dependent on the electrochemical proton potential and the presence of Na(+). The transport had an optimum pH ~7, indicating transport of the dianionic C4-dicarboxylates. Transport competition experiments suggested substrate specificity for fumarate and succinate. The transport characteristics for C4-dicarboxylate uptake by cells of aerobically grown A. succinogenes were similar to those of Asuc_0304 expressed in E. coli, suggesting that Asuc_0304 has an important role in aerobic fumarate uptake in A. succinogenes. Asuc_0304 has sequence similarity to bacterial Na(+)-dicarboxylate cotransporters and contains the carboxylate-binding signature. Asuc_0304 was named SdcA (sodium-coupled C4-dicarboxylate transporter from A. succinogenes). © 2014 The Authors.

The effect of long-term, high-volume aerobic exercise training on postprandial lipemia and oxidative stress.

PubMed

Bloomer, Richard J; Fisher-Wellman, Kelsey H; Bell, Heather K

2010-04-01

We have previously found no effect of moderate-volume aerobic exercise training (approximately 3 hrs*wk(-1)) on postprandial oxidative stress. It is possible that a higher volume of exercise is needed to impact postprandial oxidative stress in young, otherwise healthy individuals. Our purpose was to compare blood triglycerides (TAGs) and oxidative stress biomarkers in 10 healthy untrained and 10 healthy highly aerobically trained (eg, >or= 40 miles running*wk(-1) or >or= 150 miles cycling*wk(-1)) men and women following ingestion of a lipid meal. Blood samples were collected before (in a 10-hour fasted state), and 1, 2, 4, and 6 hours after ingestion of a lipid load (heavy whipping cream at 1 g*kg(-1)). Blood samples were analyzed for TAGs, malondialdehyde (MDA), hydrogen peroxide (H(2)O(2)), and nitrate/nitrite (NOx). No training status or interaction effects were noted for TAGs, MDA, H2O2, or NOx (P > 0.05). However, a time effect was noted for TAGs (P = 0.01), with values higher at 2 hours (67 +/- 6 mg*dL(-1)) compared with premeal (41 +/- 6 mg*dL(-1)). A time effect was also noted for H2O2 (P = 0.0001), with values higher at 2 hours (24 +/- 3 micromol*L(-1)), 4 hours (23 +/- 3 micromol*L(-1)), and 6 hours (21 +/- 3 mumol.L(-1)) compared with premeal (7 +/- 2 micromol*L(-1)). The time effect for MDA approached significance (P = 0.07), with values peaking at 4 hours post-meal (1.59 +/- 0.16 micromol*L(-1)) compared with premeal (0.99 +/- 0.15 micromol*L(-1)). These data indicate that aerobic exercise training (even when performed at a relatively high volume) does not attenuate postprandial lipemia or oxidative stress as compared with no exercise when healthy men and women consume a lipid load in the form of heavy whipping cream. Fasting TAG values may be most important in this regard. It is possible that long-term exercise may be capable of attenuating postprandial lipemia or oxidative stress in older individuals, those with chronic disease, or those with elevated fasting TAG values. Future work is needed to confirm these hypotheses.

Electroremovable Traceless Hydrazides for Cobalt-Catalyzed Electro-Oxidative C-H/N-H Activation with Internal Alkynes.

PubMed

Mei, Ruhuai; Sauermann, Nicolas; Oliveira, João C A; Ackermann, Lutz

2018-06-27

Electrochemical oxidative C-H/N-H activations have been accomplished with a versatile cobalt catalyst in terms of [4 + 2] annulations of internal alkynes. The electro-oxidative C-H activation manifold proved viable with an undivided cell setup under exceedingly mild reaction conditions at room temperature using earth-abundant cobalt catalysts. The electrochemical cobalt catalysis prevents the use of transition metal oxidants in C-H activation catalysis, generating H 2 as the sole byproduct. Detailed mechanistic studies provided strong support for a facile C-H cobaltation by an initially formed cobalt(III) catalyst. The subsequent alkyne migratory insertion was interrogated by mass spectrometry and DFT calculations, providing strong support for a facile C-H activation and the formation of a key seven-membered cobalta(III) cycle in a regioselective fashion. Key to success for the unprecedented use of internal alkynes in electrochemical C-H/N-H activations was represented by the use of N-2-pyridylhydrazides, for which we developed a traceless electrocleavage strategy by electroreductive samarium catalysis at room temperature.

40 CFR 98.322 - GHGs to report.

Code of Federal Regulations, 2014 CFR

2014-07-01

... this subpart the CO2 emissions from coal mine gas CH4 destruction occurring at the facility, where the gas is not a fuel input for energy generation or use (e.g., flaring and VAM oxidation). (e) You must report under subpart C of this part (General Stationary Fuel Combustion Sources) the CO2, CH4, and N2O...

Nitric oxide is an obligate bacterial nitrification intermediate produced by hydroxylamine oxidoreductase.

PubMed

Caranto, Jonathan D; Lancaster, Kyle M

2017-08-01

Ammonia (NH 3 )-oxidizing bacteria (AOB) emit substantial amounts of nitric oxide (NO) and nitrous oxide (N 2 O), both of which contribute to the harmful environmental side effects of large-scale agriculture. The currently accepted model for AOB metabolism involves NH 3 oxidation to nitrite (NO 2 - ) via a single obligate intermediate, hydroxylamine (NH 2 OH). Within this model, the multiheme enzyme hydroxylamine oxidoreductase (HAO) catalyzes the four-electron oxidation of NH 2 OH to NO 2 - We provide evidence that HAO oxidizes NH 2 OH by only three electrons to NO under both anaerobic and aerobic conditions. NO 2 - observed in HAO activity assays is a nonenzymatic product resulting from the oxidation of NO by O 2 under aerobic conditions. Our present study implies that aerobic NH 3 oxidation by AOB occurs via two obligate intermediates, NH 2 OH and NO, necessitating a mediator of the third enzymatic step.

Effect of packaging atmospheres on storage quality characteristics of heavily marbled beef longissimus steaks.

PubMed

Yang, Xiaoyin; Zhang, Yimin; Zhu, Lixian; Han, Mingshan; Gao, Shujuan; Luo, Xin

2016-07-01

The objective of this study was to investigate the effects of modified atmosphere packaging (MAP) systems on shelf-life and quality of beef steaks with high marbling. Four packaging types were used including 80% O2 MAP (80% O2+20% CO2), 50% O2 MAP (50% O2+30% CO2+20% N2), carbon monoxide MAP (0.4% CO+30% CO2+69.6% N2) and vacuum packaging (VP). Steaks were displayed under simulated retail conditions at 4°C for 12days. Purge loss, pH, color stability, oxidative stability and microbial counts were monitored. Aerobically packaged steaks exhibited a bright-red color at the first 4days. However, discoloration and oxidation became major factors limiting their shelf-life to 8days. Compared with aerobic packaging, anaerobic packaging extended shelf-life of heavily marbled beef steaks, due to better color stability, together with lower oxidation and microbial populations. Among all packaging methods, CO-MAP had the best preservation for steaks, with more red color than other packaging types. Copyright © 2016 Elsevier Ltd. All rights reserved.

