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

USGS Publications Warehouse

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

2015-01-01

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

Different Apparent Gas Exchange Coefficients for CO2 and CH4: Comparing a Brown-Water and a Clear-Water Lake in the Boreal Zone during the Whole Growing Season.

PubMed

Rantakari, Miitta; Heiskanen, Jouni; Mammarella, Ivan; Tulonen, Tiina; Linnaluoma, Jessica; Kankaala, Paula; Ojala, Anne

2015-10-06

The air-water exchange of carbon dioxide (CO2) and methane (CH4) is a central process during attempts to establish carbon budgets for lakes and landscapes containing lakes. Lake-atmosphere diffusive gas exchange is dependent on the concentration gradient between air and surface water and also on the gas transfer velocity, often described with the gas transfer coefficient k. We used the floating-chamber method in connection with surface water gas concentration measurements to estimate the gas transfer velocity of CO2 (kCO2) and CH4 (kCH4) weekly throughout the entire growing season in two contrasting boreal lakes, a humic oligotrophic lake and a clear-water productive lake, in order to investigate the earlier observed differences between kCO2 and kCH4. We found that the seasonally averaged gas transfer velocity of CH4 was the same for both lakes. When the lakes were sources of CO2, the gas transfer velocity of CO2 was also similar between the two study lakes. The gas transfer velocity of CH4 was constantly higher than that of CO2 in both lakes, a result also found in other studies but for reasons not yet fully understood. We found no differences between the lakes, demonstrating that the difference between kCO2 and kCH4 is not dependent on season or the characteristics of the lake.

Greenhouse gas (CO2 and CH4) emissions from a high altitude hydroelectric reservoir in the tropics (Riogrande II, Colombia)

NASA Astrophysics Data System (ADS)

Guérin, Frédéric; Leon, Juan

2015-04-01

Tropical hydroelectric reservoirs are considered as very significant source of methane (CH4) and carbon dioxide (CO2), especially when flooding dense forest. We report emissions from the Rio Grande II Reservoir located at 2000 m.a.s.l. in the Colombian Andes. The dam was built at the confluence of the Rio Grande and Rio Chico in 1990. The reservoir has a surface of 12 km2, a maximum depth of 40m and a residence time of 2.5 month. Water quality (temperature, oxygen, pH, conductivity), nitrate, ammonium, dissolved and particulate organic carbon (DOC and POC), CO2 and CH4 were monitored bi-monthly during 1.5 year at 9 stations in the reservoir. Diffusive fluxes of CO2 and CH4 and CH4 ebullition were measured at 5 stations. The Rio grande II Reservoir is weakly stratified thermally with surface temperature ranging from 20 to 24°C and a constant bottom temperature of 18°C. The reservoir water column is well oxygenated at the surface and usually anoxic below 10m depth. At the stations close to the tributaries water inputs, the water column is well mixed and oxygenated from the surface to the bottom. As reported for other reservoirs located in "clear water" watersheds, the concentrations of nutrients are low (NO3-<0.1ppm, NH4+<0.2ppm), the concentrations of DOC are high (2-8 mg L-1) and POC concentrations are low (< 3 mg L-1). Surface CH4 concentrations at the central stations of the reservoirs are 0.5 μmol L-1 (0.07-2.14 μmol L-1) and 3 times higher at the stations close to the tributaries inputs (up to 7 μmol L-1). In the hypolimnion, CH4 concentration is <100 μmol L-1 in the wet season and can reach up to 400 μmol L-1 in the dry season. The spatial and temporal variability are lower for CO2. Surface CO2 concentration was on average 72 μmol L-1 (up to 300) and hypolimnic concentration ranged between 250 and 1000 μmol L-1. The CO2 diffusive flux is 517±331 mmol m-2 d-1 with little seasonal and spatial variations. At the center of the reservoir, the median diffusive flux of CH4 is 1.75 mmol m-2 d-1 and sporadic high fluxes (>10 mmol m-2 d-1) were observed during the dry season. Close to the tributaries water inputs where the water column is well mixed, the average diffusive flux is 8 mmol m-2 d-1. CH4 ebullition was 3.5 mmol m-2 d-1 and no ebullition was observed for a water depth higher than 5m. The zone under the influence of the water inputs from tributaries represents 25% of the surface of the reservoir but contributed half of total CH4 emissions from the reservoir (29MgC month-1). Ebullition contributed only to 12% of total CH4 emissions over a year but it contributed up to 60% during the dry season. CH4 emissions from the Rio Grande Reservoir contributed 30% of the total GHG emissions (38GgCO2eq y-1). Overall, this study show that the majority of CH4 emissions from this reservoir occur through hotspot and hot moments and that mountainous reservoir located in the tropics could have emission factors as high as Amazonian reservoirs.

Minor methane emissions from an Alpine hydropower reservoir based on monitoring of diel and seasonal variability.

PubMed

Sollberger, Sébastien; Wehrli, Bernhard; Schubert, Carsten J; DelSontro, Tonya; Eugster, Werner

2017-10-18

We monitored CH 4 emissions during the ice-free period of an Alpine hydropower reservoir in the Swiss Alps, Lake Klöntal, to investigate mechanisms responsible for CH 4 variability and to estimate overall emissions to the atmosphere. A floating eddy-covariance platform yielded total CH 4 and CO 2 emission rates at high temporal resolution, while hydroacoustic surveys provided no indication of CH 4 ebullition. Higher CH 4 fluxes (2.9 ± 0.1 mg CH 4 per m 2 per day) occurred during the day when surface water temperatures were warmer and wind speeds higher than at night. Piston velocity estimates (k 600 ) showed an upper limit at high wind speeds that may be more generally valid also for other lakes and reservoirs with limited CH 4 dissolved in the water body: above 2.0 m s -1 a further increase in wind speed did not lead to higher CH 4 fluxes, because under such conditions it is not the turbulent mixing and transport that limits effluxes, but the resupply of CH 4 to the lake surface. Increasing CH 4 fluxes during the warm season showed a clear spatial gradient once the reservoir started to fill up and flood additional surface area. The warm period contributed 27% of the total CH 4 emissions (2.6 t CH 4 per year) estimated for the full year and CH 4 accounted for 63% of carbonic greenhouse gas emissions. Overall, the average CH 4 emissions (1.7 to 2.2 mg CH 4 per m 2 per day determined independently from surface water samplings and eddy covariance, respectively) were small compared to most tropical and some temperate reservoirs. The resulting greenhouse gas (GHG) emissions in CO 2 -equivalents revealed that electricity produced in the Lake Klöntal power plant was relatively climate-friendly with a low GHG-to-power output ratio of 1.24 kg CO 2,eq per MW h compared to 6.5 and 8.1 kg CO 2,eq per MW h associated with the operation of solar photovoltaics and wind energy, respectively, or about 980 kg CO 2,eq per MW h for coal-fired power plants.

Observationally derived rise in methane surface forcing mediated by water vapour trends

NASA Astrophysics Data System (ADS)

Feldman, D. R.; Collins, W. D.; Biraud, S. C.; Risser, M. D.; Turner, D. D.; Gero, P. J.; Tadić, J.; Helmig, D.; Xie, S.; Mlawer, E. J.; Shippert, T. R.; Torn, M. S.

2018-04-01

Atmospheric methane (CH4) mixing ratios exhibited a plateau between 1995 and 2006 and have subsequently been increasing. While there are a number of competing explanations for the temporal evolution of this greenhouse gas, these prominent features in the temporal trajectory of atmospheric CH4 are expected to perturb the surface energy balance through radiative forcing, largely due to the infrared radiative absorption features of CH4. However, to date this has been determined strictly through radiative transfer calculations. Here, we present a quantified observation of the time series of clear-sky radiative forcing by CH4 at the surface from 2002 to 2012 at a single site derived from spectroscopic measurements along with line-by-line calculations using ancillary data. There was no significant trend in CH4 forcing between 2002 and 2006, but since then, the trend in forcing was 0.026 ± 0.006 (99.7% CI) W m2 yr-1. The seasonal-cycle amplitude and secular trends in observed forcing are influenced by a corresponding seasonal cycle and trend in atmospheric CH4. However, we find that we must account for the overlapping absorption effects of atmospheric water vapour (H2O) and CH4 to explain the observations fully. Thus, the determination of CH4 radiative forcing requires accurate observations of both the spatiotemporal distribution of CH4 and the vertically resolved trends in H2O.

Air-water CO2 and CH4 fluxes along a river-reservoir continuum: Case study in the Pengxi River, a tributary of the Yangtze River in the Three Gorges Reservoir, China.

PubMed

Huang, Yang; Yasarer, Lindsey M W; Li, Zhe; Sturm, Belinda S M; Zhang, Zengyu; Guo, Jinsong; Shen, Yu

2017-05-01

Water surface greenhouse gas (GHG) emissions in freshwater reservoirs are closely related to limnological processes in the water column. Affected by both reservoir operation and seasonal changes, variations in the hydro-morphological conditions in the river-reservoir continuum will create distinctive patterns in water surface GHG emissions. A one-year field survey was carried out in the Pengxi River-reservoir continuum, a part of the Three Gorges Reservoir (TGR) immediately after the TGR reached its maximum water level. The annual average water surface CO 2 and CH 4 emissions at the riverine background sampling sites were 6.23 ± 0.93 and 0.025 ± 0.006 mmol h -1  m -2 , respectively. The CO 2 emissions were higher than those in the downstream reservoirs. The development of phytoplankton controlled the downstream decrease in water surface CO 2 emissions. The presence of thermal stratification in the permanent backwater area supported extensive phytoplankton blooms, resulting in a carbon sink during several months of the year. The CH 4 emissions were mainly impacted by water temperature and dissolved organic carbon. The greatest water surface CH 4 emission was detected in the fluctuating backwater area, likely due to a shallower water column and abundant organic matter. The Pengxi River backwater area did not show significant increase in water surface GHG emissions reported in tropical reservoirs. In evaluating the net GHG emissions by the impoundment of TGR, the net change in the carbon budget and the contribution of nitrogen and phosphorus should be taken into consideration in this eutrophic river-reservoir continuum.

Carbon dioxide and methane emissions from the Yukon River system

USGS Publications Warehouse

Striegl, Robert G.; Dornblaser, Mark M.; McDonald, Cory P.; Rover, Jennifer R.; Stets, Edward G.

2012-01-01

Carbon dioxide (CO2) and methane (CH4) emissions are important, but poorly quantified, components of riverine carbon (C) budgets. This is largely because the data needed for gas flux calculations are sparse and are spatially and temporally variable. Additionally, the importance of C gas emissions relative to lateral C exports is not well known because gaseous and aqueous fluxes are not commonly measured on the same rivers. We couple measurements of aqueous CO2 and CH4 partial pressures (pCO2, pCH4) and flux across the water-air interface with gas transfer models to calculate subbasin distributions of gas flux density. We then combine those flux densities with remote and direct observations of stream and river water surface area and ice duration, to calculate C gas emissions from flowing waters throughout the Yukon River basin. CO2emissions were 7.68 Tg C yr−1 (95% CI: 5.84 −10.46), averaging 750 g C m−2 yr−1 normalized to water surface area, and 9.0 g C m−2 yr−1 normalized to river basin area. River CH4 emissions totaled 55 Gg C yr−1 or 0.7% of the total mass of C emitted as CO2 plus CH4 and ∼6.4% of their combined radiative forcing. When combined with lateral inorganic plus organic C exports to below head of tide, C gas emissions comprised 50% of total C exported by the Yukon River and its tributaries. River CO2 and CH4 derive from multiple sources, including groundwater, surface water runoff, carbonate equilibrium reactions, and benthic and water column microbial processing of organic C. The exact role of each of these processes is not yet quantified in the overall river C budget.

Methane in the South China Sea and the Western Philippine Sea

NASA Astrophysics Data System (ADS)

Tseng, Hsiao-Chun; Chen, Chen-Tung Arthur; Borges, Alberto V.; DelValls, T. Angel; Chang, Yu-Chang

2017-03-01

Approximately 700 water samples from the South China Sea (SCS) and 300 water samples from the western Philippine Sea (wPS) were collected during eight cruises from August 2003 to July 2007 to determine methane (CH4) distributions from the surface to a depth of 4250 m. The surface CH4 concentrations exceeded atmospheric equilibrium, both in the SCS and the wPS, and the concentrations were 4.5±3.6 and 3.0±1.2 nmol L-1, respectively. The sea-to-air fluxes were calculated, and the SCS and the wPS were found to emit CH4 to the atmosphere at 8.6±6.4 μmol m-2 d-1 and 4.9±4.9 μmol m-2 d-1, respectively. In the SCS, CH4 emissions were higher over the continental shelf (11.0±7.4 μmol m-2 d-1) than over the deep ocean (6.1±6.0 μmol m-2 d-1), owing to greater biological productivity and closer coupling with the sediments on the continental shelf. The SCS emitted 30.1×106 mol d-1 CH4 to the atmosphere and exported 1.82×106 mol d-1 CH4 to the wPS. The concentrations of both CH4 and chlorophyll a were high in the 150 m surface layer of the wPS, but were not significantly correlated with each other. CH4 concentrations generally declined with increasing depth below the euphotic zone but remained constant below 1,000 m, both in the SCS and the wPS. Some high CH4 concentrations were observed at mid-depths and bottom waters in the SCS, and were most likely caused by the release of CH4 from gas hydrates or gas seepage.

Greenhouse gas emissions are enhanced by wastewater discharge into New York City coastal estuaries

NASA Astrophysics Data System (ADS)

Brigham, B. A.; O'Mullan, G. D.; Bird, J. A.

2016-12-01

The Hudson River Estuary (HRE) receives significant inputs of untreated wastewater from sewer overflow from New York City (NYC) and other urban areas. These inputs deliver large, concentrated pulses of carbon (C) and nitrogen (N) into the estuary primarily during storm events. We hypothesized that sewage inputs would increase carbon dioxide (CO2) and methane (CH4) efflux from the HRE via two mechanism: (1) direct input of these gases into estuarine surface waters from NYC's wastewater treatment system; and (2) indirect in-situ microbial production in response to the C and N additions. To test these hypotheses, CO2, CH4, dissolved organic C and inorganic N concentrations were measured in both sewage outflow and in estuarine waters. Efflux of CO2 and CH4 were also quantified from sediment cores sampled from Flushing Bay (FB), which is in close proximity to sewage delivery outlets. Wastewater discharge was found to be both a direct input in wastewater and an indirect source of CO2 and CH4 via microbial respiration. Effluent concentrations of CH4 (125 ppm), CO2 (2200 ρCO2), dissolved organic C, ammonium, and nitrate surface water concentrations, were a minimum of 3 times greater than in estuarine surface water adjacent to the sewage delivery area and up to 20 times greater than concentrations found in regional HRE surface waters. Incubation experiments with FB sediment demonstrated that acetate additions stimulated CO2 efflux by + 1.25 and CH4 efflux by +10 times, compared with unamended controls. The magnitude of CH4 produced was +40 times greater than from sediments incubated from a non-sewage affected area with similar salinity levels. However, total C mineralization (6 µg C day-1 g-1 of dry soil) was a small portion of the C amendment indicating negligible priming. These data warrant study on larger regional scales to assess the broader climate impact likely driven by CH4 efflux that results from discharge of untreated wastewater into urban estuaries.

The impact of water management practices and associated methane emissions on subtropical pasture greenhouse gas budgets and ecosystem service payments

NASA Astrophysics Data System (ADS)

Chamberlain, S.; Groffman, P. M.; Boughton, E.; Gomez-Casanovas, N.; DeLucia, E. H.; Bernacchi, C.; Sparks, J. P.

2016-12-01

Pastures are an extensive land cover type, however patterns in pasture greenhouse gas (GHG) exchange vary widely depending on climate and land management. Understanding this variation is important, as pastures may be a net GHG source or sink depending on these factors. We quantified carbon dioxide (CO2) and methane (CH4) fluxes from subtropical pastures in south Florida for three years using eddy covariance, and estimated annual budgets of CO2, CH4, and GHG equivalent emissions. We also explored the influence of water retention practices on pasture GHG budgets by combining data from a multi-year pasture water retention experiment with CH4 flux data from our eddy covariance tower to 1) estimate the influence of water retention on surface soil flooding, and 2) estimate the influence of extended surface soil flooding on CH4 emissions. These findings were then used to assess the impact of CH4 emissions on stakeholder payments for water retention services in a carbon market framework. The pastures were net CO2 sinks sequestering up to 163 ± 54 g CO2-C m-2 yr-1, but were also strong CH4 sources emitting up to 23.5 ± 2.1 g CH4-C m-2 yr-1. Accounting for the global warming potential of CH4, the pastures were strong GHG sources emitting up to 584 ± 78 g CO2 eq. m-2 yr-1. Our analysis suggests CH4 emissions due to increased flooding from water management practices is a small component of the pasture GHG budget, and water retention likely contributes 2-11% of pasture GHG emissions. These emissions could reduce water retention payments by up to 12% if stakeholders were required to pay for current GHG emissions in a carbon market. It would require at least 93.7 kg CH4-C emissions per acre-foot water storage for carbon market costs to exceed water retention payments, and this scenario is highly unlikely as we estimate current practices are responsible for 11.3 ± 7.2 kg CH4-C emissions per acre-foot of water storage. Our results demonstrate that water retention practices aimed at reducing nutrient loading to the Everglades are likely responsible for only a minor increase in pasture GHG emissions and would have a small economic consequence in a carbon market.

Evidence for a nonmonotonic relationship between ecosystem-scale peatland methane emissions and water table depth

NASA Astrophysics Data System (ADS)

Brown, Mathew G.; Humphreys, Elyn R.; Moore, Tim R.; Roulet, Nigel T.; Lafleur, Peter M.

2014-05-01

Although temporal and spatial variations in peatland methane (CH4) emissions at broad scales are often related to water table (WT) using a linear relationship, a potentially complex relationship exists between these variables locally and over shorter time scales. To explore this issue, CH4 fluxes were measured using eddy covariance at the Mer Bleue bog over two summer seasons. Peak CH4 emissions (30 to 50 mg CH4-C m-2 d-1) occurred not when the WT was closest to the surface but instead, when it dropped to 40 to 55 cm below the surface. When the WT was below or above this zone, average fluxes were 14 mg CH4-C m-2 d-1. We speculate this critical zone coincides with the necessary redox potentials and sources of fresh organic material that lead to maximum production of CH4 and/or with conditions that lead to degassing of stored CH4. However, as expected, total summer CH4 emissions were 47% lower during the drier year. This occurred in part because the WT was within the critical zone for fewer days in the drier year but also because after an extended midsummer dry period there was little recovery of CH4 emissions, even a month after rewetting.

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.

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

DOE PAGES

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

2016-10-10

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

Hydration of Sulphobetaine (SB) and Tetra(ethylene glycol) (EG4)-Terminated Self-Assembled Monolayers Studied by Sum Frequency Generation (SFG) Vibrational Spectroscopy

PubMed Central

Stein, M. Jeanette; Weidner, Tobias; McCrea, Keith; Castner, David G.; Ratner, Buddy D.

2010-01-01

Sum frequency generation (SFG) vibrational spectroscopy is used to study the surface and the underlying substrate of both homogeneous and mixed self-assembled monolayers (SAMs) of 11-mercaptoundecyl-1-sulphobetainethiol (HS(CH2)11N+(CH3)2(CH2)3SO3−, SB) and 1-mercapto-11-undecyl tetra(ethylene glycol) (HS(CH2)11O(CH2CH2O)4OH, EG4) with an 11-mercapto-1-undecanol (HS(CH2)11OH, MCU) diluent. SFG results on the C–H region of the dry and hydrated SAMs gave an in situ look into the molecular orientation and suggested an approach to maximize signal-to-noise ratio on these difficult to analyze hydrophilic SAMs. Vibrational fingerprint studies in the 3000–3600 cm−1 spectral range for the SAMs exposed serially to air, water, and deuterated water revealed that a layer of tightly-bound structured water was associated with the surface of a non-fouling monolayer but was not present on a hydrophobic N-undecylmercaptan (HS(CH2)10CH3, UnD) control. The percentage of water retained upon submersion in D2O correlated well with the relative amount of protein that was previously shown to absorb onto the monolayers. These results provide evidence supporting the current theory regarding the role of a tightly-bound vicinal water layer in the protein resistance of a non-fouling group. PMID:19639981

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.

Spatial and Temporal Variations in the Partial Pressure and Emission of CO2 and CH4 in and Amazon Floodplain Lake

NASA Astrophysics Data System (ADS)

Forsberg, B. R.; Amaral, J. H.; Barbosa, P.; Kasper, D.; MacIntyre, S.; Cortes, A.; Sarmento, H.; Borges, A. V.; Melack, J. M.; Farjalla, V.

2015-12-01

The Amazon floodplain contains a variety of wetland environments which contribute CO2 and CH4 to the regional and global atmospheres. The partial pressure and emission of these greenhouse gases (GHGs) varies: 1) between habitats, 2) seasonally, as the characteristics these habitats changes and 3) diurnally, in response to diurnal stratification. In this study, we investigated the combined influence of these factors on the partial pressure and emission of GHGs in Lago Janauacá, a central Amazon floodplain lake (3o23' S; 60o18' O). All measurements were made between August of 2014 and April of 2015 at two different sites and in three distinct habitats: open water, flooded forest, flooded macrophytes. Concentrations of CO2 and CH4 in air were measured continuously with a cavity enhanced absorption spectrometer, Los Gatos Research´s Ultraportable Greenhouse Gas Analyzer (UGGA). Vertical profiles o pCO2 and pCH4 were measured using the UGGA connected to an electric pump and equilibrator. Diffusive surface emissions were estimated with the UGGA connected to a static floating chamber. To investigate the influence of vertical stratification and mixing on GHG partial pressure and emissions, a meteorological station and submersible sensor chain were deployed at each site. Meteorological sensors included wind speed and direction. The submersible chains included thermistors and oxygen sensors. Depth profiles of partial pressure and diffusive emissions for both CO2 and CH4 varied diurnally, seasonally and between habitats. Both pCO2 and pCH4 were consistently higher in bottom than surface waters with the largest differences occurring at high water when thermal stratification was most stable. Methane emissions and partial pressures were highest at low water while pCO2 and CO2 fluxes were highest during high water periods, with 35% of CO2 fluxes at low water being negative. The highest average surface value of pCO2 (5491 μatm), encountered during rising water, was ~3 times higher than that encountered at low water (1708 μatm). Partial pressures and emissions of both CO2 and CH4 were greatest in open water habitats and consistently higher at night. These patterns reflected the higher levels of wind driven mixing and turbulence in open water environments and higher convective mixing at night which promoted diffusive emission.

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

Controls of Methane Dynamics and Emissions in an Arctic Warming Experiment

NASA Astrophysics Data System (ADS)

Nielsen, C. S.; Elberling, B.; Michelsen, A.; Strobel, B. W.; Wulff, K.; Banyasz, I.

2015-12-01

Climatic changes have resulted in increasing air temperatures across the Arctic. This may increase anaerobic decomposition of soil organic matter to methane (CH4) in wetlands and increase plant growth and thereby production of substrate. Little is known about how seasonal variations in dissolved CH4 in soil water, substrate availability, and the effect of warming affect arctic wetland dynamics of CH4 production and emission. In 2013 we established two experiments in a fen at Disko Island, W Greenland; one with year round warming by open-top chambers and removal of shrubs, and one with removal of the aerenchymatous sedge Carex aquatilis ssp. stans. Throughout the growing season 2014 we measured how the treatments affected CH4 emissions, dissolved CH4 in the soil water, and substrate availability. Ecosystem CH4 emissions peaked at August 5th 2014 (7.5 μmol m-2 h-1) without coinciding with time of highest concentrations of dissolved CH4 or acetate indicating a decoupling between production and emission of CH4. The peak in dissolved CH4 concentration, at ten cm depth (1368 ppm, September 18th 2014), followed the peak in concentration of acetate in the same depth (0.30 ppm, August 30th 2014) highlighting the importance of this substance as a substrate for methanogenesis. C. aquatilis ssp. stans accounted for 60% and 77% of the ecosystem CH4 emissions in areas of the fen with water table above and below soil surface showing the importance of the presence of this species to serve as a pipe for CH4 emission which is bypassing the upper soil zone and potential methane oxidation. Throughout the season, warming increased the air temperature at soil surface by on average 0.89°C and occasionally warming and shrub removal increased soil temperature in 2 and 5 cm depth, but there was no effect of the treatments on the CH4 emissions indicating that this wetland is quite resilient towards future climate change.

High net CO2 and CH4 release at a eutrophic shallow lake on a formerly drained fen

NASA Astrophysics Data System (ADS)

Franz, Daniela; Koebsch, Franziska; Larmanou, Eric; Augustin, Jürgen; Sachs, Torsten

2016-05-01

Drained peatlands often act as carbon dioxide (CO2) hotspots. Raising the groundwater table is expected to reduce their CO2 contribution to the atmosphere and revitalise their function as carbon (C) sink in the long term. Without strict water management rewetting often results in partial flooding and the formation of spatially heterogeneous, nutrient-rich shallow lakes. Uncertainties remain as to when the intended effect of rewetting is achieved, as this specific ecosystem type has hardly been investigated in terms of greenhouse gas (GHG) exchange. In most cases of rewetting, methane (CH4) emissions increase under anoxic conditions due to a higher water table and in terms of global warming potential (GWP) outperform the shift towards CO2 uptake, at least in the short term.Based on eddy covariance measurements we studied the ecosystem-atmosphere exchange of CH4 and CO2 at a shallow lake situated on a former fen grassland in northeastern Germany. The lake evolved shortly after flooding, 9 years previous to our investigation period. The ecosystem consists of two main surface types: open water (inhabited by submerged and floating vegetation) and emergent vegetation (particularly including the eulittoral zone of the lake, dominated by Typha latifolia). To determine the individual contribution of the two main surface types to the net CO2 and CH4 exchange of the whole lake ecosystem, we combined footprint analysis with CH4 modelling and net ecosystem exchange partitioning.The CH4 and CO2 dynamics were strikingly different between open water and emergent vegetation. Net CH4 emissions from the open water area were around 4-fold higher than from emergent vegetation stands, accounting for 53 and 13 g CH4 m-2 a-1 respectively. In addition, both surface types were net CO2 sources with 158 and 750 g CO2 m-2 a-1 respectively. Unusual meteorological conditions in terms of a warm and dry summer and a mild winter might have facilitated high respiration rates. In sum, even after 9 years of rewetting the lake ecosystem exhibited a considerable C loss and global warming impact, the latter mainly driven by high CH4 emissions. We assume the eutrophic conditions in combination with permanent high inundation as major reasons for the unfavourable GHG balance.

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

UAV Remote Sensing Can Reveal the Effects of Low-Impact Seismic Lines on Surface Morphology, Hydrology, and Methane (CH4) Release in a Boreal Treed Bog

NASA Astrophysics Data System (ADS)

Lovitt, J.; Rahman, M. M.; Saraswati, S.; McDermid, G. J.; Strack, M.; Xu, B.

2018-03-01

Peatlands are globally significant stores of soil carbon, where local methane (CH4) emissions are strongly linked to water table position and microtopography. Historically, these factors have been difficult to measure in the field, constraining our capacity to observe local patterns of variability. In this paper, we show how remote sensing surveys conducted from unmanned aerial vehicle (UAV) platforms can be used to map microtopography and depth to water over large areas with good accuracy, paving the way for spatially explicit estimates of CH4 emissions. This approach enabled us to observe—for the first time—the effects of low-impact seismic lines (LIS; petroleum exploration corridors) on surface morphology and CH4 emissions in a treed-bog ecosystem in northern Alberta, Canada. Through compaction, LIS lines were found to flatten the observed range in microtopographic elevation by 46 cm and decrease mean depth to water by 15.4 cm, compared to surrounding undisturbed conditions. These alterations are projected to increase CH4 emissions by 20-120% relative to undisturbed areas in our study area, which translates to a total rise of 0.011-0.027 kg CH4 day-1 per linear kilometer of LIS ( 2 m wide). The 16 km of LIS present at our 61 ha study site were predicted to boost CH4 emissions by 20-70 kg between May and September 2016.

Density functional theory study of acetaldehyde hydrodeoxygenation on MoO3

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

Mei, Donghai; Karim, Ayman M.; Wang, Yong

2011-04-06

Periodic spin-polarized density functional theory calculations were performed to investigate acetaldehyde (CH3CHO) hydrodeoxygenation on the reduced molybdenum trioxide (MoO3) surface. The perfect O-terminated α-MoO3(010) surface is reduced to generate an oxygen defect site in the presence of H2. H2 dissociatively adsorbs at the surface oxygen sites forming two surface hydroxyls, which can recombine into a water molecule weakly bound at the Mo site. A terminal oxygen (Ot) defect site thus forms after water desorption. CH3CHO adsorbs at the O-deficient Mo site via either the sole O-Mo bond or the O-Mo and the C-O double bonds. The possible reaction pathways ofmore » the adsorbed CH3CHO with these two configurations were thoroughly examined using the dimer searching method. Our results show that the ideal deoxygenation of CH3CHO leading to ethylene (C2H4) on the reduced MoO3(010) surface is feasible. The adsorbed CH3CHO first dehydrogenate into CH2CHO by reacting with a neighboring terminal Ot. The hydroxyl (OtH) then hydrogenates CH2CHO into CH2CH2O to complete the hydrogen transfer cycle with an activation barrier of 1.39 eV. The direct hydrogen transfer from CH3CHO to CH2CH2O is unlikely due to the high barrier of 2.00 eV. The produced CH2CH2O readily decomposes into C2H4 that directly releases to the gas phase, and regenerates the Ot atom on the Mo site. As a result, the reduced MoO3(010) surface is reoxidized to the perfect MoO3(010) surface after CH3CHO deoxygenation. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.« less

Short-term response of methane fluxes and methanogen activity to water table and soil warming manipulations in an Alaskan peatland

Treesearch

M.R. Turetsky; C.C. Treat; M. Waldrop; J.M. Waddington; J.W. Harden; A.D. McGuire

2008-01-01

Growing season CH4 fluxes were monitored over a two year period following the start of ecosystem-scale manipulations of water table position and surface soil temperatures in a moderate rich fen in interior Alaska. The largest CH4 fluxes occurred in plots that received both flooding (raised water table position) and soil...

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

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

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

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

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

Impact of mine wastewaters on greenhouse gas emissions from northern peatlands used for mine water treatment

NASA Astrophysics Data System (ADS)

Palmer, Katharina; Ronkanen, Anna-Kaisa; Klöve, Björn; Hynynen, Jenna; Maljanen, Marja

2015-04-01

The amount of wastewaters generated during mining operations is increasing along with the increasing number of operation mines, which poses great challenges for mine water management and purification. Mine wastewaters contain high concentrations of nitrogen compounds such as nitrate (NO3-) and ammonium (NH4+) originating from remnant explosives as well as sulfate (SO42-) originating from the oxidation of sulfidic ores. At a mine site in Finnish Lapland, two natural peatlands have been used for cost-effective passive wastewater treatment. One peatland have been used for the treatment of drainage waters (TP 1), while the other has been used for the treatment of process-based wastewaters (TP 4). In this study, the impact of mine water derived nitrogen compounds as well as SO42- on the emission of the potent greenhouse gases methane (CH4) and nitrous oxide (N2O) from those treatment peatlands was investigated. Contaminant concentrations in the input and output waters of the treatment peatlands were monitored which allowed for the calculation of contaminant-specific retention efficiencies. Treatment peatlands showed generally good retention efficiencies for metals and metalloids (e.g. nickel, arsenic, antimony, up to 98% reduction in concentration) with rather low input-concentrations (i.e., in the μg/l-range). On the other hand, retention of contaminants with high input-concentrations (i.e., in mg/l-range) such as NO3-, NH4+ and SO42- was much lower (4-41%, 30-60% and -42-30%, respectively), indicating the limited capability of the treatment peatlands to cope with such high input concentrations. NO3- and NH4+ concentrations were determined in surface and pore water from TP 4 in July 2013 as well as in surface water from TP 1 and TP 4 in October 2013. Up to 720 μM NO3- and up to 600 μM NH4+ were detected in surface water of TP 4 in July 2013. NO3- and NH4+ concentrations in surface waters were highest near the mine wastewater distribution ditch and decreased with increasing distances from the ditch. NO3- concentrations were lower in pore water than in surface water, and the peak in NO3- concentration shifted further away from the distribution ditch with increasing depth. On the contrary, NH4+ concentrations were generally higher in pore water than in surface water, and peak concentrations increased with increasing depth. Highest NH4+ concentrations were detected in 30 to 60 cm depth near the outlet at the south end of TP 4. Fluxes of the greenhouse gases CH4 and N2O from 4 sampling points (2 from TP 4, 1 from TP 1, 1 from reference area) were measured on 7 different occasions 2013 and 2014. CH4 emissions were in the same range as measured in other northern pristine peatlands in the reference area, which is not influenced by mine wastewaters. Treatment peatlands showed only very minor CH4 emissions or even CH4 uptake. On the other hand, treatment peatlands showed high N2O emissions, which were in the same range as N2O emissions observed from northern peat soils used for agriculture. Highest emissions were generally observed near the wastewater distribution ditch of TP 4. N2O emissions from the reference area were negligible or even negative. NO3-, NH4+ and SO42- concentrations were determined from surface waters from each sampling point and sampling occasion. N2O emissions were positively correlated with NO3- concentrations, indicating denitrification-derived N2O production in treatment peatlands. On the other hand, CH4 emissions were negatively correlated with SO42- and NO3- concentrations, indicating that the presence of alternative electron acceptors in large amounts suppresses CH4 production in treatment peatlands. In conclusion, the study revealed that (i) treatment peatlands receive high loads of NO3-, NH4+ and SO42- which are not well retained in the peatlands, (ii) mine wastewaters positively and negatively affect N2O and CH4 emissions, respectively, (iii) N2O emissions are positively correlated with NO3- concentrations, and (iv) CH4 emissions are negatively correlated with NO3- and SO42- concentrations. This study thus illustrates the pronounced impacts of mine wastewaters on processes involved in greenhouse gas turnover in peatlands ecosystems.

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

NASA Astrophysics Data System (ADS)

Zhang, Bin; Kang, Jianting; Kang, Tianhe

2018-05-01

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

Spatiotemporal variability of carbon dioxide and methane in a eutrophic lake

NASA Astrophysics Data System (ADS)

Loken, Luke; Crawford, John; Schramm, Paul; Stadler, Philipp; Stanley, Emily

2017-04-01

Lakes are important regulators of global carbon cycling and conduits of greenhouse gases to the atmosphere; however, most efflux estimates for individual lakes are based on extrapolations from a single location. Within-lake variability in carbon dioxide (CO2) and methane (CH4) arises from differences in water sources, physical mixing, and local transformations; all of which can be influenced by anthropogenic disturbances and vary at multiple temporal and spatial scales. During the 2016 open water season (March - December), we mapped surface water concentrations of CO2 and CH4 weekly in a eutrophic lake (Lake Mendota, WI, USA), which has a predominately agricultural and urban watershed. In total we produced 26 maps of each gas based on 10,000 point measurements distributed across the lake surface. Both gases displayed relatively consistent spatial patterns over the stratified period but exhibited remarkable heterogeneity on each sample date. CO2 was generally undersaturated (global mean: 0.84X atmospheric saturation) throughout the lake's pelagic zone and often differed near river inlets and shorelines. The lake was routinely extremely supersaturated with CH4 (global mean: 105X atmospheric saturation) with greater concentrations in littoral areas that contained organic-rich sediments. During fall mixis, both CO2 and CH4 increased substantially, and concentrations were not uniform across the lake surface. CO2 and CH4 were higher on the upwind side of the lake due to upwelling of enriched hypolimnetic water. While the lake acted as a modest sink for atmospheric CO2 during the stratified period, the lake released substantial amounts of CO2 during turnover and continually emitted CH4, offsetting any reduction in atmospheric warming potential from summertime CO2 uptake. These data-rich maps illustrate how lake-wide surface concentrations and lake-scale efflux estimates based on single point measurements diverge from spatially weighted calculations. Both gases are not well represented by a sample collected at lake's central buoy, and thus, extrapolations from a single sampling location may not be adequate to assess lake-wide CO2 and CH4 dynamics in human-dominated landscapes.

High pressure micromechanical force measurements of the effects of surface corrosion and salinity on CH4/C2H6 hydrate particle-surface interactions.

PubMed

Wang, Shenglong; Hu, Sijia; Brown, Erika P; Nakatsuka, Matthew A; Zhao, Jiafei; Yang, Mingjun; Song, Yongchen; Koh, Carolyn A

2017-05-24

In order to investigate the mechanism of gas hydrate deposition and agglomeration in gas dominated flowlines, a high-pressure micromechanical force (MMF) apparatus was applied to directly measure CH 4 /C 2 H 6 hydrate adhesion/cohesion forces under low temperature and high pressure conditions. A CH 4 /C 2 H 6 gas mixture was used as the hydrate former. Adhesion forces between hydrate particles and carbon steel (CS) surfaces were measured, and the effects of corrosion on adhesion forces were analyzed. The influences of NaCl concentration on the cohesion force between CH 4 /C 2 H 6 hydrate particles were also studied for gas-dominated systems. It was observed that there was no measurable adhesion force for pristine (no corrosion) and corroded surfaces, when there was no condensed water or water droplet on these surfaces. With water on the surface (the estimated water amount was around 1.7 μg mm -2 ), a hydrate film growth process was observed during the measurement. CS samples were soaked in NaCl solution to obtain different extents of corrosion on surfaces, and adhesion measurements were performed on both pristine and corroded samples. The adhesion force was found to increase with increasing soak times in 5 wt% NaCl (resulting in more visual corrosion) by up to 500%. For the effect of salinity on cohesion forces, it was found that the presence of NaCl decreased the cohesion force between hydrate particles, and a possible explanation of this phenomenon was given based on the capillary liquid bridge model.

Formation of a nanobubble and its effect on the structural ordering of water in a CH4-N2-CO2-H2O mixture.

PubMed

Kaur, Surinder Pal; Sujith, K S; Ramachandran, C N

2018-04-04

The replacement of methane (CH4) from its hydrate by a mixture of nitrogen (N2) and carbon dioxide (CO2) involves the dissociation of methane hydrate leading to the formation of a CH4-N2-CO2-H2O mixture that can significantly influence the subsequent steps of the replacement process. In the present work, we study the evolution of dissolved gas molecules in this mixture by applying classical molecular dynamics simulations. Our study shows that a higher CO2 : N2 ratio in the mixture enhances the formation of nanobubbles composed of N2, CH4 and CO2 molecules. To understand how the CO2 : N2 ratio affects nanobubble nucleation, the distribution of molecules in the bubble formed is examined. It is observed that unlike N2 and CH4, the density of CO2 in the bubble reaches a maximum at the surface of the bubble. The accumulation of CO2 molecules at the surface makes the bubble more stable by decreasing the excess pressure inside the bubble as well as surface tension at its interface with water. It is found that a frequent exchange of gas molecules takes place between the bubble and the surrounding liquid and an increase in concentration of CO2 in the mixture leads to a decrease in the number of such exchanges. The effect of nanobubbles on the structural ordering of water molecules is examined by determining the number of water rings formed per unit volume in the mixture. The role of nanobubbles in water structuring is correlated to the dynamic nature of the bubble arising from the exchange of gas molecules between the bubble and the liquid.

Origin of carbon released from ecosystems affected by permafrost degradation in Northern Siberia

NASA Astrophysics Data System (ADS)

Gandois, L.; Hoyt, A.; Xu, X.; Hatte, C.; Teisserenc, R.; Tananaev, N.

2016-12-01

Permafrost soils and peatlands store half of the soil organic carbon stock worldwide, and are rapidly evolving as a result of permafrost thaw. Determining the origin (permafrost or recent photosynthesis) of carbon which is released to surface waters and the atmosphere is crucial to assess Arctic ecosystems' potential feedback to climate change. In order to evaluate it, we investigated the stable and radioactive content of carbon in solid organic matter, dissolved organic matter (DOM) and dissolved CO2 and CH4 in a discontinuous permafrost area of Siberia affected by permafrost degradation (Igarka, Graviyka catchment (67°27'11''N, 86°32'07''E)). We collected samples from the active layer, permafrost, surface water and bubbles from thermokarst lakes. We further investigated DOM and dissolved CO2 and CH4 in porewater profiles, streams and the catchment outlet. In thermokarst lakes, DOM of surface water as well as CO2 and CH4 from bubbles from lake sediments predominantly originate from modern carbon. In two locations, CO2 and CH4 from bubbles have relatively low 14C contents, with ages greater than 700 yr BP, but still younger that what was previously reported in Eastern Siberia. In all samples the Δ14C of CH4 and CO2 were strongly correlated, with CH4 being consistently older than CO2, indicating strong interrelation between CO2 and CH4 cycles. In our study, permafrost influenced CO2 and CH4 is found in small ponds where palsa collapse and the resulting bank erosion has mobilized sequestered carbon. In peatland porewater, the Δ14C of DOM, CO2 and CH4 increases with depth (DOM: 1385 ±45 yr BP at 2m), indicating a contribution from Holocene peatlands affected by permafrost. In deep layers, CO2 reduction is the dominant pathway of CH4 production, whereas acetate fermentation dominates in thermokarst lakes. In summary, the majority of dissolved CO2 and CH4 analyzed from thermokarst lakes and degraded peatlands is modern and originates from recently fixed carbon. Additionally, the DOM exported in small streams draining peatlands is also modern. However, at the catchment scale, an additional contribution from deep groundwater or thawing permafrost results in an intermediate Δ14C of DOM (300-400 yr BP) at the outlet of the Graviyka River.

Aquatic methane dynamics in a human-impacted river-floodplain of the Danube.

PubMed

Sieczko, Anna Katarzyna; Demeter, Katalin; Singer, Gabriel Andreas; Tritthart, Michael; Preiner, Stefan; Mayr, Magdalena; Meisterl, Karin; Peduzzi, Peter

2016-11-01

River-floodplain systems are characterized by changing hydrological connectivity and variability of resources delivered to floodplain water bodies. Although the importance of hydrological events has been recognized, the effect of flooding on CH 4 concentrations and emissions from European, human-impacted river-floodplains is largely unknown. This study evaluates aquatic concentrations and emissions of CH 4 from a highly modified, yet partly restored river-floodplain system of the Danube near Vienna (Austria). We covered a broad range of hydrological conditions, including a 1-yr flood event in 2012 and a 100-yr flood in 2013. Our findings demonstrate that river-floodplain waters were supersaturated with CH 4 , hence always serving as a source of CH 4 to the atmosphere. Hydrologically isolated habitats in general have higher concentrations and produce higher fluxes despite lower physically defined velocities. During surface connection, however, CH 4 is exported from the floodplain to the river, suggesting that the main channel serves as an "exhaust pipe" for the floodplain. This mechanism was especially important during the 100-yr flood, when a clear pulse of CH 4 was flushed from the floodplain with surface floodwaters. Our results emphasize the importance of floods differing in magnitude for methane evasion from river-floodplains; 34% more CH 4 was emitted from the entire system during the year with the 100-yr flood compared to a hydrologically "normal" year. Compared to the main river channel, semiisolated floodplain waters were particularly strong sources of CH 4 . Our findings also imply that the predicted increased frequency of extreme flooding events will have significant consequences for methane emission from river-floodplain systems.

Nutrient load can lead to enhanced CH4 fluxes through changes in vegetation, peat surface elevation and water table depth in ombrotrophic bog

NASA Astrophysics Data System (ADS)

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

2016-04-01

Atmospheric nitrogen (N) deposition has led to nutrient enrichment in wetlands, particularly in temperate areas, affecting plant community composition, carbon (C) cycling, and microbial dynamics. It is vital to understand the temporal scales and mechanisms of the changes, because peatlands are long-term sinks of C, but sources of methane (CH4), an important greenhouse gas. Rainwater fed (ombrotrophic) bogs are considered to be vulnerable to nutrient loading due to their natural nutrient poor status. We fertilized Mer Bleue Bog, a Sphagnum moss and evergreen shrub-dominated ombrotrophic bog near Ottawa, Ontario, now for 11-16 years with N (NO3 NH4) at 0.6, 3.2, and 6.4 g N m-2 y-1 (~5, 10 and 20 times ambient N deposition during summer months) with and without phosphorus (P) and potassium (K). Treatments were applied to triplicate plots (3 x 3 m) from May - August 2000-2015 and control plots received distilled water. We measured CH4 fluxes with static chambers weekly from May to September 2015 and peat samples were incubated in laboratory to measure CH4 production and consumption potentials. Methane fluxes at the site were generally low, but after 16 years, mean CH4 emissions have increased and more than doubled in high nitrogen addition treatments if P and K input was also increased (3.2 and 6.4 g N m-2yr-1 with PK), owing to drastic changes in vegetation and soil moisture. Vegetation changes include a loss of Sphagnum moss and introduction of new species, typical to minerogenic mires, which together with increased decomposition have led to decreased surface elevation and to higher water table level relative to the surface. The trajectories indicate that the N only treatments may result in similar responses, but only over longer time scales. Elevated atmospheric deposition of nutrients to peatlands may increase loss of C not only due to changes in CO2 exchange but also due to enhanced CH4 emissions in peatlands through a complex suite of feedbacks and interactions among vegetation, microclimate, and microbial processes. It is uncertain, however, how the vegetation change continues due to collapsing surface and higher water table levels, and how that will affect future CH4 emissions and C balance.

Nitrous oxide and methane in Atlantic and Mediterranean waters in the Strait of Gibraltar: Air-sea fluxes and inter-basin exchange

NASA Astrophysics Data System (ADS)

de la Paz, M.; Huertas, I. E.; Flecha, S.; Ríos, A. F.; Pérez, F. F.

2015-11-01

The global ocean plays an important role in the overall budget of nitrous oxide (N2O) and methane (CH4), as both gases are produced within the ocean and released to the atmosphere. However, for large parts of the open and coastal oceans there is little or no spatial data coverage for N2O and CH4. Hence, a better assessment of marine emissions estimates is necessary. As a contribution to remedying the scarcity of data on marine regions, N2O and CH4 concentrations have been determined in the Strait of Gibraltar at the ocean Fixed Time series (GIFT). During six cruises performed between July 2011 and November 2014 samples were collected at the surface and various depths in the water column, and subsequently measured using gas chromatography. From this we were able to quantify the temporal variability of the gas air-sea exchange in the area and examine the vertical distribution of N2O and CH4 in Atlantic and Mediterranean waters. Results show that surface Atlantic waters are nearly in equilibrium with the atmosphere whereas deeper Mediterranean waters are oversaturated in N2O, and a gradient that gradually increases with depth was detected in the water column. Temperature was found to be the main factor responsible for the seasonal variability of N2O in the surface layer. Furthermore, although CH4 levels did not reveal any feature clearly associated with the circulation of water masses, vertical distributions showed that higher concentrations are generally observed in the Atlantic layer, and that the deeper Mediterranean waters are considerably undersaturated (by up to 50%). Even though surface waters act as a source of atmospheric N2O during certain periods, on an annual basis the net N2O flux in the Strait of Gibraltar is only 0.35 ± 0.27 μmol m-2 d-1, meaning that these waters are almost in a neutral status with respect to the atmosphere. Seasonally, the region behaves as a slight sink for atmospheric CH4 in winter and as a source in spring and fall. Approximating the circulation pattern in the Strait to a bi-layer scheme, N2O exchange between basins was also calculated, and a net export from the Mediterranean Sea to the Atlantic Ocean equivalent to 39 μmol m-2 d-1 was found.

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.

Methanotrophy within the water column of a large meromictic tropical lake (Lake Kivu, East Africa)

NASA Astrophysics Data System (ADS)

Morana, C.; Borges, A. V.; Roland, F. A. E.; Darchambeau, F.; Descy, J.-P.; Bouillon, S.

2015-04-01

The permanently stratified Lake Kivu is one of the largest freshwater reservoirs of dissolved methane (CH4) on Earth. Yet CH4 emissions from its surface to the atmosphere have been estimated to be 2 orders of magnitude lower than the CH4 upward flux to the mixed layer, suggesting that microbial CH4 oxidation is an important process within the water column. A combination of natural abundance stable carbon isotope analysis (δ13C) of several carbon pools and 13CH4-labelling experiments was carried out during the rainy and dry season to quantify (i) the contribution of CH4-derived carbon to the biomass, (ii) methanotrophic bacterial production (MBP), and (iii) methanotrophic bacterial growth efficiency (MBGE), defined as the ratio between MBP and gross CH4 oxidation. We also investigated the distribution and the δ13C of specific phospholipid fatty acids (PLFAs), used as biomarkers for aerobic methanotrophs. Maximal MBP rates were measured in the oxycline, suggesting that CH4 oxidation was mainly driven by oxic processes. Moreover, our data revealed that methanotrophic organisms in the water column oxidized most of the upward flux of CH4, and that a significant amount of CH4-derived carbon was incorporated into the microbial biomass in the oxycline. The MBGE was variable (2-50%) and negatively related to CH4 : O2 molar ratios. Thus, a comparatively smaller fraction of CH4-derived carbon was incorporated into the cellular biomass in deeper waters, at the bottom of the oxycline where oxygen was scarce. The aerobic methanotrophic community was clearly dominated by type I methanotrophs and no evidence was found for an active involvement of type II methanotrophs in CH4 oxidation in Lake Kivu, based on fatty acids analyses. Vertically integrated over the water column, the MBP was equivalent to 16-60% of the average phytoplankton particulate primary production. This relatively high magnitude of MBP, and the substantial contribution of CH4-derived carbon to the overall biomass in the oxycline, suggest that methanotrophic bacteria could potentially sustain a significant fraction of the pelagic food web in the deep, meromictic Lake Kivu.

Methane Fluxes and Consumption in an Oil Sands Tailings End Pit Lake

NASA Astrophysics Data System (ADS)

Slater, G. F.; Goad, C.; Arriaga, D.; Risacher, F.; Morris, P.; Lindsay, M. B.; Mumford, K. G.; Warren, L. A.