Trp64Arg Polymorphism in Beta3-Adrenergic Receptor Gene Is Associated with Decreased Fat Oxidation Both in Resting and Aerobic Exercise in the Japanese Male

PubMed Central

Morita, Emiko; Taniguchi, Hiroshi; Sakaue, Motoyoshi

2009-01-01

The purpose of our study was to investigate whether the Trp64Arg polymorphism in β3-AR gene and the −3826A/G polymorphism in the UCP1 gene were associated with the reduction in energy expenditure and fat oxidation both in resting and aerobic exercise in Japanese. Eighty-six nonobese young healthy Japanese were recruited. Energy expenditure was measured using indirect calorimetry. The subjects performed an aerobic exercise program at 60% of their maximal heart rate for 30 minutes. The level of fat oxidation at rest and aerobic exercise of the male subjects with Trp/Arg of the β3-AR gene was significantly lower than that of the Trp/Trp genotype. No difference in FO0−30 was observed in the female subjects. There was no association between UCP-1 polymorphism and energy expenditure during aerobic exercise. It was revealed that the Trp64Arg polymorphism in β3-AR gene is associated with reduction of fat oxidation both in resting and aerobic exercise in healthy, young Japanese males. PMID:20069060

Linking activity, composition and seasonal dynamics of atmospheric methane oxidizers in a meadow soil

PubMed Central

Shrestha, Pravin Malla; Kammann, Claudia; Lenhart, Katharina; Dam, Bomba; Liesack, Werner

2012-01-01

Microbial oxidation is the only biological sink for atmospheric methane. We assessed seasonal changes in atmospheric methane oxidation and the underlying methanotrophic communities in grassland near Giessen (Germany), along a soil moisture gradient. Soil samples were taken from the surface layer (0–10 cm) of three sites in August 2007, November 2007, February 2008 and May 2008. The sites showed seasonal differences in hydrological parameters. Net uptake rates varied seasonally between 0 and 70 μg CH4 m−2 h−1. Greatest uptake rates coincided with lowest soil moisture in spring and summer. Over all sites and seasons, the methanotrophic communities were dominated by uncultivated methanotrophs. These formed a monophyletic cluster defined by the RA14, MHP and JR1 clades, referred to as upland soil cluster alphaproteobacteria (USCα)-like group. The copy numbers of pmoA genes ranged between 3.8 × 105–1.9 × 106 copies g−1 of soil. Temperature was positively correlated with CH4 uptake rates (P<0.001), but had no effect on methanotrophic population dynamics. The soil moisture was negatively correlated with CH4 uptake rates (P<0.001), but showed a positive correlation with changes in USCα-like diversity (P<0.001) and pmoA gene abundance (P<0.05). These were greatest at low net CH4 uptake rates during winter times and coincided with an overall increase in bacterial 16S rRNA gene abundances (P<0.05). Taken together, soil moisture had a significant but opposed effect on CH4 uptake rates and methanotrophic population dynamics, the latter being increasingly stimulated by soil moisture contents >50 vol% and primarily related to members of the MHP clade. PMID:22189499

Linking activity, composition and seasonal dynamics of atmospheric methane oxidizers in a meadow soil.

PubMed

Shrestha, Pravin Malla; Kammann, Claudia; Lenhart, Katharina; Dam, Bomba; Liesack, Werner

2012-06-01

Microbial oxidation is the only biological sink for atmospheric methane. We assessed seasonal changes in atmospheric methane oxidation and the underlying methanotrophic communities in grassland near Giessen (Germany), along a soil moisture gradient. Soil samples were taken from the surface layer (0-10 cm) of three sites in August 2007, November 2007, February 2008 and May 2008. The sites showed seasonal differences in hydrological parameters. Net uptake rates varied seasonally between 0 and 70 μg CH(4) m(-2) h(-1). Greatest uptake rates coincided with lowest soil moisture in spring and summer. Over all sites and seasons, the methanotrophic communities were dominated by uncultivated methanotrophs. These formed a monophyletic cluster defined by the RA14, MHP and JR1 clades, referred to as upland soil cluster alphaproteobacteria (USCα)-like group. The copy numbers of pmoA genes ranged between 3.8 × 10(5)-1.9 × 10(6) copies g(-1) of soil. Temperature was positively correlated with CH(4) uptake rates (P<0.001), but had no effect on methanotrophic population dynamics. The soil moisture was negatively correlated with CH(4) uptake rates (P<0.001), but showed a positive correlation with changes in USCα-like diversity (P<0.001) and pmoA gene abundance (P<0.05). These were greatest at low net CH(4) uptake rates during winter times and coincided with an overall increase in bacterial 16S rRNA gene abundances (P<0.05). Taken together, soil moisture had a significant but opposed effect on CH(4) uptake rates and methanotrophic population dynamics, the latter being increasingly stimulated by soil moisture contents >50 vol% and primarily related to members of the MHP clade.

Bioinspired aerobic oxidation of secondary amines and nitrogen heterocycles with a bifunctional quinone catalyst.

PubMed

Wendlandt, Alison E; Stahl, Shannon S

2014-01-08

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

The stable carbon isotope composition of methane produced and emitted from northern peatlands

NASA Astrophysics Data System (ADS)

Hornibrook, Edward R. C.

Stable carbon isotope values, pore water concentration, and flux data for methane (CH4) were compiled for 26 peatlands situated in the northern hemisphere to explore relationships between trophic status and CH4 cycling. Methane produced in ombrotrophic bogs has δ13C values that are significantly more negative than CH4 formed in fens apparently because of poor dissociation of acetic acid or an absence of methanogenic archaea capable of metabolizing acetic acid under low pH conditions. The δ 13C values of CH4 in pore water of ombrotrophic and minerotrophic peatlands exhibit the opposite trend: δ13C(CH4) values become more positive with depth in rain-fed bogs and more negative with depth in fens. The key zone for methanogenesis occurs at shallow depths in both types of peatland and consequently, δ13C values of CH4 emitted from ombrotrophic bogs (-74.9 ± 9.8‰ n = 42) are more negative than from fens (-64.8 ± 4.0‰ n = 38). An abundance of graminoids in fens contributes to more positive δ13C(CH4) values in pore water through (1) release of root exudates which promotes aceticlastic methanogenesis, (2) rhizosphere oxidization of CH4 causing localized enrichment of 13CH4, and (3) preferential export of 12CH4 through aerenchyma, which also enriches pore water in 13CH4. Emissions from blanket bogs and raised bogs should be attributed more negative δ13C(CH4) values relative to fens in isotope-weighted mass balance budgets. Further study is needed of bogs that have an apparently low nutrient status but exhibit a pore water distribution of δ13C(CH4) values similar to fens.

Methane and nitrous oxide emissions from three paddy rice based cultivation systems in Southwest China

NASA Astrophysics Data System (ADS)

Jiang, Changsheng; Wang, Yuesi; Zheng, Xunhua; Zhu, Bo; Huang, Yao; Hao, Qingju

2006-05-01

To understand methane (CH4) and nitrous oxide (N2O) emissions from permanently flooded rice paddy fields and to develop mitigation options, a field experiment was conducted in situ for two years (from late 2002 to early 2005) in three rice-based cultivation systems, which are a permanently flooded rice field cultivated with a single time and followed by a non-rice season (PF), a rice-wheat rotation system (RW) and a rice-rapeseed rotation system (RR) in a hilly area in Southwest China. The results showed that the total CH4 emissions from PF were 646.3±52.1 and 215.0±45.4 kg CH4 hm-2 during the rice-growing period and non-rice period, respectively. Both values were much lower than many previous reports from similar regions in Southwest China. The CH4 emissions in the rice-growing season were more intensive in PF, as compared to RW and RR. Only 33% of the total annual CH4 emission in PF occurred in the non-rice season, though the duration of this season is two times longer than the rice season. The annual mean N2O flux in PF was 4.5±0.6 kg N2O hm-2 yr-1. The N2O emission in the rice-growing season was also more intensive than in the non-rice season, with only 16% of the total annual emission occurring in the non-rice season. The amounts of N2O emission in PF were ignorable compared to the CH4 emission in terms of the global warming potential (GWP). Changing PF to RW or RR not only eliminated CH4 emissions in the non-rice season, but also substantially reduced the CH4 emission during the following rice-growing period (ca. 58%, P<0.05). However, this change in cultivation system substantially increased N2O emissions, especially in the non-rice season, by a factor of 3.7 to 4.5. On the 100-year horizon, the integrated GWP of total annual CH4 and N2O emissions satisfies PF≫RR≈RW. The GWP of PF is higher than that of RW and RR by a factor of 2.6 and 2.7, respectively. Of the total GWP of CH4 and N2O emissions, CH4 emission contributed to 93%, 65% and 59% in PF, RW and RR, respectively. These results suggest that changing PF to RW and RR can substantially reduce not only CH4 emission but also the total GWP of the CH4 and N2O emissions.

Impact of oxidative stress defense on bacterial survival and morphological change in Campylobacter jejuni under aerobic conditions.

PubMed

Oh, Euna; McMullen, Lynn; Jeon, Byeonghwa

2015-01-01

Campylobacter jejuni, a microaerophilic foodborne pathogen, inescapably faces high oxygen tension during its transmission to humans. Thus, the ability of C. jejuni to survive under oxygen-rich conditions may significantly impact C. jejuni viability in food and food safety as well. In this study, we investigated the impact of oxidative stress resistance on the survival of C. jejuni under aerobic conditions by examining three mutants defective in key antioxidant genes, including ahpC, katA, and sodB. All the three mutants exhibited growth reduction under aerobic conditions compared to the wild-type (WT), and the ahpC mutant showed the most significant growth defect. The CFU reduction in the mutants was recovered to the WT level by complementation. Higher levels of reactive oxygen species were accumulated in C. jejuni under aerobic conditions than microaerobic conditions, and supplementation of culture media with an antioxidant recovered the growth of C. jejuni. The levels of lipid peroxidation and protein oxidation were significantly increased in the mutants compared to WT. Additionally, the mutants exhibited different morphological changes under aerobic conditions. The ahpC and katA mutants developed coccoid morphology by aeration, whereas the sodB mutant established elongated cellular morphology. Compared to microaerobic conditions, interestingly, aerobic culture conditions substantially induced the formation of coccoidal cells, and antioxidant treatment reduced the emergence of coccoid forms under aerobic conditions. The ATP concentrations and PMA-qPCR analysis supported that oxidative stress is a factor that induces the development of a viable-but-non-culturable state in C. jejuni. The findings in this study clearly demonstrated that oxidative stress resistance plays an important role in the survival and morphological changes of C. jejuni under aerobic conditions.

Subsoil methanogenesis as source of stem CH4 emission in upland forest trees: preferential CH4 transport via the root system?

NASA Astrophysics Data System (ADS)

Maier, M.; Machacova, K.; Urban, O.; Friederike, L.

2016-12-01

Quantifying and understanding green house gas fluxes in natural soil-plant-atmosphere systems are crucial to predicting global climate change. Wetland species or trees at waterlogged sites are known to emit large amounts of CH4. Yet upland forest soils are regarded as CH4 sinks and tree species like upland European beech (Fagus sylvatica, L.) are assumed not to emit CH4. We studied the soil-atmosphere and stem-atmosphere fluxes of CH4, and soil gas profiles at two upland beech forest sites in Central Europe. Soil was a net CH4 sink at both. Unusually there was one beech tree with substantial CH4 emissions that were higher than the CH4 sink of the soil. The soil gas profile at this tree indicated CH4 production at a soil depth >0.3 m, despite the net uptake of CH4 observed at the soil surface adjacent to the tree. Field soil assessment showed strong redoximorphic color patterns in the adjacent soil. We think that there is a transport link between the soil and stem via the root system representing a preferential transport mechanism for CH4 despite the fact that beech roots usually do not bear aerenchyma. The gas transport process , either via dissolved CH4 in the xylem water or in the root gas phase, is not yet clear. The observed CH4 stem emissions represent an important CH4flux in this ecosystem, und thus should be considered in future research. AcknowledgementThis research was financially supported by the Czech Academy of Sciences and the German Academic Exchange Service within the project "Methane (CH4) and nitrous oxide (N2O) emissions from Fagus sylvatica trees" (DAAD-15-03), National Programme for Sustainability I (LO1415) and project DFG (MA 5826/2-1). We would like to thank Marek Jakubik, Katerina Svobodova, Sinikka Paulus, Ellen Halaburt and Sally Haddad for technical support.

Reassessing the stable isotope composition assigned to methane flux from natural wetlands in isotope-constrained budgets

NASA Astrophysics Data System (ADS)

Hornibrook, Edward; Maxfield, Peter; Gauci, Vincent; Stott, Andrew

2013-04-01

Stable isotope ratios in CH4 preserve information about its origin and history, and are commonly used to constrain global CH4 budgets. Wetlands are key contributors to the atmospheric burden of CH4 and typically are assigned a stable carbon isotope composition of ~-60 permil in isotope-weighted stable isotope models despite the considerable range of δ13C(CH4) values (~ -100 to -40 permil) known to occur in these diverse ecosystems. Kinetic isotope effects (KIEs) associated with the metabolism of CH4-producing microorganisms generate much of the natural variation but highly negative and positive δ13C(CH4) values generally result from secondary processes (e.g., diffusive transport or oxidation by soil methanotrophs). Despite these complexities, consistent patterns exist in the isotope composition of wetland CH4 that can be linked conclusively to trophic status and consequently, natural succession or human perturbations that impact nutrient levels. Another challenge for accurate representation of wetlands in carbon cycle models is parameterisation of sporadic CH4 emission events. Abrupt release of large volumes of CH4-rich bubbles in short periods of time can account for a significant proportion of the annual CH4 flux from a wetland but such events are difficult to detect using conventional methods. New infrared spectroscopy techniques capable of high temporal resolution measurements of CH4 concentration and stable isotope composition can readily quantify short-lived CH4 pulses. Moreover, the isotope data can be used conclusively to determine shifts in the mode of CH4 transport and provide the potential to link initiation of abrupt emission events to forcing by internal or external factors.