2017-12-01

End pit lakes are engineered freshwater lakes designed to reclaim land impacted by surface mining activities via establishment of a functioning ecosystem where biogeochemical cycling mitigates release of hazardous components either by stabilization or biodegradation. End pit lakes provide unique opportunities to gain insight into microbial nutrient cycling under extreme levels of impact that can be applicable to a range of levels of anthropogenic impacts and issues. This study focuses on microbial CH4 cycling in the underlying fluid fine tailings (FFT) and surface waters of Base Mine Lake (BML), the first full demonstration of end pit lake reclamation in the Athabasca Oil Sands Region (AOSR) of northern Alberta, Canada. Over two field seasons (2015 and 2016) BML was thermally stratified, turning over in spring and fall. Oxygen concentrations in the epilimnion (70 to 80 % saturation) decreased steeply through the metalimnion to 3% saturation in the hypolimnion. Conversely, CH4 concentrations were highest in the hypolimnion of BML (25 to 140 µM) with the highest values being observed at the FFT/Water interface. Concentrations decreased to 1-2 µM at the metalimnion and further decreased to < 0.5 µM in the epilimnion. CH4 δ13C in FFT porewater indicated production via fermentative pathways. FFT settlement and dewatering of 0.73 to 1.0 m/yr results in advection of an estimated 1x107 to 2x107 moles/yr CH4 into the surface water, circa an order of magnitude greater than the 3x106 moles/year estimated for molecular diffusion. Calculated fluxes of dissolved CH4 from the FFT into the hypolimnion were 4 orders of magnitude higher than those from the hypolimnion to the metalimnion, indicating a significant sink for CH4 within the hypolimnion limiting upward dissolved CH4 transport. Dissolution of CH4 from bubbles released from the FFT may be contributing to the observed epilimnion concentrations. CH4 δ13C in the hypolimnion showed only minimal enrichment with decreasing concentrations. However, phospholipid fatty acids of bacteria in the hypolimnion were significantly δ13C depleted indicating CH4 consumption was a primary carbon source for the microbial community in the hypolimnion. Ongoing analyses of samples from 2017 will further elucidate the development of methane biogeochemical cycling in BML.

Environmental and physical controls on northern terrestrial methane emissions across permafrost zones

USGS Publications Warehouse

Olefeldt, David; Turetsky, Merritt R.; Crill, Patrick M.; McGuire, A. David

2013-01-01

Methane (CH4) emissions from the northern high-latitude region represent potentially significant biogeochemical feedbacks to the climate system. We compiled a database of growing-season CH4 emissions from terrestrial ecosystems located across permafrost zones, including 303 sites described in 65 studies. Data on environmental and physical variables, including permafrost conditions, were used to assess controls on CH4 emissions. Water table position, soil temperature, and vegetation composition strongly influenced emissions and had interacting effects. Sites with a dense sedge cover had higher emissions than other sites at comparable water table positions, and this was an effect that was more pronounced at low soil temperatures. Sensitivity analysis suggested that CH4 emissions from ecosystems where the water table on average is at or above the soil surface (wet tundra, fen underlain by permafrost, and littoral ecosystems) are more sensitive to variability in soil temperature than drier ecosystems (palsa dry tundra, bog, and fen), whereas the latter ecosystems conversely are relatively more sensitive to changes of the water table position. Sites with near-surface permafrost had lower CH4 fluxes than sites without permafrost at comparable water table positions, a difference that was explained by lower soil temperatures. Neither the active layer depth nor the organic soil layer depth was related to CH4 emissions. Permafrost thaw in lowland regions is often associated with increased soil moisture, higher soil temperatures, and increased sedge cover. In our database, lowland thermokarst sites generally had higher emissions than adjacent sites with intact permafrost, but emissions from thermokarst sites were not statistically higher than emissions from permafrost-free sites with comparable environmental conditions. Overall, these results suggest that future changes to terrestrial high-latitude CH4 emissions will be more proximately related to changes in moisture, soil temperature, and vegetation composition than to increased availability of organic matter following permafrost thaw.

A flux-gradient system for simultaneous measurement of the CH4, CO2, and H2O fluxes at a lake-air interface.

PubMed

Xiao, Wei; Liu, Shoudong; Li, Hanchao; Xiao, Qitao; Wang, Wei; Hu, Zhenghua; Hu, Cheng; Gao, Yunqiu; Shen, Jing; Zhao, Xiaoyan; Zhang, Mi; Lee, Xuhui

2014-12-16

Inland lakes play important roles in water and greenhouse gas cycling in the environment. This study aims to test the performance of a flux-gradient system for simultaneous measurement of the fluxes of water vapor, CO2, and CH4 at a lake-air interface. The concentration gradients over the water surface were measured with an analyzer based on the wavelength-scanned cavity ring-down spectroscopy technology, and the eddy diffusivity was measured with a sonic anemometer. Results of a zero-gradient test indicate a flux measurement precision of 4.8 W m(-2) for water vapor, 0.010 mg m(-2) s(-1) for CO2, and 0.029 μg m(-2) s(-1) for CH4. During the 620 day measurement period, 97%, 69%, and 67% of H2O, CO2, and CH4 hourly fluxes were higher in magnitude than the measurement precision, which confirms that the flux-gradient system had adequate precision for the measurement of the lake-air exchanges. This study illustrates four strengths of the flux-gradient method: (1) the ability to simultaneously measure the flux of H2O, CO2, and CH4; (2) negligibly small density corrections; (3) the ability to resolve small CH4 gradient and flux; and (4) continuous and noninvasive operation. The annual mean CH4 flux (1.8 g CH4 m(-2) year(-1)) at this hypereutrophic lake was close to the median value for inland lakes in the world (1.6 g CH4 m(-2) year(-1)). The system has adequate precision for CH4 flux for broad applications but requires further improvement to resolve small CO2 flux in many lakes.

Tidal variability of CO2 and CH4 emissions from the water column within a Rhizophora mangrove forest (New Caledonia).

PubMed

Jacotot, Adrien; Marchand, Cyril; Allenbach, Michel

2018-08-01

We performed a preliminary study to quantify CO 2 and CH 4 emissions from the water column within a Rhizophora spp. mangrove forest. Mean CO 2 and CH 4 emissions during the studied period were 3.35±3.62mmolCm -2 h -1 and 18.30±27.72μmolCm -2 h -1 , respectively. CO 2 and CH 4 emissions were highly variable and mainly driven by tides (flow/ebb, water column thickness, neap/spring). Indeed, an inverse relationship between the magnitude of the emissions and the thickness of the water column above the mangrove soil was observed. δ 13 CO 2 values ranged from -26.88‰ to -8.6‰, suggesting a mixing between CO 2 -enriched pore waters and lagoon incoming waters. In addition, CO 2 and CH 4 emissions were significantly higher during ebb tides, mainly due to the progressive enrichment of the water column by diffusive fluxes as its residence time over the forest floor increased. Eventually, we observed higher CO 2 and CH 4 emissions during spring tides than during neap tides, combined to depleted δ 13 CO 2 values, suggesting a higher contribution of soil-produced gases to the emissions. These higher emissions may result from higher renewable of the electron acceptor and enhanced exchange surface between the soil and the water column. This study shows that CO 2 and CH 4 emissions from the water column were not negligible and must be considered in future carbon budgets in mangroves. Copyright © 2018 Elsevier B.V. All rights reserved.

Carbon dioxide and methane exchange at a cool-temperate freshwater marsh

NASA Astrophysics Data System (ADS)

Strachan, Ian B.; Nugent, Kelly A.; Crombie, Stephanie; Bonneville, Marie-Claude

2015-06-01

Freshwater marshes have been shown to be strong sinks for carbon dioxide (CO2) on an annual basis relative to other wetland types; however it is likely that these ecosystems are also strong emitters of methane (CH4), reducing their carbon (C) sequestration potential. Multiyear C balances in these ecosystems are necessary therefore to determine their contribution to the global C cycle. Despite this, the number of multiyear studies in marshes is few, with, to the best of our knowledge, only one other Northern marsh C balance reported. This study presents five years of eddy covariance flux measurements of CO2, and four years of warm-season chamber measurements of CH4 at a cool-temperate Typha angustifolia marsh. Annual average cumulative net ecosystem exchange of CO2 (NEE) at the marsh was -224 ± 54 g C m-2 yr-1 (±SD) over the five-year period, ranging from -126 to -284 g C m-2 yr-1. Enhancement of the ecosystem respiration during warmer spring, autumn and winter periods appeared the strongest determinant of annual NEE totals. Warm season fluxes of CH4 from the Typha vegetation (avg. 1.0 ± 1.2 g C m-2 d-1) were significantly higher than fluxes from the water surface (0.5 ± 0.4 g C m-2 d-1) and unvegetated mats (0.2 ± 0.2 g C m-2 d-1). Air temperature was a primary driver of all CH4 fluxes, while water table was not a significant correlate as water levels were always at or above the vegetative mat surfaces. Weighting by the surface cover proportion of water and vegetation yielded a net ecosystem CH4 emission of 127 ± 19 g C m-2 yr-1. Combining CO2 and CH4, the annual C sink at the Mer Bleue marsh was reduced to -97 ± 57 g C m-2 yr-1, illustrating the importance of accounting for CH4 when generating marsh C budgets.

Insight into Chemistry on Cloud/Aerosol Water Surfaces.

PubMed

Zhong, Jie; Kumar, Manoj; Francisco, Joseph S; Zeng, Xiao Cheng

2018-05-15

Cloud/aerosol water surfaces exert significant influence over atmospheric chemical processes. Atmospheric processes at the water surface are observed to follow mechanisms that are quite different from those in the gas phase. This Account summarizes our recent findings of new reaction pathways on the water surface. We have studied these surface reactions using Born-Oppenheimer molecular dynamics simulations. These studies provide useful information on the reaction time scale, the underlying mechanism of surface reactions, and the dynamic behavior of the product formed on the aqueous surface. According to these studies, the aerosol water surfaces confine the atmospheric species into a specific orientation depending on the hydrophilicity of atmospheric species or the hydrogen-bonding interactions between atmospheric species and interfacial water. As a result, atmospheric species are activated toward a particular reaction on the aerosol water surface. For example, the simplest Criegee intermediate (CH 2 OO) exhibits high reactivity toward the interfacial water and hydrogen sulfide, with the reaction times being a few picoseconds, 2-3 orders of magnitude faster than that in the gas phase. The presence of interfacial water molecules induces proton-transfer-based stepwise pathways for these reactions, which are not possible in the gas phase. The strong hydrophobicity of methyl substituents in larger Criegee intermediates (>C1), such as CH 3 CHOO and (CH 3 ) 2 COO, blocks the formation of the necessary prereaction complexes for the Criegee-water reaction to occur at the water droplet surface, which lowers their proton-transfer ability and hampers the reaction. The aerosol water surface provides a solvent medium for acids (e.g., HNO 3 and HCOOH) to participate in reactions via mechanisms that are different from those in the gas and bulk aqueous phases. For example, the anti-CH 3 CHOO-HNO 3 reaction in the gas phase follows a direct reaction between anti-CH 3 CHOO and HNO 3 , whereas on a water surface, the HNO 3 -mediated stepwise hydration of anti-CH 3 CHOO is dominantly observed. The high surface/volume ratio of interfacial water molecules at the aerosol water surface can significantly lower the energy barriers for the proton transfer reactions in the atmosphere. Such catalysis by the aerosol water surface is shown to cause the barrier-less formation of ammonium bisulfate from hydrated NH 3 and SO 3 molecules rather than from the reaction of H 2 SO 4 with NH 3 . Finally, an aerosol water droplet is a polar solvent, which would favorably interact with high polarity substrates. This can accelerate interconversion of different conformers (e.g., anti and syn) of atmospheric species, such as glyoxal, depending on their polarity. The results discussed here enable an improved understanding of atmospheric processes on the aerosol water surface.

Methane efflux measured by eddy covariance in Alaskan upland tundra undergoing permafrost degradation

NASA Astrophysics Data System (ADS)

Taylor, M.; Celis, G.; Ledman, J.; Bracho, R. G.; Schuur, E.

2017-12-01

Permafrost thaw can increase landscape heterogeneity, leading to wetter and drier soil conditions that affect the magnitude and form (carbon dioxide - CO2 and methane - CH4) of carbon produced via microbial decomposition. Environmental controls on CH4 emissions, especially in drier upland tundra systems, are not well understood. In degrading upland tundra permafrost, cold season CH4 fluxes may contribute significantly to annual emissions from CH4 production within unfrozen layers deep in the soil profile. Eight Mile Lake (EML), located in Interior Alaska near Denali National Park, is a moist acidic tussock tundra ecosystem undergoing permafrost degradation. Perennially frozen soils have warmed between 1985 and 2016 from -1.2 to -0.75˚C resulting in a deeper active layer depth from 61 to 70 cm between 2004-2016. Depth from the soil/moss surface to the water table perched on the permafrost surface has decreased from 30 to 20 cm over the same interval. Here we present the first year of continuous CH4 flux measurements made at EML (May 2016 - May 2017). The site was a net source of low-level CH4 emissions throughout the year. Annual CH4 emissions (1.3 g C yr-1) made up 8.8% of total annual C emissions (14.7 g m-2yr-1). Methane flux is related with soil temperatures during both summer and non-summer seasons. Emissions increased throughout the summer season as thaw depth and soil temperatures increased. In contrast with wetland sites where water table is at or above the soil surface for much of the growing season, EML is relatively dry and there was no relationship between soil moisture and emissions. Non-summer season CH4 emissions are related to increases in atmospheric and shallow soil temperatures. Winter season emissions account for 37% of the annual CH4 budget, the bulk of which occurred between October and January when deep soils remained thawed. Non-summer season CH4 and CO2 pulses appear to be coupled, suggesting a similar mechanism for release. We hypothesize that this relationship is the result of surface soils warming and cracking, allowing for the escape of microbially produced gases at depth. While annual CH4 emissions made up 8.8% of total annual C emissions at this site, taking into account the greenhouse warming potential of CH4 relative to CO2, the climate impact of CH4 is 15.6 g m-2yr-1, or 69% of the C budget.

Was Early Mars Warmed by CH4?

NASA Astrophysics Data System (ADS)

Justh, H. L.; Kasting, J. F.

2001-12-01

Images from the Mariner, Viking and Mars Global Surveyor missions have shown geologic features on the Martian surface that seem to indicate an earlier period of hydrologic activity. Many researchers have suggested that the early Martian climate was more Earth-like with a Ts of 273 K or higher. The presence of liquid water would require a greenhouse effect much larger than needed at present since S0 is 25% lower 3.8 billion years ago when the channels are thought to have formed. Research into the effects of CO2 clouds upon the climate of early Mars have yielded results that would not effectively warm the surface to the temperature needed to account for the presence of liquid water. Forget and Pierrehumbert (Science, 1997) showed that large crystals of CO2 ice in clouds that form in the upper troposphere would produce a strong warming effect. Obtaining mean surface temperatures above 273 K would require 100% cloud cover, a condition that is unrealistic for early Mars. It has also been shown that any reduction in cloud cover makes it difficult to achieve warm Martian surface temperatures except at high pressures. CO2 clouds could also cool the Martian surface if they were low and optically thick. CO2 ice may be hard to nucleate, leading to the formation of very large particles (Glandorf, private communication). CH4 has been suggested as an important greenhouse gas on the early Earth. This has led us to look at CH4 as a potential solution to the early Mars climate issue. To investigate the possible warming effect of CH4, we utilized a modified, one-dimensional, radiative-convective climate model that has been used in previous studies of the early Martian climate. New calculations of the effects of CH4 upon the early Martian climate will be presented. The use of CH4 to warm the surface of early Mars does not necessarily imply the presence of life on Mars. Abiotic sources of CH4, such as serpentinization of ultramafic rocks, could supply the concentrations needed to warm the surface.

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.

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

NASA Astrophysics Data System (ADS)

Zhang, Y.; Xie, H.

2015-08-01

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

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

NASA Astrophysics Data System (ADS)

Zhang, Y.; Xie, H.

2015-11-01

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

Warming Early Mars With CH4

NASA Astrophysics Data System (ADS)

Justh, H. L.; Kasting, J. F.

2002-12-01

The nature of the ancient climate of Mars remains one of the fundamental unresolved problems in martian research. While the present environment is hostile to life, images from the Mariner, Viking and Mars Global Surveyor missions, have shown geologic features on the martian surface that seem to indicate an earlier period of hydrologic activity. The fact that ancient valley networks and degraded craters have been seen on the martian surface indicates that the early martian climate may have been more Earth-like, with a warmer surface temperature. The presence of liquid water would require a greenhouse effect much larger than needed at present, as the solar constant, S0, was 25% lower 3.8 billion years ago when the channels are thought to have formed (1,2). Previous calculations have shown that gaseous CO2 and H2O alone could not have warmed the martian surface to the temperature needed to account for the presence of liquid water (3). It has been hypothesized that a CO2-H2O atmosphere could keep early Mars warm if it was filled with CO2 ice clouds in the upper martian troposphere (4). Obtaining mean martian surface temperatures above 273 K would require nearly 100% cloud cover, a condition that is unrealistic for condensation clouds on early Mars. Any reduction in cloud cover makes it difficult to achieve warm martian surface temperatures except at high pressures and CO2 clouds could cool the martian surface if they were low and optically thick (5). CO2 and CH4 have been suggested as important greenhouse gases on the early Earth. Our research focuses on the effects of increased concentrations of atmospheric greenhouse gases on the surface temperature of early Mars, with emphasis on the reduced greenhouse gas, CH4. To investigate the possible warming effect of CH4, we modified a one-dimensional, radiative-convective climate model used in previous studies of the early martian climate (5). New cloud-free temperature profiles for various surface pressures and CH4 mixing ratios will be presented. This use of climate modeling is important since it is the fundamental way that the magnitude of possible geochemical and biological CH4 sources can be related to predicted CH4 concentrations in the early martian atmosphere. References: 1) Gough, D. O. Solar Physics 74, 21-34 (1981). 2) Carr, M. H. Water on Mars (1996). 3) Kasting, J. F. Icarus 94, 1-13 (1991). 4) Forget, F., and Pierrehumbert R. T. Science 278, 1273-1276 (1997). 5) Mischna, M. A., Kasting J. F., Pavlov A., and Freedman R. Icarus 145, 546-554 (2000).

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.

Mathematical Modelling of Arctic Polygonal Tundra with Ecosys: 2. Microtopography Determines How CO2 and CH4 Exchange Responds to Changes in Temperature and Precipitation

NASA Astrophysics Data System (ADS)

Grant, R. F.; Mekonnen, Z. A.; Riley, W. J.; Arora, B.; Torn, M. S.

2017-12-01

Differences of surface elevation in arctic polygonal landforms cause spatial variation in soil water contents (θ), active layer depths (ALD), and thereby in CO2 and CH4 exchange. Here we test hypotheses in ecosys for topographic controls on CO2 and CH4 exchange in trough, rim, and center features of low- and flat-centered polygons (LCP and FCP) against chamber and eddy covariance (EC) measurements during 2013 at Barrow, Alaska. Larger CO2 influxes and CH4 effluxes were measured with chambers and modeled with ecosys in LCPs than in FCPs and in lower features (troughs) than in higher (rims) within LCPs and FCPs. Spatially aggregated CO2 and CH4 fluxes from ecosys were significantly correlated with EC flux measurements. Lower features were modeled as C sinks (52-56 g C m-2 yr-1) and CH4 sources (4-6 g C m-2 yr-1), and higher features as near C neutral (-2-15 g C m-2 yr-1) and CH4 neutral (0.0-0.1 g C m-2 yr-1). Much of the spatial and temporal variations in CO2 and CH4 fluxes were modeled from topographic effects on water and snow movement and thereby on θ, ALD, and soil O2 concentrations. Model results forced with meteorological data from 1981 to 2015 indicated increasing net primary productivity in higher features and CH4 emissions in some lower and higher features since 2008, attributed mostly to recent rises in precipitation. Small-scale variation in surface elevation causes large spatial variation of greenhouse gas (GHG) exchanges and therefore should be considered in estimates of GHG exchange in polygonal landscapes.

Nitrate loading and CH4 and N2O Flux from headwater streams

NASA Astrophysics Data System (ADS)

Sousa, C. H. R. D.; Hilker, T.; Hall, F. G.; Moura, Y. M.; McAdam, E.

2014-12-01

Freshwater ecosystems transport and process significant amounts of terrestrial carbon and can be considerable sources of CO2, CH4, and N2O. A great deal of uncertainty, however, remains in both global estimates and our understanding of drivers of freshwater greenhouse gas emissions. Furthermore, small headwater streams have received insufficient attention to date and may contribute disproportionately to global GHG flux. Our objective was to quantify GHG flux and assess the impact of changes in DOC and NO3 concentrations in surface and subsurface water on flux rates in three streams in the Lamprey River watershed in New Hampshire, USA, that contrast in surface water DOC:NO3. We measured DOC, NO3 and dissolved gas concentrations in surface waters of each stream monthly from May 2011 to April 2012. Empirical measurements of reaeration coefficients were used to convert dissolved gas concentrations to fluxes. We found higher GHG concentrations and fluxes in the two streams with high DOC concentrations, particularly gases produced by anaerobic metabolism (CH4, N2O from methanogenesis and denitrification, respectively). The stream with high DOC and high NO3 showed high N2O and low CH4 flux, while the high DOC, low NO3 stream showed high CH4 and low N2O flux. Our results are consistent with a model in which C inputs drive total GHG production, while NO3 input regulates the relative importance of CH4 and N2O by suppressing methanogenesis and stimulating denitrification. The magnitude of GHG fluxes suggests that streams in this region are likely to be small sources of CO2, but potentially important sources of CH4 and N2O. Since CH4 and N2O are many times more powerful than CO2 at trapping heat in the atmosphere, freshwater emissions of these gases have the potential to offset a significant proportion of the climate benefits of the terrestrial carbon sink, a possibility that has not been sufficiently incorporated into climate models.

Nitrate loading and CH4 and N2O Flux from headwater streams

NASA Astrophysics Data System (ADS)

Schade, J. D.; Bailio, J.; McDowell, W. H.

2015-12-01

Freshwater ecosystems transport and process significant amounts of terrestrial carbon and can be considerable sources of CO2, CH4, and N2O. A great deal of uncertainty, however, remains in both global estimates and our understanding of drivers of freshwater greenhouse gas emissions. Furthermore, small headwater streams have received insufficient attention to date and may contribute disproportionately to global GHG flux. Our objective was to quantify GHG flux and assess the impact of changes in DOC and NO3 concentrations in surface and subsurface water on flux rates in three streams in the Lamprey River watershed in New Hampshire, USA, that contrast in surface water DOC:NO3. We measured DOC, NO3 and dissolved gas concentrations in surface waters of each stream monthly from May 2011 to April 2012. Empirical measurements of reaeration coefficients were used to convert dissolved gas concentrations to fluxes. We found higher GHG concentrations and fluxes in the two streams with high DOC concentrations, particularly gases produced by anaerobic metabolism (CH4, N2O from methanogenesis and denitrification, respectively). The stream with high DOC and high NO3 showed high N2O and low CH4 flux, while the high DOC, low NO3 stream showed high CH4 and low N2O flux. Our results are consistent with a model in which C inputs drive total GHG production, while NO3 input regulates the relative importance of CH4 and N2O by suppressing methanogenesis and stimulating denitrification. The magnitude of GHG fluxes suggests that streams in this region are likely to be small sources of CO2, but potentially important sources of CH4 and N2O. Since CH4 and N2O are many times more powerful than CO2 at trapping heat in the atmosphere, freshwater emissions of these gases have the potential to offset a significant proportion of the climate benefits of the terrestrial carbon sink, a possibility that has not been sufficiently incorporated into climate models.

Understanding the Temporal Variation of CO2 and CH4 Fluxes in a Subtropical Seasonal Wetland

NASA Astrophysics Data System (ADS)

Gomez-Casanovas, N.; DeLucia, N.; DeLucia, E. H.; Boughton, E.; Bernacchi, C.

2017-12-01

The magnitude of the net greenhouse gas (GHG) sink strength of wetlands and mechanisms driving C fluxes remain uncertain, particularly for subtropical and tropical wetlands that are responsible for the majority of wetland CH4 emissions globally. We determined the exchange of CO2 and CH4 fluxes between a subtropical wetland and the atmosphere, and investigated how changes in water table (WT), soil temperature (ST), and Gross Primary Productivity (GPP) alter CH4 fluxes. Measurements were made using the eddy covariance technique from June, 2013 to December, 2015. As GPP was greater than ecosystem respiration, wetland was consistently a net sink of CO2 from the atmosphere (-480 gC m-2 in 2013, -275 gC m-2 in 2014 and -258 gC m-2 in 2015). Though variable among years, wetland was a net source of CH4 to the atmosphere (24.5 gC m-2 in 2013, 26.1 gC m-2 in 2014, 32.7 gC m-2 in 2015). WT and ST were strong drivers of net CH4 fluxes. Fluxes of CH4 exponentially increased with WT near the soil surface, and they were maximal and sustained after 3 days or more of preceding flooding suggesting that flooding duration and intensity drives CH4 emissions in this system. GPP also exerted a strong control on these fluxes, particularly when water was near the soil surface. The system emitted an average of 2 g more C-CH4 m-2 during the wet seasons of 2013 and 2015 than the wet season of 2014 due to higher WT, and increases in flooding days and cumulative GPP for days with water at near-surface (GPPWT). Although WT was higher during the dry season of 2015 than the wet season of 2014, CH4 fluxes were similar likely because of increased ST and GPPWT in the wet season of 2014. The contribution of CH4 fluxes during the dry season to annual fluxes was 41% in 2014 and 48% in 2015. Wetland was a strong sink of C, and it was a net sink of GHGs in 2014 and a net source in 2015 mainly attributable to increases in net CH4 emissions. Climate models predict that subtropical and tropical regions will experience more frequent floods and droughts as well as higher temperatures, conditions that will likely alter ecosystem attributes such as GPP. Our results indicate that CH4 emissions from subtropical wetlands will likely respond to projected changes in precipitation, temperature and productivity, substantially affecting the net GHG sink strength of these systems in future climate scenarios.

Methane flux from Minnesota Peatlands

NASA Astrophysics Data System (ADS)

Crill, P. M.; Bartlett, K. B.; Harriss, R. C.; Gorham, E.; Verry, E. S.; Sebacher, D. I.; Madzar, L.; Sanner, W.

1988-12-01

Northern (>40°N) wetlands have been suggested as the largest natural source of methane (CH4) to the troposphere. To refine our estimates of source strengths from this region and to investigate climatic controls on the process, fluxes were measured from a variety of Minnesota peatlands during May, June, and August 1986. Sites included forested and unforested ombrotrophic bogs and minerotrophic fens in and near the U.S. Department of Agriculture Marcell Experimental Forest and the Red Lake peatlands. Late spring and summer fluxes ranged from 11 to 866 mg CH4 m-2 d-1, averaging 207 mg CH4 m-2 d-1 overall. At Marcell Forest, forested bogs and fen sites had lower fluxes (averages of 77 ± 21 mg CH4 m-2 d-1 and 142 ± 19 mg CH4 m-2 d-1) than open bogs (average of 294 ± 30 mg CH4 m-2 d-1). In the Red Lake peatland, circumneutral fens, with standing water above the peat surface, produced more methane than acid bog sites in which the water table was beneath the moss surface (325 ± 31 and 102 ± 13 mg CH4 m-2 d-1, respectively). Peat temperature was an important control. Methane flux increased in response to increasing soil temperature. For example, the open bog in the Marcell Forest with the highest CH4 flux exhibited a 74-fold increase in flux over a three-fold increase in temperature. We estimate that the methane flux from all peatlands north of 40° may be on the order of 70 to 90 Tg/yr though estimates of this sort are plagued by uncertainties in the areal extent of peatlands, length of the CH4 producing season, and the spatial and temporal variability of the flux.

Differential retention and release of CO 2 and CH 4 in kerogen nanopores: Implications for gas extraction and carbon sequestration

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

Ho, Tuan Anh; Wang, Yifeng; Xiong, Yongliang

Methane (CH 4) and carbon dioxide (CO 2), the two major components generated from kerogen maturation, are stored dominantly in nanometer-sized pores in shale matrix as (1) a compressed gas, (2) an adsorbed surface species and/or (3) a species dissolved in pore water (H 2O). In addition, supercritical CO 2 has been proposed as a fracturing fluid for simultaneous enhanced oil/gas recovery (EOR) and carbon sequestration. A mechanistic understanding of CH 4-CO 2-H 2O interactions in shale nanopores is critical for designing effective operational processes. Using molecular simulations, we show that kerogen preferentially retains CO 2 over CH 4 andmore » that the majority of CO 2 either generated during kerogen maturation or injected in EOR will remain trapped in the kerogen matrix. The trapped CO 2 may be released only if the reservoir pressure drops below the supercritical CO 2 pressure. When water is present in the kerogen matrix, it may block CH 4 release. Furthermore, the addition of CO 2 may enhance CH 4 release because CO 2 can diffuse through water and exchange for adsorbed methane in the kerogen nanopores.« less

Differential retention and release of CO 2 and CH 4 in kerogen nanopores: Implications for gas extraction and carbon sequestration

DOE PAGES

Ho, Tuan Anh; Wang, Yifeng; Xiong, Yongliang; ...

2018-02-06

Methane (CH 4) and carbon dioxide (CO 2), the two major components generated from kerogen maturation, are stored dominantly in nanometer-sized pores in shale matrix as (1) a compressed gas, (2) an adsorbed surface species and/or (3) a species dissolved in pore water (H 2O). In addition, supercritical CO 2 has been proposed as a fracturing fluid for simultaneous enhanced oil/gas recovery (EOR) and carbon sequestration. A mechanistic understanding of CH 4-CO 2-H 2O interactions in shale nanopores is critical for designing effective operational processes. Using molecular simulations, we show that kerogen preferentially retains CO 2 over CH 4 andmore » that the majority of CO 2 either generated during kerogen maturation or injected in EOR will remain trapped in the kerogen matrix. The trapped CO 2 may be released only if the reservoir pressure drops below the supercritical CO 2 pressure. When water is present in the kerogen matrix, it may block CH 4 release. Furthermore, the addition of CO 2 may enhance CH 4 release because CO 2 can diffuse through water and exchange for adsorbed methane in the kerogen nanopores.« less

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

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.

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

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

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

2013-03-15

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

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Non-controlled biogenic emissions to the atmosphere from Lazareto landfill, Tenerife, Canary Islands.

PubMed

Nolasco, Dácil; Lima, R Noemí; Hernández, Pedro A; Pérez, Nemesio M

2008-01-01

[corrected] Historically, landfills have been the simplest form of eliminating urban solid waste with the minimum cost. They have been the most usual method for discarding solid waste. However, landfills are considered authentic biochemical reactors that introduce large amounts of contaminants into the environment in the form of gas and leachates. The dynamics of generation and the movement of gas in landfills depend on the input and output parameters, as well as on the structure of the landfill and the kind of waste. The input parameters include water introduced through natural or artificial processes, the characteristics of the urban solid waste, and the input of atmospheric air. The main output parameters for these biochemical reactors include the gases and the leachates that are potentially pollutants for the environment. Control systems are designed and installed to minimize the impact on the environment. However, these systems are not perfect and a significant amount of landfill gas could be released to the atmosphere through the surface in a diffuse form, also known as Non-controlled emission. In this paper, the results of the Non-controlled biogenic gas emissions from the Lazareto landfill in Tenerife, Canary Islands, are presented. The purpose of this study was to evaluate the concentration of CH4 and CO2 in the soil gas of the landfill cover, the CH4 and CO2 efflux from the surface of the landfill and, finally, to compare these parameters with other similar landfills. In this way, a better understanding of the process that controls biogenic gas emissions in landfills is expected. A Non-controlled biogenic gas emission survey of 281 sampling sites was carried out during February and March, 2002. The sampling sites were selected in order to obtain a well-distributed sampling grid. Surface landfill CO2 efflux measurements were carried out at each sampling site on the surface landfill together with soil gas collection and ground temperatures at a depth of 30-40 cm. The CH4 efflux was computed from CO2 efflux and from the ratio CH4/CO2 in the soil gas. Soil gas samples were collected at a depth of 30-40 cm using a metallic probe and 20 cc hypodermic syringes, and later stored in evacuated 10 cc vacutainers for laboratory analysis of bulk composition. The gas sample was introduced in a vacutainer filled with deionized water and displacing the water until the vacutainer was filled with the gas sample in order to avoid air contamination from entering. The surface landfill temperature of the landfill was measured at a depth of 40 cm using a digital thermometer type OMEGA 871A. Landfill gases, CO2 and CH4, were analyzed within 24 hours using a double channel VARIAN micro-GC QUAD CP-2002P, with a 10 meter PORAPLOT-Q column, a TCD detector, and He as a carrier gas. The analysis temperature was 40 degrees C and the injection time was 10 msec. Surface landfill CO2 efflux measurements were performed using a portable NDIR spectrophotometer Licor-800 according to the accumulation chamber method (Chiodini et al. 1996). The data treatment, aimed at drawing the flux map and computing the total gas output, was based on the application of stochastic simulation algorithms provided by the GSLIB program (Deutsch and Journel 1998). Diffuse CH4 and CO2 efflux values range from negligible values up to 7,148 and 30,573 g m(-2) d(-1), respectively. The spatial distribution of the concentration and efflux of CO2, CH4 and soil temperature, show three areas of maximum activity in the landfill, suggesting a non-uniform pattern of diffuse degassing. This correlation between high emissions and concentration of CO2, CH4 and soil temperatures suggests that the areas of higher microbial activity and exothermic reactions are releasing CO2 and CH4 to the atmosphere from the landfill. Taking into consideration the spatial distribution of the CO2 and CH4 efflux values as well as the extension of the landfill, the Non-controlled emission of CO2 and CH4 to the atmosphere by the Lazareto's landfill are of 167 +/- 13.3 and 16 +/- 2.5 t d(-1), respectively. The patterns of gas flow within the landfill seem to be affected by boundary materials at the sides. The basalt layers have a low permeability and the gas flow in these areas is extensive. In this area, where a basalt layer does not exist, the flow gas diffuses toward the sea and the flux emissions at the landfill surface are lower. This behavior reflects the possible dissolution of gases into water and the deflection of gases towards the surface at the basalt boundary. The proximity to the sea, the installation of a palm tree garden and, as a result, the contribution of water coming from the watering of this garden has reactivated the system. The introduction of sea water into the landfill and the type of boundary could be defining the superficial gas discharges. Results from this study indicate that the spatial distribution of Non-controlled emission of CO2 and CH4 at the Lazareto's landfill shows a non-uniform pattern of diffuse degassing. The northeast, central and northwest areas of the Lazareto's landfill are the three areas of high emissions and concentration of CO2 and CH4, and high temperatures. The correlation between high emissions and the concentration of CO2, CH4, and the high temperatures suggest that the areas of higher microbial activity and exothermic reactions are releasing more CO2 and CH4 to the atmosphere from the landfill. A high concentration of CO2 is probably due to the presence of methanotrophic bacteria in the soil atmosphere of the landfill. Patterns of gas flow within the landfill seem to be affected by boundary materials (basalt layers) of low permeability, and side boundaries of the flux emissions at the surface are higher. At the sides of seawater and sediment boundaries, flux emissions at the landfill surface are lower. This behavior reflects a possible dissolution of gases into the water and the deflection of gases towards the surface at the basalt boundary. With this study, we can compare the data obtained in this landfill with other landfills and observe the different levels of emission. The proximity to the sea and the installation of the palm tree garden palms and, as a result, the contribution of water coming from the watering of this garden has reactivated the system. Many landfills worldwide located in similar settings could experience similar gas production processes. The need for investigating and monitoring sea water and sediment quality in these landfills is advisable. Concentrations and fluxes of contaminants and their impact in the area should be assessed. With this study we can compare the data obtained in these landfills with other landfills and observe the different levels of emission.

Adsorption kinetics of CO2, CH4, and their equimolar mixture on coal from the Black Warrior Basin, West-Central Alabama

USGS Publications Warehouse

Gruszkiewicz, M.S.; Naney, M.T.; Blencoe, J.G.; Cole, D.R.; Pashin, J.C.; Carroll, R.E.

2009-01-01

Laboratory experiments were conducted to investigate the adsorption kinetic behavior of pure and mixed gases (CO2, CH4, approximately equimolar CO2 + CH4 mixtures, and He) on a coal sample obtained from the Black Warrior Basin at the Littleton Mine (Twin Pine Coal Company), Jefferson County, west-central Alabama. The sample was from the Mary Lee coal zone of the Pottsville Formation (Lower Pennsylvanian). Experiments with three size fractions (45-150????m, 1-2??mm, and 5-10??mm) of crushed coal were performed at 40????C and 35????C over a pressure range of 1.4-6.9??MPa to simulate coalbed methane reservoir conditions in the Black Warrior Basin and provide data relevant for enhanced coalbed methane recovery operations. The following key observations were made: (1) CO2 adsorption on both dry and water-saturated coal is much more rapid than CH4 adsorption; (2) water saturation decreases the rates of CO2 and CH4 adsorption on coal surfaces, but it appears to have minimal effects on the final magnitude of CO2 or CH4 adsorption if the coal is not previously exposed to CO2; (3) retention of adsorbed CO2 on coal surfaces is significant even with extreme pressure cycling; and (4) adsorption is significantly faster for the 45-150????m size fraction compared to the two coarser fractions. ?? 2008 Elsevier B.V.

Carbon and hydrogen isotopic evidence for the origin of combustible gases in water-supply wells in north-central Pennsylvania

USGS Publications Warehouse

Révész, K. M.; Breen, K.J.; Baldassare, A.J.; Burruss, R.C.

2010-01-01

The origin of the combustible gases in groundwater from glacial-outwash and fractured-bedrock aquifers was investigated in northern Tioga County, Pennsylvania. Thermogenic methane (CH4) and ethane (C2H6) and microbial CH4 were found. Microbial CH4 is from natural in situ processes in the shale bedrock and occurs chiefly in the bedrock aquifer. The δ13C values of CH4 and C2H6 for the majority of thermogenic gases from water wells either matched or were between values for the samples of non-native storage-field gas from injection wells and the samples of gas from storage-field observation wells. Traces of C2H6 with microbial CH4 and a range of C and H isotopic compositions of CH4 indicate gases of different origins are mixing in sub-surface pathways; gas mixtures are present in groundwater. Pathways for gas migration and a specific source of the gases were not identified. Processes responsible for the presence of microbial gases in groundwater could be elucidated with further geochemical study.

Excess chemical potential of small solutes across water--membrane and water--hexane interfaces

NASA Technical Reports Server (NTRS)

Pohorille, A.; Wilson, M. A.

1996-01-01

The excess chemical potentials of five small, structurally related solutes, CH4, CH3F, CH2F2, CHF3, and CF4, across the water-glycerol 1-monooleate bilayer and water-hexane interfaces were calculated at 300, 310, and 340 K using the particle insertion method. The excess chemical potentials of nonpolar molecules (CH4 and CF4) decrease monotonically or nearly monotonically from water to a nonpolar phase. In contrast, for molecules that possess permanent dipole moments (CH3F, CH2F, and CHF3), the excess chemical potentials exhibit an interfacial minimum that arises from superposition of two monotonically and oppositely changing contributions: electrostatic and nonelectrostatic. The nonelectrostatic term, dominated by the reversible work of creating a cavity that accommodates the solute, decreases, whereas the electrostatic term increases across the interface from water to the membrane interior. In water, the dependence of this term on the dipole moment is accurately described by second order perturbation theory. To achieve the same accuracy at the interface, third order terms must also be included. In the interfacial region, the molecular structure of the solvent influences both the excess chemical potential and solute orientations. The excess chemical potential across the interface increases with temperature, but this effect is rather small. Our analysis indicates that a broad range of small, moderately polar molecules should be surface active at the water-membrane and water-oil interfaces. The biological and medical significance of this result, especially in relation to the mechanism of anesthetic action, is discussed.

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.

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.

Impact of organic carbon quality on methanogenesis in subterranean estuaries and implications for greenhouse gas production

NASA Astrophysics Data System (ADS)

Pain, A.; Young, C. R.; Martin, J. B.

2016-12-01

The land-sea interface is a hotspot for organic carbon (OC) remineralization reactions, which generate greenhouse gases (CO2 and CH4). Intense processing of terrestrial organic carbon occurs in surface estuaries, and the extent of reactions depends in part on OC reactivity. Subterranean estuaries (STEs) are ubiquitous along coastlines but understudied relative to surface estuaries. However, they could possess many of the same characteristics that lead to intense OC processing in surface estuaries and perhaps be even more important to C cycling considering their small water-sediment ratios. We assess OC processing in three seepage faces discharging to Indian River Lagoon, FL (Eau Gallie North, EGN; Riverwalk Park, RWP; and Banana River Lagoon, BRL), by measuring the quantity and quality of dissolved OC along with concentrations and δ13C signatures of dissolved CO2 and CH4. OC quality is assessed with fluorescence and PARAFAC modeling to depict changes in the abundance of reactive OC. CH4 concentrations vary by orders of magnitude between seepage faces, with the highest concentrations of 100 µM at RWP. RWP is more reducing than EGN and BRL and also contains the highest abundance of labile protein-like organic matter, which may fuel more extensive OC remineralization reactions. Residuals of salinity-based concentration and isotopic mixing models between lagoon surface water and inland groundwater indicate changes in concentration and isotopic compositions of CO2 and CH4 in the STE is due to reactions rather than mixing. At EGN and BRL, CO2 and CH4 are produced at a molar ratio of CO2:CH4 = 4 and 1.5, respectively, suggesting predominant methanogenesis via acetate fermentation, which produces CO2:CH4 ratios of 1. At RWP, CO2 is consumed as CH4 is produced at a molar ratio of -0.8, near the expected change in CO2:CH4 of -1 for methanogenesis via CO2 reduction. RWP δ13C-CH4 signatures are more depleted (-81‰) than EGN and BRL (-55‰), further supporting different methanogenesis pathways at the sites. OC quality may therefore not only regulate the extent of methanogenesis but also methanogenesis pathways in STEs. Why the sites differ in OC reactivity is unknown, but fluxes of greenhouse gases from STEs appear to depend on variations in OC reactivity in Indian River Lagoon seepage faces and perhaps other STEs globally.

Mathematical Modelling of Arctic Polygonal Tundra with Ecosys: 2. Microtopography Determines How CO 2 and CH 4 Exchange Responds to Changes in Temperature and Precipitation

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

Grant, R. F.; Mekonnen, Z. A.; Riley, W. J.

Differences of surface elevation in arctic polygonal landforms cause spatial variation in soil water contents (θ), active layer depths (ALD), and thereby in CO 2 and CH 4 exchange. In this paper, we test hypotheses in ecosys for topographic controls on CO 2 and CH 4 exchange in trough, rim, and center features of low- and flat-centered polygons (LCP and FCP) against chamber and eddy covariance (EC) measurements during 2013 at Barrow, Alaska. Larger CO 2 influxes and CH 4 effluxes were measured with chambers and modeled with ecosys in LCPs than in FCPs and in lower features (troughs) thanmore » in higher (rims) within LCPs and FCPs. Spatially aggregated CO 2 and CH 4 fluxes from ecosys were significantly correlated with EC flux measurements. Lower features were modeled as C sinks (52–56 g C m -2 yr -1) and CH 4 sources (4–6 g C m -2 yr -1), and higher features as near C neutral (-2–15 g C m -2 yr -1) and CH 4 neutral (0.0–0.1 g C m -2 yr -1). Much of the spatial and temporal variations in CO 2 and CH 4 fluxes were modeled from topographic effects on water and snow movement and thereby on θ, ALD, and soil O 2 concentrations. Model results forced with meteorological data from 1981 to 2015 indicated increasing net primary productivity in higher features and CH 4 emissions in some lower and higher features since 2008, attributed mostly to recent rises in precipitation. Finally, small-scale variation in surface elevation causes large spatial variation of greenhouse gas (GHG) exchanges and therefore should be considered in estimates of GHG exchange in polygonal landscapes.« less

Mathematical Modelling of Arctic Polygonal Tundra with Ecosys: 2. Microtopography Determines How CO 2 and CH 4 Exchange Responds to Changes in Temperature and Precipitation

DOE PAGES

Grant, R. F.; Mekonnen, Z. A.; Riley, W. J.; ...

2017-11-17

Differences of surface elevation in arctic polygonal landforms cause spatial variation in soil water contents (θ), active layer depths (ALD), and thereby in CO 2 and CH 4 exchange. In this paper, we test hypotheses in ecosys for topographic controls on CO 2 and CH 4 exchange in trough, rim, and center features of low- and flat-centered polygons (LCP and FCP) against chamber and eddy covariance (EC) measurements during 2013 at Barrow, Alaska. Larger CO 2 influxes and CH 4 effluxes were measured with chambers and modeled with ecosys in LCPs than in FCPs and in lower features (troughs) thanmore » in higher (rims) within LCPs and FCPs. Spatially aggregated CO 2 and CH 4 fluxes from ecosys were significantly correlated with EC flux measurements. Lower features were modeled as C sinks (52–56 g C m -2 yr -1) and CH 4 sources (4–6 g C m -2 yr -1), and higher features as near C neutral (-2–15 g C m -2 yr -1) and CH 4 neutral (0.0–0.1 g C m -2 yr -1). Much of the spatial and temporal variations in CO 2 and CH 4 fluxes were modeled from topographic effects on water and snow movement and thereby on θ, ALD, and soil O 2 concentrations. Model results forced with meteorological data from 1981 to 2015 indicated increasing net primary productivity in higher features and CH 4 emissions in some lower and higher features since 2008, attributed mostly to recent rises in precipitation. Finally, small-scale variation in surface elevation causes large spatial variation of greenhouse gas (GHG) exchanges and therefore should be considered in estimates of GHG exchange in polygonal landscapes.« less

Spatio-temporal variability of lake CH4 fluxes and its influence on annual estimates

NASA Astrophysics Data System (ADS)

Natchimuthu, S.; Sundgren, I.; Gålfalk, M.; Klemedtsson, L.; Crill, P. M.; Danielsson, Å.; Bastviken, D.

2014-12-01

Lakes are major sources of methane (CH4) to the atmosphere and it has been shown that lakes contribute significantly to the global CH4 budget. However, the data behind these global estimates are snapshots in time and space only and they typically lack information on spatial and temporal variability of fluxes which can potentially lead to biased estimates. Recent studies have shown that diffusive flux, gas exchange velocity (k), ebullition and concentration of CH4 in the surface water can vary significantly in space within lakes. CH4 fluxes can also change at a broad range of temporal scales in response to seasons, temperature, lake mixing events, short term weather events like pressure variations, shifting winds and diel cycles. We sampled CH4 fluxes and surface water concentrations from three lakes of differing characteristics in southwest Sweden over two annual cycles, approximately every 14 days from April to October 2012 and from April to November 2013. CH4 fluxes were measured using floating chambers distributed in the lakes based on depth categories and dissolved CH4 concentrations were determined by a headspace equilibration method. We observed significant differences in CH4 concentration, diffusion, ebullition and total fluxes between and within the lakes. The fluxes increased exponentially with temperature in all three lakes and water temperature, for example, explained 53-78% of variations in total fluxes in the lakes. Based on our data which relied on improved spatial and temporal information, we demonstrate that measurements which do not take into account of the spatial variability in the lakes could substantially bias the whole lake estimates. For instance, in one of the lakes, measurements from the central parts of the lake represented only 58% of our estimates from all chambers on an average. In addition, we consider how intensive sampling in one season of the year may affect the annual estimates due to the complex interaction of temperature, air pressure and lake mixing events on CH4 fluxes. For example, samples collected when the average air temperatures during chamber deployments were above 15 °C overestimated the total fluxes by 17-157% in all lakes when compared to averages from all measurement times.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

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.

Limited contribution of permafrost carbon to methane release from thawing peatlands

NASA Astrophysics Data System (ADS)

Cooper, Mark D. A.; Estop-Aragonés, Cristian; Fisher, James P.; Thierry, Aaron; Garnett, Mark H.; Charman, Dan J.; Murton, Julian B.; Phoenix, Gareth K.; Treharne, Rachael; Kokelj, Steve V.; Wolfe, Stephen A.; Lewkowicz, Antoni G.; Williams, Mathew; Hartley, Iain P.

2017-07-01

Models predict that thaw of permafrost soils at northern high latitudes will release tens of billions of tonnes of carbon (C) to the atmosphere by 2100 (refs ,,). The effect on the Earth’s climate depends strongly on the proportion of this C that is released as the more powerful greenhouse gas methane (CH4), rather than carbon dioxide (CO2) (refs ,); even if CH4 emissions represent just 2% of the C release, they would contribute approximately one-quarter of the climate forcing. In northern peatlands, thaw of ice-rich permafrost causes surface subsidence (thermokarst) and water-logging, exposing substantial stores (tens of kilograms of C per square meter, ref. ) of previously frozen organic matter to anaerobic conditions, and generating ideal conditions for permafrost-derived CH4 release. Here we show that, contrary to expectations, although substantial CH4 fluxes (>20 g CH4 m-2 yr-1) were recorded from thawing peatlands in northern Canada, only a small amount was derived from previously frozen C (<2 g CH4 m-2 yr-1). Instead, fluxes were driven by anaerobic decomposition of recent C inputs. We conclude that thaw-induced changes in surface wetness and wetland area, rather than the anaerobic decomposition of previously frozen C, may determine the effect of permafrost thaw on CH4 emissions from northern peatlands.

Comparison of atmospheric CH4 concentration observed by GOSAT and in-situ measurements in Thailand and India

NASA Astrophysics Data System (ADS)

Hayashida, S.; Ono, A.; Ishikawa, S.; Terao, Y.; Takeuchi, W.