Near-zero methane emission from an abandoned boreal peatland pasture based on eddy covariance measurements

PubMed Central

Wang, Mei; Luan, Junwei; Lafleur, Peter; Chen, Huai; Zhu, Xinbiao

2017-01-01

Although estimates of the annual methane (CH4) flux from agriculturally managed peatlands exist, knowledge of controls over the variation of CH4 at different time-scales is limited due to the lack of high temporal-resolution data. Here we present CH4 fluxes measured from May 2014 to April 2016 using the eddy covariance technique at an abandoned peatland pasture in western Newfoundland, Canada. The goals of the study were to identify the controls on the seasonal variations in CH4 flux and to quantify the annual CH4 flux. The seasonal variation in daily CH4 flux was not strong in the two study years, however a few periods of pronounced emissions occurred in the late growing season. The daily average CH4 flux was small relative to other studies, ranging from -4.1 to 9.9 nmol m-2 s-1 in 2014–15 and from -7.1 to 12.1 nmol m-2 s-1 in 2015–16. Stepwise multiple regression was used to investigate controls on CH4 flux and this analysis found shifting controls on CH4 flux at different periods of the growing season. During the early growing season CH4 flux was closely related to carbon dioxide fixation rates, suggesting substrate availability was the main control. The peak growing season CH4 flux was principally controlled by the CH4 oxidation in 2014, where the CH4 flux decreased and increased with soil temperature at 50 cm and soil water content at 10 cm, but a contrasting temperature-CH4 relation was found in 2015. The late growing season CH4 flux was found to be regulated by the variation in water table level and air temperature in 2014. The annual CH4 emission was near zero in both study years (0.36 ± 0.30 g CH4 m-2 yr-1 in 2014–15 and 0.13 ± 0.38 g CH4 m-2 yr-1 in 2015–16), but fell within the range of CH4 emissions reported for agriculturally managed peatlands elsewhere. PMID:29252998

Near-zero methane emission from an abandoned boreal peatland pasture based on eddy covariance measurements.

PubMed

Wang, Mei; Wu, Jianghua; Luan, Junwei; Lafleur, Peter; Chen, Huai; Zhu, Xinbiao

2017-01-01

Although estimates of the annual methane (CH4) flux from agriculturally managed peatlands exist, knowledge of controls over the variation of CH4 at different time-scales is limited due to the lack of high temporal-resolution data. Here we present CH4 fluxes measured from May 2014 to April 2016 using the eddy covariance technique at an abandoned peatland pasture in western Newfoundland, Canada. The goals of the study were to identify the controls on the seasonal variations in CH4 flux and to quantify the annual CH4 flux. The seasonal variation in daily CH4 flux was not strong in the two study years, however a few periods of pronounced emissions occurred in the late growing season. The daily average CH4 flux was small relative to other studies, ranging from -4.1 to 9.9 nmol m-2 s-1 in 2014-15 and from -7.1 to 12.1 nmol m-2 s-1 in 2015-16. Stepwise multiple regression was used to investigate controls on CH4 flux and this analysis found shifting controls on CH4 flux at different periods of the growing season. During the early growing season CH4 flux was closely related to carbon dioxide fixation rates, suggesting substrate availability was the main control. The peak growing season CH4 flux was principally controlled by the CH4 oxidation in 2014, where the CH4 flux decreased and increased with soil temperature at 50 cm and soil water content at 10 cm, but a contrasting temperature-CH4 relation was found in 2015. The late growing season CH4 flux was found to be regulated by the variation in water table level and air temperature in 2014. The annual CH4 emission was near zero in both study years (0.36 ± 0.30 g CH4 m-2 yr-1 in 2014-15 and 0.13 ± 0.38 g CH4 m-2 yr-1 in 2015-16), but fell within the range of CH4 emissions reported for agriculturally managed peatlands elsewhere.

Variability in aerobic methane oxidation over the past 1.2 Myrs recorded in microbial biomarker signatures from Congo fan sediments

NASA Astrophysics Data System (ADS)

Talbot, Helen M.; Handley, Luke; Spencer-Jones, Charlotte L.; Dinga, Bienvenu Jean; Schefuß, Enno; Mann, Paul J.; Poulsen, John R.; Spencer, Robert G. M.; Wabakanghanzi, Jose N.; Wagner, Thomas

2014-05-01

Methane (CH4) is a strong greenhouse gas known to have perturbed global climate in the past, especially when released in large quantities over short time periods from continental or marine sources. It is therefore crucial to understand and, if possible, quantify the individual and combined response of these variable methane sources to natural climate variability. However, past changes in the stability of greenhouse gas reservoirs remain uncertain and poorly constrained by geological evidence. Here, we present a record from the Congo fan of a highly specific bacteriohopanepolyol (BHP) biomarker for aerobic methane oxidation (AMO), 35-aminobacteriohopane-30,31,32,33,34-pentol (aminopentol), that identifies discrete periods of increased AMO as far back as 1.2 Ma. Fluctuations in the concentration of aminopentol, and other 35-aminoBHPs, follow a pattern that correlates with late Quaternary glacial-interglacial climate cycles, with highest concentrations during warm periods. We discuss possible sources of aminopentol, and the methane consumed by the precursor methanotrophs, within the context of the Congo River setting, including supply of methane oxidation markers from terrestrial watersheds and/or marine sources (gas hydrate and/or deep subsurface gas reservoir). Compound-specific carbon isotope values of -30‰ to -40‰ for BHPs in ODP 1075 and strong similarities between the BHP signature of the core and surface sediments from the Congo estuary and floodplain wetlands from the interior of the Congo River Basin, support a methanotrophic and likely terrigenous origin of the 35-aminoBHPs found in the fan sediments. This new evidence supports a causal connection between marine sediment BHP records of tropical deep sea fans and wetland settings in the feeding river catchments, and thus tropical continental hydrology. Further research is needed to better constrain the different sources and pathways of methane emission. However, this study identifies the large potential of aminoBHPs, in particular aminopentol, to trace and, once better calibrated and understood, quantify past methane sources and fluxes from terrestrial and potentially also marine sources.

Edge effects on N2O, NO and CH4 fluxes in two temperate forests.

PubMed

Remy, Elyn; Gasche, Rainer; Kiese, Ralf; Wuyts, Karen; Verheyen, Kris; Boeckx, Pascal

2017-01-01

Forest ecosystems may act as sinks or sources of nitrogen (N) and carbon (C) compounds, such as the climate relevant trace gases nitrous oxide (N 2 O), nitric oxide (NO) and methane (CH 4 ). Forest edges, which catch more atmospheric deposition, have become important features in European landscapes and elsewhere. Here, we implemented a fully automated measuring system, comprising static and dynamic measuring chambers determining N 2 O, NO and CH 4 fluxes along an edge-to-interior transect in an oak (Q. robur) and a pine (P. nigra) forest in northern Belgium. Each forest was monitored during a 2-week measurement campaign with continuous measurements every 2h. NO emissions were 9-fold higher than N 2 O emissions. The fluxes of NO and CH 4 differed between forest edge and interior, but not for N 2 O. This edge effect was more pronounced in the oak than in the pine forest. In the oak forest, edges emitted less NO (on average 60%) and took up more CH 4 (on average 177%). This suggests that landscape structure can play a role in the atmospheric budgets of these climate relevant trace gases. Soil moisture variation between forest edge and interior was a key variable explaining the magnitude of NO and CH 4 fluxes in our measurement campaign. To better understand the environmental impact of N and C trace gas fluxes from forest edges, additional and long-term measurements in other forest edges are required. Copyright © 2016 Elsevier B.V. All rights reserved.

Hypercholesterolemia Impairs Exercise Capacity in Mice

PubMed Central

Maxwell, Andrew J.; Niebauer, Josef; Lin, Patrick S.; Tsao, Philip S.; Bernstein, Daniel; Cooke, John P.

2011-01-01

Objective We previously reported an attenuation of both exercise hyperemia and measures of aerobic capacity in hypercholesterolemic mice. In this study we expanded upon the previous findings by examining the temporal and quantitative relationship of hypercholesterolemia to aerobic and anaerobic capacity and by exploring several potential mechanisms of dysfunction. Methods Eight-week old wild type (n=123) and apoE knockout (n=79) C57BL/6J mice were divided into groups with distinct cholesterol levels by feeding regular or high fat diets. At various ages the mice underwent treadmill ergospirometry. To explore mechanisms, aortic ring vasodilator function and nitrate (NOx) activity, urinary excretion of NOx, running muscle microvascular density and citrate synthase activity, as well as myocardial mass and histologic evidence of ischemia were measured. Results At 8 weeks of age, all mice had similar measures of exercise capacity. All indices of aerobic exercise capacity progressively declined at 12 and 20 weeks of age in the hypercholesterolemic mice as cholesterol levels increased while indices of anaerobic capacity remained unaffected. Across the 4 cholesterol groups, the degree of aerobic dysfunction was related to serum cholesterol levels; a relationship that was maintained after correcting for confounding factors. Associated with the deterioration in exercise capacity was a decline in measures of nitric oxide-mediated vascular function while there was no evidence of aberrations in functional or oxidative capacities or in other components of transport capacity. Conclusion Aerobic exercise dysfunction is observed in murine models of genetic and diet-induced hypercholesterolemia and is associated with a reduction in vascular nitric oxide production. PMID:19651675

Oxidative stress in response to aerobic and anaerobic power testing: influence of exercise training and carnitine supplementation.

PubMed

Bloomer, Richard J; Smith, Webb A

2009-01-01

The purpose of this study is to compare the oxidative stress response to aerobic and anaerobic power testing, and to determine the impact of exercise training with or without glycine propionyl-L-carnitine (GPLC) in attenuating the oxidative stress response. Thirty-two subjects were assigned (double blind) to placebo, GPLC-1 (1g PLC/d), GPLC-3 (3g PLC/d) for 8 weeks, plus aerobic exercise. Aerobic (graded exercise test: GXT) and anaerobic (Wingate cycle) power tests were performed before and following the intervention. Blood was taken before and immediately following exercise tests and analyzed for malondialdehyde (MDA), hydrogen peroxide (H2O2), and xanthine oxidase activity (XO). No interaction effects were noted. MDA was minimally effected by exercise but lower at rest for both GPLC groups following the intervention (p = 0.044). A time main effect was noted for H2O2 (p = 0.05) and XO (p = 0.003), with values increasing from pre- to postexercise. Both aerobic and anaerobic power testing increase oxidative stress to a similar extent. Exercise training plus GPLC can decrease resting MDA, but it has little impact on exercise-induced oxidative stress biomarkers.

Copper-catalyzed oxidative dimerizations of 3-N-hydroxy-aminoprop-1-enes to form 1,4-dihydroxy-2,3-diaminocyclohexanes with C2  symmetry.

PubMed

Ghorpade, Satish; Liu, Rai-Shung

2014-11-17

This work describes the one-step construction of complex and important molecular frameworks through copper-catalyzed oxidations of cheap tertiary amines. Copper-catalyzed aerobic oxidations of N-hydroxyaminopropenes to form C2 -symmetric N- and O-functionalized cyclohexanes are described. Such catalytic oxidations proceed with remarkable stereocontrol and high efficiency. Reductive cleavage of the two NO bonds of these products delivers 1,4-dihydroxy-2,3-diaminocyclohexanes, which are important skeletons of several bioactive molecules. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Production of biogas (methane and hydrogen) from anaerobic digestion of hemicellulosic hydrolysate generated in the oxidative pretreatment of coffee husks.

PubMed

Santos, Lívia Caroline Dos; Adarme, Oscar Fernando Herrera; Baêta, Bruno Eduardo Lobo; Gurgel, Leandro Vinícius Alves; Aquino, Sérgio Francisco de

2018-05-21

Ozone pretreatment of coffee husks (CH) was evaluated to generate hydrolysates for biogas production and to preserve cellulose of the solid phase for 2G ethanol production. Pretreatment variables included liquid-to-solid ratio (LSR), pH and specific applied ozone load (SAOL). Considering single-stage anaerobic digestion (AD), the highest methane production (36 NmL CH 4 /g CH) was achieved with the hydrolysate generated in the experiment using LSR 10 mL/g, pH 11 and SAOL 18.5 mg O 3 /g CH, leading to 0.064 kJ/g CH energy recovery. Due to the presence of toxic compounds in the hydrolysate, the addition of powdered activated carbon (4 g/L) to the reactor enhanced biogas production, leading to 86 NmL CH 4 /g CH yield and 0.58 kJ/g CH energy recovery. When two-stage AD was applied, methane production resulted in 49 NmL CH 4 /g CH, with additional 19 NmL H 2 /g CH production, resulting in a net 0.26 kJ/g CH energy recovery. Copyright © 2018 Elsevier Ltd. All rights reserved.

Effect of Combined Exercise Versus Aerobic-Only Training on Skeletal Muscle Lipid Metabolism in a Rodent Model of Type1 Diabetes.

PubMed

Dotzert, Michelle S; McDonald, Matthew W; Murray, Michael R; Nickels, J Zachary; Noble, Earl G; Melling, C W James

2017-12-04

Abnormal skeletal muscle lipid metabolism is associated with insulin resistance in people with type 1 diabetes. Although lipid metabolism is restored with aerobic exercise training, the risk for postexercise hypoglycemia is increased with this modality. Integrating resistance and aerobic exercise is associated with reduced hypoglycemic risk; however, the effects of this exercise modality on lipid metabolism and insulin resistance remain unknown. We compared the effects of combined (aerobic + resistance) versus aerobic exercise training on oxidative capacity and muscle lipid metabolism in a rat model of type 1 diabetes. Male Sprague-Dawley rats were divided into 4 groups: sedentary control (C), sedentary control + diabetes (CD), diabetes + high-intensity aerobic exercise (DAE) and diabetes + combined aerobic and resistance exercise (DARE). Following diabetes induction (20 mg/kg streptozotocin over five days), DAE rats ran for 12 weeks (5 days/week for 1 hour) on a motorized treadmill (27 m/min at a 6-degree grade), and DARE rats alternated daily between running and incremental weighted ladder climbing. After training, DAE showed reduced muscle CD36 protein content and lipid content compared to CD (p≤0.05). DAE rats also had significantly increased citrate synthase (CS) activity compared to CD (p≤0.05). DARE rats showed reduced CD36 protein content compared to CD and increased CS activity compared to CD and DAE rats (p≤0.05). DARE rats demonstrated increased skeletal muscle lipid staining, elevated lipin-1 protein content and insulin sensitivity (p≤0.05). Integration of aerobic and resistance exercise may exert a synergistic effect, producing adaptations characteristic of the "athlete's paradox," including increased capacity to store and oxidize lipids. Crown Copyright © 2017. Published by Elsevier Inc. All rights reserved.

Product distribution study of the Cl-atom initiated oxidation of ethyl methyl sulfide and diethyl sulfide

NASA Astrophysics Data System (ADS)

Oksdath-Mansilla, Gabriela; Peñéñory, Alicia B.; Barnes, Ian; Wiesen, Peter; Teruel, Mariano A.