2012-12-01

The concentration of atmospheric methane (CH4) has more than doubled since pre-industrial levels and the observed long-term changes in the CH4 concentration have been attributed to anthropogenic activity. However, despite the importance of atmospheric CH4 in global warming, the strength of individual sources of CH4 remains highly uncertain [e.g.,Dlugokencky et al., 2011]. To characterize and quantify the emissions of CH4 especially in Monsoon Asia and Siberia, which are the most important regions as CH4 source, we started a new project, "Characterization and Quantification of global methane emissions by utilizing GOSAT and in-situ measurements " by support of the Environment Research and Technology Development Fund (ERTDF) from June 2012 under the umbrella of Ministry of Environment Japan. The projects includes (1) satellite data applications, (2) in-situ measurements in Siberia, over Western Pacific and in Monsoon Asia, (3) development of the inverse model to derive CH4 emissions by top-down approach, and (4) flux measurements in Siberia and Asia to improve the bottom-up inventories. As an initiatory approach in the project, we started air sampling in Thailand and India where there are only a few CH4 data of direct sampling with high precision. We took eight air samples at Kohn Kaen and Pimai in Thailand on June 9 and 10, 2012. The high CH4 concentration near rice paddy field contrasted to the lower CH4 concentration near Cassava field. We are planning to take more samples in India in mid-August. The satellite CH4 data including GOSAT and SCIAMACHY are also compared with the Land Surface Water Coverage (LSWC) and the Normalized Difference Vegetation Index (NDVI). The analysis revealed the seasonal variation in of xCH4 is closely related to the variation of the LSWC, coupled with NDVI. However, the satellite measurements are all column-averaged mixing ratio (xCH4), and therefore do not necessarily reflect high CH4 concentration near the surface over the emission regions. To optimize "inverse approach", we need to investigate the relation between xCH4 and the surface concentration, and need to combine it to the bottom-up approach. We will also discuss representativeness of GOSAT measurement from the viewpoint of spatial and time scale when it observes such heterogeneous emission regions.

Reducing CH4 emission from rice paddy fields by altering water management

NASA Astrophysics Data System (ADS)

Sudo, S.; Itoh, M.

2010-12-01

Percentage of atmospheric methane emitted form rice paddy is estimated at 60Tg/yr (20 - 100Tg/yr) which is near 10% of total global methane emission of 535Tg/yr (410 - 660Tg) (IPCC(1995), and which is near 30% of anthropogenic CH4 emission. Thus, mitigation of CH4 emission is urgently required. CH4 in paddy soil is emanated by the activities of anaerobic bacteria which is called methane producer through reduction of CO2 or decomposition of acetic acid, and it is transported to atmosphere through soil or paddy water surface. It is effective to control methane emission from rice paddy that period is extended on intermittent drainage, composted rice straw is incorporated as fertilizer instead of flesh one, or other. However, empirical approach of these kinds of experiments had not been sufficient because such a kind of experiment required significant times and efforts. In this study, we conducted demonstrative experiments to verify the effects of water management method differences in order to reduce CH4 emission from rice paddy at 9 experimental sites in 8 prefectures. In this, we used new gas analyzer which can measure CH4, CO2 and N2O at once developed by National Institute for Agro-Environmental Sciences (NIAES), Japan. In this report, we show the results in two years of this study. 'Nakaboshi' (mid-season-drainage) is one of cultivation methods in rice paddy that surface water in paddy field is once drained for about 10 days and the field is maintained like upland field to give adequate stress to rice plant for better harvest qualities and yields. Our targeted evaluation was dependencies of Nakaboshi periods lengths and Nakaboshi periods to CH4 emission reduction amounts for total cultivation periods within harvest yield maintained. The longer length of Nakaboshi period was extended, the lesser CH4 emitted even after when Nakaboshi period lasted, as a whole. In some cases, for example in Kagoshima, exceptional phenomena of that significant high emission were observed at a later stage of cultivation season (around the end of August). Adjusting of Nakaboshi periods did not make effective performance in such cases. In most of cases, emission increase of N2O was not found during prolonged Nakaboshi period.

Integrating time-series and spatial surveys to assess annual, lake-wide emissions of carbon dioxide and methane from a eutrophic lake

NASA Astrophysics Data System (ADS)

Loken, L. C.; Crawford, J.; Schramm, P.; Stadler, P.; Stanley, E. H.

2017-12-01

Lakes are important regulators of global carbon cycling and conduits of greenhouse gases to the atmosphere; however, most efflux estimates for individual lakes are based on extrapolations from a limited number of locations. Within-lake variability in carbon dioxide (CO2) and methane (CH4) arises from differences in water sources, physical mixing, and biogeochemical transformations; all of which can vary at multiple temporal and spatial scales. We mapped surface water concentrations of CO2 and CH4 weekly across Lake Mendota (a 39.9 km2 eutrophic lake in Wisconsin, USA) spanning the majority of the 2016 ice-free season (249 days). Combining these maps with a spatially explicit gas transfer velocity (k) model, we estimated the diffusive exchange of both gases with the atmosphere taking into account both spatial and temporal heterogeneity. The cumulative efflux of CO2 (85.3 Mmol) and CH4 (9.47 Mmol) was positive, indicating that on the annual scale Lake Mendota was a net-source of both gases to the atmosphere. Although our model included variability in k, flux patterns reflected the patterns in gas concentrations. During the stratified period, CO2 was generally undersaturated throughout the pelagic zone due to high primary production and differed near river inlets and shorelines. The lake was routinely extremely supersaturated with CH4 with elevated concentrations in expansive littoral areas. During fall mixis, concentrations of both gases increased and became more variable across the lake surface, and their spatial arrangement changed reflecting hypolimentic mixing. In this system, samples collected from the lake center reasonably well-represented the lake-wide mean CO2 concentration, but they poorly represented CH4. While metabolic processes driving CO2 varied across the lake surface, pelagic phytoplankton contributed extensively to overall primary production, which acted at the lake-wide scale. Additionally Lake Mendota's high alkalinity may have masked the metabolic imprint on CO2 patterns. In contrast, heterogeneous CH4 transformations and transport lead to remarkable variation in CH4 across the lake surface that was dynamic through time. Thus, extrapolations from a limited number of locations or timepoints may not adequately describe lake-wide CH4 dynamics.

Sources and flux of natural gases from Mono Lake, California

USGS Publications Warehouse

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

1987-01-01

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

Carbon Fluxes in Dissolved and Gaseous Forms for a Restored Peatland in British Columbia, Canada

NASA Astrophysics Data System (ADS)

D'Acunha, B.; Johnson, M. S.; Lee, S. C.; Christen, A.

2016-12-01

Peatlands are wetlands where gross primary production exceeds organic matter decomposition causing an accumulation of partially decomposed matter, also called peat. These ecosystems can accumulate more carbon than tropical rainforests. However, dissolved and gaseous fluxes of carbon (as dissolved organic carbon (DOC), CO2 and methane (CH4)) must also be considered to determine if these ecosystems are net sinks or sources of greenhouse gases (GHGs) to the atmosphere, which depends in part on the environmental conditions and the state of the ecosystem. We conducted research in Burns Bog, Delta, BC, Canada, a raised domed peat bog located in the Fraser River Delta and one of the largest raised peat bogs on the west coast of the Americas, but which has been heavily impacted by a range of human activities. Currently, ecological restoration efforts are underway by a large-scale ditch blocking program, with the aim to re-establish a high water table. This is approached in partnership with research on the ecosystem services that the bog provides, including its role in a regional GHG inventory. Here we present data on ecosystem-scale fluxes of CO2 and CH4 determined by eddy covariance (EC) on a floating tower platform, and complementary data on (i) evasion fluxes of CO2, CH4 and nitrous oxide (N2O) from the water surface to the atmosphere, and (ii) the flux and composition of dissolved organic carbon in water draining Burns Bog. Concentrations of dissolved CO2, CH4 and N2O were determined by headspace equilibration, and evasion rates from the water surface were quantified and are used to estimate the role of the hydrosphere in the ecosystem-scale measurements. Water samples collected from five saturated areas in the flux tower footprint were analyzed for DOC concentrations and composition. Results indicated that, even though the whole system is a net C sink, the water surface behaved as a source of CO2 and CH4, and a sink for N2O throughout the study period. Drainage waters were high in DOC (> 30 mg L-1). DOC export was found to offset about 20% of the apparent net C uptake determined by EC, indicating that the EC system overestimates carbon accumulation by not accounting for DOC drainage.

Methanogenesis in the sediment of the acidic Lake Caviahue in Argentina

NASA Astrophysics Data System (ADS)

Koschorreck, Matthias; Wendt-Potthoff, Katrin; Scharf, Burkhard; Richnow, Hans H.

2008-12-01

The biogeochemistry of methane in the sediments of Lake Caviahue was examined by geochemical analysis, microbial activity assays and isotopic analysis. The pH in the water column was 2.6 and increased up to a pH of 6 in the deeper sediment pore waters. The carbon isotope composition of CH 4 was between - 65 and - 70‰ which is indicative for the biological origin of the methane. The enrichment factor ɛ increased from - 46‰ in the upper sediment column to more than - 80 in the deeper sediment section suggesting a transition from acetoclastic methanogenesis to CO 2 reduction with depth. In the most acidic surface layer of the sediment (pH < 4) methanogenesis is inhibited as suggested by a linear CH 4 concentration profile, activity assays and MPN analysis. The CH 4 activity assays and the CH 4 profile indicate that methanogenesis in the sediment of Lake Caviahue was active below 40 cm depth. At that depth the pH was above 4 and sulfate reduction was sulfate limited. Methane was diffusing with a flux of 0.9 mmol m - 2 d - 1 to the sediment surface where it was probably oxidized. Methanogenesis contributed little to the sediments carbon budget and had no significant impact on lake water quality. The high biomass content of the sediment, which was probably caused by the last eruption of Copahue Volcano, supported high rates of sulfate reduction which probably raised the pH and created favorable conditions for methanogens in deeper sediment layers.

Evaluation of shallow sediment methane cycling in a pockmark field on the Chatham Rise, New Zealand

NASA Astrophysics Data System (ADS)

Coffin, R. B.; Rose, P. S.; Klaucke, I.; Bialas, J.; Pecher, I. A.; Gorman, A. R.

2014-12-01

Seismic studies have identified an extensive field (>20,000 km2) of seafloor depressions, or pockmarks, on the southwestern flank of the Chatham Rise, New Zealand. It has been suggested that these pockmarks result from gas hydrate dissociation linked to sea-level changes during glacial-interglacial cycles. Gas hydrates are predominately composed of methane (CH4), a potent greenhouse gas. Surface sediment cores (~ 8 m) were collected from the pockmark field on the Chatham Rise during a research cruise in February 2013 to evaluate the association of the features with CH4 releases. A suite of geochemical parameters are interpreted to determine the methane contribution to solid phase sediment and pore water. The upward flux of CH4 in sediments is often quantified using pore water sulfate (SO42-) profiles, assuming steady-state consumption of SO42- and CH4 by anaerobic oxidation of methane (AOM): CH4 + SO42- → HCO3- + HS- + H2O. This reaction is one of the primary controls on CH4 distributions in sediments. This work will present pore water SO42-, sulfide (HS-) and chloride (Cl-) depth profiles in sediment collected from the pockmark field. Theoretical SO42- distributions in the absence of AOM are compared to observed SO42- profiles as a preliminary assessment of the influence of CH4 on sediment geochemistry in and around the seafloor depressions. In addition isotopically-light CH4 is incorporated into sediment carbon pools via AOM and subsequent CO2 fixation. Stable carbon isotope distributions in the organic and inorganic carbon pools are presented to determine the influence of CH4 in sediments in the vicinty of the pockmarks. Collectively, the geochemical data are used to assess the role of gas hydate dissociation in pockmark formation on the Chatham Rise. Despite sesimic data interpretation in this region there is no modern day contribution of CH4 to shallow sediment carbon cycling and data are presented to assess paleogeochemical methane cycling.

Investigating physical controls on methane and carbon ...

EPA Pesticide Factsheets

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

Synthesis of flat sticky hydrophobic carbon diamond-like films using atmospheric pressure Ar/CH4 dielectric barrier discharge

NASA Astrophysics Data System (ADS)

Rincón, R.; Hendaoui, A.; de Matos, J.; Chaker, M.

2016-06-01

An Ar/CH4 atmospheric pressure dielectric barrier discharge (AP-DBD) was used to synthesize sticky hydrophobic diamond-like carbon (DLC) films on glass surface. The film is formed with plasma treatment duration shorter than 30 s, and water contact angles larger than 90° together with contact angle hysteresis larger than 10° can be achieved. According to Fourier transform infrared spectroscopy and atomic force microscopy analysis, hydrocarbon functional groups are created on the glass substrate, producing coatings with low surface energy (˜35 mJ m-2) with no modification of the surface roughness. To infer the plasma processes leading to the formation of low energy DLC surfaces, optical emission spectroscopy was used. From the results, a direct relationship between the CH species present in the plasma and the carbon concentration in the hydrophobic layer was found, which suggests that the CH species are the precursors of DLC film growth. Additionally, the plasma gas temperature was measured to be below 350 K which highlights the suitability of using AP-DBD to treat thermo-sensitive surfaces.

Methane emissions from tundra environments in the Yukon-Kuskokwin Delta, Alaska

NASA Technical Reports Server (NTRS)

Bartlett, Karen B.; Crill, Patrick M.; Sass, Ronald L.; Harriss, Robert C.; Dise, Nancy B.

1992-01-01

This paper reports CH4 flux to the atmosphere from a variety of tundra environments near Bethel, Alaska during the summer months of 1988. Emissions from wet meadow tundra averaged 144 +/- 31 mg/sq m/d and ranged from 15.6 to 426 mg/sq m/d varying with soil moisture and temperature. Flux from the drier upland tundra was about two orders of magnitude lower and averaged 2.3 +/- 1.1 mg/sq m/d. Tundra lakes emit CH4 from the open water surface as well as from fringing aquatic vegetation; the presence of vegetation significantly enhanced flux over open water rates. Calculated diffusive fluxes from open water varied with lake size, the large lakes emitting 3.8 mg/sq m/d and small lakes emitting an average of 77 mg/sq m/d. An updated estimate of global emissions from tundra indicates an annual fluxes of approximately 11 +/- 3 Tg CH4.

Distribution, abundance and carbon isotopic composition of gaseous hydrocarbons in Big Soda Lake, Nevada: An alkaline, meromictic lake

USGS Publications Warehouse

Oremland, R.S.; Des Marais, D.J.

1983-01-01

Distribution and isotopic composition (??13C) of low molecular weight hydrocarbon gases were studied in Big Soda Lake (depth = 64 m), an alkaline, meromictic lake with permanently anoxic bottom waters. Methane increased with depth in the anoxic mixolimnion (depth = 20-35 m), reached uniform concentrations (55 ??M/l) in the monimolimnion (35-64 m) and again increased with depth in monimolimnion bottom sediments (>400 ??M/kg below 1 m sub-bottom depth). The ??13C[CH4] values in bottom sediment below 1 m sub-bottom depth (<-70 per mil) increased with vertical distance up the core (??13C[CH4] = -55 per mil at sediment surface). Monimolimnion ??13C[CH4] values (-55 to -61 per mil) were greater than most ??13C[CH4] values found in the anoxic mixolimnion (92% of samples had ??13C[CH4] values between -20 and -48 per mil). No significant concentrations of ethylene or propylene were found in the lake. However ethane, propane, isobutane and n-butane concentrations all increased with water column depth, with respective maximum concentrations of 260, 80, 23 and 22 nM/l encountered between 50-60 m depth. Concentrations of ethane, propane and butanes decreased with depth in the bottom sediments. Ratios of CH4 [C2H6 + C3H8] were high (250-620) in the anoxic mixolimnion, decreased to ~161 in the monimolimnion and increased with depth in the sediment to values as high as 1736. We concluded that methane has a biogenic origin in both the sediments and the anoxic water column and that C2-C4 alkanes have biogenic origins in the monimolimnion water and shallow sediments. The changes observed in ??13C[CH4] and CH4 (C2H6 + C3H8) with depth in the water column and sediments are probably caused by bacteria] processes. These might include anaerobic methane oxidation and different rates of methanogenesis and C2 to C4 alkane production by microorganisms. ?? 1983.

Carbon dioxide induced bubble formation in a CH4-CO2-H2O ternary system: a molecular dynamics simulation study.

PubMed

Sujith, K S; Ramachandran, C N

2016-02-07

The extraction of methane from its hydrates using carbon dioxide involves the decomposition of the hydrate resulting in a CH4-CO2-H2O ternary solution. Using classical molecular dynamics simulations, we investigate the evolution of dissolved gas molecules in the ternary system at different concentrations of CO2. Various compositions considered in the present study resemble the solution formed during the decomposition of methane hydrates at the initial stages of the extraction process. We find that the presence of CO2 aids the formation of CH4 bubbles by causing its early nucleation. Elucidation of the composition of the bubble revealed that in ternary solutions with high concentration of CO2, mixed gas bubbles composed of CO2 and CH4 are formed. To understand the role of CO2 in the nucleation of CH4 bubbles, the structure of the bubble formed was analyzed, which revealed that there is an accumulation of CO2 at the interface of the bubble and the surrounding water. The aggregation of CO2 at the bubble-water interface occurs predominantly when the concentration of CO2 is high. Radial distribution function for the CH4-CO2 pair indicates that there is an increasingly favorable direct contact between dissolved CH4 and CO2 molecules in the bubble-water interface. It is also observed that the presence of CO2 at the interface results in the decrease in surface tension. Thus, CO2 leads to greater stability of the bubble-water interface thereby bringing down the critical size of the bubble nuclei. The results suggest that a rise in concentration of CO2 helps in the removal of dissolved CH4 thereby preventing the accumulation of methane in the liquid phase. Thus, the presence of CO2 is predicted to assist the decomposition of methane hydrates in the initial stages of the replacement process.

Methane emissions from western Canadian peatland lakes: assessing interactive effects of groundwater connectivity and permafrost thaw

NASA Astrophysics Data System (ADS)

Kuhn, M. A.; Riechert, C.; Estop Aragones, C.; Broder, T.; Bastviken, D.; Knorr, K. H.; Olefeldt, D.

2017-12-01

Rising temperatures and the submergence of recently thawed permafrost into lakes has been identified as a major driver of methane (CH4) emissions in northern regions. Lakes on the vast Taiga Plains in western Canada represent a vital unknown with respect to CH4 fluxes and their sensitivity to permafrost thaw. The Taiga Plains has several characteristics that could influence magnitude and controls on lake CH4 emissions in comparison to other regions, including high soil organic carbon stores, distinct permafrost history, and complex groundwater interactions that influence availability of terminal electron acceptor concentrations among lakes. The goal of this research is to describe the similarities and differences in processes governing lake CH4 emissions between western Canada and other northern regions. We carried out biweekly diffusive and ebullition flux measurements and monitored sediment redox profiles from two lakes near the border between Alberta and the Northwest Territories. The two lakes differ in contributions of surface water and groundwater inputs, respectively. Floating chamber-based fluxes were measured leading from the edges to the centers of the lakes from ice-out in early May until ice-cover in the fall. Preliminary redox profile analyses suggest the groundwater-fed lake has extremely high concentrations of sulfides (>200 µmol L-1) down to a depth of 30 cm, while the surface water lake has little to no sulfide, but high concentrations of reduced iron (>200 µmol L-1 ). Despite high sulfide concentrations in the sediments, the groundwater-fed lake had generally higher diffusive fluxes compared to the surface water lake, but there were no differences between the center and along the actively collapsing thermokarst edges. However, ebullition fluxes were highest from a recently thawed lake edge compared to the center of the lake and stable, non-thaw influenced edges. The results of this project will help improve current regional CH4 models by including ground-based methane flux measurements from the vast and previously unstudied region of western Canada.

Methane production potential and emission at different water levels in the restored reed wetland of Hangzhou Bay

PubMed Central

Sheng, Xuancai; Wu, Ming; Wu, Hao; Ning, Xiao

2017-01-01

Changes in the hydrological conditions of coastal wetlands may potentially affect the role of wetlands in the methane (CH4) cycle. In this study, the CH4 production potential and emissions from restored coastal reed wetlands at different water levels were examined in eastern China at a field scale in two phenological seasons. Results showed that the total CH4 flux from reeds at various water levels were positive, indicating that they were “sources” of CH4. During the peak growing season, CH4 flux from reeds was greater than that during the spring thaw. CH4 flux from reeds in inundated conditions was greater than that in non-inundated conditions. The CH4 production potential during the peak growing season was far greater than that during the spring thaw. However, the effect of water level on wetland CH4 production potential differed among seasons. The correlations among CH4 production potential, soil properties and CH4 flux change at different water level. These results demonstrate that water level was related to CH4 production and CH4 flux. The growing season also plays a role in CH4 fluxes. Controlling the hydrological environment in restored wetlands has important implications for the maintenance of their function as carbon sinks. PMID:28968419

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Evaluation of modelled methane emissions over northern peatland sites

NASA Astrophysics Data System (ADS)

Gao, Yao; Burke, Eleanor; Chadburn, Sarah; Raivonen, Maarit; Susiluoto, Jouni; Vesala, Timo; Aurela, Mika; Lohila, Annalea; Aalto, Tuula

2017-04-01

Methane (CH4) is a powerful greenhouse gas, with approximately 34 times the global warming potential of carbon dioxide (CO2) over a century time horizon (IPCC, 2013). The strong sensitivity of methane emissions to environmental factors has led to concerns about potential positive feedbacks to climate change. Evaluation of the ability of the process-based land surface models of earth system models (ESMs) in simulating CH4 emission over peatland is needed for more precise future predictions. In this study, two peatland sites of poor and rich soil nutrient conditions, in southern and northern Finland respectively, are adopted. The measured CH4 fluxes at the two sites are used to evaluate the CH4 emissions simulated by the land surface model (JULES) of the UK Earth System model and by the Helsinki peatland methane emission model (HIMMELI), which is developed at Finnish Meteorological Institute and Helsinki University. In JULES, CH4 flux is simply related to soil temperature, wetland fraction and effective substrate availability. However, HIMMELI has detailed descriptions of microbial and transport processes for simulating CH4 flux. The seasonal dynamics of CH4 fluxes at the two sites are relatively well captured by both models, but model biases exist. Simulated CH4 flux is sensitive to water table depth (WTD) at both models. However, the simulated WTD is limited to be below ground in JULES. It is also important to have the annual cycle of LAI correct when coupling JULES with HIMMELI.

Differential response of carbon cycling to long-term nutrient input and altered hydrological conditions in a continental Canadian peatland

NASA Astrophysics Data System (ADS)

Berger, Sina; Praetzel, Leandra S. E.; Goebel, Marie; Blodau, Christian; Knorr, Klaus-Holger

2018-02-01

Peatlands play an important role in global carbon cycling, but their responses to long-term anthropogenically changed hydrologic conditions and nutrient infiltration are not well known. While experimental manipulation studies, e.g., fertilization or water table manipulations, exist on the plot scale, only few studies have addressed such factors under in situ conditions. Therefore, an ecological gradient from the center to the periphery of a continental Canadian peatland bordering a eutrophic water reservoir, as reflected by increasing nutrient input, enhanced water level fluctuations, and increasing coverage of vascular plants, was used for a case study of carbon cycling along a sequence of four differently altered sites. We monitored carbon dioxide (CO2) and methane (CH4) surface fluxes and dissolved inorganic carbon (DIC) and CH4 concentrations in peat profiles from April 2014 through September 2015. Moreover, we studied bulk peat and pore-water quality and we applied δ13C-CH4 and δ13C-CO2 stable isotope abundance analyses to examine dominant CH4 production and emission pathways during the growing season of 2015. We observed differential responses of carbon cycling at the four sites, presumably driven by abundances of plant functional types and vicinity to the reservoir. A shrub-dominated site in close vicinity to the reservoir was a comparably weak sink for CO2 (in 1.5 years: -1093 ± 794, in 1 year: +135 ± 281 g CO2 m-2; a net release) as compared to two graminoid-moss-dominated sites and a moss-dominated site (in 1.5 years: -1552 to -2260 g CO2 m-2, in 1 year: -896 to -1282 g CO2 m-2). Also, the shrub-dominated site featured notably low DIC pore-water concentrations and comparably 13C-enriched CH4 (δ13C- CH4: -57.81 ± 7.03 ‰) and depleted CO2 (δ13C-CO2: -15.85 ± 3.61 ‰) in a more decomposed peat, suggesting a higher share of CH4 oxidation and differences in predominant methanogenic pathways. In comparison to all other sites, the graminoid-moss-dominated site in closer vicinity to the reservoir featured a ˜ 30 % higher CH4 emission (in 1.5 years: +61.4 ± 32, in 1 year: +39.86 ± 16.81 g CH4 m-2). Low δ13C-CH4 signatures (-62.30 ± 5.54 ‰) indicated only low mitigation of CH4 emissions by methanotrophic activity here. Pathways of methanogenesis and methanotrophy appeared to be related to the vicinity to the water reservoir: the importance of acetoclastic CH4 production apparently increased toward the reservoir, whereas the importance of CH4 oxidation increased toward the peatland center. Plant-mediated transport was the prevailing CH4 emission pathway at all sites even where graminoids were rare. Our study thus illustrates accelerated carbon cycling in a strongly altered peatland with consequences for CO2 and CH4 budgets. However, our results suggest that long-term excess nutrient input does not necessarily lead to a loss of the peatland carbon sink function.

Probing surface sites of TiO2: reactions with [HRe(CO)5] and [CH3Re(CO)5].

PubMed

Lobo-Lapidus, Rodrigo J; Gates, Bruce C

2010-10-04

Two carbonyl complexes of rhenium, [HRe(CO)(5)] and [CH(3)Re(CO)(5)], were used to probe surface sites of TiO(2) (anatase). These complexes were adsorbed from the gas phase onto anatase powder that had been treated in flowing O(2) or under vacuum to vary the density of surface OH sites. Infrared (IR) spectra demonstrate the variation in the number of sites, including Ti(+3)-OH and Ti(+4)-OH. IR and extended X-ray absorption fine structure (EXAFS) spectra show that chemisorption of the rhenium complexes led to their decarbonylation, with formation of surface-bound rhenium tricarbonyls, when [HRe(CO)(5)] was adsorbed, or rhenium tetracarbonyls, when [CH(3)Re(CO)(5)] was adsorbed. These reactions were accompanied by the formation of water and surface carbonates and removal of terminal hydroxyl groups associated with Ti(+3) and Ti(+4) ions on the anatase. Data characterizing the samples after adsorption of [HRe(CO)(5)] or [CH(3)Re(CO)(5)] determined a ranking of the reactivity of the surface OH sites, with the Ti(+3)-OH groups being the more reactive towards the rhenium complexes but the less likely to be dehydroxylated. The two rhenium pentacarbonyl probes provided complementary information, suggesting that the carbonate species originate from carbonyl ligands initially bonded to the rhenium and from hydroxyl groups of the titania surface, with the reaction leading to the formation of water and bridging hydroxyl groups on the titania. The results illustrate the value of using a family of organometallic complexes as probes of oxide surface sites.

Laboratory estimates of trace gas emissions following surface application and injection of cattle slurry

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

Flessa, H.; Beese, F.

2000-02-01

Applying cattle slurry to soil may induce emissions of the greenhouse gases N{sub 2}O and CH{sub 4}. Their objective was to determine the effects of different application techniques (surface application and slit injection) of cattle (Bostaurus) slurry on the decomposition of slurry organic matter and the emissions of N{sub 2}O and CH{sub 4}. The effects of slurry application (43.6 m{sup 3} ha{sup {minus}1}) were studied for 9 wk under controlled laboratory conditions using a soil microcosm system with automated monitoring of the CO{sub 2}, N{sub 2}O, and CH{sub 4} fluxes. The soil used was a silty loam (Ap horizon ofmore » a cambisol) with a constant water-filled pore space of 67% during the experiment. About 38% of the organic matter applied with the slurry was decomposed within 9 wk. Production of CO{sub 2} was not affected by the application technique. Emissions of N{sub 2}O and CH{sub 4} from the injected slurry were significantly higher than from the surface-applied slurry, probably because of restricted aeration at the injected-slurry treatment. Total N{sub 2}O-N emissions were 0.2% (surface application) and 3.3% (slit injection) of the slurry N added. Methane emission occurred only during the first few days following application. The total net flux of CH{sub 4}-C for 2 wk was {minus}12 g ha{sup {minus}1} for the control (CH{sub 4} uptake), 2 g ha{sup {minus}1} for the surface-applied slurry, and 39 g ha{sup {minus}1} for the injected slurry. Slurry injection, which is recommended to reduce NH{sub 3} volatilization, appears to increase emissions of the greenhouse gases N{sub 2}O and CH{sub 4} from the fertilized fields.« less

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.

Year-Round Carbon Fluxes in a Subarctic Landscape Show the Importance of Lake Emissions According to Season

NASA Astrophysics Data System (ADS)

Jammet, M.; Crill, P. M.; Friborg, T.

2014-12-01

Lakes are increasingly recognized as important components of the global terrestrial carbon budget. Northern lakes are especially of interest due to a high density of open-water ecosystems in Northern latitudes and a potential increase in lake areal extent where permafrost is thawing. A better understanding of lake-atmosphere interactions requires long-term and direct measurement of surface fluxes. This is rarely achieved in Northern landscapes where seasonally ice-covered lakes are mostly studied during the open water season, and measurement methods do not always allow an integration of all gas transport pathways to the atmosphere. We present here ecosystem-scale data from Stordalen (68°20'N, 19°03'E), a thawing permafrost peatland in subarctic Sweden, where an eddy covariance system is used in an innovative way to quantify the importance of methane (CH4) emissions from a shallow lake. After more than a year of surface flux monitoring, it is found that spring is a crucial season for lake-atmosphere CH4 exchange. Despite its shallow depth, more than half of annual CH4 emissions from the lake were recorded at ice-out, suggesting significant winter CH4 production in lake sediments. Lake water dynamics seemed to drive the observed spring release rates. In contrast, summer methane emissions in Stordalen were dominated by the minerotrophic fens. This underlines the importance of considering the full annual budget when assessing the carbon source strength of seasonally ice-covered lakes. Carbon dioxide fluxes were also monitored and will be briefly discussed, as well as the significance of northern lakes spring burst for global atmospheric CH4 budget.

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.

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

NASA Astrophysics Data System (ADS)

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

2012-12-01

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

Temporal and spatial variations of soil carbon dioxide, methane, and nitrous oxide fluxes in a Southeast Asian tropical rainforest

NASA Astrophysics Data System (ADS)

Itoh, M.; Kosugi, Y.; Takanashi, S.; Hayashi, Y.; Kanemitsu, S.; Osaka, K.; Tani, M.; Nik, A. R.

2010-09-01

To clarify the factors controlling temporal and spatial variations of soil carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O) fluxes, we investigated these gas fluxes and environmental factors in a tropical rainforest in Peninsular Malaysia. Temporal variation of CO2 flux in a 2-ha plot was positively related to soil water condition and rainfall history. Spatially, CO2 flux was negatively related to soil water condition. When CO2 flux hotspots were included, no other environmental factors such as soil C or N concentrations showed any significant correlation. Although the larger area sampled in the present study complicates explanations of spatial variation of CO2 flux, our results support a previously reported bipolar relationship between the temporal and spatial patterns of CO2 flux and soil water condition observed at the study site in a smaller study plot. Flux of CH4 was usually negative with little variation, resulting in the soil at our study site functioning as a CH4 sink. Both temporal and spatial variations of CH4 flux were positively related to the soil water condition. Soil N concentration was also related to the spatial distribution of CH4 flux. Some hotspots were observed, probably due to CH4 production by termites, and these hotspots obscured the relationship between both temporal and spatial variations of CH4 flux and environmental factors. Temporal variation of N2O flux and soil N2O concentration was large and significantly related to the soil water condition, or in a strict sense, to rainfall history. Thus, the rainfall pattern controlled wet season N2O production in soil and its soil surface flux. Spatially, large N2O emissions were detected in wet periods at wetter and anaerobic locations, and were thus determined by soil physical properties. Our results showed that, even in Southeast Asian rainforests where distinct dry and wet seasons do not exist, variation in the soil water condition related to rainfall history controlled the temporal variations of soil CO2 flux, CH4 uptake, and N2O emission. The soil water condition associated with soil hydraulic properties was also the important controlling factor of the spatial distributions of these gas fluxes.

Characterization and Modeling Of Microbial Carbon Metabolism In Thawing Permafrost

NASA Astrophysics Data System (ADS)

Graham, D. E.; Phelps, T. J.; Xu, X.; Carroll, S.; Jagadamma, S.; Shakya, M.; Thornton, P. E.; Elias, D. A.

2012-12-01

Increased annual temperatures in the Arctic are warming the surface and subsurface, resulting in thawing permafrost. Thawing exposes large pools of buried organic carbon to microbial degradation, increasing greenhouse gas generation and emission. Most global-scale land-surface models lack depth-dependent representations of carbon conversion and GHG transport; therefore they do not adequately describe permafrost thawing or microbial mineralization processes. The current work was performed to determine how permafrost thawing at moderately elevated temperatures and anoxic conditions would affect CO2 and CH4 generation, while parameterizing depth-dependent GHG production processes with respect to temperature and pH in biogeochemical models. These enhancements will improve the accuracy of GHG emission predictions and identify key biochemical and geochemical processes for further refinement. Three core samples were obtained from discontinuous permafrost terrain in Fairbanks, AK with a mean annual temperature of -3.3 °C. Each core was sectioned into surface/near surface (0-0.8 m), active layer (0.8-1.6 m), and permafrost (1.6-2.2 m) horizons, which were homogenized for physico-chemical characterization and microcosm construction. Surface samples had low pH values (6.0), low water content (18% by weight), low organic carbon (0.8%), and high C:N ratio (43). Active layer samples had higher pH values (6.4), higher water content (34%), more organic carbon (1.4%) and a lower C:N ratio (24). Permafrost samples had the highest pH (6.5), highest water content (46%), high organic carbon (2.5%) and the lowest C:N ratio (19). Most organic carbon was quantified as labile or intermediate pool versus stable pool in each sample, and all samples had low amounts of carbonate. Surface layer microcosms, containing 20 g sediment in septum-sealed vials, were incubated under oxic conditions, while similar active and permafrost layer samples were anoxic. These microcosms were incubated at -2, +3, or +5 °C for 6 months. The pH decreased in all samples (5.5 to 5.9). The proportions of carbon in labile and intermediate turnover pools from permafrost samples decreased during incubation, while microbial biomass carbon increased in all cases. Microcosm samples and original core material were analyzed by 16S rDNA pyrosequencing and showed increased populations of bacteria that ferment simple and complex carbohydrates, as well as acidophilic bacteria. Microbial diversity declined in permafrost samples. Concentrations of CO2 and CH4 were measured monthly by gas chromatography. CO2 production was highest in the surface/near surface incubations (4-14%) while CH4 was undetectable. Active layer sediments produced considerably less CO2 (0.2-0.7%) but CH4 was detected up to 0.25%. Concentrations of CO2 found in the deep permafrost incubations were comparable to those in the active layer, while CH4 was considerably higher ranging from 0.2-0.6%. Overall, the CO2 generation rate (0.02-0.12 μmol/g/month) was roughly 50 times that of methanogenesis (0.002-0.007 μmol/g/month). GHG levels peaked after 4 months, and the decreasing pH suggested that organic acid accumulation could control GHG biogenesis. Surprisingly, increasing temperature and water content did not necessarily increase GHG emission rates or proportions of CO2 and CH4.

Quantifying shallow and deep permafrost changes using radar remote sensing

NASA Astrophysics Data System (ADS)

Teshebaeva, K.; van Huissteden, K. J.

2017-12-01

Widespread thawing of permafrost in the northern Eurasian continent cause severe problems for infrastructure and global climate. Permafrost thaw by climate warming creates land surface instability, resulting in severe problems for infrastructure, and release of organic matter to the atmosphere as CO2 and CH4. Recent discoveries of CH4 seeps in lakes, in the Arctic Ocean, and CH4 emitting craters in the permafrost. These features indicate that permafrost destabilization might no longer be a surface feature only, but that also deeper layers of the permafrost, up to tens of meters, may be affected by warming. We study two potential areas in Siberian arctic; one of the test site is the Kytalyk research station near Chokurdagh town affected with a recent inundation of the Indigirka river in July 2017, which resulted in standing surface water for the period over a month. The wet soil and standing water may cause changes in active layer thickness and influence the thermal regime of the permafrost for the next decades in the region. The second test site is Yamal peninsula with recently CH4 emitting craters, which may start to contribute to emission hotspots. We hypothesize that these deeper subsurface processes also can be detected by mapping surface elevation changes using advanced SAR techniques. We test the potential of SAR imagery to enhance detection of these features, including surface movement related to permafrost active layer changes using InSAR time-series analysis. We also apply radar backscatter signal to detect seasonal changes related to the freeze-thaw cycles. The PRISM elevation data are used to estimate elevation changes in the region along with ground-based geophysical and geodetical fieldwork.

Assessment of shallow methane (CH4) gas using stable carbon and hydrogen isotopes in the sediments of the Gunsan Basin, eastern-central Yellow Sea, off the southwest of Korea

NASA Astrophysics Data System (ADS)

Lee, J. H.; Jeong, K. S.; Woo, H. J.; Kang, J.; Tsunogai, U.

2016-12-01

In the Gunsan Basin, eastern-central Yellow Sea (YS), gas seepages were observed from the uppermost sedimentary layer charged locally with gases that are important indicators of marine resources, environmental changes, and geo-hazards. Methane (CH4) among the gases is the most abundant organic compound in the Earth's atmosphere, where it acts as a greenhouse gas and thus has implications for global climate change. Headspace CH4 was determined in surface and core sediments in order to understand the C- and H- isotopes signatures in the Gunsan Basin that were collected onboard R/V Onnuri and Eardo in 2013 to 2015. The surface sediments contain 0.2 to 16.9 µM CH4 that are mostly produced by microbial fermentation of organic materials in shallow depth, as indicated by the light values of δ13CCH4 (-70.2 -50.7‰ VPDB). CH4 is actively seeping mainly in the western central part of the Gunsan Basin where the underlying sedimentary layers are thick and heavily faulted. In the cores, CH4 is concentrated 1 to 20 μM through the core depths without any relationships to grain size, organic matter contents. Largely different from those, δ13CCH4 ranges in -62.0 -18.0‰ VPDB (δ2DCH4 range in -296.0 -144.0‰ VSMOW), that is, strongly mixed CH4 of thermogenic and biogenic origins in the core sediments. The CH4 flux at the sediment-water interface (SWI) using Fick's first law of diffusion was calculated 2 29 µM·m-2·day-1 (12 µM·m-2·day-1 on the average) by a careful examination of methane distribution within the uppermost 10 cm sediment layer of 8 box cores. It seems that CH4 flux into the water layer in the Gunsan Basin is less significant than other seep areas such as of the Black Sea, Gulf of Mexico, the Bohai Sea. However, detailed and repeated CH4 observation is needed in the Gunsan Basin, as suggested by temporarily but active gas seepage in a wide regional scale.

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.

Nonaqueous electrocatalytic water oxidation by a surface-bound Ru(bda)(L)₂ complex.

PubMed

Sheridan, Matthew V; Sherman, Benjamin D; Wee, Kyung-Ryang; Marquard, Seth L; Gold, Alexander S; Meyer, Thomas J

2016-04-21

The rate of electrocatalytic water oxidation by the heterogeneous water oxidation catalyst [Ru(bda)(4-O(CH2)3P(O3H2)2-pyr)2], , (pyr = pyridine; bda = 2,2'-bipyridine-6,6'-dicarboxylate) on metal oxide surfaces is greatly enhanced relative to water as the solvent. In these experiments with propylene carbonate (PC) as the nonaqueous solvent, water is the limiting reagent. Mechanistic studies point to atom proton transfer (APT) as the rate limiting step in water oxidation catalysis.

Emissions of carbon dioxide and methane from a headwater stream network of interior Alaska

USGS Publications Warehouse

Crawford, John T.; Striegl, Robert G.; Wickland, Kimberly P.; Dornblaser, Mark M.; Stanley, Emily H.

2013-01-01

Boreal ecosystems store significant quantities of organic carbon (C) that may be vulnerable to degradation as a result of a warming climate. Despite their limited coverage on the landscape, streams play a significant role in the processing, gaseous emission, and downstream export of C, and small streams are thought to be particularly important because of their close connection with the surrounding landscape. However, ecosystem carbon studies do not commonly incorporate the role of the aquatic conduit. We measured carbon dioxide (CO2) and methane (CH4) concentrations and emissions in a headwater stream network of interior Alaska underlain by permafrost to assess the potential role of stream gas emissions in the regional carbon balance. First-order streams exhibited the greatest variability in fluxes of CO2 and CH4,and the greatest mean pCO2. High-resolution time series of stream pCO2 and discharge at two locations on one first-order stream showed opposing pCO2 responses to storm events, indicating the importance of hydrologic flowpaths connecting CO2-rich soils with surface waters. Repeated longitudinal surveys on the stream showed consistent areas of elevated pCO2 and pCH4, indicative of discrete hydrologic flowpaths delivering soil water and groundwater having varying chemistry. Up-scaled basin estimates of stream gas emissions suggest that streams may contribute significantly to catchment-wide CH4 emissions. Overall, our results indicate that while stream-specific gas emission rates are disproportionately high relative to the terrestrial landscape, both stream surface area and catchment normalized emission rates were lower than those documented for the Yukon River Basin as a whole. This may be due to limitations of C sources and/or C transport to surface waters.

Large-scale controls of methanogenesis inferred from methane and gravity spaceborne data.

PubMed

Bloom, A Anthony; Palmer, Paul I; Fraser, Annemarie; Reay, David S; Frankenberg, Christian

2010-01-15

Wetlands are the largest individual source of methane (CH4), but the magnitude and distribution of this source are poorly understood on continental scales. We isolated the wetland and rice paddy contributions to spaceborne CH4 measurements over 2003-2005 using satellite observations of gravity anomalies, a proxy for water-table depth Gamma, and surface temperature analyses TS. We find that tropical and higher-latitude CH4 variations are largely described by Gamma and TS variations, respectively. Our work suggests that tropical wetlands contribute 52 to 58% of global emissions, with the remainder coming from the extra-tropics, 2% of which is from Arctic latitudes. We estimate a 7% rise in wetland CH4 emissions over 2003-2007, due to warming of mid-latitude and Arctic wetland regions, which we find is consistent with recent changes in atmospheric CH4.

Large-Scale Controls of Methanogenesis Inferred from Methane and Gravity Spaceborne Data

NASA Astrophysics Data System (ADS)

Bloom, A. Anthony; Palmer, Paul I.; Fraser, Annemarie; Reay, David S.; Frankenberg, Christian

2010-01-01

Wetlands are the largest individual source of methane (CH4), but the magnitude and distribution of this source are poorly understood on continental scales. We isolated the wetland and rice paddy contributions to spaceborne CH4 measurements over 2003-2005 using satellite observations of gravity anomalies, a proxy for water-table depth Γ, and surface temperature analyses TS. We find that tropical and higher-latitude CH4 variations are largely described by Γ and TS variations, respectively. Our work suggests that tropical wetlands contribute 52 to 58% of global emissions, with the remainder coming from the extra-tropics, 2% of which is from Arctic latitudes. We estimate a 7% rise in wetland CH4 emissions over 2003-2007, due to warming of mid-latitude and Arctic wetland regions, which we find is consistent with recent changes in atmospheric CH4.

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

NASA Technical Reports Server (NTRS)

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

1986-01-01

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

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.

Origin and transport of CH4 in two maar lakes fed by mantle-derived volatiles (Mt. Vulture volcano, Italy)

NASA Astrophysics Data System (ADS)

Caracausi, Antonio; Cosenza, Paolo; Favara, Rocco; Foresta Martin, Luigi; Galli, Nunzio; Grassa, Fausto; Nuccio, Pasquale Mario; Paternoster, Michele; Riccobono, Giuseppe

2014-05-01

It has been assessed that lakes contribute 6 to 16% to global CH4 emission in atmosphere. Accumulation of CH4 in the water is strongly dependent on the input of gas and the dynamic of the lake's water. Lakes located on tectonically and volcanically active areas (e.g., Kivu, Nyos) generally contain relevant amount of mantle-derived volatiles. This generated an open debate on the origin of CO2 and CH4 in volcanic lakes because the complex bio-geological cycling of these two gases. This study is a part of larger investigation carried out on two maar lakes (LPM and LGM) formed about 140.000 years ago during the last eruption of Mt. Vulture (Italy). In spite of it generally is considered to be extinct, both lakes are characterized by an active inflow of mantle-derived fluids (Caracausi et al., 2013). Although the two lakes are only 150 m apart, their respective dynamics are different being LPM a meromictic lake, while LGM a monomictic one (Caracausi et al., 2013). The stagnant waters of LPM are enriched in CO2 and CH4 but the total gas pressure is below the hydrostatic pressure, so that the transfer of gas towards the surface doesn't occur via bubbles. Vertical profiles at LPM reveal a marked decrease of the dissolved CH4 content in the shallower layers due to aerated water. The amount of CH4 dissolved in LGM water column shows seasonal variations: in autumn it is comparable to that of LPM at the same depth; in winter CH4 is fully released into atmosphere through overturn of waters. C and H isotopes of CH4 clearly indicate in both lakes an active production both by acetoclastic methanogenesis and by CO2 reduction although with different proportions. Historical reports describe intense episodic releases of gases from both lakes occurred up to about 200 years ago. Caracausi et al. (2013) highlight that these events could be caused by a release of mantle-derived CO2 accumulated in the crust or directly linked to magma degassing. In the present study the knowledge gained from previous limnological-geochemical investigations has been joined with isotope signature of gas (CH4 and CO2) collected from sediments at the bottom of LPM, by means of a specially designed robot called "Muddy". Muddy is also able to perform vertical profiles both of pH and of temperature in the water column and in the sediments as well. The obtained results lead us: 1) to assess the production ratio of CH4 through acetoclastic methanogenesis and CO2 reduction in the sediments; 2) to determinate CH4 oxidation; 3) to detect the origin of CO2 involved in methanogenic processes, evaluating the contribution organic-CO2 and the sink of mantle-derived CO2.;4) to discuss the differences in CH4 sources in the water and sediments; 5) to properly define gas hazards assessment. A. Caracausi, M. Nicolosi, P.M. Nuccio, R. Favara, M. Paternoster, A. Rosciglione (2013) Geochemical insight into differences in the physical structures and dynamics of two adjacent maar lakes at Mt. Vulture volcano (southern Italy), G. Cubed, doi: 10.1002/ggge.2011

Raman spectroscopy measurement of CH4 gas and CH4 dissolved in water for laser remote sensing in water

NASA Astrophysics Data System (ADS)

Somekawa, Toshihiro; Fujita, Masayuki

2018-04-01

We examined the applicability of Raman spectroscopy as a laser remote sensing tool for monitoring CH4 in water. The Raman technique has already been used successfully for measurements of CO2 gas in water. In this paper, considering the spectral transmittance of water, third harmonics of Q-switched Nd:YAG laser at 355 nm (UV region) was used for detection of CH4 Raman signals. The Raman signal at 2892 cm-1 from CH4 dissolved in water was detected at a tail of water Raman signal.

Conversion of 1,3-Propylene Glycol on Rutile TiO2(110)

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

Chen, Long; Li, Zhenjun; Smith, R. Scott

2014-10-09

The adsorption of 1,3-propylene glycol (1,3-PG) on partially reduced TiO2(110) and its conversion to products have been studied by a combination of molecular beam dosing and temperature programmed desorption (TPD). When the Ti surface sites are saturated by 1,3-PG, ~80% of the molecules undergo further reactions to yield products that are liberated during the TPD ramp. In contrast to ethylene glycol (EG) and 1,2- propylene glycol (1,2-PG) that yield only alkenes and water at very low coverages (< 0.05 ML), two additional products, HCHO and C2H4, along with propylene (CH3CHCH2) and water are observed for 1,3-PG. Identical TPD line shapesmore » and desorption yields for HCHO and C2H4 suggest that these products result from C-C bond cleavage and are coupled. At higher 1,3-PG coverages (> 0.1 ML), propanal (CH3CH2CHO) and two additional products, 1-propanol (CH3CH2CH2OH) and acrolein (CH2CHCHO), are observed. The desorption of 1-propanol is found to be coupled with the desorption of acrolein, suggesting that these products are formed by the disproportionation of two 1,3-PG molecules. The coverage dependent TPD results further show that propylene formation dominates at low coverages (< 0.3 ML), while the decomposition and disproportionation channels increase rapidly at higher coverages and reach yields comparable to that of propylene at the 1,3-PG saturation coverage of 0.5 ML. The observed surface chemistry clearly shows how the molecular structure of glycols influences their reaction pathways on oxide surfaces.« less

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.

Biogeochemical controls on microbial CH4 and CO2 production in Arctic polygon tundra

NASA Astrophysics Data System (ADS)

Zheng, J.

2016-12-01

Accurately simulating methane (CH4) and carbon dioxide (CO2) emissions from high latitude soils is critically important for reducing uncertainties in soil carbon-climate feedback predictions. The signature polygonal ground of Arctic tundra generates high level of heterogeneity in soil thermal regime, hydrology and oxygen availability, which limits the application of current land surface models with simple moisture response functions. We synthesized CH4 and CO2 production measurements from soil microcosm experiments across a wet-to dry permafrost degradation gradient from low-centered (LCP) to flat-centered (FCP), and high-centered polygons (HCP) to evaluate the relative importance of biogeochemical processes and their response to warming. More degraded polygon (HCP) showed much less carbon loss as CO2 or CH4, while the total CO2 production from FCP is comparable to that from LCP. Maximum CH4 production from the active layer of LCP was nearly 10 times that of permafrost and FCP. Multivariate analyses identifies gravimetric water content and organic carbon content as key predictors for CH4 production, and iron reduction as a key regulator of pH. The synthesized data are used to validate the geochemical model PHREEQC with extended anaerobic organic substrate turnover, fermentation, iron reduction, and methanogenesis reactions. Sensitivity analyses demonstrate that better representations of anaerobic processes and their pH dependency could significantly improve estimates of CH4 and CO2 production. The synthesized data suggest local decreases in CH4 production along the polygon degradation gradient, which is consistent with previous surface flux measurements. Methane oxidation occurring through the soil column of degraded polygons contributes to their low CH4 emissions as well.

Process-based approach for the detection of CO2 injectate leakage

DOEpatents

Romanak, Katherine; Bennett, Philip C.

2017-11-14

The present invention includes a method for distinguishing between a natural source of deep gas and gas leaking from a CO.sub.2 storage reservoir at a near surface formation comprising: obtaining one or more surface or near surface geological samples; measuring a CO.sub.2, an O.sub.2, a CH.sub.4, and an N.sub.2 level from the surface or near surface geological sample; determining the water vapor content at or above the surface or near surface geological samples; normalizing the gas mixture of the CO.sub.2, the O.sub.2, the CH.sub.4, the N.sub.2 and the water vapor content to 100% by volume or 1 atmospheric total pressure; determining: a ratio of CO.sub.2 versus N.sub.2; and a ratio of CO.sub.2 to N.sub.2, wherein if the ratio is greater than that produced by a natural source of deep gas CO.sub.2 or deep gas methane oxidizing to CO.sub.2, the ratio is indicative of gas leaking from a CO.sub.2 storage reservoir.

Seasonal dynamics of methane emissions from a subarctic fen in the Hudson Bay Lowlands

NASA Astrophysics Data System (ADS)

Hanis, K. L.; Tenuta, M.; Amiro, B. D.; Papakyriakou, T. N.

2013-07-01

Ecosystem-scale methane (CH4) flux (FCH4) over a subarctic fen at Churchill, Manitoba, Canada was measured to understand the magnitude of emissions during spring and fall shoulder seasons, and the growing season in relation to physical and biological conditions. FCH4 was measured using eddy covariance with a closed-path analyser in four years (2008-2011). Cumulative measured annual FCH4 (shoulder plus growing seasons) ranged from 3.0 to 9.6 g CH4 m-2 yr-1 among the four study years, with a mean of 6.5 to 7.1 g CH4 m-2 yr-1 depending upon gap-filling method. Soil temperatures to depths of 50 cm and air temperature were highly correlated with FCH4, with near-surface soil temperature at 5 cm most correlated across spring, fall, and the shoulder and growing seasons. The response of FCH4 to soil temperature at the 5 cm depth and air temperature was more than double in spring to that of fall. Emission episodes were generally not observed during spring thaw. Growing season emissions also depended upon soil and air temperatures but the water table also exerted influence, with FCH4 highest when water was 2-13 cm below and lowest when it was at or above the mean peat surface.

Seasonal dynamics of methane emissions from a subarctic fen in the Hudson Bay Lowlands

NASA Astrophysics Data System (ADS)

Hanis, K. L.; Tenuta, M.; Amiro, B. D.; Papakyriakou, T. N.

2013-03-01

Ecosystem-scale methane (CH4) flux (FCH4) over a subarctic fen at Churchill, Manitoba, Canada was measured to understand the magnitude of emissions during spring and fall shoulder seasons, and the growing season in relation to physical and biological conditions. FCH4 was measured using eddy covariance with a closed-path analyzer in four years (2008-2011). Cumulative measured annual FCH4 (shoulder plus growing seasons) ranged from 3.0 to 9.6 g CH4 m-2 yr-1 among the four study years, with a mean of 6.5 to 7.1 g CH4 m-2 yr-1 depending upon gap-filling method. Soil temperatures to depths of 50 cm and air temperature were highly correlated with FCH4, with near surface soil temperature at 5 cm most correlated across spring, fall, and the whole season. The response of FCH4 to soil temperature at the 5 cm depth and air temperature was more than double in spring to that of fall. Emission episodes were generally not observed during spring thaw. Growing season emissions also depended upon soil and air temperatures but water table also exerted influence with FCH4 highest when water was 2-13 cm below and least when it was at or above the mean peat surface.

A conversion of CO2-ECBM related lab observations to reservoir requirements

NASA Astrophysics Data System (ADS)

Gensterblum, Yves; Merkel, Alexej; Busch, Andreas; Krooß, Bernhard

2013-04-01

To predict a CBM production profile either during primary or secondary production, aspects like coal permeability and porosity, density, ash and moisture content, initial gas-in-place (GIP) (from canister desorption tests), gas sorption capacity from laboratory isotherms (to obtain gas saturations and desorption pressure), gas diffusivities, coal volumetrics (thickness and areal extent) need to be understood as a minimum requirement. When dealing with CO2-ECBM selective adsorption, counter diffusion in the coal matrix, or coal shrinkage and swelling (from CH4 desorption and CO2 adsorption, respectively) and the influence of moisture need to be investigated in addition to the parameters above. During CO2-ECBM processes, the areal distribution of the CO2 injected is accomplished by flow through the cleat network. When CO2 is entering the coal matrix by a combined sorption/diffusion process it will adsorb to the coal inner surface and at the same time replace part of the CH4. This replacement occurs either by a reduction in the CH4 partial pressure or by a higher selective sorption of CO2 over CH4. Because of a concentration gradient between CH4 in the matrix compared to the cleat system, CH4 diffuses from the coal matrix into the cleat system where, by pressure drawdown towards a production well, it can be produced. In this context this presentation summarizes gas (CO2, CH4) and water sorption on coal and specifically addresses the following topics: • CH4 and CO2 sorption capacity as a function depth and rank • CO2 and CH4 sorption on natural coals and its dependence on coal specific parameters like coal rank, maceral composition or ash content (Busch and Gensterblum, 2011). • Water sorption on coal, its dependence on coal properties such as rank and coal chemistry and gas sorption in the presence of water (Busch and Gensterblum, 2011). • Uncertainties in reservoir characterisation (Gensterblum et al., 2010; Gensterblum et al., 2009) • Sorption uptake kinetic as a function of surface coverage and the influence of moisture on the kinetic Busch, A. and Gensterblum, Y., 2011. CBM and CO2-ECBM related sorption processes in coal: A review. International Journal of Coal Geology, 87: 49-71. Gensterblum, Y. et al., 2010. European inter-laboratory comparison of high pressure CO2 sorption isotherms II: Natural coals. International Journal of Coal Geology, 84(2): 115-124. Gensterblum, Y. et al., 2009. European inter-laboratory comparison of high pressure CO2 sorption isotherms. I: Activated carbon. Carbon, 47(13): 2958-2969.

Enhanced winter soil frost reduces methane emission during the subsequent growing season in a boreal peatland.

PubMed

Zhao, Junbin; Peichl, Matthias; Nilsson, Mats B

2016-02-01

Winter climate change may result in reduced snow cover and could, consequently, alter the soil frost regime and biogeochemical processes underlying the exchange of methane (CH4 ) in boreal peatlands. In this study, we investigated the short-term (1-3 years) vs. long-term (11 years) effects of intensified winter soil frost (induced by experimental snow exclusion) on CH4 exchange during the following growing season in a boreal peatland. In the first 3 years (2004-2006), lower CH4 emissions in the treatment plots relative to the control coincided with delayed soil temperature increase in the treatment plots at the beginning of the growing season (May). After 11 treatment years (in 2014), CH4 emissions were lower in the treatment plots relative to the control over the entire growing season, resulting in a reduction in total growing season CH4 emission by 27%. From May to July 2014, reduced sedge leaf area coincided with lower CH4 emissions in the treatment plots compared to the control. From July to August, lower dissolved organic carbon concentrations in the pore water of the treatment plots explained 72% of the differences in CH4 emission between control and treatment. In addition, greater Sphagnum moss growth in the treatment plots resulted in a larger distance between the moss surface and the water table (i.e., increasing the oxic layer) which may have enhanced the CH4 oxidation potential in the treatment plots relative to the control in 2014. The differences in vegetation might also explain the lower temperature sensitivity of CH4 emission observed in the treatment plots relative to the control. Overall, this study suggests that greater soil frost, associated with future winter climate change, might substantially reduce the growing season CH4 emission in boreal peatlands through altering vegetation dynamics and subsequently causing vegetation-mediated effects on CH4 exchange. © 2015 John Wiley & Sons Ltd.

A conversion of CO2-ECBM related lab observations to reservoir requirements

NASA Astrophysics Data System (ADS)

Gensterblum, Y.; Merkel, A.; Busch, A.; Krooss, B. M.

2012-04-01

To predict a CBM production profile either during primary or secondary production, aspects like coal permeability and porosity, density, ash and moisture content, initial gas-in-place (GIP) (from canister desorption tests), gas sorption capacity from laboratory isotherms (to obtain gas saturations and desorption pressure), gas diffusivities, coal volumetrics (thickness and areal extent) need to be understood as a minimum requirement. When dealing with CO2-ECBM selective adsorption, counter diffusion in the coal matrix, or coal shrinkage and swelling (from CH4 desorption and CO2 adsorption, respectively) and the influence of moisture need to be investigated in addition to the parameters above. During CO2-ECBM processes, the areal distribution of the CO2 injected is accomplished by flow through the cleat network. When CO2 is entering the coal matrix by a combined sorption/diffusion process it will adsorb to the coal inner surface and at the same time replace part of the CH4. This replacement occurs either by a reduction in the CH4 partial pressure or by a higher selective sorption of CO2 over CH4. Because of a concentration gradient between CH4 in the matrix compared to the cleat system, CH4 diffuses from the coal matrix into the cleat system where, by pressure drawdown towards a production well, it can be produced. In this context this presentation summarizes gas (CO2, CH4) and water sorption on coal and specifically addresses the following topics: • CH4 and CO2 sorption capacity as a function depth and rank • CO2 and CH4 sorption on natural coals and its dependence on coal specific parameters like coal rank, maceral composition or ash content (Busch and Gensterblum, 2011). • Water sorption on coal, its dependence on coal properties such as rank and coal chemistry and gas sorption in the presence of water (Busch and Gensterblum, 2011). • N2, CH4, CO2 displacement experiments and the volumetric response of the coal on the present gas type (sorbing or inert) in the pore system • Uncertainties in reservoir characterisation (Gensterblum et al., 2010; Gensterblum et al., 2009) • Sorption uptake kinetic as a function of surface coverage and the influence of moisture on the kinetic Busch, A. and Gensterblum, Y., 2011. CBM and CO2-ECBM related sorption processes in coal: A review. International Journal of Coal Geology, 87: 49-71. Gensterblum, Y. et al., 2010. European inter-laboratory comparison of high pressure CO2 sorption isotherms II: Natural coals. International Journal of Coal Geology, 84(2): 115-124. Gensterblum, Y. et al., 2009. European inter-laboratory comparison of high pressure CO2 sorption isotherms. I: Activated carbon. Carbon, 47(13): 2958-2969.

Effects of experimental warming and elevated CO2 on surface methane and CO­2 fluxes from a boreal black spruce peatland

NASA Astrophysics Data System (ADS)

Gill, A. L.; Finzi, A.; Giasson, M. A.

2015-12-01

High latitude peatlands represent a major terrestrial carbon store sensitive to climate change, as well as a globally significant methane source. While elevated atmospheric carbon dioxide concentrations and warming temperatures may increase peat respiration and C losses to the atmosphere, reductions in peatland water tables associated with increased growing season evapotranspiration may alter the nature of trace gas emission and increase peat C losses as CO2 relative to methane (CH4). As CH4 is a greenhouse gas with twenty times the warming potential of CO2, it is critical to understand how surface fluxes of CO2 and CH4 will be influenced by factors associated with global climate change. We used automated soil respiration chambers to assess the influence of elevated atmospheric CO2 and whole ecosystem warming on peatland CH4 and CO2 fluxes at the SPRUCE (Spruce and Peatland Responses Under Climatic and Environmental Change) Experiment in northern Minnesota. Belowground warming treatments were initiated in July 2014 and whole ecosystem warming and elevated CO2 treatments began in August 2015. Here we report soil iCO2 and iCH4 flux responses to the first year of belowground warming and the first two months of whole ecosystem manipulation. We also leverage the spatial and temporal density of measurements across the twenty autochambers to assess how physical (i.e., plant species composition, microtopography) and environmental (i.e., peat temperature, water table position, oxygen availability) factors influence observed rates of CH4 and CO2 loss. We find that methane fluxes increased significantly across warming treatments following the first year of belowground warming, while belowground warming alone had little influence on soil CO2 fluxes. Peat microtopography strongly influenced trace gas emission rates, with higher CH4 fluxes in hollow locations and higher CO2 fluxes in hummock locations. While there was no difference in the isotopic composition of the methane fluxes between hollow and hummock locations, δ13CH4 was more depleted in the early and late growing season, indicating a transition from hydrogenotrophic to acetoclastic methanogenesis during periods of high photosynthetic input.

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.

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.

A global wetland methane emissions and uncertainty dataset for atmospheric chemical transport models (WetCHARTs version 1.0)

NASA Astrophysics Data System (ADS)

Bloom, A. Anthony; Bowman, Kevin W.; Lee, Meemong; Turner, Alexander J.; Schroeder, Ronny; Worden, John R.; Weidner, Richard; McDonald, Kyle C.; Jacob, Daniel J.

2017-06-01

Wetland emissions remain one of the principal sources of uncertainty in the global atmospheric methane (CH4) budget, largely due to poorly constrained process controls on CH4 production in waterlogged soils. Process-based estimates of global wetland CH4 emissions and their associated uncertainties can provide crucial prior information for model-based top-down CH4 emission estimates. Here we construct a global wetland CH4 emission model ensemble for use in atmospheric chemical transport models (WetCHARTs version 1.0). Our 0.5° × 0.5° resolution model ensemble is based on satellite-derived surface water extent and precipitation reanalyses, nine heterotrophic respiration simulations (eight carbon cycle models and a data-constrained terrestrial carbon cycle analysis) and three temperature dependence parameterizations for the period 2009-2010; an extended ensemble subset based solely on precipitation and the data-constrained terrestrial carbon cycle analysis is derived for the period 2001-2015. We incorporate the mean of the full and extended model ensembles into GEOS-Chem and compare the model against surface measurements of atmospheric CH4; the model performance (site-level and zonal mean anomaly residuals) compares favourably against published wetland CH4 emissions scenarios. We find that uncertainties in carbon decomposition rates and the wetland extent together account for more than 80 % of the dominant uncertainty in the timing, magnitude and seasonal variability in wetland CH4 emissions, although uncertainty in the temperature CH4 : C dependence is a significant contributor to seasonal variations in mid-latitude wetland CH4 emissions. The combination of satellite, carbon cycle models and temperature dependence parameterizations provides a physically informed structural a priori uncertainty that is critical for top-down estimates of wetland CH4 fluxes. Specifically, our ensemble can provide enhanced information on the prior CH4 emission uncertainty and the error covariance structure, as well as a means for using posterior flux estimates and their uncertainties to quantitatively constrain the biogeochemical process controls of global wetland CH4 emissions.

Patterns of in-soil methane production and atmospheric emission among different land covers of a Lake Erie estuarine wetland

NASA Astrophysics Data System (ADS)

Rey Sanchez, C.; Morin, T. H.; Stefanik, K. C.; Angle, J.; Wrighton, K. C.; Bohrer, G.

2017-12-01

Wetland soils store a great amount of carbon, but also accumulate and emit methane (CH4), a powerful greenhouse gas. To better understand the vertical and horizontal spatial variability of CH4 emissions, we monitored production and fluxes of CH4 in Old Woman Creek, an estuarine wetland of Lake Erie, Ohio, during the growing seasons of 2015 and 2016. Our combined observation methods targeted three different scales: 1) the eddy covariance technique provided continuous high frequency observations integrated over a large spatial footprint; 2) monthly chamber measurements provided sparse point measurements of fluxes in four distinct land-cover types in the wetland: open water, emergent vegetation (Typha spp.), floating vegetation (Nelumbo spp.) and mud flats; and 3) in-situ porewater dialysis samplers, "peepers", provided vertical CH4 concentration data in the soil at the same locations and temporal time steps as the chambers. In addition, we studied gene transcripts to quantify methanogenesis activity along the vertical soil profile. Using integrated chamber and EC measurements, we found an average surface emission rate from Typha, the most abundant vegetated land cover, of 219.4 g CH4-C m-2 y-1, which was much higher than rates reported in similar emergent vegetation types in other wetlands. There was large spatial variation of flux rates, with mud flats having the highest rates of CH4 emission, followed by Nelumbo and Typha patches, and with open water having the lowest emissions. Within the soil column, we applied a numerical model to convert soil methane concentrations to emissions rates. We found that, contrary to current ideas of methane production, most methane was being produced in the well-oxygenated surface soils, probably in anoxic microsites within the oxic layer. Our metatranscriptomic data supported these findings, clearly showing nine times greater methanogenic activity in oxic surface soils relative to deeper anoxic soils. Combined, our results provide important insights for the representation of processes of methane production and consumption in models, which can largely affect the estimates of methane emission from wetlands.

Warming Early Mars by Impact Degassing of Reduced Greenhouse Gases

NASA Technical Reports Server (NTRS)

Haberle, R. M.; Zahnle, K.; Barlow, N. G.

2018-01-01

Reducing greenhouse gases are once again the latest trend in finding solutions to the early Mars climate dilemma. In its current form collision induced absorptions (CIA) involving H2 and/or CH4 provide enough extra greenhouse power in a predominately CO2 atmosphere to raise global mean surface temperatures to the melting point of water provided the atmosphere is thick enough and the reduced gases are abundant enough. Surface pressures must be at least 500 mb and H2 and/or CH4 concentrations must be at or above the several percent level for CIA to be effective. Atmospheres with 1-2 bars of CO2 and 2- 10% H2 can sustain surface environments favorable for liquid water. Smaller concentrations of H2 are sufficient if CH4 is also present. If thick CO2 atmospheres with percent level concentrations of reduced gases are the solution to the faint young Sun paradox for Mars, then plausible mechanisms must be found to generate and sustain the gases. Possible sources of reducing gases include volcanic outgassing, serpentinization, and impact delivery; sinks include photolyis, oxidation, and escape to space. The viability of the reduced greenhouse hypothesis depends, therefore, on the strength of these sources and sinks. In this paper we focus on impact delivered reduced gases.

The structural evolution of magnesium acetate complex in aerosols by FTIR-ATR spectra

NASA Astrophysics Data System (ADS)

Pang, Shu-Feng; Wu, Chang-Qin; Zhang, Qing-Nuan; Zhang, Yun-Hong

2015-05-01

The structural evolution of magnesium acetate complex in aerosols with the relative humidity (RH) has been studied by ATR-FTIR technique. When the RH is higher than 66%, the ν4 band lies at 929 cm-1 meaning the free CH3COO- ions in Mg(CH3COO)2 droplets. At the 66% RH, ν4 band positioned at 939 cm-1, accompanying the ν8 band shift to 1554 cm-1, which indicats that the free CH3COO- ions are bounded to Mg2+ ions to form [Mg(H2O)5(CH3COO)]+ species. At the 57.7% RH, the ν8-COO band shifts to 1556 cm-1 accompanying the ν3 band at 1421 cm-1 and the appearance of shoulder at 1452 cm-1, which suggests the formation of chain-structure connected by the bridging bidentate of Mg2(CH3COO)4(H2O)2. In the region of 57.7-18.7% RH, the shoulder at 1452 cm-1 increases with the decrease in RH, showing the increase of Mg2(CH3COO)4(H2O)2. From the water-content, the water-transfer from and to the surface of the aerosols became limited, showing the aerosols enter the gel state. Below 18.7%RH, water-loss becomes rapid and the ν8 band performs blue-shift. At 3.8%RH, the ν8 band positioned at 1581 cm-1, showing the anhydrous Mg(CH3COO)2 solid, which can be reflected by the ν4 band at 947 cm-1. During the humidification process, the reverse structural evolution can be found.

Fluid properties control degassing or storage of abiogenic CH4 during slab exhumation: the fluid inclusion record from the Western Alps.

NASA Astrophysics Data System (ADS)

Ferrando, S.; Castelli, D.; Frezzotti, M. L.

2017-12-01

Abiogenic CH4 can be produced by interaction between carbonates and reducing fluids derived from the hydration of ultramafics (e.g., mantle peridotite or HP Ol-serpentinite). This process occurs during slab exhumation because cooling promotes serpentinization of olivine in presence of water (Fo + H2O = Atg + Brc and the linked reactions: Fa + H2O = Fe-Atg + Mag + H2 and Atg + CaCO3 + H2 = Di + Brc + CH4 + H2O) at ca. 500-375°C (P=2.0-0.2 GPa). Experiments in the CH4-H2O-NaCl system indicate that, at these conditions, fluids are immiscible even for very low salinity (ca. 3 wt%) and that the NaCl content in the aqueous part of the fluid increases with temperature whereas the CH4 content in the gaseous part shows an opposite trend (Lamb et al., 2002; Li, 2017).In HP rodingite from the Piemonte ophiolite Zone (W Alps), primary fluid inclusions consisting of a brine (6 wt% CaCl2 + 6 wt% NaCl) with H2 + CH4 ≤ 1 mol % [CH4/(H2+CH4) = 0.37-10] occur in vesuvianite veins that formed at P=0.2 GPa and T=375°C. We interpret them as the aqueous part of an immiscible reducing fluid produced during late Alpine serpentinization of the surrounding ultramafics. Interestingly, CH4-H2 gaseous fluids are never reported in rodingite, whereas early CH4-H2O-H2±graphite and CH4-H2±graphite fluid inclusions, with variable gas-water proportions, trapped in calcite at P≤1.0 GPa and T≤450°C, are recently reported from HP "graphitized" ophicarbonate from the Lanzo peridotite Massif (W Alps; Vitale Brovarone et al., 2017).Both HP ophiolites and partially-serpentinized peridotite massifs are, thus, efficient lithologies to produce CH4 during exhumation. The amount of released CH4 depends on the amount of water available during exhumation. However, when fluids immiscibility occurs, the gaseous-rich part (CH4-H2) of the immiscible fluid produced in ultramafics likely remains confined in the slab because it is less mobile with respect to the aqueous-rich part due to its high dihedral angle. If C saturation conditions are reached, graphite precipitates in the rock. Conversely, the aqueous-rich part (brine with minor CH4-H2) of the immiscible fluid is more mobile and, then, able to migrate to the surface. Lamb et al. (2002): Geochim. Cosmochi. Acta, 66, 3971-3986 Li (2017): Geochem. Persp. Let., 3, 12-21 Vitale Brovarone et al. (2017): Nat. Comm., 8, 14134

Influence of water table on carbon dioxide, carbon monoxide, and methane fluxes from taiga bog microcosms

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

Funk, D.W.; Pullmann, E.R.; Peterson, K.M.

1994-09-01

Hydrological changes, particularly alterations in water table level, may largely overshadow the more direct effects of global temperature increase upon carbon cycling in arctic and subarctic wetlands. Frozen cores (n=40) of intact soils and vegetation were collected from a bog near Fairbanks, Alaska, and fluxes of CO{sub 2}, CH{sub 4}, and Co in response to water table variation were studied under controlled conditions in the Duke University phytotron. Core microcosms thawed to a 20-cm depth over 30 days under a 20 hour photoperiod with a day/night temperature regime of 20/10{degrees}C. After 30 days the water table in 20 microcosms wasmore » decreased from the soil surface to -15 cm and maintained at the soil surface in 20 control cores. Outward fluxes of CO{sub 2} (9-16 g m{sup -2}d{sup -1}) and CO (3-4 mg m{sup -2}d{sup -1}) were greatest during early thaw and decreased to near zero for both gases before the water table treatment started. Lower water table tripled CO{sub 2} flux to the atmosphere when compared with control cores. Carbon monoxide was emitted at low rates from high water table cores and consumed by low water table cores. Methane fluxes were low (<1 mg m{sup -2}d{sup -1}) in all cores during thaw. High water table cores increased CH{sub 4} flux to 8-9 mg m{sup -2}d{sup -1} over 70 days and remained high relative to the low water table cores (<0.74 mg m{sup -2}d{sup -1}). Although drying of wetland taiga soils may decrease CH{sub 4} emissions to the atmosphere, the associated increase in CO{sub 2} due to aerobic respiration will likely increase the global warming potential of gas emissions from these soils. 43 refs., 4 figs.« less

Methane emission through ebullition from an estuarine mudflat: 2. Field observations and modeling of occurrence probability

NASA Astrophysics Data System (ADS)

Chen, Xi; Schäfer, Karina V. R.; Slater, Lee

2017-08-01

Ebullition can transport methane (CH4) at a much faster rate than other pathways, albeit over limited time and area, in wetland soils and sediments. However, field observations present large uncertainties in ebullition occurrences and statistic models are needed to describe the function relationship between probability of ebullition occurrence and water level changes. A flow-through chamber was designed and installed in a mudflat of an estuarine temperate marsh. Episodic increases in CH4 concentration signaling ebullition events were observed during ebbing tides (15 events over 456 ebbing tides) and occasionally during flooding tides (4 events over 455 flooding tides). Ebullition occurrence functions were defined using logistic regression as the relative initial and end water levels, as well as tidal amplitudes were found to be the key functional variables related to ebullition events. Ebullition of methane was restricted by a surface frozen layer during winter; melting of this layer during spring thaw caused increases in CH4 concentration, with ebullition fluxes similar to those associated with large fluctuations in water level around spring tides. Our findings suggest that initial and end relative water levels, in addition to tidal amplitude, partly regulate ebullition events in tidal wetlands, modulated by the lunar cycle, storage of gas bubbles at different depths and seasonal changes in the surface frozen layer. Maximum tidal strength over a few days, rather than hourly water level, may be more closely associated with the possibility of ebullition occurrence as it represents a trade-off time scale in between hourly and lunar periods.

Vadose Zone and Surficial Monitoring a Controlled Release of Methane in the Borden Aquifer, Ontario.

NASA Astrophysics Data System (ADS)

Forde, O.; Mayer, K. U.; Cahill, A.; Parker, B. L.; Cherry, J. A.

2015-12-01

Development of shale gas resources and potential impacts on groundwater and fugitive gas emissions necessitates further research on subsurface methane gas (CH4) migration and fate. To address this issue, a controlled release experiment is undertaken at the Borden research aquifer, Ontario, Canada. Due to low solubility, it is expected that the injection will lead to gas exsolution and ebullition. Gas migration is expected to extend to the unsaturated zone and towards the ground surface, and may possibly be affected by CH4 oxidation. The project consists of multiple components targeting the saturated zone, unsaturated zone, and gas emissions at the ground surface. This presentation will focus on the analysis of surficial CO2 and CH4 effluxes and vadose zone gas composition to track the temporal and spatial evolution of fugitive gas. Surface effluxes are measured with flux chambers connected to a laser-based gas analyzer, and subsurface gas samples are being collected via monitoring wells equipped with sensors for oxygen, volumetric water content, electrical conductivity, and temperature to correlate with changes in gas composition. First results indicate rapid migration of CH4 to the ground surface in the vicinity of the injection locations. We will present preliminary data from this experiment and evaluate the distribution and rate of gas migration. This research specifically assesses environmental risks associated with fugitive gas emissions related to shale gas resource development.

Martian CH(4): sources, flux, and detection.

PubMed

Onstott, T C; McGown, D; Kessler, J; Lollar, B Sherwood; Lehmann, K K; Clifford, S M

2006-04-01

Recent observations have detected trace amounts of CH(4) heterogeneously distributed in the martian atmosphere, which indicated a subsurface CH(4) flux of ~2 x 10(5) to 2 x 10(9) cm(2) s(1). Four different origins for this CH(4) were considered: (1) volcanogenic; (2) sublimation of hydrate- rich ice; (3) diffusive transport through hydrate-saturated cryosphere; and (4) microbial CH(4) generation above the cryosphere. A diffusive flux model of the martian crust for He, H(2), and CH(4) was developed based upon measurements of deep fracture water samples from South Africa. This model distinguishes between abiogenic and microbial CH(4) sources based upon their isotopic composition, and couples microbial CH(4) production to H(2) generation by H(2)O radiolysis. For a He flux of approximately 10(5) cm(2) s(1) this model yields an abiogenic CH(4) flux and a microbial CH(4) flux of approximately 10(6) and approximately 10(9) cm(2) s(1), respectively. This flux will only reach the martian surface if CH(4) hydrate is saturated in the cryosphere; otherwise it will be captured within the cryosphere. The sublimation of a hydrate-rich cryosphere could generate the observed CH(4) flux, whereas microbial CH(4) production in a hypersaline environment above the hydrate stability zone only seems capable of supplying approximately 10(5) cm(2) s(1) of CH(4). The model predicts that He/H(2)/CH(4)/C(2)H(6) abundances and the C and H isotopic values of CH(4) and the C isotopic composition of C(2)H(6) could reveal the different sources. Cavity ring-down spectrometers represent the instrument type that would be most capable of performing the C and H measurements of CH(4) on near future rover missions and pinpointing the cause and source of the CH(4) emissions.

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

Treesearch

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

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...

Tidal variability in methane and nitrous oxide emissions along a subtropical estuarine gradient

NASA Astrophysics Data System (ADS)

Sturm, Katrin; Werner, Ursula; Grinham, Alistair; Yuan, Zhiguo

2017-06-01

This study investigates the tidal variability in methane (CH4) and nitrous oxide (N2O) emissions along a gradient of the subtropical Brisbane River estuary. Sampling was conducted at the upper, middle and lower reaches over two tidal cycles in 2013 and 2014. Methane and N2O emissions varied significantly over tidal cycles at all sites. Methane and N2O emissions measured at all locations and in both campaigns varied substantially in time, with the maximum to minimum flux ratio in a cycle varying between 2.5 - 9 and 1.7-4.7 times, respectively. Methane emissions peaked just before or at slack tides. In comparison, no clear patterns were observed between the N2O emissions and the tidal cycle despite there being large variations in N2O emissions in some cases. Methane concentrations were elevated during low tides whereas N2O concentrations showed no clear pattern over the tidal cycle. Surface water concentrations and tidal currents played important roles in CH4 and N2O emissions, but wind did not. Our findings show that measurements at a single point in time and site would result in significant errors in CH4 and N2O emission estimates. An adequate and careful sampling scheme is required to capture spatial and temporal variations of CH4 and N2O emissions and surface water concentrations which should cover at least one tidal cycle in different estuarine sections.

Temporal variation in methane emissions in a shallow lake at a southern mid latitude during high and low rainfall periods.

PubMed

Fusé, Victoria S; Priano, M Eugenia; Williams, Karen E; Gere, José I; Guzmán, Sergio A; Gratton, Roberto; Juliarena, M Paula

2016-10-01

The global methane (CH 4 ) emission of lakes is estimated at between 6 and 16 % of total natural CH 4 emissions. However, these values have a high uncertainty due to the wide variety of lakes with important differences in their morphological, biological, and physicochemical parameters and the relatively scarse data from southern mid-latitude lakes. For these reasons, we studied CH 4 fluxes and CH 4 dissolved in water in a typical shallow lake in the Pampean Wetland, Argentina, during four periods of consecutive years (April 2011-March 2015) preceded by different rainfall conditions. Other water physicochemical parameters were measured and meteorological data were reported. We identified three different states of the lake throughout the study as the result of the irregular alternation between high and low rainfall periods, with similar water temperature values but with important variations in dissolved oxygen, chemical oxygen demand, water turbidity, electric conductivity, and water level. As a consequence, marked seasonal and interannual variations occurred in CH 4 dissolved in water and CH 4 fluxes from the lake. These temporal variations were best reflected by water temperature and depth of the Secchi disk, as a water turbidity estimation, which had a significant double correlation with CH 4 dissolved in water. The mean CH 4 fluxes values were 0.22 and 4.09 mg/m 2 /h for periods with low and high water turbidity, respectively. This work suggests that water temperature and turbidity measurements could serve as indicator parameters of the state of the lake and, therefore, of its behavior as either a CH 4 source or sink.

Seasonal Variation in Abundance and Diversity of Bacterial Methanotrophs in Five Temperate Lakes

PubMed Central

Samad, Md Sainur; Bertilsson, Stefan

2017-01-01

Lakes are significant sources of methane (CH4) to the atmosphere. Within these systems, methanotrophs consume CH4 and act as a potential biofilter mitigating the emission of this potent greenhouse gas. However, it is still not well understood how spatial and temporal variation in environmental parameters influence the abundance, diversity, and community structure of methanotrophs in lakes. To address this gap in knowledge, we collected water samples from three depths (surface, middle, and bottom) representing oxic to suboxic or anoxic zones of five different Swedish lakes in winter (ice-covered) and summer. Methanotroph abundance was determined by quantitative real time polymerase chain reaction and a comparison to environmental variables showed that temperature, season as well as depth, phosphate concentration, dissolved oxygen, and CH4 explained the observed variation in methanotroph abundance. Due to minimal differences in methane concentrations (0.19 and 0.29 μM for summer and winter, respectively), only a weak and even negative correlation was observed between CH4 and methanotrophs, which was possibly due to usage of CH4. Methanotrophs were present at concentrations ranging from 105 to 106 copies/l throughout the oxic (surface) and suboxic/anoxic (bottom) water mass of the lakes, but always contributed less than 1.3% to the total microbial community. Relative methanotroph abundance was significantly higher in winter than in summer and consistently increased with depth in the lakes. Phylogenetic analysis of pmoA genes in two clone libraries from two of the ice-covered lakes (Ekoln and Ramsen) separated the methanotrophs into five distinct clusters of Methylobacter sp. (Type I). Terminal restriction fragment length polymorphism analysis of the pmoA gene further revealed significant differences in methanotrophic communities between lakes as well as between winter and summer while there were no significant differences between water layers. The study provides new insights into diversity, abundance, community composition and spatial as well as temporal distribution of freshwater methanotrophs in low-methane dimictic lakes. PMID:28217121

Effect of organic matter properties, clay mineral type and thermal maturity on gas adsorption in organic-rich shale systems

USGS Publications Warehouse

Zhang, Tongwei; Ellis, Geoffrey S.; Ruppel, Stephen C.; Milliken, Kitty; Lewan, Mike; Sun, Xun; Baez, Luis; Beeney, Ken; Sonnenberg, Steve

2013-01-01

A series of CH4 adsorption experiments on natural organic-rich shales, isolated kerogen, clay-rich rocks, and artificially matured Woodford Shale samples were conducted under dry conditions. Our results indicate that physisorption is a dominant process for CH4 sorption, both on organic-rich shales and clay minerals. The Brunauer–Emmett–Teller (BET) surface area of the investigated samples is linearly correlated with the CH4 sorption capacity in both organic-rich shales and clay-rich rocks. The presence of organic matter is a primary control on gas adsorption in shale-gas systems, and the gas-sorption capacity is determined by total organic carbon (TOC) content, organic-matter type, and thermal maturity. A large number of nanopores, in the 2–50 nm size range, were created during organic-matter thermal decomposition, and they significantly contributed to the surface area. Consequently, methane-sorption capacity increases with increasing thermal maturity due to the presence of nanopores produced during organic-matter decomposition. Furthermore, CH4 sorption on clay minerals is mainly controlled by the type of clay mineral present. In terms of relative CH4 sorption capacity: montmorillonite ≫ illite – smectite mixed layer > kaolinite > chlorite > illite. The effect of rock properties (organic matter content, type, maturity, and clay minerals) on CH4 adsorption can be quantified with the heat of adsorption and the standard entropy, which are determined from adsorption isotherms at different temperatures. For clay-mineral rich rocks, the heat of adsorption (q) ranges from 9.4 to 16.6 kJ/mol. These values are considerably smaller than those for CH4 adsorption on kerogen (21.9–28 kJ/mol) and organic-rich shales (15.1–18.4 kJ/mol). The standard entropy (Δs°) ranges from -64.8 to -79.5 J/mol/K for clay minerals, -68.1 to -111.3 J/mol/K for kerogen, and -76.0 to -84.6 J/mol/K for organic-rich shales. The affinity of CH4 molecules for sorption on organic matter is stronger than for most common clay minerals. Thus, it is expected that CH4 molecules may preferentially occupy surface sites on organic matter. However, active sites on clay mineral surfaces are easily blocked by water. As a consequence, organic-rich shales possess a larger CH4-sorption capacity than clay-rich rocks lacking organic matter. The thermodynamic parameters obtained in this study can be incorporated into model predictions of the maximum Langmuir pressure and CH4- sorption capacity of shales under reservoir temperature and pressure conditions.

Subterranean karst environments as a global sink for atmospheric methane

NASA Astrophysics Data System (ADS)

Webster, Kevin D.; Drobniak, Agnieszka; Etiope, Giuseppe; Mastalerz, Maria; Sauer, Peter E.; Schimmelmann, Arndt

2018-03-01

The air in subterranean karst cavities is often depleted in methane (CH4) relative to the atmosphere. Karst is considered a potential sink for the atmospheric greenhouse gas CH4 because its subsurface drainage networks and solution-enlarged fractures facilitate atmospheric exchange. Karst landscapes cover about 14% of earth's continental surface, but observations of CH4 concentrations in cave air are limited to localized studies in Gibraltar, Spain, Indiana (USA), Vietnam, Australia, and by incomplete isotopic data. To test if karst is acting as a global CH4 sink, we measured the CH4 concentrations, δ13CCH4, and δ2HCH4 values of cave air from 33 caves in the USA and three caves in New Zealand. We also measured CO2 concentrations, δ13CCO2, and radon (Rn) concentrations to support CH4 data interpretation by assessing cave air residence times and mixing processes. Among these caves, 35 exhibited subatmospheric CH4 concentrations in at least one location compared to their local atmospheric backgrounds. CH4 concentrations, δ13CCH4, and δ2HCH4 values suggest that microbial methanotrophy within caves is the primary CH4 consumption mechanism. Only 5 locations from 3 caves showed elevated CH4 concentrations compared to the atmospheric background and could be ascribed to local CH4 sources from sewage and outgassing swamp water. Several associated δ13CCH4 and δ2HCH4 values point to carbonate reduction and acetate fermentation as biochemical pathways of limited methanogenesis in karst environments and suggest that these pathways occur in the environment over large spatial scales. Our data show that karst environments function as a global CH4 sink.

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.

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

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.

Eutrophication increases methane emission to the atmosphere in tropical lagoons: insights from two Ivory Coast sites

NASA Astrophysics Data System (ADS)

José-mathieu Koné, Yéfanlan; Vieira Borges, Alberto

2017-04-01

Eutrophication increases methane emission to the atmosphere in tropical lagoons: insights from two Ivory Coast sites. Y J M Koné (1) & A.V. Borges (2) (1) Centre de recherches océanologiques (CRO) d'Abidjan, (Ivory Coast) (2) University of Liège, Chemical Oceanography Unit, Liège, Belgium (Belgium) Eutrophication is a worldwide environmental problem and a definitive solution is far from being achieved, despite the large number of studies documenting its causes. In small aquatic ecosystems, excessive growth of macrophytes is a well known undesirable consequence of eutrophication. When these plants die and sink to the bottom the decomposing biomass depletes oxygen content in the water column thus leading to anoxia promoting methane (CH4) production. Here, we reported the CH4 data obtained during six campaigns covering the annual cycle in two small lagoons of Ivory Coast (Ono, Kodjoboué) that are contrasted in the degree of eutrophication and the corresponding coverage of macrophytes (e.g. Echinochloa pyramidalis, Eichhornia crassipes, Hydrilla verticillata). Our data showed a high spatio-temporal variability of CH4 within the lagoons and between the two systems, with CH4 concentrations in surface waters ranging between 80 to 74,604 nmol L-1. The highest CH4 concentration values were observed in the eutrophic Ono lagoon that is covered by 80% of macrophytes, suggesting that lagoons dominated by macrophytes are significant sources of CH4 toward the atmosphere.

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.

Patterns in CH4 and CO2 concentrations across boreal rivers: Major drivers and implications for fluvial greenhouse emissions under climate change scenarios.

PubMed

Campeau, Audrey; Del Giorgio, Paul A

2014-04-01

It is now widely accepted that boreal rivers and streams are regionally significant sources of carbon dioxide (CO2), yet their role as methane (CH4) emitters, as well as the sensitivity of these greenhouse gas (GHG) emissions to climate change, are still largely undefined. In this study, we explore the large-scale patterns of fluvial CO2 and CH4 partial pressure (pCO2 , pCH4) and gas exchange (k) relative to a set of key, climate-sensitive river variables across 46 streams and rivers in two distinct boreal landscapes of Northern Québec. We use the resulting models to determine the direction and magnitude of C-gas emissions from these boreal fluvial networks under scenarios of climate change. River pCO2 and pCH4 were positively correlated, although the latter was two orders of magnitude more variable. We provide evidence that in-stream metabolism strongly influences the dynamics of surface water pCO2 and pCH4 , but whereas pCO2 is not influenced by temperature in the surveyed streams and rivers, pCH4 appears to be strongly temperature-dependent. The major predictors of ambient gas concentrations and exchange were water temperature, velocity, and DOC, and the resulting models indicate that total GHG emissions (C-CO2 equivalent) from the entire network may increase between by 13 to 68% under plausible scenarios of climate change over the next 50 years. These predicted increases in fluvial GHG emissions are mostly driven by a steep increase in the contribution of CH4 (from 36 to over 50% of total CO2 -equivalents). The current role of boreal fluvial networks as major landscape sources of C is thus likely to expand, mainly driven by large increases in fluvial CH4 emissions. © 2013 John Wiley & Sons Ltd.

Effects of experimental warming and elevated CO2 on surface methane and CO­2 fluxes from a boreal black spruce peatland

NASA Astrophysics Data System (ADS)

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

2016-12-01

High latitude peatlands represent a major terrestrial carbon store sensitive to climate change, as well as a globally significant methane source. While elevated atmospheric carbon dioxide concentrations and warming temperatures may increase peat respiration and C losses to the atmosphere, reductions in peatland water tables associated with increased growing season evapotranspiration may alter the nature of trace gas emission and increase peat C losses as CO2 relative to methane (CH4). As CH4 is a greenhouse gas with twenty times the warming potential of CO2, it is critical to understand how surface fluxes of CO2 and CH4 will be influenced by factors associated with global climate change. We used automated soil respiration chambers to assess the influence of elevated atmospheric CO2 and whole ecosystem warming on peatland CH4 and CO2 fluxes at the SPRUCE (Spruce and Peatland Responses Under Climatic and Environmental Change) Experiment in northern Minnesota. Here we report soil iCO2 and iCH4 flux responses to the first year of belowground warming and the first season of whole ecosystem warming and elevated CO2 treatments. We find that peat methane fluxes are more sensitive to warming treatments than peat CO2 fluxes, particularly in hollow peat microforms. Surface CO2:CH4 flux ratios decreased across warming treatments, suggesting that the temperature sensitivity of methane production overshadows the effect of peat drying and surface aeration in the short term. δ13C of the emitted methane was more depleted in the early and late growing season, indicating a transition from hydrogenotrophic to acetoclastic methanogenesis during periods of high photosynthetic input. The measurement record demonstrates that belowground warming has measureable impacts on the nature of peat greenhouse gas emission within one year of treatment.

Using satellite observations to improve model estimates of CO2 and CH4 flux: a Metropolis Hastings Markov Chain Monte Carlo approach

NASA Astrophysics Data System (ADS)

MacBean, Natasha; Disney, Mathias; Lewis, Philip; Ineson, Phil

2010-05-01

Peatlands are wetlands with an organic soil layer of >30cm (Limpens et al., 2008) that occur beneath a living plant layer as a result of the waterlogged nature of the soil restricting complete decay of the biomass (Charman, 2002). Peatlands are important ecosystems; boreal and subarctic peatlands are estimated to contain 455Pg of carbon (Gorham, 1991), about 15-30% of the world's soil carbon (Limpens et al., 2008), and yet constitute less than 3% of the world's total land area (Lai, 2009). Peatlands not only sequester CO2 through photosynthesis and the partial decomposition of organic matter but they release methane (CH4) due to anaerobic microbial activity under waterlogged conditions. The balance is even more complex, as microbial consumption of CH4 can result in additional CO2 being emitted to the atmosphere. Wetlands are the main source of natural CH4 (Le Mer and Roger, 2001). Northern wetlands contribute about 35Tgyr-1 (Bubier and Moore, 1994). The uncertainty on this estimate is large 1 mgm-2yr-1 to 2200 mgm-2yr-1. Given that CH4 is 20 to 30 times more efficient at absorbing infrared radiation than CO2 there is a need to better quantify CH4 emissions and their role in the net carbon balance of peatlands. Two of the key variables in the calculation of CH4 production are water table depth and soil temperature. Water table depth is important as methanogenic bacteria are predominantly active in the anoxic zone. In order to accurately model the water table depth a correct representation of the whole soil moisture profile is important. Soil moisture and soil temperature are important variables in model calculations, as they affect the decomposition of carbon in the soil, as well as influencing the water and energy fluxes at the surface - atmosphere boundary. Microwave measurements of surface soil moisture and thermal measurements of land surface temperature from satellites can theoretically be used to improve the representation of the hydrology and soil temperature profile as a whole. We present results from an Observing System Simulation Experiment (OSSE) designed to investigate the impact of management and climate change on peatland carbon fluxes, as well as how observations from satellites may be able to constrain modeled carbon fluxes. We use an adapted version of the Carnegie-Ames-Stanford Approach (CASA) model (Potter et al., 1993) that includes a representation of methane dynamics (Potter, 1997). The model formulation is further modified to allow for assimilation of satellite observations of surface soil moisture and land surface temperature. The observations are used to update model estimates using a Metropolis Hastings Markov Chain Monte Carlo (MCMC) approach. We examine the effect of temporal frequency and precision of satellite observations with a view to establishing how, and at what level, such observations would make a significant improvement in model uncertainty. We compare this with the system characteristics of existing and future satellites. We believe this is the first attempt to assimilate surface soil moisture and land surface temperature into an ecosystem model that includes a full representation of CH4 flux. Bubier, J., and T. Moore (1994), An ecological perspective on methane emissions from northern wetlands, TREE, 9, 460-464. Charman, D. (2002), Peatlands and Environmental Change, JohnWiley and Sons, Ltd, England. Gorham, E. (1991), Northern peatlands: Role in the carbon cycle and probable responses to climatic warming, Ecological Applications, 1, 182-195. Lai, D. (2009), Methane dynamics in northern peatlands: A review, Pedosphere, 19, 409-421. Le Mer, J., and P. Roger (2001), Production, oxidation, emission and consumption of methane by soils: A review, European Journal of Soil Biology, 37, 25-50. Limpens, J., F. Berendse, J. Canadell, C. Freeman, J. Holden, N. Roulet, H. Rydin, and Potter, C. (1997), An ecosystem simulation model for methane production and emission from wetlands, Global Biogeochemical Cycles, 11, 495-506. Potter, C., J. Randerson, C. Field, P. Matson, P. Vitousek, H. Mooney, and S. Klooster (1993), Terrestrial ecosystem production: A process model based on global satellite and surface data, Global Biogeochemical Cycles, 7, 811-841.

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.

Methanogenic Pathway and Fraction of CH4 Oxidized in Paddy Fields: Seasonal Variation and Effect of Water Management in Winter Fallow Season

PubMed Central

Zhang, Guangbin; Liu, Gang; Zhang, Yi; Ma, Jing; Xu, Hua; Yagi, Kazuyuki

2013-01-01

A 2-year field and incubation experiment was conducted to investigate δ13C during the processes of CH4 emission from the fields subjected to two water managements (flooding and drainage) in the winter fallow season, and further to estimate relative contribution of acetate to total methanogenesis (Fac) and fraction of CH4 oxidized (Fox) based on the isotopic data. Compared with flooding, drainage generally caused CH4, either anaerobically or aerobically produced, depleted in 13C. There was no obvious difference between the two in transport fractionation factor (εtransport) and δ13C-value of emitted CH4. CH4 emission was negatively related to its δ13C-value in seasonal variation (P<0.01). Acetate-dependent methanogenesis in soil was dominant (60–70%) in the late season, while drainage decreased Fac-value by 5–10%. On roots however, CH4 was mostly produced through H2/CO2 reduction (60–100%) over the season. CH4 oxidation mainly occurred in the first half of the season and roughly 10–90% of the CH4 was oxidized in the rhizosphere. Drainage increased Fox-value by 5–15%, which is possibly attributed to a significant decrease in production while no simultaneous decrease in oxidation. Around 30–70% of the CH4 was oxidized at the soil-water interface when CH4 in pore water was released into floodwater, although the amount of CH4 oxidized therein might be negligible relative to that in the rhizosphere. CH4 oxidation was also more important in the first half of the season in lab conditions and about 5–50% of the CH4 was oxidized in soil while almost 100% on roots. Drainage decreased Fox-value on roots by 15% as their CH4 oxidation potential was highly reduced. The findings suggest that water management in the winter fallow season substantially affects Fac in the soil and Fox in the rhizosphere and roots rather than Fac on roots and Fox at the soil-water interface. PMID:24069259

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.

Methane production by anaerobic digestion of water hyacinth (Eichhornia crassipes)

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

Klass, D.L.; Ghosh, S.

1980-01-01

Water hyacinth under conventional high-rate digestion conditions exhibited higher CH4 yields and energy recovery efficiencies when grown in sewage-fed lagoons than when grown in a fresh water pond. Mesophilic digestion provided the highest recovery of feed energy in the product gas as CH4, while thermophilic digestion, when operated at sufficiently high loading rates and reduced detention times, gave the highest specific CH4 production rates. CH4 yields, volatile solids reduction, and energy recovery as CH4 from the sewage-grown water hyacinth were in the same range as those observed for other biomass substrates when digested under similar conditions.

Eddy Covariance Measurements of Methane Flux at a Tropical Peat Forest in Sarawak, Malaysian Borneo

NASA Astrophysics Data System (ADS)

Tang, Angela C. I.; Stoy, Paul C.; Hirata, Ryuichi; Musin, Kevin K.; Aeries, Edward B.; Wenceslaus, Joseph; Melling, Lulie

2018-05-01

Tropical biogenic sources are a likely cause of the recent increase in global atmospheric methane concentration. To improve our understanding of tropical methane sources, we used the eddy covariance technique to measure CH4 flux (FCH4) between a tropical peat forest ecosystem and the atmosphere in Malaysian Borneo over a 2-month period during the wet season. Mean daily FCH4 during the measurement period, on the order of 0.024 g C-CH4·m-2·day-1, was similar to eddy covariance FCH4 measurements from tropical rice agroecosystems and boreal fen ecosystems. A linear modeling analysis demonstrated that air temperature (Tair) was critical for modeling FCH4 before the water table breached the surface and that water table alone explained some 20% of observed FCH4 variability once standing water emerged. Future research should measure FCH4 on an annual basis from multiple tropical ecosystems to better constrain tropical biogenic methane sources.