2014-03-01

The products formed in the gas-phase reactions of Cl atoms with (CH3CH2)2S and CH3CH2SCH3 have been investigated in a large volume reactor in NOx-free air at atmospheric pressure and (298 ± 2) K using long path “in situ” FTIR spectroscopy for the analysis. HCl, SO2 and CH3CHO were identified as the major products for both reactions. For the Cl + CH3CH2SCH3 reaction HCHO was also identified as a major product. The yields of the products obtained for the reaction of Cl with (CH3CH2)2S were (59 ± 2) %, (52 ± 5) % and (103 ± 4) % for HCl, SO2 and CH3CHO, respectively. For the reaction of Cl with CH3CH2SCH3 yields of (43 ± 5) %, (55 ± 3) %, (58 ± 3) % and (53 ± 5) % were obtained for HCl, SO2, CH3CHO and HCHO, respectively. This is the first products and mechanistic study for the gas-phase Cl-initiated oxidation of non-CH3SCH3 alkyl sulfides. Comparison with previous results for the reaction of Cl with dimethyl sulfide is made and simple atmospheric degradation mechanisms are postulated to explain the formation of the observed products.

Role of atmospheric oxidation in recent methane growth

PubMed Central

Rigby, Matthew; Montzka, Stephen A.; Prinn, Ronald G.; White, James W. C.; Young, Dickon; Lunt, Mark F.; Ganesan, Anita L.; Manning, Alistair J.; Simmonds, Peter G.; Salameh, Peter K.; Harth, Christina M.; Mühle, Jens; Weiss, Ray F.; Fraser, Paul J.; Steele, L. Paul; McCulloch, Archie; Park, Sunyoung

2017-01-01

The growth in global methane (CH4) concentration, which had been ongoing since the industrial revolution, stalled around the year 2000 before resuming globally in 2007. We evaluate the role of the hydroxyl radical (OH), the major CH4 sink, in the recent CH4 growth. We also examine the influence of systematic uncertainties in OH concentrations on CH4 emissions inferred from atmospheric observations. We use observations of 1,1,1-trichloroethane (CH3CCl3), which is lost primarily through reaction with OH, to estimate OH levels as well as CH3CC3 emissions, which have uncertainty that previously limited the accuracy of OH estimates. We find a 64–70% probability that a decline in OH has contributed to the post-2007 methane rise. Our median solution suggests that CH4 emissions increased relatively steadily during the late 1990s and early 2000s, after which growth was more modest. This solution obviates the need for a sudden statistically significant change in total CH4 emissions around the year 2007 to explain the atmospheric observations and can explain some of the decline in the atmospheric 13CH4/12CH4 ratio and the recent growth in C2H6. Our approach indicates that significant OH-related uncertainties in the CH4 budget remain, and we find that it is not possible to implicate, with a high degree of confidence, rapid global CH4 emissions changes as the primary driver of recent trends when our inferred OH trends and these uncertainties are considered. PMID:28416657

A Highly Practical Copper(I)/TEMPO Catalyst System for Chemoselective Aerobic Oxidation of Primary Alcohols

PubMed Central

Hoover, Jessica M.; Stahl, Shannon S.

2011-01-01

Aerobic oxidation reactions have been the focus of considerable attention, but their use in mainstream organic chemistry has been constrained by limitations in their synthetic scope and by practical factors, such as the use of pure O2 as the oxidant or complex catalyst synthesis. Here, we report a new (bpy)CuI/TEMPO catalyst system that enables efficient and selective aerobic oxidation of a broad range of primary alcohols, including allylic, benzylic and aliphatic derivatives, to the corresponding aldehydes using readily available reagents, at room temperature with ambient air as the oxidant. The catalyst system is compatible with a wide range of functional groups and the high selectivity for 1° alcohols enables selective oxidation of diols that lack protecting groups. PMID:21861488

Laboratory Studies on the Formation of Three C2H4O Isomers-Acetaldehyde (CH3CHO), Ethylene Oxide (c-C2H4O), and Vinyl Alcohol (CH2CHOH)-in Interstellar and Cometary Ices

NASA Astrophysics Data System (ADS)

Bennett, Chris J.; Osamura, Yoshihiro; Lebar, Matt D.; Kaiser, Ralf I.

2005-11-01

Laboratory experiments were conducted to unravel synthetic routes to form three C2H4O isomers-acetaldehyde (CH3CHO), ethylene oxide (c-C2H4O), and vinyl alcohol (CH2CHOH)-in extraterrestrial ices via electronic energy transfer processes initiated by electrons in the track of MeV ion trajectories. Here we present the results of electron irradiation on a 2:1 mixture of carbon dioxide (CO2) and ethylene (C2H4). Our studies suggest that suprathermal oxygen atoms can add to the carbon-carbon π bond of an ethylene molecule to form initially an oxirene diradical (addition to one carbon atom) and the cyclic ethylene oxide molecule (addition to two carbon atoms) at 10 K. The oxirene diradical can undergo a [1, 2]-H shift to the acetaldehyde molecule. Both the ethylene oxide and the acetaldehyde isomers can be stabilized in the surrounding ice matrix. To a minor amount, suprathermal oxygen atoms can insert into a carbon-hydrogen bond of the ethylene molecule, forming vinyl alcohol. Once these isomers have been synthesized inside the ice layers of the coated grains in cold molecular clouds, the newly formed molecules can sublime as the cloud reaches the hot molecular core stage. These laboratory investigations help to explain astronomical observations by Nummelin et al. and Ikeda et al. toward massive star-forming regions and hot cores, where observed fractional abundances of these isomers are higher than can be accounted for by gas-phase reactions alone. Similar synthetic routes could help explain the formation of acetaldehyde and ethylene oxide in comet C/1995 O1 (Hale-Bopp) and also suggest a presence of both isomers in Titan's atmosphere.

The CH2O column as a possible constraint on methane oxidation

NASA Astrophysics Data System (ADS)

Valin, L. C.; Fiore, A. M.; Lin, M.

2013-12-01

We explore the potential for space-based measurements of the CH2O column to quantify variations of methane oxidation in the remote atmosphere due to changes in climate (e.g., T, H2O, stratospheric O3) and atmospheric composition (e.g., NOxO, O3, CO, CH4). We investigate the variability of methane oxidation and the formaldehyde column using available global simulations (MOZART-2 chemistry-transport model, GFDL AM3 climate-chemistry model). Over a large region (135° - 175° W; 0° - 16° S), the rate of methane oxidation simulated in the models varies intraseasonally (×10%), seasonally (×20%) and interannually (×5%), and is well correlated with the simulated variability of the CH2O column (R2 = 0.75; ~1x1015 molecules cm-2). The precision of a single space-based measurement is approximately 1×1016 molecules cm-2, an order of magnitude larger than the simulated variability of the CH2O column. However, in a large region such as the tropical Pacific, UV/Vis spectrometers are capable of making thousands of measurements daily, enough sampling to theoretically increase the precision by √N, such that variations on the order of 1×1015 molecules cm-2 should be observable on intraseasonal and interannual timescales.