NASA Astrophysics Data System (ADS)

Shakhova, N. E.; Semiletov, I. P.

2007-12-01

Importance of huge pool of old carbon stored within off-shore permafrost in Siberian region is determined by gradual mobilization of old carbon during permafrost degradation and its incorporation into modern carbon cycle in form of methane. Acceleration of this process due to both natural and anthropogenic disturbance of coastal environment may not only enhance a positive feedback to a global warming, but also can potentially cause rapid or even abrupt climate change on Earth. Theoretically, during times of marine transgression, the sub-sea permafrost could reduce in thickness and develops nearly isothermal conditions close to the melting point. This might occur early on after the marine transgression (high heat flow), or it might take up to several thousand years (low heat flow). Due to the time lag existing between the maximum heat flow and maximum permafrost transformation, the most drastic changes in thermal regime of permafrost might occur not at a warmest time, (for example, at Holocene optimum), but further. Moreover, the key changes in permafrost properties might not be reaching a phase transition stages, but more likely reaching permeability for gas on a larger scale. As sub-sea permafrost does not necessarily represent a rocklike ice-bonded layer, but is sometimes ice free under negative temperatures as its salinity increases, this allows permeability for upward migration of gases, stored within permafrost and/or beneath it. Our recent study in the East-Siberian Arctic shelf (2003-2006) detected CH4 super-saturation of surface water in some areas up to 10,000 % above background level, implying that strong air-to-sea fluxes must occur at times. It leads to significant increase in atmospheric concentrations of methane above the sea surface - up to 8 ppm (latitude specific monthly mean concentrations is 1.85 ppm). Our first wintertime data (April 2007) shows extremely high CH4 concentrations (up to 5.7 µmol l-1) in the surface water beneath the sea ice. Being commensurable with concentrations, measured during the wintertime in thermokarst lakes of Siberian Lowland, these values represent the highest CH4 concentrations, observed in the Arctic Ocean, and are comparable to those registered over decaying gas hydrate fields in the Sea of Okhotsk. The vertical distribution of dissolved CH4, as well as the size and number of CH4 bubbles, trapped within the sea ice, strongly indicate ebullition as a mechanism of CH4 transfer to the water surface. The areas, which should be considered as favorable for opening potentially perennial pathways for methane escape after over 6,000 year inundation, are following: large rivers taliks; a meandering river system (paleo- valleys), running across the shelf; so-called geological disjunctives (fault zones, tectonically and seismically active areas); sedimentary basins; completely submerged, or transformed into sea lagoons, thaw lake taliks.

Does Juncus effusus enhance methane emissions from grazed pastures on peat?

NASA Astrophysics Data System (ADS)

Henneberg, A.; Elsgaard, L.; Sorrell, B. K.; Brix, H.; Petersen, S. O.

2015-06-01

Methane (CH4) emissions from drained organic soils are generally low, but internal gas transport in aerenchymatous plants may result in local emission hotspots. In a paired-sample field study at three different sites we measured fluxes of CH4 with static chambers from adjacent sampling quadrats with and without Juncus effusus during four field campaigns. At all three sites, CH4 was observed in the soil at all sampling depths (5-100 cm), and in most cases both above and below the groundwater table. During spring, local maxima suggested methanogenesis took place above the water table at all three sites. We found significant CH4 emissions at all three sites, but emission controls were clearly different. Across the three sites, average emission rates (±1 SE) for sampling quadrats with and without J. effusus were 1.47 ± 0.28 and 1.37 ± 0.33 mg CH4 m-2 h-1 respectively, with no overall effect of J. effusus on CH4 emissions, but a significant effect at one of the three sites. At this site, local CH4 maxima were closer to the soil surface than at the other sites, and the upper soil layers were dryer. This could have affected both root CH4 accessibility and CH4 oxidation respectively, and together with limited gas diffusivity in the soil column, cause elevated CH4 emissions from J. effusus. We conclude that aerenchymatous plants has the potential to act as point sources of CH4 from drained peatlands, but more studies on the specific conditions under which there is an effect, are needed before the results can be used in modelling of CH4 emissions.

Does uncus effusus enhance methane emissions from grazed pastures on peat?

NASA Astrophysics Data System (ADS)

Henneberg, A.; Elsgaard, L.; Sorrell, B. K.; Brix, H.; Petersen, S. O.

2015-10-01

Methane (CH4) emissions from drained organic soils are generally low, but internal gas transport in aerenchymatous plants may result in local emission hotspots. In a paired-sample field study at three different sites we measured fluxes of CH4 with static chambers from adjacent sampling quadrats with and without Juncus effusus during four field campaigns. At all three sites, CH4 was observed in the soil at all sampling depths (5 to 100 cm), and in most cases both above and below the groundwater table. During spring, local maxima suggested methanogenesis also took place above the water table at all three sites. We found significant CH4 emissions at all three sites, but emission controls were clearly different. Across the three sites, average emission rates (±1 SE) for sampling quadrats with and without J. effusus were 1.47 ± 0.28 and 1.37 ± 0.33 mg CH4 m-2 h-1, respectively, with no overall effect of J. effusus on CH4 emissions. However, a significant effect of J. effusus was seen at one of the three sites. At this site, local CH4 maxima were closer to the soil surface than at the other sites, and the upper soil layers were dryer. This could have affected both root CH4 accessibility and CH4 oxidation respectively, and together with limited gas diffusivity in the soil column, cause elevated CH4 emissions from J. effusus. We conclude that J. effusus has the potential to act as point sources of CH4 from drained peatlands, but more studies on the specific conditions under which there is an effect, are needed before the results can be used in modelling of CH4 emissions.

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

(CH3)3SiCl/SiCl4 azeotrope grows superhydrophobic nanofilaments.

PubMed

Gao, Lichao; McCarthy, Thomas J

2008-01-15

We describe the vapor-phase reaction (at room temperature and 40-45% relative humidity) of silicon wafers with the azeotropic mixture of trimethylchlorosilane and tetrachlorosilane. Water contact angle analysis indicates that surfaces become nearly perfectly hydrophobic (thetaA/thetaR > or =176 degrees/> or =176 degrees) after 2 min of reaction. SEM analysis at various reaction times shows the growth of nanofilaments with diameters of approximately 30 nm. X-ray photoelectron spectroscopy of oxidized titanium surfaces that were exposed to the azeotrope vapor indicates that the product is derived from a approximately 10:1 ratio of SiCl4 and (CH3)3SiCl. A mechanism for filament growth is proposed.

12 years of Pluto surface's evolution investigated with radiative transfer modeling

NASA Astrophysics Data System (ADS)

Philippe, Sylvain; Schmitt, Bernard; Grundy, William; Protopapa, Silvia; Olkin, Cathy

2015-11-01

The evolution of Pluto’s surface through time, due to surface - atmosphere interactions, remains unknown. New Horizons will provide very high spatial resolution data of its surface state but only as a snapshot. Furthermore, this evolution during the last decades is supposed to be fast due to the recent passage of Pluto through its perihelion (1989). Ground based survey data over a long period of time are thus crucial to understand the long-term evolution of the dwarf planet surface.IRTF/SpeX reflectance spectra of Pluto have been acquired during 13 years (2001-2013) between 0.8-2.4 μm (Grundy et al., 2013; Grundy et al., 2014). This set of data present the opportunity to monitor possible changes of the surface in terms of geographical distribution and segregation between different chemical species that are known to be present at the surface in an icy state (N2, CH4 and CO, Owen et al., 1993, Douté et al., 1999). These variations are recorded through changes in the infrared absorption bands of the different ices. A study based on band criteria variation (Grundy et al., 2013) showed that CH4 absorption bands are increasing through time, whereas N2 and CO absorptions bands are decreasing (Grundy et al. 2014). However, quantitative interpretation of these data needs further investigation and detailed radiative transfer modeling.We used the bidirectional reflectance model of Douté & Schmitt (1998) to fit the IRTF/SpeX spectral data. This model takes into account a possible stratification of chemical species, a phenomenon that is likely to occur on Pluto where CH4 is supposed to accumulate on a sublimating molecular mixture of N2-CH4-CO (Douté et al., 1999). Different modelings take into account pure CH4 ice, a molecular mixture of N2-CH4-CO, tholins and water ice. We modeled the grand average spectra and then allowed the parameters to vary around the average values to model individual spectra and get quantitative variations of the different species.Preliminary results of these modelings will be presented in terms of longitudinal and temporal variations. This study could provide a useful precursor for the analysis of the spatially resolved New Horizon hyper spectral data acquired by the RALPH/Leisa instrument.

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

Bohn, T. J.; Melton, J. R.; Ito, A.

Wetlands are the world's largest natural source of methane, a powerful greenhouse gas. The strong sensitivity of methane emissions to environmental factors such as soil temperature and moisture has led to concerns about potential positive feedbacks to climate change. This risk is particularly relevant at high latitudes, which have experienced pronounced warming and where thawing permafrost could potentially liberate large amounts of labile carbon over the next 100 years. However, global models disagree as to the magnitude and spatial distribution of emissions, due to uncertainties in wetland area and emissions per unit area and a scarcity of in situ observations.more » Recent intensive field campaigns across the West Siberian Lowland (WSL) make this an ideal region over which to assess the performance of large-scale process-based wetland models in a high-latitude environment. Here we present the results of a follow-up to the Wetland and Wetland CH 4 Intercomparison of Models Project (WETCHIMP), focused on the West Siberian Lowland (WETCHIMP-WSL). We assessed 21 models and 5 inversions over this domain in terms of total CH 4 emissions, simulated wetland areas, and CH 4 fluxes per unit wetland area and compared these results to an intensive in situ CH 4 flux data set, several wetland maps, and two satellite surface water products. We found that (a) despite the large scatter of individual estimates, 12-year mean estimates of annual total emissions over the WSL from forward models (5.34 ± 0.54 Tg CH 4 yr⁻¹), inversions (6.06 ± 1.22 Tg CH 4 yr⁻¹), and in situ observations (3.91 ± 1.29 Tg CH 4 yr⁻¹) largely agreed; (b) forward models using surface water products alone to estimate wetland areas suffered from severe biases in CH 4 emissions; (c) the interannual time series of models that lacked either soil thermal physics appropriate to the high latitudes or realistic emissions from unsaturated peatlands tended to be dominated by a single environmental driver (inundation or air temperature), unlike those of inversions and more sophisticated forward models; (d) differences in biogeochemical schemes across models had relatively smaller influence over performance; and (e) multiyear or multidecade observational records are crucial for evaluating models' responses to long-term climate change.« less

WETCHIMP-WSL: Intercomparison of wetland methane emissions models over West Siberia

DOE PAGES

Bohn, T. J.; Melton, J. R.; Ito, A.; ...

2015-06-03

Wetlands are the world's largest natural source of methane, a powerful greenhouse gas. The strong sensitivity of methane emissions to environmental factors such as soil temperature and moisture has led to concerns about potential positive feedbacks to climate change. This risk is particularly relevant at high latitudes, which have experienced pronounced warming and where thawing permafrost could potentially liberate large amounts of labile carbon over the next 100 years. However, global models disagree as to the magnitude and spatial distribution of emissions, due to uncertainties in wetland area and emissions per unit area and a scarcity of in situ observations.more » Recent intensive field campaigns across the West Siberian Lowland (WSL) make this an ideal region over which to assess the performance of large-scale process-based wetland models in a high-latitude environment. Here we present the results of a follow-up to the Wetland and Wetland CH 4 Intercomparison of Models Project (WETCHIMP), focused on the West Siberian Lowland (WETCHIMP-WSL). We assessed 21 models and 5 inversions over this domain in terms of total CH 4 emissions, simulated wetland areas, and CH 4 fluxes per unit wetland area and compared these results to an intensive in situ CH 4 flux data set, several wetland maps, and two satellite surface water products. We found that (a) despite the large scatter of individual estimates, 12-year mean estimates of annual total emissions over the WSL from forward models (5.34 ± 0.54 Tg CH 4 yr⁻¹), inversions (6.06 ± 1.22 Tg CH 4 yr⁻¹), and in situ observations (3.91 ± 1.29 Tg CH 4 yr⁻¹) largely agreed; (b) forward models using surface water products alone to estimate wetland areas suffered from severe biases in CH 4 emissions; (c) the interannual time series of models that lacked either soil thermal physics appropriate to the high latitudes or realistic emissions from unsaturated peatlands tended to be dominated by a single environmental driver (inundation or air temperature), unlike those of inversions and more sophisticated forward models; (d) differences in biogeochemical schemes across models had relatively smaller influence over performance; and (e) multiyear or multidecade observational records are crucial for evaluating models' responses to long-term climate change.« less

CO2 adsorption-assisted CH4 desorption on carbon models of coal surface: A DFT study

NASA Astrophysics Data System (ADS)

Xu, He; Chu, Wei; Huang, Xia; Sun, Wenjing; Jiang, Chengfa; Liu, Zhongqing

2016-07-01

Injection of CO2 into coal is known to improve the yields of coal-bed methane gas. However, the technology of CO2 injection-enhanced coal-bed methane (CO2-ECBM) recovery is still in its infancy with an unclear mechanism. Density functional theory (DFT) calculations were performed to elucidate the mechanism of CO2 adsorption-assisted CH4 desorption (AAD). To simulate coal surfaces, different six-ring aromatic clusters (2 × 2, 3 × 3, 4 × 4, 5 × 5, 6 × 6, and 7 × 7) were used as simplified graphene (Gr) carbon models. The adsorption and desorption of CH4 and/or CO2 on these carbon models were assessed. The results showed that a six-ring aromatic cluster model (4 × 4) can simulate the coal surface with limited approximation. The adsorption of CO2 onto these carbon models was more stable than that in the case of CH4. Further, the adsorption energies of single CH4 and CO2 in the more stable site were -15.58 and -18.16 kJ/mol, respectively. When two molecules (CO2 and CH4) interact with the surface, CO2 compels CH4 to adsorb onto the less stable site, with a resulting significant decrease in the adsorption energy of CH4 onto the surface of the carbon model with pre-adsorbed CO2. The Mulliken charges and electrostatic potentials of CH4 and CO2 adsorbed onto the surface of the carbon model were compared to determine their respective adsorption activities and changes. At the molecular level, our results showed that the adsorption of the injected CO2 promoted the desorption of CH4, the underlying mechanism of CO2-ECBM.

The global methane budget 2000-2012

NASA Astrophysics Data System (ADS)

Saunois, Marielle; Bousquet, Philippe; Poulter, Ben; Peregon, Anna; Ciais, Philippe; Canadell, Josep G.; Dlugokencky, Edward J.; Etiope, Giuseppe; Bastviken, David; Houweling, Sander; Janssens-Maenhout, Greet; Tubiello, Francesco N.; Castaldi, Simona; Jackson, Robert B.; Alexe, Mihai; Arora, Vivek K.; Beerling, David J.; Bergamaschi, Peter; Blake, Donald R.; Brailsford, Gordon; Brovkin, Victor; Bruhwiler, Lori; Crevoisier, Cyril; Crill, Patrick; Covey, Kristofer; Curry, Charles; Frankenberg, Christian; Gedney, Nicola; Höglund-Isaksson, Lena; Ishizawa, Misa; Ito, Akihiko; Joos, Fortunat; Kim, Heon-Sook; Kleinen, Thomas; Krummel, Paul; Lamarque, Jean-François; Langenfelds, Ray; Locatelli, Robin; Machida, Toshinobu; Maksyutov, Shamil; McDonald, Kyle C.; Marshall, Julia; Melton, Joe R.; Morino, Isamu; Naik, Vaishali; O'Doherty, Simon; Parmentier, Frans-Jan W.; Patra, Prabir K.; Peng, Changhui; Peng, Shushi; Peters, Glen P.; Pison, Isabelle; Prigent, Catherine; Prinn, Ronald; Ramonet, Michel; Riley, William J.; Saito, Makoto; Santini, Monia; Schroeder, Ronny; Simpson, Isobel J.; Spahni, Renato; Steele, Paul; Takizawa, Atsushi; Thornton, Brett F.; Tian, Hanqin; Tohjima, Yasunori; Viovy, Nicolas; Voulgarakis, Apostolos; van Weele, Michiel; van der Werf, Guido R.; Weiss, Ray; Wiedinmyer, Christine; Wilton, David J.; Wiltshire, Andy; Worthy, Doug; Wunch, Debra; Xu, Xiyan; Yoshida, Yukio; Zhang, Bowen; Zhang, Zhen; Zhu, Qiuan

2016-12-01

The global methane (CH4) budget is becoming an increasingly important component for managing realistic pathways to mitigate climate change. This relevance, due to a shorter atmospheric lifetime and a stronger warming potential than carbon dioxide, is challenged by the still unexplained changes of atmospheric CH4 over the past decade. Emissions and concentrations of CH4 are continuing to increase, making CH4 the second most important human-induced greenhouse gas after carbon dioxide. Two major difficulties in reducing uncertainties come from the large variety of diffusive CH4 sources that overlap geographically, and from the destruction of CH4 by the very short-lived hydroxyl radical (OH). To address these difficulties, we have established a consortium of multi-disciplinary scientists under the umbrella of the Global Carbon Project to synthesize and stimulate research on the methane cycle, and producing regular (˜ biennial) updates of the global methane budget. This consortium includes atmospheric physicists and chemists, biogeochemists of surface and marine emissions, and socio-economists who study anthropogenic emissions. Following Kirschke et al. (2013), we propose here the first version of a living review paper that integrates results of top-down studies (exploiting atmospheric observations within an atmospheric inverse-modelling framework) and bottom-up models, inventories and data-driven approaches (including process-based models for estimating land surface emissions and atmospheric chemistry, and inventories for anthropogenic emissions, data-driven extrapolations). For the 2003-2012 decade, global methane emissions are estimated by top-down inversions at 558 Tg CH4 yr-1, range 540-568. About 60 % of global emissions are anthropogenic (range 50-65 %). Since 2010, the bottom-up global emission inventories have been closer to methane emissions in the most carbon-intensive Representative Concentrations Pathway (RCP8.5) and higher than all other RCP scenarios. Bottom-up approaches suggest larger global emissions (736 Tg CH4 yr-1, range 596-884) mostly because of larger natural emissions from individual sources such as inland waters, natural wetlands and geological sources. Considering the atmospheric constraints on the top-down budget, it is likely that some of the individual emissions reported by the bottom-up approaches are overestimated, leading to too large global emissions. Latitudinal data from top-down emissions indicate a predominance of tropical emissions (˜ 64 % of the global budget, < 30° N) as compared to mid (˜ 32 %, 30-60° N) and high northern latitudes (˜ 4 %, 60-90° N). Top-down inversions consistently infer lower emissions in China (˜ 58 Tg CH4 yr-1, range 51-72, -14 %) and higher emissions in Africa (86 Tg CH4 yr-1, range 73-108, +19 %) than bottom-up values used as prior estimates. Overall, uncertainties for anthropogenic emissions appear smaller than those from natural sources, and the uncertainties on source categories appear larger for top-down inversions than for bottom-up inventories and models. The most important source of uncertainty on the methane budget is attributable to emissions from wetland and other inland waters. We show that the wetland extent could contribute 30-40 % on the estimated range for wetland emissions. Other priorities for improving the methane budget include the following: (i) the development of process-based models for inland-water emissions, (ii) the intensification of methane observations at local scale (flux measurements) to constrain bottom-up land surface models, and at regional scale (surface networks and satellites) to constrain top-down inversions, (iii) improvements in the estimation of atmospheric loss by OH, and (iv) improvements of the transport models integrated in top-down inversions. The data presented here can be downloaded from the Carbon Dioxide Information Analysis Center (http://doi.org/10.3334/CDIAC/GLOBAL_METHANE_BUDGET_2016_V1.1) and the Global Carbon Project.

The Global Methane Budget 2000-2012

NASA Technical Reports Server (NTRS)

Saunois, Marielle; Bousquet, Philippe; Poulter, Benjamin; Peregon, Anna; Ciais, Philippe; Canadell, Josep G.; Dlugokencky, Edward J.; Etiope, Giuseppe; Bastviken, David; Houweling, Sander;

One-step formation of bifunctionnal aryl/alkyl grafted films on conducting surfaces by the reduction of diazonium salts in the presence of alkyl iodides.

PubMed

Hetemi, Dardan; Hazimeh, Hassan; Decorse, Philippe; Galtayries, Anouk; Combellas, Catherine; Kanoufi, Frédéric; Pinson, Jean; Podvorica, Fetah I

2015-05-19

The formation of partial perfluoroalkyl or alkyl radicals from partial perfluoroalkyl or alkyl iodides (ICH2CH2C6F13 and IC6H13) and their reaction with surfaces takes place at low driving force (∼-0.5 V/SCE) when the electrochemical reaction is performed in acetonitrile in the presence of diazonium salts (ArN2(+)), at a potential where the latter is reduced. By comparison to the direct grafting of ICH2CH2C6F13, this corresponds to a gain of ∼2.1 V in the case of 4-nitrobenzenediazonium. Such electrochemical reaction permits the modification of gold surfaces (and also carbon, iron, and copper) with mixed aryl-alkyl groups (Ar = 3-CH3-C6H4, 4-NO2-C6H4, and 4-Br-C6H4, R = C6H13 or (CH2)2-C6F13). These strongly bonded mixed layers are characterized by IRRAS, XPS, ToF-SIMS, ellipsometry, water contact angles, and cyclic voltammetry. The relative proportions of grafted aryl and alkyl groups can be varied along with the relative concentrations of diazonium and iodide components in the grafting solution. The formation of the films is assigned to the reaction of aryl and alkyl radicals on the surface and on the first grafted layer. The former is obtained from the electrochemical reduction of the diazonium salt; the latter results from the abstraction of an iodine atom by the aryl radical. The mechanism involved in the growth of the film provides an example of complex surface radical chemistry.

Electron-hole pair effects in methane dissociative chemisorption on Ni(111)

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

Luo, Xuan; Jiang, Bin, E-mail: bjiangch@ustc.edu.cn; Juaristi, J. Iñaki

The dissociative chemisorption of methane on metal surfaces has attracted much attention in recent years as a prototype of gas-surface reactions in understanding the mode specific and bond selective chemistry. In this work, we systematically investigate the influence of electron-hole pair excitations on the dissociative chemisorption of CH{sub 4}/CH{sub 3}D/CHD{sub 3} on Ni(111). The energy dissipation induced by surface electron-hole pair excitations is modeled as a friction force introduced in the generalized Langevin equation, in which the independent atomic friction coefficients are determined within the local-density friction approximation. Quasi-classical trajectory calculations for CH{sub 4}/CH{sub 3}D/CHD{sub 3} have been carried outmore » on a recently developed twelve-dimensional potential energy surface. Comparing the dissociation probabilities obtained with and without friction, our results clearly indicate that the electron-hole pair effects are generally small, both on absolute reactivity of each vibrational state and on the mode specificity and bond selectivity. Given similar observations in both water and methane dissociation processes, we conclude that electron-hole pair excitations would not play an important role as long as the reaction is direct and the interaction time between the molecule and metal electrons is relatively short.« less

CO 2 is dominant greenhouse gas emitted from six hydropower reservoirs in southeastern United States during peak summer emissions

DOE PAGES

Bevelhimer, Mark S.; Stewart, Aurthur J.; Fortner, Allison M.; ...

2016-01-06

During August-September 2012, we sampled six hydropower reservoirs in southeastern United States. for CO 2 and CH 4 emissions via three pathways: diffusive emissions from water surface; ebullition in the water column; and losses from dam tailwaters during power generation. Average total emission rates of CO 2 for the six reservoirs ranged from 1,127 to 2,051 mg m -2 d -1, which is low to moderate compared to CO 2 emissions rates reported for tropical hydropower reservoirs and boreal ponds and lakes, and similar to rates reported for other temperate reservoirs. Similar average rates for CH 4 were also relativelymore » low, ranging from 5 to 83 mg m -2 d -1. On a whole-reservoir basis, total emissions of CO 2 ranged nearly 10-fold, from ~51,000 kg per day for Fontana to ~486,000 kg per day for Guntersville, and total emissions of CH 4 ranged nearly 20-fold, from ~5 kg per day for Fontana to ~83 kg per day for Allatoona. Emissions through the tailwater pathway varied among reservoirs, comprising from 20 to 50% of total CO 2 emissions and 0 to 90% of CH 4 emissions, depending on the reservoir. Furthermore, several explanatory factors related to reservoir morphology and water quality were considered for observed differences among reservoirs.« less

Intermediate-scale community-level flux of CO 2 and CH 4 in a Minnesota peatland: Putting the SPRUCE project in a global context

DOE PAGES

Hanson, Paul J.; Gill, Allison; Xu, Xiaofeng; ...

2016-08-20

Peatland measurements of CO 2 and CH 4 flux were obtained at scales appropriate to the in situ biological community below the tree layer to demonstrate representativeness of the spruce and peatland responses under climatic and environmental change (SPRUCE) experiment. Surface flux measurements were made using dual open-path analyzers over an area of 1.13 m 2 in daylight and dark conditions along with associated peat temperatures, water table height, hummock moisture, atmospheric pressure and incident radiation data. Observations from August 2011 through December 2014 demonstrated seasonal trends correlated with temperature as the dominant apparent driving variable. The S1-Bog for themore » SPRUCE study was found to be representative of temperate peatlands in terms of CO 2 and CH 4 flux. Maximum net CO 2 flux in midsummer showed similar rates of C uptake and loss: daytime surface uptake was -5 to -6 µmol m -2 s -1 and dark period loss rates were 4–5 µmol m -2 s -1 (positive values are carbon lost to the atmosphere). Maximum midsummer CH4-C flux ranged from 0.4 to 0.5 µmol m -2 s -1 and was a factor of 10 lower than dark CO 2–C efflux rates. Midwinter conditions produced near-zero flux for both CO 2 and CH 4 with frozen surfaces. Integrating temperature-dependent models across annual periods showed dark CO 2–C and CH 4–C flux to be 894 ± 34 and 16 ± 2 gC m -2 y -1, respectively. Net ecosystem exchange of carbon from the shrub-forb-Sphagnum-microbial community (excluding tree contributions) ranged from -3.1 gCO2–C m -2 y -1 in 2013, to C losses from 21 to 65 gCO 2–C m -2 y -1 for the other years.« less

Air–water CO2 and CH4 fluxes along a river–reservoir continuum: Case study in the Pengxi River, a tributary of the Yangtze River in the Three Gorges Reservoir, China

USDA-ARS?s Scientific Manuscript database

Water surface greenhouse gas (GHG) emissions in freshwater reservoirs are closely related to limnological processes in the water column. Affected by both reservoir operation and seasonal changes, variations in the hydro-morphological conditions in the river–reservoir continuum will create distinctiv...

Methanogenic biodegradation of creosote contaminants in natural and simulated ground-water ecosystems

USGS Publications Warehouse

Godsy, E. Michael; Goerlitz, Donald; Grbic-Galic, Dunja

1992-01-01

Wastes from a wood preserving plant in Pensacola, Florida have contaminated the near-surface sand-and-gravel aquifer with creosote-derived compounds and pentachlorophenol. Contamination resulted from the discharge of plant waste waters to and subsequent seepage from unlined surface impoundments that were in direct hydraulic contact with the ground water. Two distinct phases resulted when the creosote and water mixed: a denser than water hydrocarbon phase that moved vertically downward, and an organic-rich aqueous phase that moved laterally with the ground-water flow. The aqueous phase is enriched in organic acids, phenolic compounds, single- and double-ring nitrogen, sulfur, and oxygen containing compounds, and single- and double-ring aromatic hydrocarbons. The ground water is devoid of dissolved O2, is 60-70% saturated with CH4 and contains H2S. Field analyses document a greater decrease in concentration of organic fatty acids, benzoic acid, phenol, 2-, 3-, 4-methylphenol, quinoline, isoquinoline, 1(2H)-quinolinone, and 2(1H)-isoquinolinone during downgradient movement in the aquifer than could be explained by dilution and/or dispersion. Laboratory microcosm studies have shown that within the study region, this effect can be attributed to microbial degradation to CH4 and CO2. A small but active methanogenic population was found on sediment materials taken from highly contaminated parts of the aquifer.

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.

Experimental research on the effects of water application on greenhouse gas emissions from beef cattle feedlots

USDA-ARS?s Scientific Manuscript database

The effect of water application (e.g., through rainfall or sprinkler system) on emissions of greenhouse gases (GHGs), such as nitrous oxide (N2O), methane (CH4), and carbon dioxide (CO2), from pen surfaces of open-lot beef cattle feedlots was evaluated under controlled laboratory conditions. Soil/ma...

The temperature response of methane emission in Arctic wet sedge tundra

NASA Astrophysics Data System (ADS)

Lim, Edward; Zona, Donatella

2015-04-01

Since the last glacial maximum Arctic tundra soils have acted as an important carbon sink, having accumulated carbon under cold, anaerobic conditions (Zona et al. 2009). Several studies indicate that recent climate warming has altered this balance, with the Arctic tundra now posited to be a significant annual source of atmospheric methane (CH4) (McGuire et al. 2012). Nonetheless, the response of Arctic tundra CH4 fluxes to continued climate warming remains uncertain. Laboratory and field studies indicate that CH4 fluxes are temperature sensitive, thus accurate calculation of the temperature sensitivity is vital for the prediction of future CH4 emission. For this, the increase in reaction rate over a 10°C range (Q10) is frequently used, with single fixed Q10 values (between 2 and 4) commonly incorporated into climate-carbon cycle models. However, the temperature sensitivity of CH4 emission can vary considerably depending on factors such as vegetation composition, water table and season. This promotes the use of spatially and seasonally variable Q10 values for accurate CH4 flux estimation under different future climate change scenarios. This study investigates the temperature sensitivity (Q10) of Arctic tundra methane fluxes, using an extensive number of soil cores (48) extracted from wet sedge polygonal tundra (Barrow Experimental Observatory, Alaska). 'Wet' and 'dry' cores were taken from the centre and raised perimeter of ice-wedge polygons, where the water tables are 0cm and -15cm respectively. Cores were incubated in two controlled environment chambers (University of Sheffield, UK) for 12 weeks under different thaw depth treatments (control and control + 6.8cm), water tables (surface and -15cm), and CO2 concentrations (400ppm and 850ppm) in a multifactorial manner. Chamber temperature was gradually increased from -5°C to 20°C, then gradually decreased to -5°C, with each temperature stage lasting one week. Average CH4 fluxes from 'dry' cores were consistently low and did not change significantly with temperature, indicating that CH4 emission from drier Arctic tundra soils is not particularly temperature sensitive. Average CH4 emission from 'wet' cores increased with increasing temperature between -5°C and 20°C. Interestingly, continued increases in average CH4 emission as chamber temperature decreased (20°C to 0°C) were observed. Importantly, when chamber temperature was increased (-5°C to 20°C), average CH4 emission in the 'wet' cores was consistently lower at the end of each week-long temperature stage compared to at the start. This suggests that the response of CH4 emission to climate warming might acclimate. Overall, this study is critical for refining the temperature sensitivity of Arctic tundra CH4 emission, and thus improving model predictions of the response of CH4 fluxes to climate change. References McGuire, AD; Christensen, TR; Hayes, D. et al. (2012). An assessment of the carbon balance of Arctic tundra: comparisons among observations, process models, and atmospheric inversions. Biogeosciences. Vol.9, p.3185-3204, doi:10.5194/bg-9-3185-2012. Zona, D; Oechel, WC; Kochendorfer, J. et al. (2009). Methane fluxes during the initiation of a large-scale water table manipulation experiment in the Alaskan Arctic tundra. Global Biogeochemical Cycles. Vol.23, GB2013, doi:10.1029/2009GB003487.

Spatial variability of greenhouse gases emissions (CO2, CH4, N2O) in a tropical hydroelectric reservoir flooding primary forest (Petit Saut Reservoir, French Guiana)

NASA Astrophysics Data System (ADS)

Cailleaud, Emilie; Guérin, Frédéric; Bouillon, Steven; Sarrazin, Max; Serça, Dominique

2014-05-01

At the Petit Saut Reservoir (PSR, French Guiana, South America), vertical profiles were performed at 5 stations in the open waters (OW) and 6 stations in two shallow flooded forest (FF) areas between April 2012 and September 2013. Measurements included physico-chemical parameters, ammonium, nitrate and dissolved greenhouse gas (CO2, CH4, N2O) concentrations, dissolved and particulate organic carbon (DOC, POC) and nitrogen (PN), δ13C-POC and δ15N-PN . The diffusive fluxes were calculated from surface concentrations. The aim of this study was to estimate the spatial variations of greenhouse gas emissions at a dentrical hydroelectric reservoir located in the tropics and flooding primary forest. Twenty years after impoundment, the water column of the PSR is permanently and tightly stratified thermally in the FF whereas in the OW, the thermal gradients are not as stable. The different hydrodynamical behaviours between the two different zones have significant consequences on the biogeochemistry: oxygen barely diffuses down to the hypolimnion in the FF whereas destratification occurs sporadically during the rainy season in the OW. Although we found the same range of POC in the FF and the OW (2.5-29 μmol L-1) and 20% more DOC at the bottom of OW than in the FF (229-878 μmol L-1), CO2 and CH4 concentrations were always significantly higher in the FF (CO2: 11-1412 μmol L-1, CH4: 0.001-1015 μmol L-1) than in the OW. On average, the CO2 concentrations were 30-40% higher in the FF than in the OW and the CH4 concentrations were three times higher in the FF than in the OW. The δ13C-POC and C:N values did not suggest substantial differences in the sources of OM between the FF and OW. At all stations, POC at the bottom has an isotopic signature slightly lighter than the terrestrial OM in the surrounding forest whereas the isotopic signature of surface POM would result from phytoplankton and methanotrophs. The vertical profiles of nitrogen compounds reveal that the main source of nitrogen in the water column of the PSR is the NH4+ produced during the mineralisation of the OM at the bottom of the reservoir. In OW, the production of NO3- and N2O is enhanced compared to the FF. As a result, N2O concentrations are three times higher at the bottom of OW but surface concentrations are similar in the FF and OW. CO2 diffusive fluxes are 40% higher and CH4 diffusive fluxes are three times higher in FF (CO2: 42±20 mmol m-2 d-1 ; CH4: 0.7±1.4 mmol m-2 d-1) than in OW (CO2: 27±17 mmol m-2 d-1 ; CH4: 0.2±0.3 mmol m-2 d-1). In shallow FF, average CH4 ebullition is 3±10 mmol m-2 d-1 whereas ebullition was never observed in OW. N2O emissions did not exhibit any spatial variability (9±4 μmol m-2 d-1). At the PSR, FF which represents one third of the surface area, is responsible of half of the GHG emissions from the reservoir. This implies that the emissions from most of the tropical reservoirs flooding primary forest need to be reassessed since FF environments are usually overlooked.

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

Molecular Level Investigation of CH 4 and CO 2 Adsorption in Hydrated Calcium–Montmorillonite

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

Lee, Mal-Soon; McGrail, B. Peter; Rousseau, Roger

2017-11-17

We have studied the mechanism of intercalation and methane adsorption from a H2O/CH4/CO2 mixture on a prototypical shale component, Ca-montmorillonite. We employed ab initio molecular dynamics simulations at 323 K and 90 bar to obtain molecular level information of adsorption energetics, speciation, and structural and thermodynamic properties. Interaction of CH4 with surface Lewis acidic sites (Ca2+, surface OH) results in large induced dipoles (~1 D) that lead to relatively strong adsorption energies that level off once a full CH4 layer is formed. Intercalated CH4, also exhibits induced dipoles at low hydration levels, when the interaction with Ca2+ cations are lessmore » hindered. CO2 displaces CH4 in the coordination sphere of the cations (in the interlayer) or in the surface, thereby driving CH4 extraction. Our simulations indicate that there is a Goldilocks pressure range (~60-100 bar) where scCO2 –facilitated CH4 extraction will be maximized.« less

Factors controlling the photochemical degradation of methylmercury in coastal and oceanic waters

PubMed Central

DiMento, Brian P.; Mason, Robert P.

2018-01-01

Many studies have recognized abiotic photochemical degradation as an important sink of methylmercury (CH3Hg) in sunlit surface waters, but the rate-controlling factors remain poorly understood. The overall objective of this study was to improve our understanding of the relative importance of photochemical reactions in the degradation of CH3Hg in surface waters across a variety of marine ecosystems by extending the range of water types studied. Experiments were conducted using surface water collected from coastal sites in Delaware, New Jersey, Connecticut, and Maine, as well as offshore sites on the New England continental shelf break, the equatorial Pacific, and the Arctic Ocean. Filtered water amended with additional CH3Hg at environmentally relevant concentrations was allowed to equilibrate with natural ligands before being exposed to natural sunlight. Water quality parameters – salinity, dissolved organic carbon, and nitrate – were measured, and specific UV absorbance was calculated as a proxy for dissolved aromatic carbon content. Degradation rate constants (0.87–1.67 day−1) varied by a factor of two across all water types tested despite varying characteristics, and did not correlate with initial CH3Hg concentrations or other environmental parameters. The rate constants in terms of cumulative photon flux values were comparable to, but at the high end of, the range of values reported in other studies. Further experiments investigating the controlling parameters of the reaction observed little effect of nitrate and chloride, and potential for bromide involvement. The HydroLight radiative transfer model was used to compute solar irradiance with depth in three representative water bodies – coastal wetland, estuary, and open ocean – allowing for the determination of water column integrated rates. Methylmercury loss per year due to photodegradation was also modeled across a range of latitudes from the Arctic to the Equator in the three model water types, resulting in an estimated global demethylation rate of 25.3 Mmol yr−1. The loss of CH3Hg was greatest in the open ocean due to increased penetration of all wavelengths, especially the UV portion of the spectrum which has a greater ability to degrade CH3Hg. Overall, this study provides additional insights and information to better constrain the importance of photochemical degradation in the cycling of CH3Hg in marine surface waters and its transport from coastal waters to the open ocean. PMID:29515285

Climate change impact of livestock CH4 emission in India: Global temperature change potential (GTP) and surface temperature response.

PubMed

Kumari, Shilpi; Hiloidhari, Moonmoon; Kumari, Nisha; Naik, S N; Dahiya, R P

2018-01-01

Two climate metrics, Global surface Temperature Change Potential (GTP) and the Absolute GTP (AGTP) are used for studying the global surface temperature impact of CH 4 emission from livestock in India. The impact on global surface temperature is estimated for 20 and 100 year time frames due to CH 4 emission. The results show that the CH 4 emission from livestock, worked out to 15.3 Tg in 2012. In terms of climate metrics GTP of livestock-related CH 4 emission in India in 2012 were 1030 Tg CO 2 e (GTP 20 ) and 62 Tg CO 2 e (GTP 100 ) at the 20 and 100 year time horizon, respectively. The study also illustrates that livestock-related CH 4 emissions in India can cause a surface temperature increase of up to 0.7mK and 0.036mK over the 20 and 100 year time periods, respectively. The surface temperature response to a year of Indian livestock emission peaks at 0.9mK in the year 2021 (9 years after the time of emission). The AGTP gives important information in terms of temperature change due to annual CH 4 emissions, which is useful when comparing policies that address multiple gases. Copyright © 2017 Elsevier Inc. All rights reserved.

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.

Influence of increasing active-layer depth and continued permafrost degradation on carbon, water and energy fluxes over two forested permafrost landscapes in the Taiga Plains, NWT, Canada

NASA Astrophysics Data System (ADS)

Sonnentag, O.; Baltzer, J.; Chasmer, L. E.; Detto, M.; Marsh, P.; Quinton, W. L.

2012-12-01

Recent research suggests an increase in active-layer depth (ALD) in the continuous permafrost zone and degradation of the discontinuous permafrost zone into seasonally frozen. Increasing ALD and continued permafrost degradation will have far-reaching consequences for northern ecosystems including altered regional hydrology and the exposure of additional soil organic carbon (C) to microbial decomposition. These changes might cause positive or negative net feedbacks to the climate system by altering important land surface properties and/or by releasing stored soil organic C to the atmosphere as CO2 and/or CH4. Knowledge gaps exist regarding the links between increasing ALD and/or permafrost degradation, regional hydrology, vegetation composition and structure, land surface properties, and CO2 and CH4 sink-source strengths. The goal of our interdisciplinary project is to shed light on these links by providing a mechanistic understanding of permafrost-thawing consequences for hydrological, ecophysiological and biogeochemical processes at two forested permafrost landscapes in the Taiga Plains, NWT, Canada: Scotty Creek and Havikpak Creek in the discontinuous and in the continuous permafrost zones, respectively (Fig.). The sites will be equipped with identical sets of instrumentation (start: 2013), to measure landscape-scale net exchanges of CO2, CH4, water and energy with the eddy covariance technique. These measurements will be complemented by repeated surveys of surface and frost table topography and vegetation, by land cover-type specific fluxes of CO2 and CH4 measured with a static chamber technique, and by remote sensing-based footprint analysis. With this research we will address the following questions: What is the net effect of permafrost thawing-induced biophysical and biogeochemical feedbacks to the climate system? How do these two different types of feedback differ between the discontinuous and continuous permafrost zones? Is the decrease (increase) in net CO2 (CH4) exchange measured over mostly tundra sites in the continuous permafrost zone generalizable to forested landscapes in both the discontinuous and continuous permafrost zones? With this contribution, we report on the project status, present its objectives and hypotheses, and outline its timeline and sampling design.

Utilizing patch and site level greenhouse-gas concentration measurements in tandem with the prognostic model, ecosys

NASA Astrophysics Data System (ADS)

Morin, T. H.; Rey Sanchez, C.; Bohrer, G.; Riley, W. J.; Angle, J.; Mekonnen, Z. A.; Stefanik, K. C.; Wrighton, K. C.

2016-12-01

Estimates of wetland greenhouse gas (GHG) budgets currently have large uncertainties. While wetlands are the largest source of natural methane (CH4) emissions worldwide, they are also important carbon dioxide (CO2) sinks. Determining the GHG budget of a wetland is challenging, particularly because wetlands have intrinsically temporally and spatially heterogeneous land cover patterns and complex dynamics of CH4 production and emissions. These issues pose challenges to both measuring and modeling GHG budgets from wetlands. To improve wetland GHG flux predictability, we utilized the ecosys model to predict CH4 fluxes from a natural temperate estuarine wetland in northern Ohio. Multiple patches of terrain (that included Typha spp. and Nelumbo lutea) were represented as separate grid cells in the model. Cells were initialized with measured values but were allowed to dynamically evolve in response to meteorological, hydrological, and thermodynamic conditions. Trace gas surface emissions were predicted as the end result of microbial activity, physical transport, and plant processes. Corresponding to each model gridcell, measurements of dissolved gas concentrations were conducted with pore-water dialysis samplers (peepers). The peeper measurements were taken via a series of tubes, providing an undisturbed observation of the pore water concentrations of in situ dissolved gases along a vertical gradient. Non-steady state chambers and a flux tower provided both patch level and integrated site-level fluxes of CO2 and CH4. New Typha chambers were also developed to enclose entire plants and segregate the plant fluxes from soil/water fluxes. We expect ecosys to predict the seasonal and diurnal fluxes of CH4 from within each land cover type and to resolve where CH4 is generated within the soil column and its transmission mechanisms. We demonstrate the need for detailed information at both the patch and site level when using models to predict whole wetland ecosystem-scale GHG budgets.

Thermokarst lake methanogenesis along a complete talik profile

USGS Publications Warehouse

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

2015-01-01

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

Physical State and Distribution of Materials at the Surface of Pluto from New Horizons LEISA Imaging Spectrometer

NASA Technical Reports Server (NTRS)

Schmitt, B.; Philippe, S.; Grundy, W. M.; Reuter, D. C.; Cote, R.; Quirico, E.; Protopappa, S.; Young, L. A.; Binzel, R. P.; Cook, J. C.;

Physical state and distribution of materials at the surface of Pluto from New Horizons LEISA imaging spectrometer

NASA Astrophysics Data System (ADS)

Schmitt, B.; Philippe, S.; Grundy, W. M.; Reuter, D. C.; Côte, R.; Quirico, E.; Protopapa, S.; Young, L. A.; Binzel, R. P.; Cook, J. C.; Cruikshank, D. P.; Dalle Ore, C. M.; Earle, A. M.; Ennico, K.; Howett, C. J. A.; Jennings, D. E.; Linscott, I. R.; Lunsford, A. W.; Olkin, C. B.; Parker, A. H.; Parker, J. Wm.; Singer, K. N.; Spencer, J. R.; Stansberry, J. A.; Stern, S. A.; Tsang, C. C. C.; Verbiscer, A. J.; Weaver, H. A.; New Horizons Science Team

2017-05-01

From Earth based observations Pluto is known to be the host of N2, CH4 and CO ices and also a dark red material. Very limited spatial distribution information is available from rotational visible and near-infrared spectral curves obtained from hemispheric measurements. In July 2015 the New Horizons spacecraft reached Pluto and its satellite system and recorded a large set of data. The LEISA spectro-imager of the RALPH instruments are dedicated to the study of the composition and physical state of the materials composing the surface. In this paper we report a study of the distribution and physical state of the ices and non-ice materials on Pluto's illuminated surface and their mode and degree of mixing. Principal Component analysis as well as various specific spectral indicators and correlation plots are used on the first set of 2 high resolution spectro-images from the LEISA instrument covering the whole illuminated face of Pluto at the time of the New Horizons encounter. Qualitative distribution maps have been obtained for the 4 main condensed molecules, N2, CH4, CO, H2O as well as for the visible-dark red material. Based on specific spectral indicators, using either the strength or the position of absorption bands, these 4 molecules are found to indicate the presence of 3 different types of ices: N2-rich:CH4:CO ices, CH4-rich(:CO:N2?) ices and H2O ice. The mixing lines between these ices and with the dark red material are studied using scatter plots between the various spectral indicators. CH4 is mixed at the molecular level with N2, most probably also with CO, thus forming a ternary molecular mixture that follows its phase diagram with low solubility limits. The occurrence of a N2-rich - CH4-rich ices mixing line associated with a progressive decrease of the CO/CH4 ratio tells us that a fractionation sublimation sequence transforms one type of ice to the other forming either a N2-rich - CH4-rich binary mixture at the surface or an upper CH4-rich ice crust that may hide the N2-rich ice below. The strong CH4-rich - H2O mixing line witnesses the subsequent sublimation of the CH4-rich ice lag left behind by the N2:CO sublimation (N spring-summer), or a direct condensation of CH4 ice on the cold H2O ice (S autumn). The weak mixing line between CH4-containing ices and the dark red material and the very sharp spatial transitions between these ices and this non-volatile material are probably due to thermal incompatibility. Finally the occurrence of a H2O ice - red material mixing line advocates for a spatial mixing of the red material covering H2O ice, with possibly a small amount intimately mixed in water ice. From this analysis of the different materials distribution and their relative mixing lines, H2O ice appears to be the substratum on which other ices condense or non-volatile organic material is deposited from the atmosphere. N2-rich ices seem to evolve to CH4-dominated ices, possibly still containing traces of CO and N2, as N2 and CO sublimate away. The spatial distribution of these materials is very complex. The high spatial definition of all these composition maps, as well as those at even higher resolution that will be soon available, will allow us to compare them with Pluto's geologic features observed by LORRI panchromatic and MVIC multispectral imagers to better understand the geophysical processes in action at the surface of this astonishingly active frozen world.

Organics and other molecules in the surfaces of Callisto and Ganymede

USGS Publications Warehouse

McCord, T.B.; Carlson, R.W.; Smythe, W.D.; Hansen, G.B.; Clark, R.N.; Hibbitts, C.A.; Fanale, F.P.; Granahan, J.C.; Segura, M.; Matson, D.L.; Johnson, T.V.; Martin, P.D.

1997-01-01

Five absorption features are reported at wavelengths of 3.4, 3.88, 4.05, 4.25, and 4.57 micrometers in the surface materials of the Galilean satellites Callisto and Ganymede from analysis of reflectance spectra returned by the Galileo mission near-infrared mapping spectrometer. Candidate materials include CO2, organic materials (such as tholins containing C???N and C-H), SO2, and compounds containing an SH-functional group; CO2, SO2, and perhaps cyanogen [(CN)2] may be present within the surface material itself as collections of a few molecules each. The spectra indicate that the primary surface constituents are water ice and hydrated minerals.

Ultrafast photochemistry of methyl hydroperoxide on ice particles

PubMed Central

Kamboures, M. A.; Nizkorodov, S. A.; Gerber, R. B.

2009-01-01

Simulations show that photodissociation of methyl hydroperoxide, CH3OOH, on water clusters produces a surprisingly wide range of products on a subpicosecond time scale, pointing to the possibility of complex photodegradation pathways for organic peroxides on aerosols and water droplets. Dynamics are computed at several excitation energies at 50 K using a semiempirical PM3 potential surface. CH3OOH is found to prefer the exterior of the cluster, with the CH3O group sticking out and the OH group immersed within the cluster. At atmospherically relevant photodissociation wavelengths the OH and CH3O photofragments remain at the surface of the cluster or embedded within it. However, none of the 25 completed trajectories carried out at the atmospherically relevant photodissociation energies led to recombination of OH and CH3O to form CH3OOH. Within the limited statistics of the available trajectories the predicted yield for the recombination is zero. Instead, various reactions involving the initial fragments and water promptly form a wide range of stable molecular products such as CH2O, H2O, H2, CO, CH3OH, and H2O2. PMID:19846778

Evolution of CO2, CH4, and OCS abundances relative to H2O in the coma of comet 67P around perihelion from Rosetta/VIRTIS-H observations

NASA Astrophysics Data System (ADS)

Bockelée-Morvan, Dominique; Crovisier, J.; Erard, S.; Capaccioni, F.; Leyrat, C.; Filacchione, G.; Drossart, P.; Encrenaz, T.; Biver, N.; de Sanctis, M.-C.; Schmitt, B.; Kührt, E.; Capria, M.-T.; Combes, M.; Combi, M.; Fougere, N.; Arnold, G.; Fink, U.; Ip, W.; Migliorini, A.; Piccioni, G.; Tozzi, G.