Gas production, composition and emission at a modern disposal site receiving waste with a low-organic content

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

Scheutz, Charlotte, E-mail: chs@env.dtu.dk; Fredenslund, Anders M., E-mail: amf@env.dtu.dk; Nedenskov, Jonas, E-mail: jne@amfor.dk

2011-05-15

AV Miljo is a modern waste disposal site receiving non-combustible waste with a low-organic content. The objective of the current project was to determine the gas generation, composition, emission, and oxidation in top covers on selected waste cells as well as the total methane (CH{sub 4}) emission from the disposal site. The investigations focused particularly on three waste disposal cells containing shredder waste (cell 1.5.1), mixed industrial waste (cell 2.2.2), and mixed combustible waste (cell 1.3). Laboratory waste incubation experiments as well as gas modeling showed that significant gas generation was occurring in all three cells. Field analysis showed thatmore » the gas generated in the cell with mixed combustible waste consisted of mainly CH{sub 4} (70%) and carbon dioxide (CO{sub 2}) (29%) whereas the gas generated within the shredder waste, primarily consisted of CH{sub 4} (27%) and nitrogen (N{sub 2}) (71%), containing no CO{sub 2}. The results indicated that the gas composition in the shredder waste was governed by chemical reactions as well as microbial reactions. CH{sub 4} mass balances from three individual waste cells showed that a significant part (between 15% and 67%) of the CH{sub 4} generated in cell 1.3 and 2.2.2 was emitted through leachate collection wells, as a result of the relatively impermeable covers in place at these two cells preventing vertical migration of the gas. At cell 1.5.1, which is un-covered, the CH{sub 4} emission through the leachate system was low due to the high gas permeability of the shredder waste. Instead the gas was emitted through the waste resulting in some hotspot observations on the shredder surface with higher emission rates. The remaining gas that was not emitted through surfaces or the leachate collection system could potentially be oxidized as the measured oxidation capacity exceeded the potential emission rate. The whole CH{sub 4} emission from the disposal site was found to be 820 {+-} 202 kg CH{sub 4} d{sup -1}. The total emission rate through the leachate collection system at AV Miljo was found to be 211 kg CH{sub 4} d{sup -1}. This showed that approximately 1/4 of the emitted gas was emitted through the leachate collections system making the leachate collection system an important source controlling the overall gas migration from the site. The emission pathway for the remaining part of the gas was more uncertain, but emission from open cells where waste is being disposed of or being excavated for incineration, or from horizontal leachate drainage pipes placed in permeable gravel layers in the bottom of empty cells was likely.« less

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

NASA Astrophysics Data System (ADS)

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

2008-12-01

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

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

PubMed

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

2016-03-30

Macrocyclic metal complexes and p-benzoquinones are commonly used as co-catalytic redox mediators in aerobic oxidation reactions. In an effort to gain insight into the mechanism and energetic efficiency of these reactions, we investigated Co(salophen)-catalyzed aerobic oxidation of p-hydroquinone. Kinetic and spectroscopic data suggest that the catalyst resting-state consists of an equilibrium between a Co(II)(salophen) complex, a Co(III)-superoxide adduct, and a hydrogen-bonded adduct between the hydroquinone and the Co(III)-O2 species. The kinetic data, together with density functional theory computational results, reveal that the turnover-limiting step involves proton-coupled electron transfer from a semi-hydroquinone species and a Co(III)-hydroperoxide intermediate. Additional experimental and computational data suggest that a coordinated H2O2 intermediate oxidizes a second equivalent of hydroquinone. Collectively, the results show how Co(salophen) and p-hydroquinone operate synergistically to mediate O2 reduction and generate the reactive p-benzoquinone co-catalyst.

Methylmercury oxidative degradation potentials in contaminated and pristine sediments of the Carson River, Nevada

USGS Publications Warehouse

Oremland, R.S.; Miller, L.G.; Dowdle, P.; Connell, T.; Barkay, T.

1995-01-01

Sediments from mercury-contaminated and uncontaminated reaches of the Carson River, Nevada, were assayed for sulfate reduction, methanogenesis, denitrification, and monomethylmercury (MeHg) degradation. Demethylation of [14C]MeHg was detected at all sites as indicated by the formation of 14CO2 and 14CH4. Oxidative demethylation was indicated by the formation of 14CO2 and was present at significant levels in all samples. Oxidized/reduced demethylation product ratios (i.e., 14CO2/14CH4 ratios) generally ranged from 4.0 in surface layers to as low as 0.5 at depth. Production of 14CO2 was most pronounced at sediment surfaces which were zones of active denitrification and sulfate reduction but was also significant within zones of methanogenesis. In a core taken from an uncontaminated site having a high proportion of oxidized, coarse-grain sediments, sulfate reduction and methanogenic activity levels were very low and 14CO2 accounted for 98% of the product formed from [14C]MeHg. There was no apparent relationship between the degree of mercury contamination of the sediments and the occurrence of oxidative demethylation. However, sediments from Fort Churchill, the most contaminated site, were most active in terms of demethylation potentials. Inhibition of sulfate reduction with molybdate resulted in significantly depressed oxidized/reduced demethylation product ratios, but overall demethylation rates of inhibited and uninhibited samples were comparable. Addition of sulfate to sediment slurries stimulated production of 14CO2 from [14C]MeHg, while 2-bromoethanesulfonic acid blocked production of 14CH4. These results reveal the importance of sulfate-reducing and methanogenic bacteria in oxidative demethylation of MeHg in anoxic environments.

Genetic and Biochemical Analysis of High Iron Toxicity in Yeast

PubMed Central

Lin, Huilan; Li, Liangtao; Jia, Xuan; Ward, Diane McVey; Kaplan, Jerry

2011-01-01

Iron storage in yeast requires the activity of the vacuolar iron transporter Ccc1. Yeast with an intact CCC1 are resistant to iron toxicity, but deletion of CCC1 renders yeast susceptible to iron toxicity. We used genetic and biochemical analysis to identify suppressors of high iron toxicity in Δccc1 cells to probe the mechanism of high iron toxicity. All genes identified as suppressors of high iron toxicity in aerobically grown Δccc1 cells encode organelle iron transporters including mitochondrial iron transporters MRS3, MRS4, and RIM2. Overexpression of MRS3 suppressed high iron toxicity by decreasing cytosolic iron through mitochondrial iron accumulation. Under anaerobic conditions, Δccc1 cells were still sensitive to high iron toxicity, but overexpression of MRS3 did not suppress iron toxicity and did not result in mitochondrial iron accumulation. We conclude that Mrs3/Mrs4 can sequester iron within mitochondria under aerobic conditions but not anaerobic conditions. We show that iron toxicity in Δccc1 cells occurred under both aerobic and anaerobic conditions. Microarray analysis showed no evidence of oxidative damage under anaerobic conditions, suggesting that iron toxicity may not be solely due to oxidative damage. Deletion of TSA1, which encodes a peroxiredoxin, exacerbated iron toxicity in Δccc1 cells under both aerobic and anaerobic conditions, suggesting a unique role for Tsa1 in iron toxicity. PMID:21115478

Nitric Oxide Mediates Biofilm Formation and Symbiosis in Silicibacter sp. Strain TrichCH4B.