2016-11-01

Infrared observations of the coma of 67P/Churyumov-Gerasimenko were carried out from 2015 July to September, I.e. around perihelion (2015 August 13), with the high-resolution channel of the Visible and Infrared Thermal Imaging Spectrometer instrument onboard Rosetta. We present the analysis of fluorescence emission lines of H2O, CO2, 13CO2, OCS, and CH4 detected in limb sounding with the field of view at 2.7-5 km from the comet centre. Measurements are sampling outgassing from the illuminated Southern hemisphere, as revealed by H2O and CO2 raster maps, which show anisotropic distributions, aligned along the projected rotation axis. An abrupt increase of water production is observed 6 d after perihelion. In the meantime, CO2, CH4, and OCS abundances relative to water increased by a factor of 2 to reach mean values of 32, 0.47, and 0.18 per cent, respectively, averaging post-perihelion data. We interpret these changes as resulting from the erosion of volatile-poor surface layers. Sustained dust ablation due to the sublimation of water ice maintained volatile-rich layers near the surface until at least the end of the considered period, as expected for low thermal inertia surface layers. The large abundance measured for CO2 should be representative of the 67P nucleus original composition, and indicates that 67P is a CO2-rich comet. Comparison with abundance ratios measured in the Northern hemisphere shows that seasons play an important role in comet outgassing. The low CO2/H2O values measured above the illuminated Northern hemisphere are not original, but the result of the devolatilization of the uppermost layers.

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.

Role of regional wetland emissions in atmospheric methane variability

NASA Astrophysics Data System (ADS)

McNorton, J.; Gloor, E.; Wilson, C.; Hayman, G. D.; Gedney, N.; Comyn-Platt, E.; Marthews, T.; Parker, R. J.; Boesch, H.; Chipperfield, M. P.

2016-11-01

Atmospheric methane (CH4) accounts for 20% of the total direct anthropogenic radiative forcing by long-lived greenhouse gases. Surface observations show a pause (1999-2006) followed by a resumption in CH4 growth, which remain largely unexplained. Using a land surface model, we estimate wetland CH4 emissions from 1993 to 2014 and study the regional contributions to changes in atmospheric CH4. Atmospheric model simulations using these emissions, together with other sources, compare well with surface and satellite CH4 data. Modeled global wetland emissions vary by ±3%/yr (σ = 4.8 Tg), mainly due to precipitation-induced changes in wetland area, but the integrated effect makes only a small contribution to the pause in CH4 growth from 1999 to 2006. Increasing temperature, which increases wetland area, drives a long-term trend in wetland CH4 emissions of +0.2%/yr (1999 to 2014). The increased growth post-2006 was partly caused by increased wetland emissions (+3%), mainly from Tropical Asia, Southern Africa, and Australia.

Carbon and hydrogen isotopic systematics of dissolved methane in small seasonally ice-covered lakes near the margin of the Greenland ice sheet

NASA Astrophysics Data System (ADS)

Cadieux, S. B.; White, J. R.; Pratt, L. M.; Peng, Y.; Young, S. A.

2013-12-01

Northern lakes contribute from 6-16% of annual methane inputs to Earth's atmosphere, yet little is known about the seasonal biogeochemistry of CH4 cycling, particularly for lakes in the Arctic. Studies during ice-free conditions have been conducted in Alaskan, Swedish and Siberian lakes. However, there is little information on CH4 cycling under ice-covered conditions, and few stable isotopic measurements, which can help elucidate production and consumption pathways. In order to better understand methane dynamics of ice-covered Arctic lakes, 4 small lakes (surface area <1 km2) within a narrow valley extending from the Russells Glacier to Søndre Strømfjord in Southwestern Greenland were examined during summer stratification and winter ice-cover. Lakes in the study area are ice-covered from mid-September to mid-June. In both seasons, variations in the concentrations and isotopic composition of methane with depth were related to redox fluctuations. During late winter under~2 m of ice, the entire water column was anoxic with wide variation in methane concentrationsand isotopic composition from lake to lake. In three of the lakes, CH4 concentrations and δ13C were relatively stable over the depth of the water column, averaging from 120 to 480μM, with δ13CH4 values from -56‰ to -66‰, respectively. Methane concentrations in the other lake increased with depth from <1 μM below the ice to 800 μM at the sediment/water interface, while δ13C decreased by 30‰ from -30‰ to -70‰ over this depth. In all the lakes, δ13C of sediment porewater was lighter than the overlying water by at least 10‰. The δD-CH4 in the water column ranged from -370‰ to -50‰, exhibiting covariance with δ13C consistent with significant methanotrophic activity. In the sediment, δD-CH4 values ranged from -330‰ to -275‰, and were inversely correlated with δ13C. We will present detailed information on redox dynamics as a controlling factor in methane cycling, and explore the effects of differing microbial communities and carbon supply. Our study suggests that shallow lakes in continuous permafrost landscapes of the Arctic develop distinct methane cycling dynamics despite their close proximity.

Effects of permafrost thaw on CO2 and CH4 exchange in a western Alaska peatland chronosequence

USGS Publications Warehouse

Carmel E. Johnston,; Stephanie A. Ewing,; Harden, Jennifer W.; Ruth K. Varner,; Wickland, Kimberly P.; Koch, Joshua C.; Fuller, Christopher C.; Manies, Kristen L.; M. Torre Jorgenson,

2014-01-01

Permafrost soils store over half of global soil carbon (C), and northern frozen peatlands store about 10% of global permafrost C. With thaw, inundation of high latitude lowland peatlands typically increases the surface-atmosphere flux of methane (CH4), a potent greenhouse gas. To examine the effects of lowland permafrost thaw over millennial timescales, we measured carbon dioxide (CO2) and CH4 exchange along sites that constitute a ~1000 yr thaw chronosequence of thermokarst collapse bogs and adjacent fen locations at Innoko Flats Wildlife Refuge in western Alaska. Peak CH4exchange in July (123 ± 71 mg CH4–C m−2 d−1) was observed in features that have been thawed for 30 to 70 (<100) yr, where soils were warmer than at more recently thawed sites (14 to 21 yr; emitting 1.37 ± 0.67 mg CH4–C m−2 d−1 in July) and had shallower water tables than at older sites (200 to 1400 yr; emitting 6.55 ± 2.23 mg CH4–C m−2 d−1 in July). Carbon lost via CH4 efflux during the growing season at these intermediate age sites was 8% of uptake by net ecosystem exchange. Our results provide evidence that CH4 emissions following lowland permafrost thaw are enhanced over decadal time scales, but limited over millennia. Over larger spatial scales, adjacent fen systems may contribute sustained CH4 emission, CO2 uptake, and DOC export. We argue that over timescales of decades to centuries, thaw features in high-latitude lowland peatlands, particularly those developed on poorly drained mineral substrates, are a key locus of elevated CH4 emission to the atmosphere that must be considered for a complete understanding of high latitude CH4 dynamics.

[Impacts of meteorological factors on atmospheric methane mole fractions in the background area of Yangtze River delta].

PubMed

Pu, Jing-Jiao; Xu, Hong-Hui; Gu, Jun-Qiang; Ma, Qian-Li; Fang, Shuang-Xi; Zhou, Ling-Xi

2013-03-01

Impacts of surface wind direction, surface wind speed, surface air temperature and sunshine hours on the CH4 concentration at Lin'an regional atmospheric background station were studied based on the results from Jan. 2009 to Dec. 2011. The results revealed that the diurnal variation of atmospheric CH4 concentration presented a single-peak curve at Lin'an regional background station. The diurnal amplitude varied from 19.0 x 10(-9) to 74.7 x 10(-9), with the lowest value observed in the afternoon and the highest at dawn. The monthly mean CH4 concentrations varied from 1955.7 x 10(-9) to 2036.2 x 10(-9), with the highest concentration observed in autumn and the lowest in spring. The wind directions NE-SSE could induce higher CH4 concentrations while SW-NNW wind directions had negative effects on the observed results. The CH4 concentration turned out to be lower with higher surface wind speed. With the increase of surface air temperature or sunshine hours, the CH4 concentration went up first till reaching a peak, and then decreased.

Ecosystem CO2 and CH4 exchange in a mixed tundra and a fen within a hydrologically diverse Arctic landscape: 1. Modeling versus measurements

NASA Astrophysics Data System (ADS)

Grant, R. F.; Humphreys, E. R.; Lafleur, P. M.

2015-07-01

CO2 and CH4 exchange are strongly affected by hydrology in landscapes underlain by permafrost. Hypotheses for these effects in the model ecosys were tested by comparing modeled CO2 and CH4 exchange with CO2 fluxes measured by eddy covariance from 2006 to 2009, and with CH4 fluxes measured with surface chambers in 2008, along a topographic gradient at Daring Lake, NWT. In an upland tundra, rises in net CO2 uptake in warmer years were constrained by declines in CO2 influxes when vapor pressure deficits (D) exceeded 1.5 kPa and by rises in CO2 effluxes with greater active layer depth. Consequently, net CO2 uptake rose little with warming. In a lowland fen, CO2 influxes declined less with D and CO2 effluxes rose less with warming, so that rises in net CO2 uptake were greater than those in the tundra. Greater declines in CO2 influxes with warming in the tundra were modeled from greater soil-plant-atmosphere water potential gradients that developed under higher D in drained upland soil, and smaller rises in CO2 effluxes with warming in the fen were modeled from O2 constraints to heterotrophic and belowground autotrophic respiration from a shallow water table in poorly drained lowland soil. CH4 exchange modeled during July and August indicated very small influxes in the tundra and larger effluxes characterized by afternoon emission events caused by degassing of warming soil in the fen. Emissions of CH4 modeled from degassing during soil freezing in October-November contributed about one third of the annual total.

A Rapid One-Step Process for Fabrication of Biomimetic Superhydrophobic Surfaces by Pulse Electrodeposition

PubMed Central

Jiang, Shuzhen; Guo, Zhongning; Liu, Guixian; Gyimah, Glenn Kwabena; Li, Xiaoying; Dong, Hanshan

2017-01-01

Inspired by some typical plants such as lotus leaves, superhydrophobic surfaces are commonly prepared by a combination of low surface energy materials and hierarchical micro/nano structures. In this work, superhydrophobic surfaces on copper substrates were prepared by a rapid, facile one-step pulse electrodepositing process, with different duty ratios in an electrolyte containing lanthanum chloride (LaCl3·6H2O), myristic acid (CH3(CH2)12COOH), and ethanol. The equivalent electrolytic time was only 10 min. The surface morphology, chemical composition and superhydrophobic property of the pulse electrodeposited surfaces were fully investigated with SEM, EDX, XRD, contact angle meter and time-lapse photographs of water droplets bouncing method. The results show that the as-prepared surfaces have micro/nano dual scale structures mainly consisting of La[CH3(CH2)12COO]3 crystals. The maximum water contact angle (WCA) is about 160.9°, and the corresponding sliding angle is about 5°. This method is time-saving and can be easily extended to other conductive materials, having a great potential for future applications. PMID:29068427

Flux to the atmosphere of CH4 and CO2 from wetland ponds on the Hudson Bay lowlands (HBLs)

NASA Technical Reports Server (NTRS)

Hamilton, J. David; Kelly, Carol A.; Rudd, John W. M.; Hesslein, Raymond H.; Roulet, Nigel T.

1994-01-01

Ponds on peatlands of the Hudson Bay lowlands (HBLs) are complex ecosystems in which the fluxes to the atmosphere of CH4 and CO2 were controlled by interacting physical and biological factors. This resulted in strong diel variations of both dissolved gas concentrations and gas fluxes to the atmosphere, necessitating frequent sampling on a 24-hour schedule to enable accurate estimates of daily fluxes. Ponds at three sites on the HBL were constant net sources of CH4 and CO2 to the atmosphere at mean rates of 110-180 mg CH4 m(exp -2)/d and 3700-11,000 mg CO2 m(exp -2)/d. Rates peaked in August and September. For CH4 the pond fluxes were 3-30 times higher than adjacent vegetated surfaces. For CO2 the net pond fluxes were similar in magnitude to the vegetated fluxes but the direction of the flux was opposite, toward atmosphere. Even though ponds cover only 8-12% of the HBL area, they accounted for 30% of its total CH4 flux to the atmosphere. There is some circumstantial evidence that the ponds are being formed by decomposition of the underlying peat and that this decomposition is being stimulated by the activity of N2 fixing cyanobacteria that grow in mats at the peat-water interface. The fact that the gas fluxes from the ponds were so different from the surrounding vegetated surfaces means that any change in the ratio of pond to vegetated area, as may occur in response to climate change, would affect the total HBL fluxes.

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

PubMed

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

2010-01-01

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

Sulfate-enhanced catalytic destruction of 1,1,1-trichlorethane over Pt(111).

PubMed

Lee, Adam F; Wilson, Karen

2006-01-19

The catalytic destruction of 1,1,1-trichloroethane (TCA) over model sulfated Pt(111) surfaces has been investigated by fast X-ray photoelectron spectroscopy and mass spectrometry. TCA adsorbs molecularly over SO4 precovered Pt(111) at 100 K, with a saturation coverage of 0.4 monolayer (ML) comparable to that on the bare surface. Surface crowding perturbs both TCA and SO4 species within the mixed adlayer, evidenced by strong, coverage-dependent C 1s and Cl and S 2p core-level shifts. TCA undergoes complete dechlorination above 170 K, accompanied by C-C bond cleavage to form surface CH3, CO, and Cl moieties. These in turn react between 170 and 350 K to evolve gaseous CO2, C2H6, and H2O. Subsequent CH3 dehydrogenation and combustion occurs between 350 and 450 K, again liberating CO2 and water. Combustion is accompanied by SO4 reduction, with the coincident evolution of gas phase SO2 and CO2 suggesting the formation of a CO-SOx surface complex. Reactively formed HCl desorbs in a single state at 400 K. Only trace (<0.06 ML) residual atomic carbon and chlorine remain on the surface by 500 K.

Large CH4 production fueled by autochthonous OC in an anoxic sediment

NASA Astrophysics Data System (ADS)

Grasset, Charlotte; Mendonça, Raquel; Villamor Saucedo, Gabriella; Sobek, Sebastian

2017-04-01

River damming and human-induced eutrophication both affect river and lake functioning, increase organic carbon (OC) sedimentation rates and generate anoxic conditions in bottom waters. Under these conditions, OC in sediments is decomposed into CO2 and CH4, a high potential greenhouse gas. It has been shown that the decomposition of land-derived (allochthonous) OC is inhibited at anoxic conditions, compared to OC internally produced (autochthonous). However, the overall extent and end products (CO2 or CH4) of anoxic decomposition remain poorly known for different types of OC, making it difficult to judge the effect of river damming and eutrophication on greenhouse gas emissions from inland waters. We incubated different types of allochthonous OC (terrestrial plants) and autochthonous OC (phytoplankton and aquatic vascular plants) in an anoxic sediment during 130 days. We aimed to test 1) if this addition of relatively fresh OC resulted in an increase of CH4 production and 2) if autochthonous OC would produce more CH4 than allochthonous OC. We assessed the contribution to CH4 production of the different OC sources (i.e. sediment or added OC) with stable isotope measurements. We found that the addition of relatively fresh OC greatly increased CH4 production. Autochthonous OC generally produced more CH4 than allochthonous OC, but the overall extent of CH4 production was highly variable between the different autochthonous OC types. The d13C-CH4 measurements indicated that CH4 originated exclusively from the added OC. We conclude that the production of CH4 is likely to to be high in eutrophic as well as in artificial lakes, especially when these systems have anoxic bottom waters and high internal primary productivity and thus a high supply of autochthonous OC to the sediment. The current expansion of reservoir construction in concert with almost globally prevalent anthropogenic eutrophication are therefore likely to increase CH4 production in inland waters.

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.

Sensitivity of subtropical wetland CH4 flux predictions to inundation parameterizations: A case study over the southeastern U.S.

NASA Astrophysics Data System (ADS)

Resovsky, A.; Yang, Z. L.

2015-12-01

Methane (CH4) is an important greenhouse gas, and the predominant source of natural atmospheric CH4 globally is its production in wetland soils. Wetlands and marshes in the southeastern U.S. comprise over 40 million acres of land and thus represent a significant component of the global climate system. CH4 contributions from these and other subtropical systems remain difficult to quantify, however. Existing field measurements are lacking in both spatial and temporal coverage, inhibiting efforts to produce regional estimates through upscaling. Top-down constraints on emissions have been generated using satellite remote sensing retrievals of column CH4 (e.g., Frankenberg et al., 2005, 2008, Bergamaschi et al., 2007, 2013, Bloom et al., 2010, Wecht et al., 2014), but such approaches typically require preexisting emissions estimates to discern individual source contributions. Land Surface Models (LSMs) have the potential to produce realistic results, but such predictions rely on accurate representations of sub-grid scale processes responsible for emissions. Since net fluxes are governed by complex interactions between local environmental and biogeochemical factors including water table position, soil temperature, soil substrate availability and vegetation type, reliable flux simulations depend not only upon how such processes are resolved but how skillfully the land surface state itself is predicted by a given model. Here, we examine simulations using CLM4Me, a CH4 biogeochemistry model run within CESM, and compare results to recently compiled flux estimations from satellite remote sensing data. We then examine how seasonal CH4 flux simulations in CLM4Me are affected by alternative parameterizations of inundated land fraction. A global inundation dataset is calculated using DYPTOP, a newly-developed TOPMODEL implementation specifically designed to simulate the dynamics of wetland spatial distribution. We find evidence that DYPTOP may improve wetland CH4 flux predictions over subtropical regions in CLM4.5, and propose a computationally efficient framework for fine-scale tuning of this scheme to more accurately represent the role of subtropical and temperate wetlands in global climate projections.

Eddy Covariance Measurements of CO2 and CH4 before and after a Wetland Restoration, Tomago NSW, Australia: A Blue Carbon Investigation

NASA Astrophysics Data System (ADS)

Macsween, K.; Edwards, G. C.; Saintilan, N.; Negandhi, K.; Kelleway, J.; Rogers, K.; Safari, D.; Tewari, K.

2017-12-01

Australia holds 33% of the world's tidal marsh area. Scientific and policy interest has recently turned to the value of coastal wetlands for carbon sequestration ("Blue Carbon"). These coastal mangrove and saltmarsh restorations are now at the forefront of developments for ecosystem-based climate change mitigation and adaptation. The Tomago wetland located near Newcastle, NSW, Australia is undergoing rehabilitation restoring tidal inundation to a previously leveed floodplain. It is hypothesised that the restoration of tidal inundation would convert a methane source into a sink as a consequence of soil salinization. At Tomago a Before-After-Control-Impact experimental design has been undertaken to measure the impact of tidal reinstatement on wetland floodplain accretion and gas flux. Prior to tidal reinstatement, eddy covariance towers (CO2 and CH4) were installed as well as surface elevation tables, and continuous water level and water quality loggers. Hydrodynamic modelling identified the sites within the wetland predicted to remain disconnected from tidal flow. Concurrent with the micrometeorological energy balance and gas flux measurements environmental variables such as soil water salinity, inundation regime, and soil microbial communities were undertaken. This comprehensive set of data facilitated the predictive power to explain variation in greenhouse gas flux. Results showed the average CO2 and CH4 fluxes before tidal reinstatement to be -22.70 and 0.25 mg m-2 hr-1 respectively and after tidal reinstatement to be 6.41 and 0.16 mg m-2 hr-1. Over the year the average CO2 and CH4 fluxes were -3.29 and 0.20 mg m-2 hr-1. Results showed CO2 is driving the system in terms of net carbon. Two extreme precipitation events during the measurement period had significant influence on the carbon pool. It was shown that it is possible to regulate CH4 flux through management of water and salinity levels.

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

Rincón, R., E-mail: rocio.rincon@emt.inrs.ca, E-mail: chaker@emt.inrs.ca; Matos, J. de; Chaker, M., E-mail: rocio.rincon@emt.inrs.ca, E-mail: chaker@emt.inrs.ca

An Ar/CH{sub 4} atmospheric pressure dielectric barrier discharge (AP-DBD) was used to synthesize sticky hydrophobic diamond-like carbon (DLC) films on glass surface. The film is formed with plasma treatment duration shorter than 30 s, and water contact angles larger than 90° together with contact angle hysteresis larger than 10° can be achieved. According to Fourier transform infrared spectroscopy and atomic force microscopy analysis, hydrocarbon functional groups are created on the glass substrate, producing coatings with low surface energy (∼35 mJ m{sup −2}) with no modification of the surface roughness. To infer the plasma processes leading to the formation of low energymore » DLC surfaces, optical emission spectroscopy was used. From the results, a direct relationship between the CH species present in the plasma and the carbon concentration in the hydrophobic layer was found, which suggests that the CH species are the precursors of DLC film growth. Additionally, the plasma gas temperature was measured to be below 350 K which highlights the suitability of using AP-DBD to treat thermo-sensitive surfaces.« less

Methane emissions from boreal peatlands in a changing climate: Quantifying the sensitivity of methane fluxes to experimental manipulations of water table and soil temperature regimes in an Alaskan boreal fen

NASA Astrophysics Data System (ADS)

Treat, C. C.; Turetsky, M.; Harden, J.; McGuire, A.

2006-12-01

Peatlands cover only 3-5 % of the world's land surface but store 30 % of the world's soil carbon (C) pool. Peatlands currently are thought to function globally as a net sink for atmospheric CO2, sequestering approximately 76 Tg (1012 g) C yr-1. However, peatlands also function as a net source of atmospheric CH4. Approximately 25% of the 270 Tg CH4 yr-1 emitted from natural sources are emitted from northern wetlands. Methane production (methanogenesis) and consumption (methane oxidation) in peatlands are sensitive to both fluctuations in soil moisture and temperature. Boreal regions already are experiencing rapid changes in climate, including longer and drier growing seasons and the degradation of permafrost. Changes in peat environments in response to these climate changes could have significant implications for CH4 emissions to the atmosphere, and thus the radiative forcing of high latitude regions. In 2005, we initiated a large scale in situ climate experiment in a moderately rich fen near the Bonanza Creek LTER site in central Alaska (APEX: www.apex.msu.edu). The goal of our project is to understand vegetation and C cycling processes under altered water table and soil thermal regimes. We established three water table plots (control, raised, lowered), each about 120 m2 in area, using drainage ditches to lower the water table by 5-10 cm and solar powered pumps to raise the water table by about 5-15 cm. Within each water table plot, we constructed replicate open top chambers (OTCs) to passively increase surface temperatures by about 1 ° C. We used static chambers and gas chromatography to quantify methane fluxes at each water table x soil warming plot through the growing seasons of 2005 and 2006. Additionally, we quantified seasonal CH4 fluxes along an adjacent moisture gradient that included four distinct soil moisture and vegetation zones, including a moderately rich fen (APEX site), an emergent macrophyte marsh, a shrubby permafrost fen, and a black spruce permafrost forest. Our results thus far show that methane fluxes varied by a warming x water table interaction across our experimental treatments (Proc Mixed SAS Repeated Measures ANOVA; F2,8=4.07; p=0.05), with the largest methane fluxes in the warm, wet peatland plots and the lowest methane fluxes in the unwarmed, dry peatland plots. Sites along the moisture gradient transitioned from methane sources in the rich fen site (APEX plots) to small sinks of CH4 in the permafrost forest under drying soil moisture conditions. Our soil climate manipulations allow us to quantify interactions among biogeophysical variables that control CH4 emissions from peatlands. Our coupled experimental and gradient based measurements allow us to explore controls on microbial populations and methane emissions across a wider range of terrestrial boreal environments. This work so far shows that methane cycling in interior Alaskan ecosystems is extremely sensitive to soil climate conditions, and that the fate of methane emissions from high latitudes will be affected primarily by changes in precipitation and soil drainage that control water table position in peatlands and permafrost ecosystems.

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

NASA Astrophysics Data System (ADS)

Zhao, Yan; Yu, Qingchun

2018-01-01

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

Stable Aluminum Metal-Organic Frameworks (Al-MOFs) for Balanced CO2 and Water Selectivity.

PubMed

Li, Haiwei; Feng, Xiao; Ma, Dou; Zhang, Mengxi; Zhang, Yuanyuan; Liu, Yi; Zhang, Jinwei; Wang, Bo

2018-01-31

Three new Al-MOFs in the formation of [Al 4 (OH) 2 (OCH 3 ) 4 (OH-BDC) 3 ]·xH 2 O (BIT-72), [Al 4 (OH) 2 (OCH 3 ) 4 (CH 3 -BDC) 3 ]·xH 2 O (BIT-73) and {Al 4 (OH) 2 (OCH 3 ) 4 [(CH 3 ) 2 -BDC] 3 }·xH 2 O (BIT-74) have been synthesized by assembling Al 3+ ion with terephthalic acid ions decorated with monohydroxyl, monomethyl or dimethyl groups, respectively. All of these three MOFs exhibit high stability in boiling water and acidic conditions. Among them, BIT-72 shows the highest surface area of 1618 m 2 ·g -1 and IAST CO 2 /N 2 selectivity of 48, while BIT-73 and BIT-74 present moderate IAST CO 2 /N 2 selectivity and much lower H 2 O capacity below P/P 0 = 0.3. The high CO 2 /N 2 selectivity together with alleviative H 2 O sorption at low water relative pressure may provide promising potential in postcombustion CO 2 capture.

Estimating wetland methane emissions from the northern high latitudes from 1990 to 2009 using artificial neural networks

NASA Astrophysics Data System (ADS)

Zhu, Xudong; Zhuang, Qianlai; Qin, Zhangcai; Glagolev, Mikhail; Song, Lulu

2013-04-01

Methane (CH4) emissions from wetland ecosystems in nothern high latitudes provide a potentially positive feedback to global climate warming. Large uncertainties still remain in estimating wetland CH4 emisions at regional scales. Here we develop a statistical model of CH4 emissions using an artificial neural network (ANN) approach and field observations of CH4 fluxes. Six explanatory variables (air temperature, precipitation, water table depth, soil organic carbon, soil total porosity, and soil pH) are included in the development of ANN models, which are then extrapolated to the northern high latitudes to estimate monthly CH4 emissions from 1990 to 2009. We estimate that the annual wetland CH4 source from the northern high latitudes (north of 45°N) is 48.7 Tg CH4 yr-1 (1 Tg = 1012 g) with an uncertainty range of 44.0 53.7 Tg CH4 yr-1. The estimated wetland CH4 emissions show a large spatial variability over the northern high latitudes, due to variations in hydrology, climate, and soil conditions. Significant interannual and seasonal variations of wetland CH4 emissions exist in the past 2 decades, and the emissions in this period are most sensitive to variations in water table position. To improve future assessment of wetland CH4 dynamics in this region, research priorities should be directed to better characterizing hydrological processes of wetlands, including temporal dynamics of water table position and spatial dynamics of wetland areas.

Remote-Raman and Micro-Raman Studies of Solid CO2, CH4, Gas Hydrates and Ice

NASA Technical Reports Server (NTRS)

Sharma, S. K.; Misra, A. K.; Lucey, P. G.; Exarhos, G. J.; Windisch, C. F., Jr.

2004-01-01

It is well known that on Mars CO2 is the principal constituent of the thin atmosphere and on a seasonal basis CO2 snow and frost coats the polar caps. Also over 25% of the Martian atmosphere freezes out and sublimes again each year. The Mars Odyssey Emission Imaging system (THEMIS) has discovered water ice exposed near the edge of Mars southern perennials cap. In recent years, it has been suggested that in Martian subsurface CO2 may exist as gas hydrate (8CO2 + 44 H2O) with melting temperature of 10C. Since the crust of Mars has been stable for enough time there is also a possibility that methane formed by magmatic processes and/or as a byproduct of anaerobic deep biosphere activity to have raised toward the planet s surface. This methane would have been captured and stored as methane hydrate, which concentrates methane and water. Determination of abundance and distribution of these ices on the surface and in the near surface are of fundamental importance for understanding Martian atmosphere, and for future exploration of Mars. In this work, we have evaluated feasibility of using remote Raman and micro-Raman spectroscopy as potential nondestructive and non-contact techniques for detecting solid CO2, CH4 gas, and gas hydrates as well as water-ice on planetary surfaces.

Measuring the Impact of Rising CO2 and CH4 on the Surface Energy Balance

NASA Astrophysics Data System (ADS)

Feldman, D.; Collins, W.; Biraud, S.; Turner, D. D.; Mlawer, E. J.; Gero, P. J.; Xie, S.; Shippert, T.; Torn, M. S.

2015-12-01

We use observations at the North Slope of Alaska (NSA) and Southern Great Plains (SGP) ARM sites to improve understanding both of the distribution of CO2 and CH4and their influence on the surface energy balance. We use aircraft and ground-based in situ data to characterize the temporal distribution of these greenhouse gases, and spectroscopic observations to derive their collocated surface radiative forcing. The spectroscopically-measured surface radiative forcing from rising CO2 is 0.2 W/m2/decade at both sites, with a seasonal cycle of 0.2 W/m2. This finding is largely consistent with theoretical predictions, providing robust evidence of radiative perturbations to the Earth's surface energy budget due to anthropogenic influences. The contribution from CH4 to the surface energy balance is more spatially and temporally heterogeneous. The ground-based measurements of CH4 at NSA and SGP indicate rising atmospheric concentrations except for a hiatus from 1995-2005, while more recent aircraft profiles indicate that concentrations in the boundary layer and free troposphere are correlated at NSA and decorrelated at SGP. The probability density functions of boundary layer concentrations of CH4 at NSA show little skew, but at SGP show positive skewness, which increased with the introduction of nearby fossil-fuel extraction. The correlated increases in atmospheric measurements of C2H6 and CH4that only occur at SGP are consistent with an anthropogenic influence there. Time-series of spectroscopically-measured CH4 surface radiative forcing at SGP and NSA also indicate positive trends of 0.1 W/m2/decade associated with the end of the hiatus, marked seasonal cycles, and little skew at NSA and a positive skew at SGP. The combination of in situ and spectroscopic measurements at these sites enables the quantification of surface radiative forcing from anthropogenic CH4. Implications are discussed for how advanced spectroscopic remote sensing measurements of CH4 can be used to quantify the impact of fossil fuel extraction on surface energy budget.

Monitoring concentration and isotopic composition of methane in groundwater in the Utica Shale hydraulic fracturing region of Ohio.

PubMed

Claire Botner, E; Townsend-Small, Amy; Nash, David B; Xu, Xiaomei; Schimmelmann, Arndt; Miller, Joshua H

2018-05-03

Degradation of groundwater quality is a primary public concern in rural hydraulic fracturing areas. Previous studies have shown that natural gas methane (CH 4 ) is present in groundwater near shale gas wells in the Marcellus Shale of Pennsylvania, but did not have pre-drilling baseline measurements. Here, we present the results of a free public water testing program in the Utica Shale of Ohio, where we measured CH 4 concentration, CH 4 stable isotopic composition, and pH and conductivity along temporal and spatial gradients of hydraulic fracturing activity. Dissolved CH 4 ranged from 0.2 μg/L to 25 mg/L, and stable isotopic measurements indicated a predominantly biogenic carbonate reduction CH 4 source. Radiocarbon dating of CH 4 in combination with stable isotopic analysis of CH 4 in three samples indicated that fossil C substrates are the source of CH 4 in groundwater, with one 14 C date indicative of modern biogenic carbonate reduction. We found no relationship between CH 4 concentration or source in groundwater and proximity to active gas well sites. No significant changes in CH 4 concentration, CH 4 isotopic composition, pH, or conductivity in water wells were observed during the study period. These data indicate that high levels of biogenic CH 4 can be present in groundwater wells independent of hydraulic fracturing activity and affirm the need for isotopic or other fingerprinting techniques for CH 4 source identification. Continued monitoring of private drinking water wells is critical to ensure that groundwater quality is not altered as hydraulic fracturing activity continues in the region. Graphical abstract A shale gas well in rural Appalachian Ohio. Photo credit: Claire Botner.

What controls the seasonal cycle of columnar methane observed by GOSAT over different regions in India?

NASA Astrophysics Data System (ADS)

Chandra, Naveen; Hayashida, Sachiko; Saeki, Tazu; Patra, Prabir K.

2017-10-01

Methane (CH4) is one of the most important short-lived climate forcers for its critical roles in greenhouse warming and air pollution chemistry in the troposphere, and the water vapor budget in the stratosphere. It is estimated that up to about 8 % of global CH4 emissions occur from South Asia, covering less than 1 % of the global land. With the availability of satellite observations from space, variability in CH4 has been captured for most parts of the global land with major emissions, which were otherwise not covered by the surface observation network. The satellite observation of the columnar dry-air mole fractions of methane (XCH4) is an integrated measure of CH4 densities at all altitudes from the surface to the top of the atmosphere. Here, we present an analysis of XCH4 variability over different parts of India and the surrounding cleaner oceanic regions as measured by the Greenhouse gases Observation SATellite (GOSAT) and simulated by an atmospheric chemistry-transport model (ACTM). Distinct seasonal variations of XCH4 have been observed over the northern (north of 15° N) and southern (south of 15° N) parts of India, corresponding to the peak during the southwestern monsoon (July-September) and early autumn (October-December) seasons, respectively. Analysis of the transport, emission, and chemistry contributions to XCH4 using ACTM suggests that a distinct XCH4 seasonal cycle over northern and southern regions of India is governed by both the heterogeneous distributions of surface emissions and a contribution of the partial CH4 column in the upper troposphere. Over most of the northern Indian Gangetic Plain regions, up to 40 % of the peak-to-trough amplitude during the southwestern (SW) monsoon season is attributed to the lower troposphere ( ˜ 1000-600 hPa), and ˜ 40 % to uplifted high-CH4 air masses in the upper troposphere ( ˜ 600-200 hPa). In contrast, the XCH4 seasonal enhancement over semi-arid western India is attributed mainly ( ˜ 70 %) to the upper troposphere. The lower tropospheric region contributes up to 60 % in the XCH4 seasonal enhancement over the Southern Peninsula and oceanic region. These differences arise due to the complex atmospheric transport mechanisms caused by the seasonally varying monsoon. The CH4 enriched air mass is uplifted from a high-emission region of the Gangetic Plain by the SW monsoon circulation and deep cumulus convection and then confined by anticyclonic wind in the upper tropospheric heights ( ˜ 200 hPa). The anticyclonic confinement of surface emission over a wider South Asia region leads to a strong contribution of the upper troposphere in the formation of the XCH4 peak over northern India, including the semi-arid regions with extremely low CH4 emissions. Based on this analysis, we suggest that a link between surface emissions and higher levels of XCH4 is not always valid over Asian monsoon regions, although there is often a fair correlation between surface emissions and XCH4. The overall validity of ACTM simulation for capturing GOSAT observed seasonal and spatial XCH4 variability will allow us to perform inverse modeling of XCH4 emissions in the future using XCH4 data.

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

PubMed

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

2013-01-01

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

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.

Thermokarst lake methanogenesis along a complete talik profile

DOE PAGES

Heslop, J. K.; Walter Anthony, K. M.; Sepulveda-Jauregui, A.; ...

2015-07-24

Here, thermokarst (thaw) lakes emit methane (CH 4) to the atmosphere formed from thawed permafrost organic matter (OM), but the relative magnitude of CH 4 production in surface lake sediments vs. deeper thawed permafrost horizons is not well understood. We assessed anaerobic CH 4 production potentials from various depths along a 590 cm long lake sediment core that captured the entire sediment package of the talik (thaw bulb) beneath the center of an interior Alaska thermokarst lake, Vault Lake, and the top 40 cm of thawing permafrost beneath the talik. We also studied the adjacent Vault Creek permafrost tunnel thatmore » extends through ice-rich yedoma permafrost soils surrounding the lake and into underlying gravel. Our results showed CH 4 production potentials were highest in the organic-rich surface lake sediments, which were 151 cm thick (mean ± SD: 5.95 ± 1.67 μg C–CH 4 g dw –1 d –1; 125.9 ± 36.2 μg C–CH 4 g C −1 org d –1). High CH 4 production potentials were also observed in recently thawed permafrost (1.18 ± 0.61 μg C–CH 4g dw –1 d –1; 59.60± 51.5 μg C–CH 4 g C −1 org d –1) at the bottom of the talik, but the narrow thicknesses (43 cm) of this horizon limited its overall contribution to total sediment column CH 4 production in the core. Lower rates of CH 4 production were observed in sediment horizons representing permafrost that has been thawing in the talik for a longer period of time. No CH 4 production was observed in samples obtained from the permafrost tunnel, a non-lake environment. Our findings imply that CH 4 production is highly variable in thermokarst lake systems and that both modern OM supplied to surface sediments and ancient OM supplied to both surface and deep lake sediments by in situ thaw and shore erosion of yedoma permafrost are important to lake CH 4 production.« less

Thermokarst lake methanogenesis along a complete talik profile

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

Heslop, J. K.; Walter Anthony, K. M.; Sepulveda-Jauregui, A.

Here, thermokarst (thaw) lakes emit methane (CH 4) to the atmosphere formed from thawed permafrost organic matter (OM), but the relative magnitude of CH 4 production in surface lake sediments vs. deeper thawed permafrost horizons is not well understood. We assessed anaerobic CH 4 production potentials from various depths along a 590 cm long lake sediment core that captured the entire sediment package of the talik (thaw bulb) beneath the center of an interior Alaska thermokarst lake, Vault Lake, and the top 40 cm of thawing permafrost beneath the talik. We also studied the adjacent Vault Creek permafrost tunnel thatmore » extends through ice-rich yedoma permafrost soils surrounding the lake and into underlying gravel. Our results showed CH 4 production potentials were highest in the organic-rich surface lake sediments, which were 151 cm thick (mean ± SD: 5.95 ± 1.67 μg C–CH 4 g dw –1 d –1; 125.9 ± 36.2 μg C–CH 4 g C −1 org d –1). High CH 4 production potentials were also observed in recently thawed permafrost (1.18 ± 0.61 μg C–CH 4g dw –1 d –1; 59.60± 51.5 μg C–CH 4 g C −1 org d –1) at the bottom of the talik, but the narrow thicknesses (43 cm) of this horizon limited its overall contribution to total sediment column CH 4 production in the core. Lower rates of CH 4 production were observed in sediment horizons representing permafrost that has been thawing in the talik for a longer period of time. No CH 4 production was observed in samples obtained from the permafrost tunnel, a non-lake environment. Our findings imply that CH 4 production is highly variable in thermokarst lake systems and that both modern OM supplied to surface sediments and ancient OM supplied to both surface and deep lake sediments by in situ thaw and shore erosion of yedoma permafrost are important to lake CH 4 production.« less

Environmental factors controlling methane emissions from peatlands in northern Minnesota

NASA Technical Reports Server (NTRS)

Dise, Nancy B.; Gorham, Eville; Verry, Elon S.

1993-01-01

The environmental factors affecting the emission of methane from peatlands were investigated by correlating CH4 emission data for two years, obtained from five different peatland ecosystems in northern Minnesota, with peat temperature, water table position, and degree of peat humification. The relationship obtained between the CH4 flux and these factors was compared to results from a field manipulation experiment in which the water table was artificially raised in three experimental plots within the driest peatland. It was found that peat temperature, water table position, and degree of peat humification explained 91 percent of the variance in log CH4 flux, successfully predicted annual CH4 emission from individual wetlands, and predicted the change in flux due to the water table manipulation. Raising the water table in the bog corrals by an average of 6 cm in autumn 1989 and 10 cm in summer 1990 increased CH4 emission by 2.5 and 2.2 times, respectively.

Hydrogeology, Chemical and Microbial Activity Measurement Through Deep Permafrost

USGS Publications Warehouse

Stotler, R.L.; Frape, S.K.; Freifeld, B.M.; Holden, B.; Onstott, T.C.; Ruskeeniemi, T.; Chan, E.

2011-01-01

Little is known about hydrogeochemical conditions beneath thick permafrost, particularly in fractured crystalline rock, due to difficulty in accessing this environment. The purpose of this investigation was to develop methods to obtain physical, chemical, and microbial information about the subpermafrost environment from a surface-drilled borehole. Using a U-tube, gas and water samples were collected, along with temperature, pressure, and hydraulic conductivity measurements, 420 m below ground surface, within a 535 m long, angled borehole at High Lake, Nunavut, Canada, in an area with 460-m-thick permafrost. Piezometric head was well above the base of the permafrost, near land surface. Initial water samples were contaminated with drill fluid, with later samples <40% drill fluid. The salinity of the non-drill fluid component was <20,000 mg/L, had a Ca/Na ratio above 1, with ??18O values ???5??? lower than the local surface water. The fluid isotopic composition was affected by the permafrost-formation process. Nonbacteriogenic CH4 was present and the sample location was within methane hydrate stability field. Sampling lines froze before uncontaminated samples from the subpermafrost environment could be obtained, yet the available time to obtain water samples was extended compared to previous studies. Temperature measurements collected from a distributed temperature sensor indicated that this issue can be overcome easily in the future. The lack of methanogenic CH4 is consistent with the high sulfate concentrations observed in cores. The combined surface-drilled borehole/U-tube approach can provide a large amount of physical, chemical, and microbial data from the subpermafrost environment with few, controllable, sources of contamination. ?? 2010 The Author(s). Journal compilation ?? 2010 National Ground Water Association.

Environmental Problems Associated with Decommissioning of Chernobyl Power Plant Cooling Pond

NASA Astrophysics Data System (ADS)

Foley, T. Q.; Oskolkov, B. Y.; Bondarkov, M. D.; Gashchak, S. P.; Maksymenko, A. M.; Maksymenko, V. M.; Martynenko, V. I.; Jannik, G. T.; Farfan, E. B.; Marra, J. C.

2009-12-01

Decommissioning of nuclear power plants and other nuclear fuel cycle facilities associated with residual radioactive contamination is a fairly pressing issue. Significant problems may result from decommissioning of cooling ponds. The Chernobyl Nuclear Power Plant (ChNPP) Cooling Pond is one of the largest self-contained bodies of water in the Chernobyl Region and Ukrainian Polesye with a water surface area of 22.9 km2. The major hydrological feature of the ChNPP Cooling Pond is that its water level is 6-7 m higher than the water level in the Pripyat River and water losses due to seepage and evaporation are replenished by pumping water from the Pripyat River. In 1986, the accident at the ChNPP #4 Reactor Unit significantly contaminated the ChNPP Cooling Pond. According to the 2001 data, the total radionuclide inventory in the ChNPP Cooling Pond bottom deposits was as follows: 16.28 ± 2.59 TBq for 137Cs; 2.4 ± 0.48 TBq for 90Sr, and 0.00518 ± 0.00148 TBq for 239+240Pu. Since ChNPP is being decommissioned, the ChNPP Cooling Pond of such a large size will no longer be needed and cost effective to maintain. However, shutdown of the water feed to the Pond would expose the contaminated bottom deposits and change the hydrological features of the area, destabilizing the radiological and environmental situation in the entire region in 2007 - 2008, in order to assess potential consequences of draining the ChNPP Cooling Pond, the authors conducted preliminary radio-ecological studies of its shoreline ecosystems. The radioactive contamination of the ChNPP Cooling Pond shoreline is fairly variable and ranges from 75 to 7,500 kBq/m2. Three areas with different contamination levels were selected to sample soils, vegetation, small mammals, birds, amphibians, and reptilians in order to measure their 137Cs and 90Sr content. Using the ERICA software, their dose exposures were estimated. For the 2008 conditions, the estimated dose rates were found to be as follows: amphibians - 11.4 µGy/hr; birds - 6.3 µGy/hr; mammals - 15.1 µGy/hr; reptilians - 10.3 µGy/hr, with the recommended maximum allowable limit of 40 µGy/hr. The conservative risk coefficient ranged from 0.51 for birds to 1.82 for amphibians. In spite of a high contamination level of the shoreline areas, the current total doses received by the animals do not reach the recommended maximum allowable doses. However, drainage of the ChNPP Cooling Pond is likely to increase the dose rates as follows: amphibians - 94.5, birds - 95.2, mammals - 284.0, reptilians - 847.0 µGy/hr, which will significantly exceed the maximum allowable values. These predictions are conservative and prior to making the final decision on the fate of the ChNPP Cooling Pond, a detailed radio-ecological assessment of its drainage will have to be performed.

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.

Organics and other molecules in the surfaces of Callisto and Ganymede.

PubMed

McCord, T B; Carlson, R W; Smythe, W D; Hansen, G B; Clark, R N; Hibbitts, C A; Fanale, F P; Granahan, J C; Segura, M; Matson, D L; Johnson, T V; Martin, P D

1997-10-10

Five absorption features are reported at wavelengths of 3.4, 3.88, 4. 05, 4.25, and 4.57 micrometers in the surface materials of the Galilean satellites Callisto and Ganymede from analysis of reflectance spectra returned by the Galileo mission near-infrared mapping spectrometer. Candidate materials include CO2, organic materials (such as tholins containing C(triple bond)N and C-H), SO2, and compounds containing an SH-functional group; CO2, SO2, and perhaps cyanogen [(CN)2] may be present within the surface material itself as collections of a few molecules each. The spectra indicate that the primary surface constituents are water ice and hydrated minerals.

Aerobic Methane Oxidation in Alaskan Lakes Along a Latitudinal Transect

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

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

PubMed

Yang, Shuang; Yang, Wei; Chen, Guojun; Fang, Xuan; Lv, Chengfu; Zhong, Jiaai; Xue, Lianhua

2016-08-01

Greenhouse gas (GHG) emissions from oil and gas systems are an important component of the GHG emission inventory. To assess the carbon emissions from oilfield-produced water under atmospheric conditions correctly, in situ detection and simulation experiments were developed to study the natural release of GHG into the atmosphere in the Shengli Oilfield, the second largest oilfield in China. The results showed that methane (CH4) and carbon dioxide (CO2) were the primary gases released naturally from the oilfield-produced water. The atmospheric temperature and release time played important roles in determining the CH4 and CO2 emissions under atmospheric conditions. Higher temperatures enhanced the carbon emissions. The emissions of both CH4 and CO2 from oilfield-produced water were highest at 27°C and lowest at 3°C. The bulk of CH4 and CO2 was released from the oilfield-produced water during the first release period, 0-2hr, for each temperature, with a maximum average emission rate of 0.415gCH4/(m(3)·hr) and 3.934gCO2/(m(3)·hr), respectively. Then the carbon emissions at other time periods gradually decreased with the extension of time. The higher solubility of CO2 in water than CH4 results in a higher emission rate of CH4 than CO2 over the same release duration. The simulation proved that oilfield-produced water is one of the potential emission sources that should be given great attention in oil and gas systems. Copyright © 2016. Published by Elsevier B.V.

The role of Zn2+ dopants in the acid-basic catalysis on MgO(001) surface: Ab initio simulations of the dissociative chemisorption of R-O-R‧ and R-S-R‧ (R, R ‧ = H , CH3, C2H5)

NASA Astrophysics Data System (ADS)

Fonseca, Carla G.; Tavares, Sérgio R.; Soares, Carla V.; daFonseca, Bruno G.; Henrique, Fábio J. F. S.; Vaiss, Viviane S.; Souza, Wladmir F.; Chiaro, Sandra S. X.; Diniz, Renata; Leitão, Alexandre A.

2017-07-01

Ab initio calculations were performed to study the effect of the Zn2+ dopant on the reactivity and the catalytic activity of the MgO(001) surface toward molecular adsorption and dissociation reactions of the H2O, H2S, CH3CH2OH, CH3CH2SH and CH3SCH3 molecules. The electronic analysis showed that Zn2+ cation increased the reactivity of the surface locally. All molecules dissociate on both surfaces except for water and ethanol which only dissociate on the MgO:Zn(001) surface, confirming the increased reactivity in this surface. The ΔG ° for the dissociation reactions of the CH3CH2SH and CH3SCH3 molecules on pure MgO(001) surface is positive in the entire temperature range. On the other hand, the ΔG ° for H2S molecule is negative until 148.7 °C. In the case of the MgO:Zn(001) surface, the CH3CH2SH molecule dissociates in the entire temperature range and, for H2S molecule, the dissociation is spontaneous until 349.7 °C. The rate constants obtained for the dissociation reactions were very large because the reaction barriers are very low in both surfaces for all the studied molecules, except for CH3SCH3 molecule. The Zn-doped MgO(001) surface, besides being more reactive, presented a better catalytic activity than the MgO(001) surface for the dissociation of this molecule.

[Short-term effects of fire disturbance on greenhouse gases emission from Betula platyphylla-forested wetland in Xiaoxing'an Mountains, Northeast China].

PubMed

Mu, Chang-cheng; Zhang, Bo-wen; Han, Li-dong; Yu, Li-li; Gu, Han

2011-04-01

By the methods of static chamber and gas chromatography, this paper studied the effects of fire disturbance on the seasonal dynamics and source/sink functions of CH4, CO2 and N2O emissions from Betula platyphylla-forested wetland as well as their relations with environmental factors in Xiaoxing' an Mountains of China. In growth season, slight fire disturbance on the wetland induced an increase of air temperature and ground surface temperature by 1.8-3.9 degrees C and a decrease of water table by 6.3 cm; while heavy fire disturbance led to an increase of air temperature and 0-40 cm soil temperature by 1.4-3.8 degrees C and a decrease of water table by 33.9 cm. Under slight or no fire disturbance, the CH4 was absorbed by the wetland soil in spring but emitted in summer and autumn; under heavy fire disturbance, the CH4 was absorbed in spring and summer but emitted in autumn. The CO2 flux had a seasonal variation of summer > spring = autumn under no fire disturbance, but of summer > autumn > spring under fire disturbance; and the N2O flux varied in the order of spring > summer > autumn under no fire disturbance, but of autumn > spring > summer under slight fire disturbance, and of summer > spring = autumn under heavy fire disturbance. At unburned site, the CO2 flux was significantly positively correlated with air temperature and ground surface temperature; at slightly burned site, the CO2 flux had significant positive correlations with air temperature, 5-10 cm soil temperature, and water table; at heavily burned sites, there was a significant positive correlation between CO2 flux and 5-40 cm soil temperature. Fire disturbance made the CH4 emission increased by 169.5% at lightly burned site or turned into weak CH4 sink at heavily burned site, and made the CO2 and N2O emissions and the global warming potential (GWP) at burned sites decreased by 21.2% -34.7%, 65.6% -95.8%, and 22.9% -36.6% respectively, compared with those at unburned site. Therefore, fire disturbance could decrease the greenhouse gases emission from Betula platyphylla-forested wetland, and planned firing could be properly implemented in wetland management.