PubMed

Rao, Minxi; Smith, Brian C; Marletta, Michael A

2015-05-05

Nitric oxide (NO) plays an important signaling role in all domains of life. Many bacteria contain a heme-nitric oxide/oxygen binding (H-NOX) protein that selectively binds NO. These H-NOX proteins often act as sensors that regulate histidine kinase (HK) activity, forming part of a bacterial two-component signaling system that also involves one or more response regulators. In several organisms, NO binding to the H-NOX protein governs bacterial biofilm formation; however, the source of NO exposure for these bacteria is unknown. In mammals, NO is generated by the enzyme nitric oxide synthase (NOS) and signals through binding the H-NOX domain of soluble guanylate cyclase. Recently, several bacterial NOS proteins have also been reported, but the corresponding bacteria do not also encode an H-NOX protein. Here, we report the first characterization of a bacterium that encodes both a NOS and H-NOX, thus resembling the mammalian system capable of both synthesizing and sensing NO. We characterized the NO signaling pathway of the marine alphaproteobacterium Silicibacter sp. strain TrichCH4B, determining that the NOS is activated by an algal symbiont, Trichodesmium erythraeum. NO signaling through a histidine kinase-response regulator two-component signaling pathway results in increased concentrations of cyclic diguanosine monophosphate, a key bacterial second messenger molecule that controls cellular adhesion and biofilm formation. Silicibacter sp. TrichCH4B biofilm formation, activated by T. erythraeum, may be an important mechanism for symbiosis between the two organisms, revealing that NO plays a previously unknown key role in bacterial communication and symbiosis. Bacterial nitric oxide (NO) signaling via heme-nitric oxide/oxygen binding (H-NOX) proteins regulates biofilm formation, playing an important role in protecting bacteria from oxidative stress and other environmental stresses. Biofilms are also an important part of symbiosis, allowing the organism to remain in a nutrient-rich environment. In this study, we show that in Silicibacter sp. strain TrichCH4B, NO mediates symbiosis with the alga Trichodesmium erythraeum, a major marine diazotroph. In addition, Silicibacter sp. TrichCH4B is the first characterized bacteria to harbor both the NOS and H-NOX proteins, making it uniquely capable of both synthesizing and sensing NO, analogous to mammalian NO signaling. Our study expands current understanding of the role of NO in bacterial signaling, providing a novel role for NO in bacterial communication and symbiosis. Copyright © 2015 Rao et al.

Gas-exfoliated porous monolayer boron nitride for enhanced aerobic oxidative desulfurization performance.

PubMed

Wu, Yingcheng; Wu, Peiwen; Chao, Yanhong; He, Jing; Li, Hongping; Lu, Linjie; Jiang, Wei; Zhang, Beibei; Li, Huaming; Zhu, Wenshuai

2018-01-12

Hexagonal boron nitride has been regarded to be an efficient catalyst in aerobic oxidation fields, but limited by the less-exposed active sites. In this contribution, we proposed a simple green liquid nitrogen gas exfoliation strategy for preparation of porous monolayer nanosheets (BN-1). Owing to the reduced layer numbers, decreased lateral sizes and artificially-constructed pores, increased exposure of active sites was expected, further contributed to an enhanced aerobic oxidative desulfurization (ODS) performance up to ∼98% of sulfur removal, achieving ultra-deep desulfurization. This work not only introduced an excellent catalyst for aerobic ODS, but also provided a strategy for construction of some other highly-efficient monolayer two-dimensional materials for enhanced catalytic performance.

Gas-exfoliated porous monolayer boron nitride for enhanced aerobic oxidative desulfurization performance

NASA Astrophysics Data System (ADS)

Wu, Yingcheng; Wu, Peiwen; Chao, Yanhong; He, Jing; Li, Hongping; Lu, Linjie; Jiang, Wei; Zhang, Beibei; Li, Huaming; Zhu, Wenshuai

2018-01-01

Hexagonal boron nitride has been regarded to be an efficient catalyst in aerobic oxidation fields, but limited by the less-exposed active sites. In this contribution, we proposed a simple green liquid nitrogen gas exfoliation strategy for preparation of porous monolayer nanosheets (BN-1). Owing to the reduced layer numbers, decreased lateral sizes and artificially-constructed pores, increased exposure of active sites was expected, further contributed to an enhanced aerobic oxidative desulfurization (ODS) performance up to ˜98% of sulfur removal, achieving ultra-deep desulfurization. This work not only introduced an excellent catalyst for aerobic ODS, but also provided a strategy for construction of some other highly-efficient monolayer two-dimensional materials for enhanced catalytic performance.

Above- and belowground fluxes of CH4 from boreal shrubs and Scots pine

NASA Astrophysics Data System (ADS)

Halmeenmäki, Elisa; Heinonsalo, Jussi; Santalahti, Minna; Putkinen, Anuliina; Fritze, Hannu; Pihlatie, Mari

2016-04-01

Boreal upland forests are considered as an important sink for the greenhouse gas methane (CH4) due to CH4 oxidizing microbes in the soil. However, recent evidence suggests that vegetation can act as a significant source of CH4. Also, preliminary measurements indicate occasional emissions of CH4 above the tree canopies of a boreal forest. Nevertheless, the sources and the mechanisms of the observed CH4 emissions are still mostly unknown. Furthermore, the majority of CH4 flux studies have been conducted with the soil chamber method, thus not considering the role of the vegetation itself. We conducted a laboratory experiment to study separately the above- and belowground CH4 fluxes of bilberry (Vaccinium myrtillus), lingonberry (Vaccinium vitis-idaea), heather (Calluna vulgaris), and Scots pine (Pinus sylvestris), which were grown in microcosms. The above- and belowground fluxes of the plants were measured separately, and these fluxes were compared to fluxes of microcosms containing only humus soil. In addition to the flux measurements, we analysed the CH4 producing archaea (methanogens) and the CH4 consuming bacteria (methanotrophs) with the qPCR method to discover whether these microbes contribute to the CH4 exchange from the plant material and the soil. The results of the flux measurements indicate that the humus soil with roots of lingonberry, heather, and Scots pine consume CH4 compared to bare humus soil. Simultaneously, the shoots of heather and Scots pine emit small amounts of CH4. We did not find detectable amounts of methanogens from any of the samples, suggesting the produced CH4 could be of non-microbial origin, or produced by very small population of methanogens. Based on the first preliminary results, methanotrophs were present in all the studied plant species, and especially in high amounts in the rooted soils, thus implying that the methanotrophs could be responsible of the CH4 uptake in the root-soil systems.

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

PubMed

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

2017-02-01

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

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

PubMed Central

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

2017-01-01

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

The Aerobic Oxidation of Bromide to Dibromine Catalyzed by Homogeneous Oxidation Catalysts and Initiated by Nitrate in Acetic Acid

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

Partenheimer, Walt; Fulton, John L.; Sorensen, Christina M.

A small amount of nitrate, ~0.002 molal, initiates the Co/Mn catalyzed aerobic oxidation of bromide compounds (HBr,NaBr,LiBr) to dibromine in acetic acid at room temperature. At temperatures 40oC or less , the reaction is autocatalytic. Co(II) and Mn(II) themselves and mixed with ionic bromide are known homogeneous oxidation catalysts. The reaction was discovered serendipitously when a Co/Br and Co/Mn/Br catalyst solution was prepared for the aerobic oxidation of methyaromatic compounds and the Co acetate contained a small amount of impurity i.e. nitrate. The reaction was characterized by IR, UV-VIS, MALDI and EXAFS spectroscopies and the coordination chemistry is described. Themore » reaction is inhibited by water and its rate changed by pH. The change in these variables, as well as others, are identical to those observed during homogeneous, aerobic oxidation of akylaromatics. A mechanism is proposed. Accidental addition of a small amount of nitrate compound into a Co/Mn/Br/acetic acid mixture in a large, commercial feedtank is potentially dangerous.« less