Geochemistry of mineral waters and associated gases of the Sakhalin Island (Far East of Russia)

NASA Astrophysics Data System (ADS)

Chelnokov, George A.; Bragin, Ivan V.; Kharitonova, Natalia A.

2018-04-01

Isotopic and chemical data on the mineral water, mud volcanoes fluid and associated gases from the biggest Russian island Sakhalin, together with previous stable isotope data (d18O, dD, 13C), allow elucidation of their origin and general evolution. The water fluid circulation is mainly related to marine environment inducing three distinct types: Na-HCO3-Cl alkali carbonate groundwaters, Na-Cl-HCO3 highly evolved saline and Na-Cl mature groundwaters, indicating different evolution. Chemical evolution of groundwater on Sakhalin Island demonstrated cation exchange and salinization as dominant evolutionary pathways. Isotopic composition of groundwaters varies from meteoric to metamorphic waters. These metamorphic waters consist of water hydration from the clay and seawater are traced in fluids of Yuzhno-Sakhalin mud volcano despite modification by mixing with meteoric waters and water-rock interaction processes. Fault systems that define the areas of highly mineralized water circulation appear to play a major role in the CO2 migration to the surface and CH4 generation. The δ13C(CO2) values have pointed that gas phase in high-pCO2 waters mostly consists of mantle-derived CO2. The carbon isotope signature of methane δ13C(CH4) and δD(CH4) indicates its distinct origin which is specified by tectonics. Methane manifestation in the south of the Sakhalin Island is mainly related to thermogenic reservoirs as they are more often dislocate by tectonics, and crossed by active and permeable faults. The sources of biogenous methane in the north of Sakhalin Island is related to younger and shallower reservoirs, and less affected by tectonic processes. The determinations of 222Rn have allowed observing that maximal radon flux is associated with high pCO2 waters.

Global trends in peatland methane production

NASA Astrophysics Data System (ADS)

Hoyt, A.; Corbett, J. E.; Gandois, L.; Cobb, A.; Pangala, S. R.; Gauci, V.; Harvey, C. F.

2017-12-01

Peatland methane production rates and fluxes to the atmosphere vary globally. Here we present a systematic comparison of peatland CH4 production across latitudes. We developed and applied an isotope-based mass transport model to characterize rates of methanogenesis and recharge rates across ten ombrotrophic peatlands from around the world. We validated our model against peat incubations and surface fluxes where data was available. We found striking similarities in the DIC and CH4 concentrations and δ13C isotope profiles across northern bogs, despite highly variable precipitation, recharge rates, and peat characteristics. Profiles from northern sites were similar because increased recharge rates were always compensated by increased CH4 production rates. This could represent a feedback mechanism between recharge rates and methanogenesis in northern bogs or could represent a shared dependence of these two properties on the degree of peat decomposition. We also found strong differences between northern and tropical sites, both in the rate of CH4 production, the recharge rate, and in the transport pathways and fluxes to the atmosphere. Our findings have important implications for methane transport and release to the atmosphere. In northern bogs, low flow rates allow CH4 concentrations to build up, and CH4 escapes by surface diffusion, ebullition, and plant-mediated transport. Thus, the majority of CH4 produced escapes through the peat surface. In tropical peatlands, high flow rates suppress CH4 concentrations, which do not build up above the threshold for ebullition. Instead, CH4 leaves the peat by lateral transport and surface fluxes are small. This work provides evidence that peat properties and hydrology are fundamental controls on decomposition, CH4 production, and peat formation across latitudes.

The glycoinositol-phospholipids of Phytomonas.

PubMed

Redman, C A; Schneider, P; Mehlert, A; Ferguson, M A

1995-10-15

The Phytomonas spp. are trypanosomatid parasites of plants. A polar glycolipid fraction of a Phytomonas sp., isolated from the plant Euphorbia characias and grown in culture, was fractionated into four major glycolipid species (Phy 1-4). The glycolipids were analysed by chemical and enzymic modifications, composition and methylation analyses, electrospray mass spectrometry and microsequencing after HNO2 deamination and NaB3H4 reduction. The water-soluble headgroup of the Phy2 glycolipid was also analysed by 1H NMR. All four glycolipids were shown to be glycoinositol-phospholipids (GIPLs) with phosphatidylinositol (PI) moieties containing the fully saturated alkylacylglycerol lipids 1-O-hexadecyl-2-O-palmitoylglycerol and 1-O-hexadecyl-2-O-stearoylglycerol. The structures of the Phy 1-4 GIPLs are: Man alpha 1-2Man alpha 1-6Man alpha 1-4GlcN alpha 1-6PI, Glc alpha 1-2(NH2-CH2CH2-HPO4-)Man alpha 1-2Man alpha 1-6Man alpha 1-4GlcN alpha 1-6PI, [formula: see text] Glc alpha 1-2(NH2CH2CH2-HPO4-)Man alpha 1-2Man alpha 1-6Man alpha 1-4(NH2-CH2CH2-HPO4-)GlcN alpha 1-6PI [formula: see text] and Glc alpha 1-2Glc alpha 1-2(NH2CH2-CH2-HPO4-)Man alpha 1-2Man alpha 1-6Man alpha 1-4(NH2CH2CH2-HPO4-)-GlcN alpha 1-6PI. [formula: see text] The Phytomonas GIPLs represent a novel series of structures. This is the first description of the chemical structure of cell-surface molecules of this plant pathogen. The Phytomonas GIPLs are compared with those of other trypanosomatid parasites and are discussed with respect to trypanosomatid phylogenetic relationships.

The glycoinositol-phospholipids of Phytomonas.

PubMed Central

Redman, C A; Schneider, P; Mehlert, A; Ferguson, M A

1995-01-01

The Phytomonas spp. are trypanosomatid parasites of plants. A polar glycolipid fraction of a Phytomonas sp., isolated from the plant Euphorbia characias and grown in culture, was fractionated into four major glycolipid species (Phy 1-4). The glycolipids were analysed by chemical and enzymic modifications, composition and methylation analyses, electrospray mass spectrometry and microsequencing after HNO2 deamination and NaB3H4 reduction. The water-soluble headgroup of the Phy2 glycolipid was also analysed by 1H NMR. All four glycolipids were shown to be glycoinositol-phospholipids (GIPLs) with phosphatidylinositol (PI) moieties containing the fully saturated alkylacylglycerol lipids 1-O-hexadecyl-2-O-palmitoylglycerol and 1-O-hexadecyl-2-O-stearoylglycerol. The structures of the Phy 1-4 GIPLs are: Man alpha 1-2Man alpha 1-6Man alpha 1-4GlcN alpha 1-6PI, Glc alpha 1-2(NH2-CH2CH2-HPO4-)Man alpha 1-2Man alpha 1-6Man alpha 1-4GlcN alpha 1-6PI, [formula: see text] Glc alpha 1-2(NH2CH2CH2-HPO4-)Man alpha 1-2Man alpha 1-6Man alpha 1-4(NH2-CH2CH2-HPO4-)GlcN alpha 1-6PI [formula: see text] and Glc alpha 1-2Glc alpha 1-2(NH2CH2-CH2-HPO4-)Man alpha 1-2Man alpha 1-6Man alpha 1-4(NH2CH2CH2-HPO4-)-GlcN alpha 1-6PI. [formula: see text] The Phytomonas GIPLs represent a novel series of structures. This is the first description of the chemical structure of cell-surface molecules of this plant pathogen. The Phytomonas GIPLs are compared with those of other trypanosomatid parasites and are discussed with respect to trypanosomatid phylogenetic relationships. Images Figure 1 Figure 2 Figure 3 Figure 6 Figure 7 PMID:7487886

Energy from vascular plant wastewater treatment systems

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

Wolverton, B.C.; McDonald, R.C.

1981-04-01

Water hyacinth (Eichhornia crassipes) duckweed (Spirodela sp. and Lemna sp.), water pennywort (Hydrocotyle ranunculoides), and kudzu (Pueraria lobata) were anaerobically fermented using an anaerobic filter technique that reduced the total digestion time from 90 d to an average of 23 d and produced 0.14 to 0.22 m/sup 3/ CH/sub 4//kg (dry weight) (2.3 to 3.6 ft/sup 3//lb) from mature filters for the 3 aquatic species. Kudzu required an average digestion time of 33 d and produced an average of 0.21 m/sup 3/ CH/sub 4//kg (dry weight) (3.4 ft/sup 3//lb). The anaerobic filter provided a large surface area for the anaerobicmore » bacteria to establish and maintain an optimal balance of facultative, acid-forming, and methane-producing bacteria. Consequently the efficiency of the process was greatly improved over prior batch fermentations.« less

Cerebral acetylcholine and choline contents and turnover following low-dose acetylcholinesterase inhibitors treatment in rats.

PubMed

Shih, Tsung-Ming; Scremin, Oscar U; Roch, Margareth; Huynh, Ly; Sun, Wei; Jenden, Donald J

2006-11-01

Male Sprague-Dawley rats were treated for 3 weeks with (1) regular tap drinking water plus subcutaneous (s.c.) saline (0.5 ml/kg) injections three times/week, (2) pyridostigmine bromide (PB) in drinking water (80 mg/L) plus s.c. saline injections three times/week, (3) regular tap drinking water plus s.c. sarin (0.5 x LD(50)) injections three times/week, or (4) PB in drinking water plus s.c. sarin injections three times/week. Repeated doses of sarin, in the presence or absence of PB, were devoid of acute toxicity during the three-week treatment period. Two, 4, and 16 weeks post-treatment, animals were given an intravenous pulse injection of choline labeled with 4 deuterium atoms (D4Ch) followed, after 1 min, by microwave fixation of the brain in vivo. Tissue levels of endogenous acetylcholine (D0ACh), endogenous choline (D0Ch), D4Ch, and ACh synthesized from D4Ch (D4ACh) were measured by gas-chromatography mass-spectrometry in hippocampus, infundibulum, mesencephalon, neocortex, piriform cortex, and striatum. Ch uptake from blood and ACh turnover were estimated from D4Ch and D4ACh concentrations in brain tissue, respectively. Statistically significant differences among brain regions were found for D0Ch, D4Ch, D0ACh and D4ACh at 2, 4 and 16 weeks post-treatment. However, differences in the values of these parameters between control and drug treatments were found only for D0ACh and D0Ch at 2 and 4 weeks, but not at 16 weeks post-treatment. In conclusion, the results from these experiments do not support a delayed or persistent alteration in cholinergic function after exposure to low doses of PB and/or sarin.

Influence of preadsorbed oxygen on activated chemisorption of methane on Pd(110)

NASA Astrophysics Data System (ADS)

Valden, M.; Pere, J.; Xiang, N.; Pessa, M.

1996-07-01

Dissociative chemisorption of methane on clean and oxygen modified Pd(110) has been studied by using molecular beam surface scattering. The absolute dissociation probability of CH 4 ( Stot) is found to increase exponentially with the incident normal energy ( En) of CH 4 and with surface temperature ( TS) on clean Pd(110). The kinetic isotope effect is also found; namely, Stot of CD 4 is 4 to 5 times smaller than Stot of CH 4 throughout the entire range of En studied. These results are consistent with a direct dissociation mechanism. Measurements on preadsorbed oxygen on Pd(110) show that Stot of CH 4 decreases linearly, as oxygen coverage is increased from 0 to 0.4 ML in good agreement with the first-order Langmuir kinetics when approximately two active sites are blocked by one oxygen atom. No influence of the oxygen induced surface reconstructions on the dissociative adsorption kinetics of CH 4 is observed.

Microtopographic and Hydrological Controls over Respiratory Efflux and Late-Season Arctic Methane Emissions

NASA Astrophysics Data System (ADS)

Wilkman, E.; Zona, D.; Oechel, W. C.

2014-12-01

In recent years, Arctic peatlands have released approximately 35 Tg (3.5 x 1012g) of CH4 annually, corresponding to around 1/3 of the aggregate wetland CH4 fluxes and 16% of all natural emissions. As climate models increasingly suggest that current warming trends in the Arctic (4-8 °C higher annual surface air temperatures) will continue by century's end, carbon (C) cycling in these northern climes may be further amplified. Although much has been learned in recent decades, uncertainty remains in regard to the spatial and temporal extent of CO2 and CH4 emissions from these systems. Chamber based carbon flux measurements were gathered for three growing seasons from June 2007 to September 2013 in Barrow, Alaska to investigate the diurnal, weekly, and monthly patterns of CO2 and CH4 flux in the North American Arctic. For the 2007 and 2008 growing seasons, high temporal frequency auto-chambers (LI-8100A Automated Soil Flux System, LI-COR Biosciences) were used to gather over 18,000 individual flux measurements. From July to September 2013 an Ultraportable Greenhouse Gas Analyzer (Los Gatos Research Inc.) was deployed in concert with this soil flux system to gather high temporal frequency soil CO2 and CH4 fluxes. Nearby eddy covariance towers provided auxiliary meteorological and environmental data, while weekly transects amassed further surficial hydrological measures (pH, thaw depth, water table). For earlier periods of data, respiratory fluxes were partitioned into five microtopographic classes (polygon rims and troughs, low centered basins, high ridges, and flat mesic terrain). Conversely, for the later periods of data covered chamber fluxes were partitioned into three 'habitat' types (High, Medium, Wet) based on corresponding aboveground average water table extent. Marked dissimilarities were noted across habitat types and microtopographic classes. In general more mesic, waterlogged regions released greater quantities of CO2 across the growing season, while intermediate (Medium) water table regimes dominated CH4 release in the fall. Additionally, temperature generally delimited CO2 release throughout the growing season, while CH4 release was strongly tied to thaw depth expansion. This large dataset thus greatly underscores the importance of microscale heterogeneity on C flux in the Arctic.

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.

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

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.

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

The importance of groundwater discharge to the methane budgets of nearshore and continental shelf waters of the northeastern Gulf of Mexico

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

Bugna, G.C.; Chanton, J.P.; Cable, P.H.

1996-12-01

Methane concentrations in groundwater (wells, sinkholes, and springs) averaged 61 {+-} 9 {mu}M, while concentrations in nearshore and continental shelf waters within the study area averaged 62 {+-} 7 nM and 27 {+-} 5 nM, respectively. We tested the hypothesis that the three orders of magnitude difference between groundwater and seawater concentration would make CH{sub 4} an indicator of submarine groundwater discharge to surficial waters. Methane budgets for nearshore and continental shelf water columns were consistent with the hypothesis that groundwater seepage or seawater recirculation through the seabed is the dominant source of CH{sub 4} relative to benthic diffusive flux,more » riverine flux, and in situ water column production. Seepage/recirculation appears to account for approximately 83-99% of the total CH{sub 4} input into the water column within the study area. Utilizing measured porewater CH{sub 4} concentrations, the calculated amounts of seepage required to support the observed benthic fluxes were comparable to seepage rates measured in the field. Nearshore seepage meter transacts showed a strong and direct correlation between the integrated quantity of groundwater seepage along a shoreline and the inventory of CH{sub 4} in those waters. Our study further showed a similar correlation between {sup 222}Rn (another potential groundwater tracer) and CH{sub 4} in offshore waters supporting the hypothesis of a common benthic source for these constituents. 67 refs., 10 figs., 2 tabs.« less

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.

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

NASA Astrophysics Data System (ADS)

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

2012-04-01

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

Methane-methanol cycle for the thermochemical production of hydrogen

DOEpatents

Dreyfuss, Robert M.; Hickman, Robert G.

1976-01-01

A thermochemical reaction cycle for the generation of hydrogen from water comprising the following sequence of reactions wherein M represents a metal: CH.sub.4 + H.sub.2 O .fwdarw. CO + 3H.sub.2 (1) co + 2h.sub.2 .fwdarw. ch.sub.3 oh (2) ch.sub.3 oh + so.sub.2 + mo .fwdarw. mso.sub.4 + ch.sub.4 (3) mso.sub.4 .fwdarw. mo + so.sub.2 + 1/2o.sub.2 (4) the net reaction is the decomposition of water into hydrogen and oxygen.

Temporal variability of methane fluxes in West Siberian taiga bogs and its implications for estimating regional methane emission

NASA Astrophysics Data System (ADS)

Sabrekov, Alexander; Ilyasov, Danil; Terentieva, Irina; Glagolev, Mikhail; Maksyutov, Shamil

2017-04-01

The West Siberia Lowland (WSL) is the biggest peatland area in Eurasia and is situated in the high latitudes experiencing enhanced rate of climate change. During 2015-16 summer periods, seasonal measurements of methane emission were made at the field station «Mukhrino» in the WSL middle taiga zone. The study was made at 3 wetland ecosystem types covering 80% of the taiga wetland area: i) waterlogged hollows or depressed areas with water level above the moss surface, ii) oligotrophic hollows or depressed parts of bogs with water level beneath the moss surface, iii) forested bogs with dwarf shrubs-sphagnum vegetation. Seven series of measurements were made by a static chamber method in 2016 and four series - in 2015. In 2015, we observed non-typical weather conditions including early dry spring and short cold rainy summer. Oppositely, weather conditions in 2016 were closer to average long-term with warmer drier summer. Significant difference between these years allowed analyzing the temporal variability and its sources. Average methane flux rates from forested bogs were 0.57 mgCH4/m2/h in 2016 and 0.33 mgCH4/m2/h in 2015. Seasonal dynamic during both years had similar concave downward shape. The highest fluxes were observed in June and were corresponded to the highest WTL, the main limiting factor of emission from forested bogs. The lowest fluxes in July were related to the low WTL combining with the highest temperature of upper methanotrophy layer. Average methane flux rates from oligotrophic hollows were 7.18 mgCH4/m2/h in 2016 and 4.28 mgCH4/m2/h in 2015. Seasonal dynamic of methane emission was indistinct in 2015. On the contrary, in 2016 it had regular seasonal pattern with peak emissions in July, which were four times higher than in 2015. WTL was not the limiting factor for CH4 emission from oligotrophic hollows, because even in the driest ones it was only 10 cm below the surface. Thus, the difference between peak emissions in 2015 and 2016 was mainly related to the temperature, which was considerably higher in 2016. Average methane flux rates from waterlogged hollows were 2.19 mgCH4/m2/h in 2016 and 4.07 mgCH4/m2/h in 2015. Seasonal dynamic had prominent shape in both years, however, peak emissions were observed in different months. Overall, patterns of emission in these ecosystems had more complicate nature and needs future investigations. Regional methane emission was estimated using new wetland map by Terentieva et al. (2016). Seasonal dynamic data for 2015-16 years gave the regional flux of 161 and 1257 ktCH4/yr for forested bogs and oligotrophic hollows, respectively. Similar values were obtained using not seasonal dynamic but only flux medians for 2015-16 years. However, the usage of old dataset gave only 32 and 841 ktCH4/yr for forested bogs and oligotrophic hollows, respectively. Thus, seasonal dynamics data had lower impact on regional methane emission estimate comparing to interannual variability data. Terentieva, I.E., Glagolev, M.V., Lapshina, E.D., Sabrekov, A.F., Maksyutov, S. Mapping of West Siberian taiga wetland complexes using Landsat imagery: implications for methane emissions // Biogeosciences. 2016. V. 13. № 16. P. 4615-4626.

Toward an annual estimate of methane emissions from Lake Erie

NASA Astrophysics Data System (ADS)

Fernandez, J.; Townsend-Small, A.

2017-12-01

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

Energy Input is a Primary Controller of Methane Bubbling in Subarctic Lakes (Invited)

NASA Astrophysics Data System (ADS)

Wik, M.; Thornton, B.; Bastviken, D.; MacIntyre, S.; Varner, R. K.; Crill, P. M.

2013-12-01

Methane (CH4) emission from inland waters is suggested to be equal in greenhouse gas strength to approximately 25% of the carbon (C) uptake of all land-based ecosystems combined. A substantial amount of CH4 escapes lake surfaces via ebullition (bubbling), which is considered a highly heterogeneous and difficult pathway to predict. We use four summer seasons of ebullition data from three subarctic lakes to demonstrate striking (r2 of up to 0.997) linear relationships between cumulative bubble CH4 flux from June to September and four easily measurable, energy-related parameters of the lakes (solar shortwave input, number of ice-free days and shallow and deep water sediment temperature). In our lakes, there is essentially no ebullition at low temperatures, but ebullition increases exponentially above 6°C. It appears that persistent gas releases cannot start immediately after ice out due to a delay in the recharge of enough gas to form bubbles. Lack of continuous sampling procedures has until now made it difficult to identify relationships and confirm that heat energy transfer alone is a strong driver for ebullition that is independent of possible seasonal changes in organic substrate. In contrast to earlier studies highlighting the extreme variability of ebullition, we suggest that gas venting is a highly predictable process if measurements are made in a consistent manner across many different lake zones and over long time periods. Future changes to energy input to lakes and ponds may thus predictably alter the CH4 source strength of water bodies across northern landscapes.

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.

Temperate Forest Methane Sink Diminished by Tree Emissions

NASA Astrophysics Data System (ADS)

Megonigal, P.; Pitz, S.

2015-12-01

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

Agricultural peat lands; towards a greenhouse gas sink - a synthesis of a Dutch landscape study

NASA Astrophysics Data System (ADS)

Schrier-Uijl, A. P.; Kroon, P. S.; Hendriks, D. M. D.; Hensen, A.; Van Huissteden, J. C.; Leffelaar, P. A.; Berendse, F.; Veenendaal, E. M.

2013-06-01

It is generally known that managed, drained peatlands act as carbon sources. In this study we examined how mitigation through the reduction of management and through rewetting may affect the greenhouse gas (GHG) emission and the carbon balance of intensively managed, drained, agricultural peatlands. Carbon and GHG balances were determined for three peatlands in the western part of the Netherlands from 2005 to 2008 by considering spatial and temporal variability of emissions (CO2, CH4 and N2O). One area (Oukoop) is an intensively managed grass-on-peatland, including a dairy farm, with the ground water level at an average annual depth of 0.55 m below the soil surface. The second area (Stein) is an extensively managed grass-on-peatland, formerly intensively managed, with a dynamic ground water level at an average annual depth of 0.45 m below the soil surface. The third area is an (since 1998) rewetted former agricultural peatland (Horstermeer), close to Oukoop and Stein, with the average annual ground water level at a depth of 0.2 m below the soil surface. During the measurement campaigns we found that both agriculturally managed sites acted as carbon and GHG sources but the rewetted agricultural peatland acted as a carbon and GHG sink. The terrestrial GHG source strength was 1.4 kg CO2-eq m-2 yr-1 for the intensively managed area and 1.0 kg CO2-eq m-2 yr-1 for the extensively managed area; the unmanaged area acted as a GHG sink of 0.7 kg CO2-eq m-2 yr-1. Water bodies contributed significantly to the terrestrial GHG balance because of a high release of CH4 and the loss of DOC only played a minor role. Adding the farm-based CO2 and CH4 emissions increased the source strength for the managed sites to 2.7 kg CO2-eq m-2 yr-1 for Oukoop and 2.1 kg CO2-eq m-2 yr-1 for Stein. Shifting from intensively managed to extensively managed grass-on-peat reduced GHG emissions mainly because N2O emission and farm-based CH4 emissions decreased. Overall, this study suggests that managed peatlands are large sources of GHG and carbon, but, if appropriate measures are taken they can be turned back into GHG and carbon sinks within 15 yr of abandonment and rewetting.

Surface modification of paper on a continuous atmospheric-pressure-plasma system

NASA Astrophysics Data System (ADS)

Cruz-Barba, Luis Emilio

Plasma technologies for the continuous modification of materials in atmospheric-pressure-plasma conditions were used to evaluate the surface modification of paper under different plasma conditions. The generation of hydrophobic layers was used to characterize the efficiency of the originally designed system for future application in the paper industry. Generation of hydrophobic layers was carried out by deposition of thin layers from fluorine containing gases, as well as cross-linking of pre-deposited thin layers of hydrophobic materials, such as fluoropolymers and silicones, in a continuous system plasma reactor (CSPR). Physical and chemical characterization of these layers was carried out by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), scanning electron microscopy (SEM), contact angle goniometry, and water absorption evaluations. Pure gaseous CF4 and a CF4/CH4 mixture were used to deposit fluorinated layers, rendering paper surfaces with low to moderate relative surface atomic contents of fluorine (2.5 to 16.3%). Morphological characterization revealed that the deposition consists of small clusters of fluorinated species scattered on the surface. Contact angle evaluations (50°--70°) indicated a reduction in the water affinity of the paper. Thin layers of fluoropolymer pre-deposited on paper surfaces were cross-linked in the presence of CF4, CF4/CH4, and NH 3 plasmas. All of the gases proved to be effective for the cross-linking under different conditions. These cross-linked layers were determined to maintain the original polymer structure, consisting mainly of CF2-CF 2 and small quantities of CFx. Surface characterization by AFM indicated lower roughness values compared to the untreated additive-free paper (45.1 vs 67.1 nm). Paper samples treated by this approach showed a highly hydrophobic character with up to 160° contact angles, and water absorption was reduced by as much as 61.6%. Silicone layers were cross-linked in the presence of argon and oxygen plasmas. Characterization of the silicone-coated paper indicated, as in the case of fluoropolymers, the retention of the original chemical structure. Surface roughness values (AFM) were in the range of 11.8 to 18.2 nm, evidence of a very smooth surface. High hydrophobicity levels were reached, as shown by contact angles of up to 126°, and water absorption showed a maximum reduction of 76.8%.

Interior and its implications for the atmosphere. [effects of Titan interior structure on its atmospheric composition

NASA Technical Reports Server (NTRS)

Lewis, J. S.

1974-01-01

The bulk composition and interior structure of Titan required to explain the presence of a substantial methane atmosphere are shown to imply the presence of solid CH4 - 7H2O in Titan's primitive material. Consideration of the possible composition and structure of the present atmosphere shows plausible grounds for considering models with total atmospheric pressures ranging from approximately 20 mb up to approximately 1 kb. Expectations regarding the physical state of the surface and its chemical composition are strongly conditioned by the mass of atmosphere believed to be present. A surface of solid CH4, liquid CH4 solid, CH4 hydrate, H2O ice, aqueous NH3 solution, or even a non-surface of supercritical H2O-NH3-CH4 fluid could be rationalized.

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.

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.

The effect of water regime and soil management on methane (CH4) emission of rice field

NASA Astrophysics Data System (ADS)

Naharia, O.; Setyanto, P.; Arsyad, M.; Burhan, H.; Aswad, M.

2018-05-01

Mitigation of CH4 emission of rice field is becoming a serious issue. The Agricultural Environment Preservation Research Station in Central Java conducted a field study to investigate the effect of water regime and soil tillage on CH4 emission from paddy fields. Treatments consisted of two factors. The first factor was water regime, e.g., 1) continuously flooded 5 cm, 2) intermittent irrigation and 3) saturated water condition at 0-1 cm water level. The second factor was soil management, e.g., 1) normal tillage, 2) zero tillage + 3 sulfosate ha-1 and 3) zero tillage + 3 L paraquat ha-1. Most of treatments gave a significant reduction of total CH4 emission between 34 – 85% during the wet season crop as compared to normal rice cropping practice, while in the dry season the CH4 reduction ranged between 16 – 92%. No-tillage with non-selective herbicides combined with intermittent/saturated irrigation system significantly reduced methane emission without significantly affecting rice productivity as compared to normal tillage with continuous flooding (farmers practice)

Contrasting Extreme Flooding Events and their Influence on Carbon Dynamics in a Salt Marsh

NASA Astrophysics Data System (ADS)

Vargas, R.; Kowalska, N.; Lule, A. V.; Seyfferth, A.; Reimer, J.; Cai, W. J.; Moffat, C. F.

2017-12-01

Coastal ecosystems are threatened by sea level rise, making them vulnerable to more frequent extreme flooding events. Thus, it is critical to understand the effect of different flooding events on carbon dynamics to test the resiliency of these ecosystems. We used the eddy covariance method to measure CO2 and CH4 fluxes and instrumented an adjacent creek to measure pCO2 and pCH4 in a temperate salt marsh. The site was influenced by flooding caused by a hurricane storm surge and then a freshwater flood during September-October of 2015 and 2016, respectively. Water level, salinity, dissolved oxygen and turbidity were significantly influenced by the events. Daily mean CO2 fluxes show that during the hurricane surge, the ecosystem became a source of CO2 to the atmosphere releasing about 1.8 umol CO2 m-2 s-1 daily. Ecosystem CH4 fluxes were generally low ( 0.05 umol CH4 m-2 s-1) and showed high temporal variability (maximum of 0.6 umol CH4 m-2 s-1). There was an intermittent temporal coherence at 12-hour period (i.e., subdaily tides) between water level and net ecosystem exchange (NEE) or ecosystem CH4 fluxes. There was strong temporal coherence between water level and pCO2 at 12-hour period during the hurricane surge. During the freshwater surge we did not observe temporal coherence between water level and pCO2 or pCH4, but concentrations of both gases increased in the water of the marsh. These results show that extreme flooding events significantly influence short-term carbon dynamics and provide insights on ecosystem resiliency and lateral transport of pCO2 and pCH4 to the coastal ocean.

Tree CH4 fluxes in forestry drained peatland in southern Finland

NASA Astrophysics Data System (ADS)

Haikarainen, Iikka; Putkinen, Anuliina; Pyykkö, Petteri; Halmeenmäki, Elisa; Pihlatie, Mari

2017-04-01

Methane (CH4) is among the most important greenhouse gases and its atmospheric concentration is increasing. Boreal forests are commonly considered a net sink of atmospheric CH4 due to CH4 consuming bacteria in aerated soil layers. Recent studies have, however, demonstrated that trees are capable of emitting CH4 from their stems and shoots by transporting anaerobically produced CH4 from deeper soil layers to the atmosphere. Furthermore, trees may act as independent sources of CH4. We have measured tree stem CH4 exchange of boreal tree species at Lettosuo, a nutrient rich peatland forest in Tammela, southern Finland (60˚ 38' N, 23˚ 57' E), using the static chamber technique. Three species, downy birch (Betula pubescens), Norway spruce (Picea abies) and Scots pine (Pinus sylvestris), were selected under investigation as they represent common boreal tree species. Fluxes of CH4 were measured during 7.6.2016 - 17.10.2016 from in total 25 sample trees growing on two different plots: a treatment plot where all the pines were removed to raise the water table level (WTL) and a control plot. Three birches from the treatment plot were selected to measure CH4 flux variation within vertical profile of the trees. Characterization of microbial communities, quantification of methanogenic and methanotrophic functional genes, and measurements of potential CH4 production and consumption from peat profile and forest floor moss samples were also carried out to obtain insight to the CH4 flux dynamics at the studied sites. The pine removal treatment did not markedly change the average WTL, but it made the WTL more variable with frequently 10-15 cm closer to soil surface compared to the WTL on the control plot. We found small and variable CH4 emissions from the stems of trees on both of the plots, while occasional consumption of CH4 was also present. Generally the CH4 emissions were higher and more dominant at the treatment plot compared to the control plot, and the fluxes were significantly different between the plots (p < 0.001). The CH4 emission rates from the birches at the treatment plot decreased exponentially in the stem vertical profile. Clear seasonal flux dynamics or significant differences in the CH4 flux between the species were not found at either of the plots. Microbial experiments showed that anaerobic CH4 production, CH4 oxidation potential (under 1000 ppm CH4) and the amount of methanogens were higher in the peat of the treatment site. The difference in the CH4 flux rates between the plots indicates that the WTL is a major regulator of tree CH4 emissions on forestry drained peatlands, supporting our hypothesis that the stem emitted CH4 originates from anaerobic soil conditions. This hypothesis is further supported by the results of the microbial analysis and by the observation that more CH4 is emitting from the lower parts of the stems compared to the upper stem.

Ancient dissolved methane in inland waters at low concentrations revealed by a new collection method for radiocarbon (^{14}C) analysis

NASA Astrophysics Data System (ADS)

Dean, Joshua F.; Billett, Michael F.; Murray, Callum; Garnett, Mark H.

2017-04-01

Methane (CH4) is a powerful greenhouse gas and is released to the atmosphere from freshwater systems in numerous biomes globally. Radiocarbon (14C) analysis of methane can provide unique information about its age, source and rate of cycling in natural environments. Methane is often released from aquatic sediments in bubbles (ebullition), but dissolved methane is also present in lakes and streams at lower concentrations, and may not be of the same age or source. Obtaining sufficient non-ebullitive aquatic methane for 14C analysis remains a major technical challenge. Previous studies have shown that freshwater methane, in both dissolved and ebullitive form, can be significantly older than other forms of aquatic carbon (C), and it is therefore important to characterise this part of the terrestrial C balance. We present a novel method to capture sufficient amounts of dissolved methane from freshwater environments for 14C analysis by circulating water across a hydrophobic, gas-permeable membrane and collecting the methane in a large collapsible vessel. The results of laboratory and field tests show that reliable dissolved δ13CH4 and 14CH4 samples can be readily collected over short time periods (˜4 to 24 hours), at relatively low cost and from a variety of surface water types. The initial results further support previous findings that dissolved methane can be significantly older than other forms of aquatic C, especially in organic-rich catchments, and is currently unaccounted for in many terrestrial C balances and models. This method is suitable for use in remote locations, and could potentially be used to detect the leakage of unique 14CH4 signatures from point sources into waterways, e.g. coal seam gas and landfill gas.

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

EPA Pesticide Factsheets

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

Storage capacity and vibration frequencies of guest molecules in CH4 and CO2 hydrates by first-principles calculations.

PubMed

Cao, Xiaoxiao; Su, Yan; Liu, Yuan; Zhao, Jijun; Liu, Changling

2014-01-09

Using first-principle calculations at B97-D/6-311++G(2d,2p) level, we systematically explore the gas capacity of five standard water cavities (5(12), 4(3)5(6)6(3), 5(12)6(2), 5(12)6(4), and 5(12)6(8)) in clathrate hydrate and study the inclusion complexes to infer general trends in vibrational frequencies of guest molecules as a function of cage size and number of guest molecules. In addition, the Raman spectra of hydrates from CO2/CH4 gases are simulated. From our calculations, the maximum cage occupancy of the five considered cages (5(12), 4(3)5(6)6(3), 5(12)6(2), 5(12)6(4), and 5(12)6(8)) is one, one, two, three, and seven for both CH4 and CO2 guest molecules, respectively. Meanwhile, the optimum cage occupancy are one, one, one, two, and four for CO2 molecules and one, one, two, three, and five for CH4 molecules, respectively. Both the C-H stretching frequency of CH4 and the C-O stretching frequency of CO2 gradually decrease as size of the water cages increases. Meanwhile, the C-H stretching frequency gradually increases as the amount of CH4 molecules in the water cavity (e.g., 5(12)6(8)) increases.

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.

Soil degassing at the Los Humeros geothermal field (Mexico)

NASA Astrophysics Data System (ADS)

Peiffer, Loïc; Carrasco-Núñez, Gerardo; Mazot, Agnès; Villanueva-Estrada, Ruth Esther; Inguaggiato, Claudio; Bernard Romero, Rubén; Rocha Miller, Roberto; Hernández Rojas, Javier

2018-05-01

The Los Humeros geothermal field is the third most important producer of geothermal electricity (70 MW) in Mexico. Geothermal fluids are hosted in fractured andesitic lavas and mostly consist of high enthalpy steam with limited water content (vapor fraction > 0.9). Despite the high reservoir temperature ( 300-400 °C), thermal manifestations at the surface are scarce and locally appear as steaming grounds, weak steam vents and advanced argillic alteration. Geothermal fluid upflow from the reservoir towards the surface is limited by welded ignimbrite deposits that act as a low-permeability barrier. In this study, we present the first measurements of CO2, CH4 and H2S degassing rates from the soil performed at Los Humeros. Flux measurements were complemented with δ13C composition of degassing CO2 and soil temperatures to discuss gas origin and thermal anomalies. We measured high soil degassing rates (up to 7530 g m-2 d-1 CO2, 33 g m-2 d-1 CH4 and 22 g m-2 d-1 H2S) in three localized areas (Humeros North - HN, Humeros South - HS and Xalapazco - XA) as well as high soil temperatures reaching the boiling temperature at the local altitude (90.6 °C). The particular location of these three areas suggests that the steam-dominated reservoir degases to the surface through permeable faults crossing the ignimbritic deposits. The remaining surveyed areas are characterized by weak CO2 fluxes (≤44 g m-2 d-1), non-detectable CH4 and H2S fluxes, and lower soil temperatures (5-21 °C). The compositions in δ13CCO2 from HN-HS-XA areas (δ13CCO2 = -7.94 to -2.73‰) reflect a magmatic source with some possible contribution from the sedimentary basement, as well as fractionation induced by boiling and CO2 dissolution in shallow water bodies. We also discuss the processes causing the spread in CO2/CH4 flux ratios. Finally, we estimate the heat output from the three high degassing areas to a value of 16.4 MWt.

Diurnal and seasonal variations in surface methane at a tropical coastal station: Role of mesoscale meteorology.

PubMed

Kavitha, M; Nair, Prabha R; Girach, I A; Aneesh, S; Sijikumar, S; Renju, R

2018-08-01

In view of the large uncertainties in the methane (CH 4 ) emission estimates and the large spatial gaps in its measurements, studies on near-surface CH 4 on regional basis become highly relevant. This paper presents the first time observational results of a study on the impacts of mesoscale meteorology on the temporal variations of near-surface CH 4 at a tropical coastal station, in India. It is based on the in-situ measurements conducted during January 2014 to August 2016, using an on-line CH 4 analyzer working on the principle of gas chromatography. The diurnal variation shows a daytime low (1898-1925ppbv) and nighttime high (1936-2022ppbv) extending till early morning hours. These changes are closely associated with the mesoscale circulations, namely Sea Breeze (SB) and Land Breeze (LB), as obtained through the meteorological observations, WRF simulations of the circulations and the diurnal variation of boundary layer height as observed by the Microwave Radiometer Profiler. The diurnal enhancement always coincides with the onset of LB. Several cases of different onset timings of LB were examined and results presented. The CH 4 mixing ratio also exhibits significant seasonal patterns being maximum in winter and minimum in pre-monsoon/monsoon with significant inter-annual variations, which is also reflected in diurnal patterns, and are associated with changing synoptic meteorology. This paper also presents an analysis of in-situ measured near-surface CH 4 , column averaged and upper tropospheric CH 4 retrieved by Atmospheric Infrared Sounder (AIRS) onboard Earth Observing System (EOS)/Aqua which gives insight into the vertical distribution of the CH 4 over the location. An attempt is also made to estimate the instantaneous radiative forcing for the measured CH 4 mixing ratio. Copyright © 2018 Elsevier B.V. All rights reserved.

Adsorption of CH4 on nitrogen- and boron-containing carbon models of coal predicted by density-functional theory

NASA Astrophysics Data System (ADS)

Liu, Xiao-Qiang; Xue, Ying; Tian, Zhi-Yue; Mo, Jing-Jing; Qiu, Nian-Xiang; Chu, Wei; Xie, He-Ping

2013-11-01

Graphene doped by nitrogen (N) and/or boron (B) is used to represent the surface models of coal with the structural heterogeneity. Through the density functional theory (DFT) calculations, the interactions between coalbed methane (CBM) and coal surfaces have been investigated. Several adsorption sites and orientations of methane (CH4) on graphenes were systematically considered. Our calculations predicted adsorption energies of CH4 on graphenes of up to -0.179 eV, with the strongest binding mode in which three hydrogen atoms of CH4 direct to graphene surface, observed for N-doped graphene, compared to the perfect (-0.154 eV), B-doped (-0.150 eV), and NB-doped graphenes (-0.170 eV). Doping N in graphene increases the adsorption energies of CH4, but slightly reduced binding is found when graphene is doped by B. Our results indicate that all of graphenes act as the role of a weak electron acceptor with respect to CH4. The interactions between CH4 and graphenes are the physical adsorption and slightly depend upon the adsorption sites on graphenes and the orientations of methane as well as the electronegativity of dopant atoms in graphene.

On the parameters influencing air-water gas exchange

NASA Astrophysics Data System (ADS)

JäHne, Bernd; Münnich, Karl Otto; BöSinger, Rainer; Dutzi, Alfred; Huber, Werner; Libner, Peter

1987-02-01

Detailed gas exchange measurements from two circular and one linear wind/wave tunnels are presented. Heat, He, CH4, CO2, Kr, and Xe have been used as tracers. The experiments show the central importance of waves for the water-side transfer process. With the onset of waves the Schmidt number dependence of the transfer velocity k changes from k ∝ Sc-⅔ to k ∝ Sc-½indicating a change in the boundary conditions at the surface. Moreover, energy put into the wave field by wind is transferred to near-surface turbulence enhancing gas transfer. The data show that the mean square slope of the waves is the best parameter to characterize the free wavy surface with respect to water-side transfer processes.

New measurements of the sticking coefficient and binding energy of molecules on non-porous amorphous solid water in the submonolayer regime

NASA Astrophysics Data System (ADS)

He, Jiao; Acharyya, Kinsuk; Emtiaz, S. M.; Vidali, Gianfranco

2016-06-01

Sticking and adsorption of molecules on dust grains are two important processes in gas-grain interactions. We accurately measured both the sticking coefficient and the binding energy of several key molecules on the surface of amorphous solid water as a function of coverage.A time-resolved scattering technique was used to measure sticking coefficient of H2, D2, N2, O2, CO, CH4, and CO2 on non-porous amorphous solid water (np-ASW) in the low coverage limit over a wide range of surface temperatures. We found that the time-resolved scattering technique is advantageous over the conventional King-Wells method that underestimates the sticking coefficient. Based on the measured values we suggest a useful general formula of the sticking coefficient as a function of grain temperature and molecule-surface binding energy.We measured the binding energy of N2, CO, O2, CH4, and CO2 on np-ASW, and of N2 and CO on porous amorphous solid water (p-ASW). We were able to measure binding energies down to a fraction of 1% of a layer, thus making these measurements more appropriate for astrochemistry than the existing values. We found that CO2 forms clusters on np-ASW surface even at very low coverage; this may help in explaining the segregation of CO2 in ices. The binding energies of N2, CO, O2, and CH4 on np-ASW decrease with coverage in the submonolayer regime. Their values in the low coverage limit are much higher than what is commonly used in gas-grain models. An empirical formula was used to describe the coverage dependence of the binding energies. We used the newly determined binding energy distributions in a simulation of gas-grain chemistry for cold dense clouds and hot core models. We found that owing to the higher value of desorption energy in the sub-monlayer regime a fraction of all these ices stays much longer and to higher temperature on the grain surface compared to the case using single value energies as currently done in astrochemical models.This work was supported in part by a grant to GV from NSF --- Astronomy & Astrophysics Division (#1311958)

Computational Study of Interstellar Glycine Formation Occurring at Radical Surfaces of Water-ice Dust Particles

NASA Astrophysics Data System (ADS)

Rimola, Albert; Sodupe, Mariona; Ugliengo, Piero

2012-07-01

Glycine is the simplest amino acid, and due to the significant astrobiological implications that suppose its detection, the search for it in the interstellar medium (ISM), meteorites, and comets is intensively investigated. In the present work, quantum mechanical calculations based on density functional theory have been used to model the glycine formation on water-ice clusters present in the ISM. The removal of either one H atom or one electron from the water-ice cluster has been considered to simulate the effect of photolytic radiation and of ionizing particles, respectively, which lead to the formation of OH• radical and H3O+ surface defects. The coupling of incoming CO molecules with the surface OH• radicals on the ice clusters yields the formation of the COOH• radicals via ZPE-corrected energy barriers and reaction energies of about 4-5 kcal mol-1 and -22 kcal mol-1, respectively. The COOH• radicals couple with incoming NH=CH2 molecules (experimentally detected in the ISM) to form the NHCH2COOH• radical glycine through energy barriers of 12 kcal mol-1, exceedingly high at ISM cryogenic temperatures. Nonetheless, when H3O+ is present, one proton may be barrierless transferred to NH=CH2 to give NH2=CH2 +. This latter may react with the COOH• radical to give the NH2CH2COOH+• glycine radical cation which can then be transformed into the NH2CHC(OH)2 +• species (the most stable form of glycine in its radical cation state) or into the NH2CHCOOH• neutral radical glycine. Estimated rate constants of these events suggest that they are kinetically feasible at temperatures of 100-200 K, which indicate that their occurrence may take place in hot molecular cores or in comets exposed to warmer regions of solar systems. Present results provide quantum chemical evidence that defects formed on water ices due to the harsh-physical conditions of the ISM may trigger reactions of cosmochemical interest. The relevance of surface H3O+ ions to facilitate chemical processes by proton transfer (i.e., acting as acidic catalysts) is highlighted, and plausible ways of their formation at the water-ice surface in the ISM are also discussed.

One-step synthesis, wettability and foaming properties of high-performance non-ionic hydro-fluorocarbon hybrid surfactants

NASA Astrophysics Data System (ADS)

Peng, Ying-ying; Lu, Feng; Tong, Qing-Xiao

2018-03-01

In this work, a series of non-ionic hydro-fluorocarbon hybrid surfactants (C9F19CONH(CH2)3N(CmH2m+1)2, abbreviated as C9F19AM (m = 1), C9F19AE (m = 2) and C9F19AB (m = 4) were easily synthesized by one-step reaction and characterized by 1HNMR, 19FNMR and MS spectroscopy. Unlike conventional non-ionic surfactants (most hydrophilic units consisted of hydroxy or ether groups), their hydrophilic groups were composed of amide group, an eco-friendly unit. The surface activity, wettability, thermal stability and foaming performance were investigated. The results showed that the C9F19AE (C9F19CONH(CH2)3N[CH2CH3]2) had superior surface and interface activities, which could reduce the surface tension of water down to 15.37 mN/m and the interfacial tension (cyclohexane/water/surfactants) to 5.8 mN/m with a low cmc (critical micelle concentration) of 0.12 mmol/L. Through the calculation of Amin (the minimum area occupied per-surfactant molecule), we speculated this higher surface activity was related to the compatibility between hydrocarbon and fluorocarbon chains. When used as wetting and foaming agents, the C9F19AE also outperformed great advantages over conventional non-ionic fluorocarbon and hydrocarbon surfactants, which could decrease the contact angle of water on PTFE plate from 107.7° to 3.6°, and increase the foam integrated value F to 536 500 ± 3066.5 mL s. Moreover, the decomposition temperature (Td) of C9F19AE could reach up to 173 °C. This work demonstrates a valuable strategy to develop a kind of high-efficiency foaming agent via facile synthesis.

Hydration of the sulfuric acid-methylamine complex and implications for aerosol formation.

PubMed

Bustos, Danielle J; Temelso, Berhane; Shields, George C

2014-09-04

The binary H2SO4-H2O nucleation is one of the most important pathways by which aerosols form in the atmosphere, and the presence of ternary species like amines increases aerosol formation rates. In this study, we focus on the hydration of a ternary system of sulfuric acid (H2SO4), methylamine (NH2CH3), and up to six waters to evaluate its implications for aerosol formation. By combining molecular dynamics (MD) sampling with high-level ab initio calculations, we determine the thermodynamics of forming H2SO4(NH2CH3)(H2O)n, where n = 0-6. Because it is a strong acid-base system, H2SO4-NH2CH3 quickly forms a tightly bound HSO4(-)-NH3CH3(+) complex that condenses water more readily than H2SO4 alone. The electronic binding energy of H2SO4-NH2CH3 is -21.8 kcal mol(-1) compared with -16.8 kcal mol(-1) for H2SO4-NH3 and -12.8 kcal mol(-1) for H2SO4-H2O. Adding one to two water molecules to the H2SO4-NH2CH3 complex is more favorable than adding to H2SO4 alone, yet there is no systematic difference for n ≥ 3. However, the average number of water molecules around H2SO4-NH2CH3 is consistently higher than that of H2SO4, and it is fairly independent of temperature and relative humidity.

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.

Generation of Hydrogen and Methane during Experimental Low-Temperature Reaction of Ultramafic Rocks with Water

NASA Astrophysics Data System (ADS)

McCollom, Thomas M.; Donaldson, Christopher

2016-06-01

Serpentinization of ultramafic rocks is widely recognized as a source of molecular hydrogen (H2) and methane (CH4) to support microbial activity, but the extent and rates of formation of these compounds in low-temperature, near-surface environments are poorly understood. Laboratory experiments were conducted to examine the production of H2 and CH4 during low-temperature reaction of water with ultramafic rocks and minerals. Experiments were performed by heating olivine or harzburgite with aqueous solutions at 90°C for up to 213 days in glass bottles sealed with butyl rubber stoppers. Although H2 and CH4 increased steadily throughout the experiments, the levels were very similar to those found in mineral-free controls, indicating that the rubber stoppers were the predominant source of these compounds. Levels of H2 above background were observed only during the first few days of reaction of harzburgite when CO2 was added to the headspace, with no detectable production of H2 or CH4 above background during further heating of the harzburgite or in experiments with other mineral reactants. Consequently, our results indicate that production of H2 and CH4 during low-temperature alteration of ultramafic rocks may be much more limited than some recent experimental studies have suggested. We also found no evidence to support a recent report suggesting that spinels in ultramafic rocks may stimulate H2 production. While secondary silicates were observed to precipitate during the experiments, formation of these deposits was dominated by Si released by dissolution of the glass bottles, and reaction of the primary silicate minerals appeared to be very limited. While use of glass bottles and rubber stoppers has become commonplace in experiments intended to study processes that occur during serpentinization of ultramafic rocks at low temperatures, the high levels of H2, CH4, and SiO2 released during heating indicate that these reactor materials are unsuitable for this purpose.

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

Carbon isotopes in peat, DOC, CO2, and CH4 in a Holocene peatland on Dartmoor, southwest England

NASA Astrophysics Data System (ADS)

Charman, Dan J.; Aravena, Ramon; Bryant, Charlotte L.; Harkness, Doug D.

1999-06-01

Carbon gases with younger 14C ages than those of the surrounding peat have been reported from continental boreal peatlands, a fact which suggests that significant movement of CO2, CH4, or DOC (dissolved organic carbon) and export of C via subsurface processes are not accounted for in most estimates of contributions to the C cycle. This paper tests the hypothesis that similar processes can occur in oceanic ombrotrophic mires where water and gas movement is theoretically minimal. Measurements of 14C and δ13C in CO2, CH4, and DOC, and of tritium, are reported from depths to 250 cm at Tor Royal, a raised mire in southwest England. Radiocarbon ages of gases are 1460 to 500 yr younger than those of peat from the same depths, and CO2 is consistently younger than CH4. DOC is 1260 to 830 yr younger than the peat, and significant amounts of tritium were found at all depths. Gas ages are mostly intermediate between the age of the peat and that of the DOC, which suggests that C is principally transported as DOC. However, some gases are younger than their associated DOC, which implies that movement of dissolved gases may also take place. δ13C values in gases suggest that CO2 reduction is the major pathway for CH4 production. Transport of C in deep peats is likely to be a significant component in the overall C budget of ombrotrophic oceanic peatlands, and C export via discharge to ground or surface waters may be an important mechanism for gaseous C emissions.

Carbon isotopes in peat, DOC, CO{sub 2}, and CH{sub 4} in a Holocene peatland on Dartmoor, southwest England

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

Charman, D.J.; Aravena, R.; Bryant, C.L.

1999-06-01

Carbon gases with younger {sup 14}C ages than those of the surrounding peat have been reported from continental boreal peatlands, a fact which suggests that significant movement of CO{sub 2}, CH{sub 4}, or DOC (dissolved organic carbon) and export of C via subsurface processes are not accounted for in most estimates of contributions to the C cycle. This paper tests the hypothesis that similar processes can occur in oceanic ombrotrophic mires where water and gas movement is theoretically minimal. Measurements of {sup 14}C and {delta}{sup 13}C in CO{sub 2}, CH{sub 4}, and DOC, and of tritium, are reported from depthsmore » to 250 cm at Tor Royal, a raised mire in southwest England. Radiocarbon ages of gases are 1,460 to 500 yr younger than those of peat from the same depths, and CO{sub 2} is consistently younger than CH{sub 4}. DOC is 1,260 to 830 yr younger than the peat, and significant amounts of tritium were found at all depths. Gas ages are mostly intermediate between the age of the peat and that of the DOC, which suggests that C is principally transported as DOC. However, some gases are younger than their associated DOC, which implies that movement of dissolved gases may also take place. {delta}{sup 13}C values in gases suggest that CO{sub 2} reduction is the major pathway for CH{sub 4} production. Transport of C in deep peats is likely to be a significant component in the overall C budget of ombrotrophic oceanic peatlands, and C export via discharge to ground or surface waters may be an important mechanism for gaseous C emissions.« less

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...

Energy, chemical disequilibrium, and geological constraints on Europa.

PubMed

Hand, Kevin P; Carlson, Robert W; Chyba, Christopher F

2007-12-01

Europa is a prime target for astrobiology. The presence of a global subsurface liquid water ocean and a composition likely to contain a suite of biogenic elements make it a compelling world in the search for a second origin of life. Critical to these factors, however, may be the availability of energy for biological processes on Europa. We have examined the production and availability of oxidants and carbon-containing reductants on Europa to better understand the habitability of the subsurface ocean. Data from the Galileo Near-Infrared Mapping Spectrometer were used to constrain the surface abundance of CO(2) to 0.036% by number relative to water. Laboratory results indicate that radiolytically processed CO(2)-rich ices yield CO and H(2)CO(3); the reductants H(2)CO, CH(3)OH, and CH(4) are at most minor species. We analyzed chemical sources and sinks and concluded that the radiolytically processed surface of Europa could serve to maintain an oxidized ocean even if the surface oxidants (O(2), H(2)O(2), CO(2), SO(2), and SO(4) (2)) are delivered only once every approximately 0.5 Gyr. If delivery periods are comparable to the observed surface age (30-70 Myr), then Europa's ocean could reach O(2) concentrations comparable to those found in terrestrial surface waters, even if approximately 10(9) moles yr(1) of hydrothermally delivered reductants consume most of the oxidant flux. Such an ocean would be energetically hospitable for terrestrial marine macrofauna. The availability of reductants could be the limiting factor for biologically useful chemical energy on Europa.

Role of water and carbonates in photocatalytic transformation of CO{sub 2} to CH{sub 4} on titania.

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

Dimitrijevic, N. M.; Vijayan, B. K.; Poluektov, O. G.

Using the electron paramagnetic resonance technique, we have elucidated the multiple roles of water and carbonates in the overall photocatalytic reduction of carbon dioxide to methane over titania nanoparticles. The formation of H atoms (reduction product) and {center_dot}OH radicals (oxidation product) from water, and CO{sub 3}{sup -} radical anions (oxidation product) from carbonates, was detected in CO{sub 2}-saturated titania aqueous dispersion under UV illumination. Additionally, methoxyl, {center_dot}OCH{sub 3}, and methyl, {center_dot}CH{sub 3}, radicals were identified as reaction intermediates. The two-electron, one-proton reaction proposed as an initial step in the reduction of CO{sub 2} on the surface of TiO{sub 2} ismore » supported by the results of first-principles calculations.« less

Role of Water and Carbonates in Photocatalytic Transformation of CO2 to CH4 on Titania

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

Dimitrijevic, Nada; Vijayan, Baiju K.; Poluektov, Oleg G.

Using the electron paramagnetic resonance technique, we have elucidated the multiple roles of water and carbonates in the overall photocatalytic reduction of carbon dioxide to methane over titania nanoparticles. The formation of H atoms (reduction product) and {sm_bullet}OH radicals (oxidation product) from water, and CO{sub 3}{sup -} radical anions (oxidation product) from carbonates, was detected in CO{sub 2}-saturated titania aqueous dispersion under UV illumination. Additionally, methoxyl, {sm_bullet}OCH{sub 3}, and methyl, {sm_bullet}CH{sub 3}, radicals were identified as reaction intermediates. The two-electron, one-proton reaction proposed as an initial step in the reduction of CO{sub 2}, on the surface of TiO{sub 2}, ismore » supported by the results of first-principles calculations.« less

Are closed landfills free of CH_{4} emissions? A case study of Arico's landfill, Tenerife, Canary Islands

NASA Astrophysics Data System (ADS)

Barrancos, José; Cook, Jenny; Phillips, Victoria; Asensio-Ramos, María; Melián, Gladys; Hernández, Pedro A.; Pérez, Nemesio M.

2016-04-01

Landfills are authentic chemical and biological reactors that introduce in the environment a wide amount of gas pollutants (CO2, CH4, volatile organic compounds, etc.) and leachates. Even after years of being closed, a significant amount of landfill gas could be released to the atmosphere through the surface in a diffuse form, also known as non-controlled emission. The study of the spatial-temporal distribution of diffuse emissions provides information of how a landfill degassing takes place. The main objective of this study was to estimate the diffuse uncontrolled emission of CH4 into the atmosphere from the closed Arico's landfill (0.3 km2) in Tenerife Island, Spain. To do so, a non-controlled biogenic gas emission survey of nearly 450 sampling sites was carried out during August 2015. Surface gas sampling and surface landfill CO2 efflux measurements were carried out at each sampling site by means of a portable non-dispersive infrared spectrophotometer (NDIR) model LICOR Li800 following the accumulation chamber method. Landfill gases, CO2 and CH4, were analyzed using a double channel VARIAN 4900 micro-GC. The CH4 efflux was computed combining CO2 efflux and CH4/CO2 ratio in the landfill's surface gas. To quantify the total CH4 emission, CH4 efflux contour map was constructed using sequential Gaussian simulation (sGs) as interpolation method. The total diffuse CH4 emission was estimated in 2.2 t d-1, with CH4 efflux values ranging from 0-922 mg m-2 d-1. This type of studies provides knowledge of how a landfill degasses and serves to public and private entities to establish effective systems for extraction of biogas. This aims not only to achieve higher levels of controlled gas release from landfills resulting in a higher level of energy production but also will contribute to minimize air pollution caused by them.

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

Geochemical variations during the 2012 Emilia seismic sequence

NASA Astrophysics Data System (ADS)

Sciarra, Alessandra; Cantucci, Barbara; Galli, Gianfranco; Cinti, Daniele; Pizzino, Luca

2015-04-01

Several geochemical surveys (soil gas and shallow water) were performed in the Modena province (Massa Finalese, Finale Emilia, Medolla and S. Felice sul Panaro), during 2006-2014 period. In May-June 2012, a seismic sequence (main shocks of ML 5.9 and 5.8) was occurred closely to the investigated area. In this area 300 CO2 and CH4 fluxes measurements, 150 soil gas concentrations (He, H2, CO2, CH4 and C2H6), 30 shallow waters and their isotopic analyses (δ13C- CH4, δD- CH4 and δ13C- CO2) were performed in April-May 2006, October and December 2008, repeated in May and September 2012, June 2013 and July 2014 afterwards the 2012 Emilia seismic sequences. Chemical composition of soil gas are dominated by CH4 in the southern part by CO2 in the northern part. Very anomalous fluxes and concentrations are recorded in spot areas; elsewhere CO2 and CH4 values are very low, within the typical range of vegetative and of organic exhalation of the cultivated soil. After the seismic sequence the CH4 and CO2 fluxes are increased of one order of magnitude in the spotty areas, whereas in the surrounding area the values are within the background. On the contrary, CH4 concentration decrease (40%v/v in the 2012 surveys) and CO2 concentration increase until to 12.7%v/v (2013 survey). Isotopic gas analysis were carried out only on samples with anomalous values. Pre-seismic data hint a thermogenic origin of CH4 probably linked to leakage from a deep source in the Medolla area. Conversely, 2012/2013 isotopic data indicate a typical biogenic origin (i.e. microbial hydrocarbon production) of the CH4, as recognized elsewhere in the Po Plain and surroundings. The δ13C-CO2 value suggests a prevalent shallow origin of CO2 (i.e. organic and/or soil-derived) probably related to anaerobic oxidation of heavy hydrocarbons. Water samples, collected from domestic, industrial and hydrocarbons exploration wells, allowed us to recognize different families of waters. Waters are meteoric in origin and, apart one sample, are not thermally anomalous. Stable isotopes of H and O point out the absence of mixing with connate waters, prolonged interaction with the host-rock at high temperature and/or heavy gas-water exchange at depth. Isotopic carbon composition emphasizes its organic (i.e. shallow) origin; only "La Canonica" site, the deepest well sampled in this study, shows a probable deep(er) provenance of dissolved carbon. Waters trend away from the atmospheric end-member composition, dissolving CO2 or CH4 depending on their redox state. Dissolved radon activity is very low, likely due to the particular hydrogeological setting of the study area (i.e. the presence of waters with long residence times in the considered aquifers). Obtained results highlight a different behavior before and after the seismic events, proved also by the different carbon isotopic signature of CH4. These variations could be produced by increasing of bacterial (e.g. peat strata) and methanogenic fermentation processes in the first meters of the soil.

Methane and CO2 Adsorption Capacities of Kerogen in the Eagle Ford Shale from Molecular Simulation.

PubMed

Psarras, Peter; Holmes, Randall; Vishal, Vikram; Wilcox, Jennifer

2017-08-15

Over the past decade, the United States has become a world leader in natural gas production, thanks in part to a large-fold increase in recovery from unconventional resources, i.e., shale rock and tight oil reservoirs. In an attempt to help mitigate climate change, these depleted formations are being considered for their long-term CO 2 storage potential. Because of the variability in mineral and structural composition from one formation to the next (even within the same region), it is imperative to understand the adsorption behavior of CH 4 and CO 2 in the context of specific conditions and pore surface chemistry, i.e., relative total organic content (TOC), clay, and surface functionality. This study examines two Eagle Ford shale samples, both recovered from shale that was extracted at depths of approximately 3800 m and having low clay content (i.e., less than 5%) and similar mineral compositions but distinct TOCs (i.e., 2% and 5%, respectively). Experimentally validated models of kerogen were used to the estimate CH 4 and CO 2 adsorption capacities. The pore size distributions modeled were derived from low-pressure adsorption isotherm data using CO 2 and N 2 as probe gases for micropores and mesopores, respectively. Given the presence of water in these natural systems, the role of surface chemistry on modeled kerogen pore surfaces was investigated. Several functional groups associated with surface-dissociated water were considered. Pressure conditions from 10 to 50 bar were investigated using grand canonical Monte Carlo simulations along with typical outgassing temperatures used in many shale characterization and adsorption studies (i.e., 60 and 250 °C). Both CO 2 and N 2 were used as probe gases to determine the total pore volume available for gas adsorption spanning pore diameters ranging from 0.3 to 30 nm. The impacts of surface chemistry, outgassing temperature, and the inclusion of nanopores with diameters of less than 1.5 nm were determined for applications of CH 4 and CO 2 storage from samples of the gas-producing region of the Eagle Ford Shale. At 50 bar and temperatures of 60 and 250 °C, CH 4 adsorption increased across all surface chemistries considered by 60% and 2-fold, respectively. In the case of CO 2 , the surface chemistry played a role at both 10 and 50 bar. For instance, at temperatures of 60 and 250 °C, CO 2 adsorption increased across all surface chemistries by 6-fold and just over 2-fold, respectively. It was also found that at both 10 and 50 bar, if too low an outgassing temperature is used, this may lead to a 2-fold underestimation of gas in place. Finally, neglecting to include pores with diameters of less than 1.5 nm has the potential to underestimate pore volume by up to 28%. Taking into consideration these aspects of kerogen and shale characterization in general will lead to improvements in estimating the CH 4 and CO 2 storage potential of gas shales.

A multi-year estimate of methane fluxes in Alaska from CARVE atmospheric observations

PubMed Central

Miller, Scot M.; Miller, Charles E.; Commane, Roisin; Chang, Rachel Y.-W.; Dinardo, Steven J.; Henderson, John M.; Karion, Anna; Lindaas, Jakob; Melton, Joe R.; Miller, John B.; Sweeney, Colm; Wofsy, Steven C.; Michalak, Anna M.

2016-01-01

Methane (CH4) fluxes from Alaska and other arctic regions may be sensitive to thawing permafrost and future climate change, but estimates of both current and future fluxes from the region are uncertain. This study estimates CH4 fluxes across Alaska for 2012–2014 using aircraft observations from the Carbon in Arctic Reservoirs Vulnerability Experiment (CARVE) and a geostatistical inverse model (GIM). We find that a simple flux model based on a daily soil temperature map and a static map of wetland extent reproduces the atmospheric CH4 observations at the state-wide, multi-year scale more effectively than global-scale, state-of-the-art process-based models. This result points to a simple and effective way of representing CH4 flux patterns across Alaska. It further suggests that contemporary process-based models can improve their representation of key processes that control fluxes at regional scales, and that more complex processes included in these models cannot be evaluated given the information content of available atmospheric CH4 observations. In addition, we find that CH4 emissions from the North Slope of Alaska account for 24% of the total statewide flux of 1.74 ± 0.44 Tg CH4 (for May–Oct.). Contemporary global-scale process models only attribute an average of 3% of the total flux to this region. This mismatch occurs for two reasons: process models likely underestimate wetland area in regions without visible surface water, and these models prematurely shut down CH4 fluxes at soil temperatures near 0°C. As a consequence, wetlands covered by vegetation and wetlands with persistently cold soils could be larger contributors to natural CH4 fluxes than in process estimates. Lastly, we find that the seasonality of CH4 fluxes varied during 2012–2014, but that total emissions did not differ significantly among years, despite substantial differences in soil temperature and precipitation; year-to-year variability in these environmental conditions did not affect obvious changes in total CH4 fluxes from the state. PMID:28066129

A multi-year estimate of methane fluxes in Alaska from CARVE atmospheric observations.

PubMed

Miller, Scot M; Miller, Charles E; Commane, Roisin; Chang, Rachel Y-W; Dinardo, Steven J; Henderson, John M; Karion, Anna; Lindaas, Jakob; Melton, Joe R; Miller, John B; Sweeney, Colm; Wofsy, Steven C; Michalak, Anna M

2016-10-01

Methane (CH 4 ) fluxes from Alaska and other arctic regions may be sensitive to thawing permafrost and future climate change, but estimates of both current and future fluxes from the region are uncertain. This study estimates CH 4 fluxes across Alaska for 2012-2014 using aircraft observations from the Carbon in Arctic Reservoirs Vulnerability Experiment (CARVE) and a geostatistical inverse model (GIM). We find that a simple flux model based on a daily soil temperature map and a static map of wetland extent reproduces the atmospheric CH 4 observations at the state-wide, multi-year scale more effectively than global-scale, state-of-the-art process-based models. This result points to a simple and effective way of representing CH 4 flux patterns across Alaska. It further suggests that contemporary process-based models can improve their representation of key processes that control fluxes at regional scales, and that more complex processes included in these models cannot be evaluated given the information content of available atmospheric CH 4 observations. In addition, we find that CH 4 emissions from the North Slope of Alaska account for 24% of the total statewide flux of 1.74 ± 0.44 Tg CH 4 ( for May-Oct.). Contemporary global-scale process models only attribute an average of 3% of the total flux to this region. This mismatch occurs for two reasons: process models likely underestimate wetland area in regions without visible surface water, and these models prematurely shut down CH 4 fluxes at soil temperatures near 0°C. As a consequence, wetlands covered by vegetation and wetlands with persistently cold soils could be larger contributors to natural CH 4 fluxes than in process estimates. Lastly, we find that the seasonality of CH 4 fluxes varied during 2012-2014, but that total emissions did not differ significantly among years, despite substantial differences in soil temperature and precipitation; year-to-year variability in these environmental conditions did not affect obvious changes in total CH 4 fluxes from the state.

Effect of Thaw Depth on Fluxes of CO2 and CH4 in Manipulated Arctic Coastal Tundra of Barrow, Alaska

NASA Astrophysics Data System (ADS)

Kim, Y.

2014-12-01

Changes in CO2 and CH4 emissions represent one of the most significant consequences of drastic climate change in the Arctic, by way of thawing permafrost, a deepened active layer, and decline of thermokarst lakes in the Arctic. This study conducted flux-measurements of CO2 and CH4, as well as environmental factors such as temperature, moisture, and thaw depth, as part of a water table manipulation experiment in the Arctic coastal plain tundra of Barrow, Alaska during autumn. The manipulation treatment consisted of draining, controlling, and flooding treated sections by adjusting standing water. Inundation increased CH4 emission by a factor of 4.3 compared to non-flooded sections. This may be due to the decomposition of organic matter under a limited oxygen environment by saturated standing water. On the other hand, CO2 emission in the dry section was 3.9-fold higher than in others. CH4 emission tends to increase with deeper thaw depth, which strongly depends on the water table; however, CO2 emission is not related to thaw depth. Quotients of global warming potential (GWPCO2) (dry/control) and GWPCH4 (wet/control) increased by 464 and 148 %, respectively, and GWPCH4 (dry/control) declined by 66 %. This suggests that CO2 emission in a drained section is enhanced by soil and ecosystem respiration, and CH4 emission in a flooded area is likely stimulated under an anoxic environment by inundated standing water. The findings of this manipulation experiment during the autumn period demonstrate the different production processes of CO2 and CH4, as well as different global warming potentials, coupled with change in thaw depth. Thus the outcomes imply that the expansion of tundra lakes leads the enhancement of CH4 release, and the disappearance of the lakes causes the stimulated CO2 production in response to the Arctic climate change.

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.

Sensitivity of Methane Lifetime and Transport to Sulfate Geoengineering

NASA Astrophysics Data System (ADS)

Aquila, V.; Pitari, G.; Tilmes, S.; Cionni, I.; de Luca, N.; Di Genova, G.; Iachetti, D.

2014-12-01

Sulfate geoengineering, made by sustained injection of SO2 in the tropical lower stratosphere, may impact the abundance of tropospheric methane through several photochemical mechanisms affecting the tropospheric OH abundance and hence the methane lifetime. Changes of the stratospheric Brewer-Dobson circulation also play a role in the upper tropospheric CH4 transport. Three mechanisms lead to lower OH concentrations and a longer CH4 lifetime: (a) solar radiation scattering increases the planetary albedo and cools the surface, with a tropospheric water vapor decrease as a response to this cooling. (b) The tropospheric UV budget is upset by the additional aerosol scattering and stratospheric ozone changes: the net effect is meridionally not uniform, with a net decrease in the tropics, thus producing less tropospheric O(1D). (c) The extra-tropical downwelling motion from the lower stratosphere tends to increase the sulfate aerosol surface area density available for heterogeneous chemical reactions in the mid-upper troposphere, thus reducing the amount of NOx and tropospheric O3 production. On the other hand, the tropical lower stratosphere is warmed by solar and planetary radiation absorption by the aerosols. The heating rates perturbation are strongly latitude dependent, producing a significant change of the pole-to-equator temperature gradient and mean zonal wind distribution, with a net increase of tropical upwelling. A stronger meridional component of the Brewer-Dobson circulation increases the extra-tropical stratosphere to troposphere transport of CH4 poorer air, resulting in less CH4 transported in the UTLS. The net effect on tropospheric OH may be positive or negative depending on the net result of different superimposed species perturbations in the UTLS, i.e. CH4 (negative), NOy and O3 (positive). Three climate-chemistry coupled models are used here to explore the above radiative, chemical and dynamical mechanisms affecting the methane lifetime (ULAQ-CCM, GEOSCCM, CCSM-CAM4). First results show that the CH4 lifetime may become significantly longer (by about 10%) with a sustained injection of 2.5 Tg-S/yr started in year 2020, which implies an increase of tropospheric CH4 (200 ppbv) and a positive indirect radiative forcing of sulfate geoengineering due to CH4 changes (+0.1 W/m2 in the 2045).

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.

Metalimnetic oxygen minima alter the vertical profiles of carbon dioxide and methane in a managed freshwater reservoir.

PubMed

McClure, Ryan P; Hamre, Kathleen D; Niederlehner, B R; Munger, Zackary W; Chen, Shengyang; Lofton, Mary E; Schreiber, Madeline E; Carey, Cayelan C

2018-04-30

Metalimnetic oxygen minimum zones (MOMs) commonly develop during the summer stratified period in freshwater reservoirs because of both natural processes and water quality management. While several previous studies have examined the causes of MOMs, much less is known about their effects, especially on reservoir biogeochemistry. MOMs create distinct redox gradients in the water column which may alter the magnitude and vertical distribution of dissolved methane (CH 4 ) and carbon dioxide (CO 2 ). The vertical distribution and diffusive efflux of CH 4 and CO 2 was monitored for two consecutive open-water seasons in a eutrophic reservoir that develops MOMs as a result of the operation of water quality engineering systems. During both summers, elevated concentrations of CH 4 accumulated within the anoxic MOM, reaching a maximum of 120 μM, and elevated concentrations of CO 2 accumulated in the oxic hypolimnion, reaching a maximum of 780 μM. Interestingly, the largest observed diffusive CH 4 effluxes occurred before fall turnover in both years, while peak diffusive CO 2 effluxes occurred both before and during turnover. Our data indicate that MOMs can substantially change the vertical distribution of CH 4 and CO 2 in the water column in reservoirs, resulting in the accumulation of CH 4 in the metalimnion (vs. at the sediments) and CO 2 in the hypolimnion. Copyright © 2018 Elsevier B.V. All rights reserved.

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.

Distribution, physical state and mixing of materials at the surface of Pluto from New Horizons

NASA Astrophysics Data System (ADS)

Schmitt, Bernard; Philippe, Sylvain; Grundy, Will; Reuter, D. C.; Quirico, Eric; Protopapa, Silvia; Côte, Rémi; Young, Leslie; Binzel, Richard; Cook, Jason C.; Cruikshank, Dale P.; Dalle Ore, Cristina M.; Earle, Alissa M.; Ennico, Kimberly; Howett, Carly; Jennings, Donald; Linscott, Ivan; Lunsford, A. W.; Olkin, Catherine B.; Parker, Joel Wm.; Parker, Alex; Singer, Kelsi N.; Spencer, John R.; Stansberry, John A.; Stern, S. Alan; Tsang, Constantine; Verbiscer, Anne J.; Weaver, Harold A.; New Horizons Science Team

2016-10-01

In July 2015 the New Horizons spacecraft recorded a large set of data on Pluto, in particular with the LEISA spectro-imager dedicated to the study of the surface composition.In this talk we report a study of the distribution and physical state of the ices and non-ice materials on Pluto's surface and their mode and degree of mixing. Principal Component analysis as well as specific spectral indicators and correlation plots are used on high resolution LEISA spectro-images covering the whole illuminated face of Pluto. Qualitative distribution maps have been obtained for the 4 main condensed molecules, N2, CH4, CO, H2O as well as for the visible-dark red material. These maps indicate the presence of 3 different types of ices: N2-rich:CH4:CO ices, CH4-rich:(CO:N2?) ices and H2O ice. Their mixing lines and with the dark reddish material are studied. CH4 is mixed at the molecular level with N2 and CO, thus forming a ternary molecular mixture that follows its phase diagram with low solubility limits. The occurrence of a N2-rich - CH4-rich ices mixing line associated with a decrease of the CO/CH4 ratio tell us that a fractionation sublimation sequence transforms N2-rich ice into either a N2-rich - CH4-rich binary mixture at the surface or an upper CH4-rich(:CO:N2) ice crust that may hide the N2-rich ice below. The CH4-rich - H2O mixing line witnesses the subsequent sublimation of CH4 ice left behind by the N2:CO sublimation (N spring-summer), or a direct condensation of CH4 ice on cold H2O ice (S autumn). The very sharp spatial transitions between CH4-containing ices and the dark red material are probably due to thermal incompatibility. Finally there is some spatial mixing of the reddish material covering H2O ice. H2O ice appears to be the substratum on which other ices condense or non-volatile organic material is deposited from the atmosphere. The spatial distribution of these materials is very complex.The high spatial definition of all these composition maps will allow us to compare them with Pluto's geologic features observed by LORRI panchromatic and MVIC multispectral imagers to better understand the geophysical processes in action at the surface of this astonishingly active cold world.

Evaluation of factors affecting accurate measurements of atmospheric CO2 and CH4 by wavelength-scanned cavity ring-down spectroscopy

NASA Astrophysics Data System (ADS)

Nara, H.; Tanimoto, H.; Tohjima, Y.; Mukai, H.; Nojiri, Y.; Katsumata, K.; Rella, C.

2012-07-01

We examined potential interferences from water vapor and atmospheric background gases (N2, O2, and Ar), and biases by isotopologues of target species, on accurate measurement of atmospheric CO2 and CH4 by means of wavelength-scanned cavity ring-down spectroscopy (WS-CRDS). Variations in the composition of the background gas substantially impacted the CO2 and CH4 measurements: the measured amounts of CO2 and CH4 decreased with increasing N2 mole fraction, but increased with increasing O2 and Ar, suggesting that the pressure-broadening effects (PBEs) increased as Ar < O2 < N2. Using these experimental results, we inferred PBEs for the measurement of synthetic standard gases. The PBEs were negligible (up to 0.05 ppm for CO2 and 0.01 ppb for CH4) for gas standards balanced with purified air, although the PBEs were substantial (up to 0.87 ppm for CO2 and 1.4 ppb for CH4) for standards balanced with synthetic air. For isotopic biases on CO2 measurements, we compared experimental results and theoretical calculations, which showed excellent agreement within their uncertainty. We derived empirical correction functions for water vapor for three WS-CRDS instruments (Picarro EnviroSense 3000i, G-1301, and G-2301). Although the transferability of the functions was not clear, no significant difference was found in the water vapor correction values among these instruments within the typical analytical precision at sufficiently low water concentrations (< 0.3%V for CO2 and < 0.4%V for CH4). For accurate measurements of CO2 and CH4 in ambient air, we concluded that WS-CRDS measurements should be performed under complete dehumidification of air samples, or moderate dehumidification followed by application of a water vapor correction function, along with calibration by natural air-based standard gases or purified air-balanced synthetic standard gases with isotopic correction.

Emission of greenhouse gases from geographically isolated wetlands of Western Siberia

NASA Astrophysics Data System (ADS)

Golovatskaya, E.; Dyukarev, E.; Veretennikova, E.

2014-12-01

Wetlands are integral components of landscapes with specific nutrient dynamics and carbon sequestration potentials, which frequently differ, based on hydroperiod and seasonal hydropattern, as well as the constituent concentration of inputs, site-specific storages and vegetation structures. Human modifications have the potential to significantly alter controls on carbon dynamics. This study focused on determining carbon emissions (CO2 and CH4) from geographically isolated peatlands within the Ob-Tom River Interfluve area of Western Siberia affected by water diversion for municipal use by the city of Tomsk, Russia. Two oligotrophic wetlands within the study area were selected for site-specific CO2 studies, the Timiryazevskoe (16 ha) and Kirsanovskoe wetlands (29 ha), both affected by the Tomsk water intake (177 water wells 250 000 m3 water daily). Measurements of СО2 and CH4 emissions from peat surfaces were carried out bi-monthly in growing periods from 2008-2013 in two dominate vegetation zones, pine- shrub-sphagnum phytocenosis (ryam) and sedge-sphagnum fens. СО2 emissions were measured using OPTOGAS-500.4 infrared gas analyzer and dark chamber. Methane emissions were measured using static chamber method. Air samples were collected by syringes and analyzed at gas chromatograph Shimadzu-GC14B. Observations were accompanied by measurement of air temperature and humidity, surface temperature, peat temperature at various depths and the water table level. CО2 emission over the vegetative growing period had clearly pronounced seasonal dynamics with maximum values in the middle of the growing season (mid-July) and minimum values in spring and autumn. The average total flux over the studied period is 123±55 gС/m2 at sedge-sphagnum fen of Kirsanovskoe wetland and 323±66 gС/m2 at fen of Timiryazevskoe wetland. Total СО2 flux for the snow-free period at ryam sites of Timiryazevskoe and Kirsanovskoe wetlands is 238±84 and 260±47 gС/m2 accordingly. Methane emission from the surface of isolated wetlands for the snow-free period varies from 0.3±1.1 to 2.9±2.3 gC/m2 on ryam sites of Kirsanovskoe and Timiryazevskoe wetlands respectively. The total CH4 flux on sedge-sphagnum fen varies from 2.5±3.0 at Kirsanovskoe wetlands to 31.6±26.3 gC/m2 at Timiryazevskoe wetland.

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Surfactant Facilitated Spreading of Aqueous Drops on Hydrophobic Surfaces

NASA Technical Reports Server (NTRS)

Kumar, Nitin; Couzis, Alex; Maldarelli, Charles; Singh, Bhim S. (Technical Monitor)

2000-01-01

Microgravity technologies often require aqueous phases to spread over nonwetting hydrophobic solid/surfaces. At a hydrophobic surface, the air/hydrophobic solid tension is low, and the solid/aqueous tension is high. A large contact angle forms as the aqueous/air tension acts together with the solid/air tension to balance the large solid/aqueous tension. The aqueous phase, instead of spreading, is held in a meniscus by the large angle. Surfactants facilitate the wetting of water on hydrophobic surfaces by adsorbing on the water/air and hydrophobic solid/water interfaces and lowering the surface tensions of these interfaces. The tension reductions decrease the contact angle, which increases the equilibrium wetted area. Hydrocarbon surfactants (i.e. amphiphiles with a hydrophobic chain of methylene groups attached to a large polar group to give aqueous solubility) do not reduce significantly the contact angles of the very hydrophobic surfaces such as parafilm or polyethylene. Trisiloxane surfactants (amphiphiles with a hydrophobe consisting of methyl groups linked to a trisiloxane backbone in the form of a disk ((CH3)3-Si-O-Si-O-Si(CH3)3)) and an extended ethoxylate (-(OCH2CH2)n-) polar group in the form of a chain with seven or eight units) can significantly reduce the contact angle of water on a very hydrophobic surface and cause rapid and complete (or nearly complete) spreading (lermed superspreading). The overall goal of the research described in this proposal is to establish and verify a theory for how trisiloxanes cause superspreading, and then use this knowledge as a guide to developing more general hydrocarbon based surfactant systems which superspread and can be used in microgravity. We propose that the trisiloxane surfactants superspread when the siloxane adsorbs, the hydrophobic disk parts of the molecule adsorb onto the surface removing the surface water. Since the cross sectional area of the disk is larger than that of the extended ethoxylate chain, the disks can form a space filling mat on the surface which removes a significant amount of the surface water. The water adjacent to the hydrophobic solid surface is of high energy due to incomplete hydrogen bonding; its removal significantly lowers the tension and reduces the contact angle. Hydrocarbon surfactants cannot remove as much surface water because their large polar groups prevent the chains from cohering lengthwise. In our report last year we presented a poster describing the preparation of model very hydrophobic surfaces which are homogeneous and atomically smooth using self assembled monolayers of octadecyl trichlorosilane (OTS). In this poster we will use these surfaces as test substrates in developing hydrocarbon based surfactant systems which superspread. We studied a binary hydrocarbon surfactant systems consisting of a very soluble large polar group polyethylene oxide surfactant (C12E6 (CH3(CH2)11(OCH2CH2)6OH) and a long chain alcohol dodecanol. By mixing the alcohol with this soluble surfactant we have found that the contact angle of the mixed system on our test hydrophobic surfaces is very low. We hypothesize that the alcohol fills in the gaps between adjacent adsorbed chains of the large polar group surfactant. This filling in removes the surface water and effects the decrease in contact angle. We confirm this hypothesis by demonstrating that at the air/water interface the mixed layer forms condensed phases while the soluble large polar group surfactant by itself does not. We present drop impact experiments which demonstrate that the dodecanol/C12E6 mixture is effective in causing impacting drops to spread on the very hydrophobic model OTS surfaces.

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.

Comparison of CH4 Emission from Rice Paddy Soils between Coastal Zone and Inland Regions

NASA Astrophysics Data System (ADS)

Sun, M.; Li, X.

2016-12-01

Numerous measurements of methane (CH4) emission fluxes have been carried out in rice paddy soil between coastal zone and inland regions. However, the differences of CH4 emission from rice paddy soils in these two locations were unavailable. A database of CH4 emission in paddy rice was compiled from previous published references and field observations with major parameters including water regimes, fertilizer application, CH4 fluxes, and environmental variables. Results showed that CH4 emission from inland paddy fields was significantly higher than that in the coastal zone (p < 0.05). Fertilizer application and water management played an important role in CH4 emission. The application of organic fertilizer and continuous flooding significantly promoted CH4 emission from paddy fields. CH4 fluxes showed significantly positive correlations with organic matter, total nitrogen, available potassium and annual temperature (R2 = 0.39, 0.53, 0.27 and 0.23, p < 0.05), and negative correlations with pH and available phosphorus (R2 = 0.29 and 0.37, p < 0.05). Significant differences occurred in available potassium between inland and coastal rice paddy (p < 0.05), which might account for the difference of CH4 emission between inland and coastal rice paddy. The contrasting of CH4 fluxes between inland and coastal wetlands could improve our understanding of the roles of rice paddies in the regional CH4 regulation. Our results also have implications for informing rice paddy management and climate change policy making the efforts being made by agricultural organizations and enterprises to restore coastal rice paddies for mitigating CH4 emissions.

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.

Little evidence for significant increases of methane emissions from oil and gas operations in the U.S.

NASA Astrophysics Data System (ADS)

Lan, X.; Tans, P. P.; Sweeney, C.; Andrews, A. E.; Dlugokencky, E. J.; Lang, P. M.; Crotwell, M.; Miller, B.; Kofler, J.; Newberger, T.; McKain, K.; Wolter, S.; Montzka, S. A.

2016-12-01

Recent studies on whether methane (CH4) emissions from oil and natural gas (ONG) operations in the U.S. have increased are still inconclusive. To provide observational evidence we carefully analyzed the in-situ CH4 measurements from the NOAA/ESRL Global Greenhouse Gas Reference Network (GGGRN) for the best estimates of CH4 trends for 2006-2016. Methane data from more than 20 surface and aircraft sites across the U.S. were included in this study. Variations of sampling frequencies in different seasons were taken into account for accurate trend detection. Correlations among measurements within short sampling intervals were also considered for uncertainty estimates. We found that most of our sites had similar CH4 trends of 6 ppb/yr, which was comparable with the recent global background CH4 trend. Substantially higher growth rates were found at the Southern Great Plain site in Oklahoma (SGP, downwind of the Eagle Ford, Barnett Shale and Woodford ONG fields) and the Dahlen sites in North Dakota (DND, downwind of the Bakken ONG field), which indicated influences from regional ONG activities. Ethane (C2H6) measurements from SGP (C2H6 measurements were not available from DND) and propane (C3H8) measurements from both SPG and DND exhibited significant increasing trends, while trends at other sites were either non-significant (trend < 2*S.D.) or only marginally significant. Linear correlations were well identified for surface C3H8 and CH4 enhancements at these two sites, relative to observations at higher altitudes. However, by applying the observed enhancement ratios of surface C3H8 /CH4 and the C3H8 trends (as indicator for ONG emissions) on CH4 trend estimates, we would infer much larger surface CH4 trends than what we actually observed at these two sites. This discrepancy suggests that using enhancement ratios of C3H8 /CH4 is not likely a reliable approach to compute CH4 emission trends.

A doping technique that suppresses undesirable H2 evolution derived from overall water splitting in the highly selective photocatalytic conversion of CO2 in and by water.

PubMed

Teramura, Kentaro; Wang, Zheng; Hosokawa, Saburo; Sakata, Yoshihisa; Tanaka, Tsunehiro

2014-08-04

Photocatalytic conversion of CO2 to reduction products, such as CO, HCOOH, HCHO, CH3OH, and CH4, is one of the most attractive propositions for producing green energy by artificial photosynthesis. Herein, we found that Ga2O3 photocatalysts exhibit high conversion of CO2. Doping of Zn species into Ga2O3 suppresses the H2 evolution derived from overall water splitting and, consequently, Zn-doped, Ag-modified Ga2O3 exhibits higher selectivity toward CO evolution than bare, Ag-modified Ga2O3. We observed stoichiometric amounts of evolved O2 together with CO. Mass spectrometry clarified that the carbon source of the evolved CO is not the residual carbon species on the photocatalyst surface, but the CO2 introduced in the gas phase. Doping of the photocatalyst with Zn is expected to ease the adsorption of CO2 on the catalyst surface. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Cellulose and Lignin Carbon Isotope Signatures in Sphagnum Moss Reveal Complementary Environmental Properties

NASA Astrophysics Data System (ADS)

Loisel, J.; Nichols, J. E.; Kaiser, K.; Beilman, D. W.; Yu, Z.

2016-12-01

The carbon isotope signature (δ13C) of Sphagnum moss is increasingly used as a proxy for past surface wetness in peatlands. However, conflicting interpretations of these carbon isotope records have recently been published. While the water film hypothesis suggests that the presence of a thick (thin) water film around hollow (hummock) mosses leads to less (more) negative δ13C values, the carbon source hypothesis poses that a significant (insignificant) amount of CH4 assimilation by hollow (hummock) mosses leads to more (less) negative δ13C values. To evaluate these competing mechanisms and their impact on moss δ13C, we gathered 30 moss samples from 6 peatlands in southern Patagonia. Samples were collected along a strong hydrological gradient, from very dry hummocks (80 cm above water table depth) to submerged hollows (5 cm below water surface). These peat bogs have the advantage of being colonized by a single cosmopolitan moss species, Sphagnum magellanicum, limiting potential biases introduced by species-specific carbon discrimination. We measured δ13C from stem cellulose and leaf waxes on the same samples to quantify compound-specific carbon signatures. We found that stem cellulose and leaf-wax lipids were both strongly negatively correlated with moss water content, suggesting a primary role of water film thickness on carbon assimilation. In addition, isotopic fractionation during wax synthesis was greater than for cellulose. This offset decreases as conditions get drier, due to (i) a more effective carbon assimilation, or (ii) CH4 uptake through symbiosis with methanotrophic bacteria within the leaves of wet mosses. Biochemical analysis (carbohydrates, amino acids, hydrophenols, cutin acids) of surface moss are currently being conducted to characterize moss carbon allocation under different hydrological conditions. Overall, this modern calibration work should be of use for interpreting carbon isotope records from peatlands.

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.

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.

Controls on gas transfer velocities in a large river

NASA Astrophysics Data System (ADS)

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

2012-06-01

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

Impact Delivery of Reduced Greenhouse Gases on Early Mars

NASA Technical Reports Server (NTRS)

Haberle, R. M.; Zahnle, K.; Barlow, N.

2017-01-01

Reducing greenhouse gases are once again the latest trend in finding solutions to the early Mars climate dilemma. In its current form - as proposed by Ramirez et al. [1], later refined by Wordsworth et al. [2], and confirmed by Ramirez [3] - collision induced absorptions between CO2-H2 or CO2-CH4 provide enough extra greenhouse power to raise global mean surface temperatures to the melting point of water provided the atmosphere is thick enough and the reduced gases are abundant enough. To raise surface temperatures significantly by this mechanism, surface pressures must be at least 500 mb and H2 and/or CH4 concentrations must be at or above the several percent level. Both Wordsworth et al. [2] and Ramirez [3] show that the melting point can be reached in atmospheres with 1-2 bars of CO2 and 2-10% H2; smaller concentrations of H2 will suffice if CH4 is also present. If thick weakly reducing atmospheres are the solution to the faint young Sun paradox, then plausible mechanisms must be found to generate and sustain the gases. Possible sources of reducing gases include volcanic outgassing, serpentinization, and impact delivery; sinks include photolyis, oxidation, and escape to space. The viability of the reduced greenhouse hypothesis depends, therefore, on the strength of these sources and sinks.

Atomic and Molecular Adsorption on Cu(111)

DOE PAGES

Xu, Lang; Lin, Joshua; Bai, Yunhai; ...

2018-05-15

Here, due to the wide use of copper-based catalysts in industrial chemical processes, fundamental understanding of the interactions between copper surfaces and various reaction intermediates is highly desired. Here, we performed periodic, self-consistent density functional theory (DFT-GGA) calculations to study the adsorption of five atomic species (H, C, N, O, and S), seven molecular species (NH 3, CH 4, N 2, CO, HCN, NO, and HCOOH), and 13 molecular fragments (CH, CH 2, CH 3, NH, NH 2, OH, CN, COH, HCO, COOH, HCOO, NOH, and HNO) on the Cu(111) surface at a coverage of 0.25 monolayer. The preferred bindingmore » site, binding energy, and the corresponding surface deformation energy of each species were determined, as well as the estimated diffusion barrier and diffusion pathway. The binding strengths calculated using the PW91 functional decreased in the following order: CH > C > O > S > CN > NH > N > CH 2 > OH > HCOO > COH > H > NH 2 > NOH > COOH > HNO > HCO > CH 3 > NO > CO > NH 3 > HCOOH. No stable binding structures were observed for N 2, HCN, and CH 4. The adsorbate–surface and intramolecular vibrational modes of all the adsorbates at their preferred binding sites were deternined. Using the calculated adsorption energetics, potential energy surfaces were constructed for the direct decomposition of CO, CO 2, NO, N 2, NH 3, and CH 4 and the hydrogen-assisted decomposition of CO, CO 2, and NO.« less

Atomic and Molecular Adsorption on Cu(111)

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

Xu, Lang; Lin, Joshua; Bai, Yunhai

Here, due to the wide use of copper-based catalysts in industrial chemical processes, fundamental understanding of the interactions between copper surfaces and various reaction intermediates is highly desired. Here, we performed periodic, self-consistent density functional theory (DFT-GGA) calculations to study the adsorption of five atomic species (H, C, N, O, and S), seven molecular species (NH 3, CH 4, N 2, CO, HCN, NO, and HCOOH), and 13 molecular fragments (CH, CH 2, CH 3, NH, NH 2, OH, CN, COH, HCO, COOH, HCOO, NOH, and HNO) on the Cu(111) surface at a coverage of 0.25 monolayer. The preferred bindingmore » site, binding energy, and the corresponding surface deformation energy of each species were determined, as well as the estimated diffusion barrier and diffusion pathway. The binding strengths calculated using the PW91 functional decreased in the following order: CH > C > O > S > CN > NH > N > CH 2 > OH > HCOO > COH > H > NH 2 > NOH > COOH > HNO > HCO > CH 3 > NO > CO > NH 3 > HCOOH. No stable binding structures were observed for N 2, HCN, and CH 4. The adsorbate–surface and intramolecular vibrational modes of all the adsorbates at their preferred binding sites were deternined. Using the calculated adsorption energetics, potential energy surfaces were constructed for the direct decomposition of CO, CO 2, NO, N 2, NH 3, and CH 4 and the hydrogen-assisted decomposition of CO, CO 2, and NO.« less

Atmospheric CH4 in the first decade of the 21st century: Inverse modeling analysis using SCIAMACHY satellite retrievals and NOAA surface measurements

NASA Astrophysics Data System (ADS)

Bergamaschi, P.; Houweling, S.; Segers, A.; Krol, M.; Frankenberg, C.; Scheepmaker, R. A.; Dlugokencky, E.; Wofsy, S. C.; Kort, E. A.; Sweeney, C.; Schuck, T.; Brenninkmeijer, C.; Chen, H.; Beck, V.; Gerbig, C.

2013-07-01

causes of renewed growth in the atmospheric CH4 burden since 2007 are still poorly understood and subject of intensive scientific discussion. We present a reanalysis of global CH4 emissions during the 2000s, based on the TM5-4DVAR inverse modeling system. The model is optimized using high-accuracy surface observations from NOAA ESRL's global air sampling network for 2000-2010 combined with retrievals of column-averaged CH4 mole fractions from SCIAMACHY onboard ENVISAT (starting 2003).Using climatological OH fields, derived global total emissions for 2007-2010 are 16-20 Tg CH4/yr higher compared to 2003-2005. Most of the inferred emission increase was located in the tropics (9-14 Tg CH4/yr) and mid-latitudes of the northern hemisphere (6-8 Tg CH4/yr), while no significant trend was derived for Arctic latitudes. The atmospheric increase can be attributed mainly to increased anthropogenic emissions, but the derived trend is significantly smaller than estimated in the EDGARv4.2 emission inventory. Superimposed on the increasing trend in anthropogenic CH4 emissions are significant inter-annual variations (IAV) of emissions from wetlands (up to ±10 Tg CH4/yr), and biomass burning (up to ±7 Tg CH4/yr). Sensitivity experiments, which investigated the impact of the SCIAMACHY observations (versus inversions using only surface observations), of the OH fields used, and of a priori emission inventories, resulted in differences in the detailed latitudinal attribution of CH4 emissions, but the IAV and trends aggregated over larger latitude bands were reasonably robust. All sensitivity experiments show similar performance against independent shipboard and airborne observations used for validation, except over Amazonia where satellite retrievals improved agreement with observations in the free troposphere.

Spatio-temporal variation of methane over Indian region: Seasonal and inter-annual variation .

NASA Astrophysics Data System (ADS)

M, K.; Nair, P. R.

2015-12-01

Methane (CH4) has an important role in the radiation budget and chemistry in the lower and middle atmosphere as a greenhouse and reactive trace gas. The rapid developments in the agriculture and industry over India have lead to the emission of many pollutants like CO, O3, CH4, CO2, SO2 etc into the atmosphere. However, their sources, sinks and concentration levels are poorly understood because of the lack of systematic sampling and monitoring. The advent of satellite remote sensing has helped to analyze the chemical composition of atmosphere with good spatial coverage especially over tropical region which was poorly sampled with the existing surface network. This work attempts an analysis of spatial distribution, seasonal cycle and inter annual variation of CH4 over Indian region during 2003-2009 using SCIAMACHY data onboard ENVISAT. Column CH4 varies from 1740-1890 ppbv over Indian region with distinct spatial and temporal features. We observed a dependence of seasonal CH4 variation on rice cultivation, convective activities and changes in boundary layer characteristics. The comparative study using satellite, aircraft and surface measurement shown CH4 has non-homogeneity in its distribution and seasonal variation in different layers of atmosphere. A comparative study of CH4 at different hot spot regions over the globe was carried out which showed prominent hemispherical variations. Large spread in column CH4 was observed at India and Chinese region compared to other regions with a significant seasonal variability. This study points to the blending of satellite, aircraft and surface measurements for the realization of regional distribution of CH4.

Controls on methane released through ebullition in peatlands affected by permafrost degradation

USGS Publications Warehouse

Klapstein, Sara J.; Turetsky, Merritt R.; McGuire, A. David; Harden, Jennifer W.; Czimczik, C.I.; Xu, Xiaomei; Chanton, J.P.; Waddington, James Michael

2014-01-01

Permafrost thaw in peat plateaus leads to the flooding of surface soils and the formation of collapse scar bogs, which have the potential to be large emitters of methane (CH4) from surface peat as well as deeper, previously frozen, permafrost carbon (C). We used a network of bubble traps, permanently installed 20 cm and 60 cm beneath the moss surface, to examine controls on ebullition from three collapse bogs in interior Alaska. Overall, ebullition was dominated by episodic events that were associated with changes in atmospheric pressure, and ebullition was mainly a surface process regulated by both seasonal ice dynamics and plant phenology. The majority (>90%) of ebullition occurred in surface peat layers, with little bubble production in deeper peat. During periods of peak plant biomass, bubbles contained acetate-derived CH4 dominated (>90%) by modern C fixed from the atmosphere following permafrost thaw. Post-senescence, the contribution of CH4 derived from thawing permafrost C was more variable and accounted for up to 22% (on average 7%), in the most recently thawed site. Thus, the formation of thermokarst features resulting from permafrost thaw in peatlands stimulates ebullition and CH4 release both by creating flooded surface conditions conducive to CH4 production and bubbling as well as by exposing thawing permafrost C to mineralization.

Carbon dioxide and methane dynamics in estuaries

NASA Astrophysics Data System (ADS)

Borges, Alberto V.; Abril, Gwenaël.

2010-05-01

We carried out a literature overview to synthesize current knowledge on CO2 and CH4 dynamics and fluxes with the atmosphere in estuarine environments. Estuarine systems are highly dynamic in terms of carbon cycling and emit CO2 to the atmosphere at rates that are quantitatively significant for the global C cycle. This emission of CO2 to the atmosphere is strongly supported by the net heterotrophic nature of these ecosystems. The robustness of the evaluation of the emission of CO2 from estuarine ecosystems has increased in last years due to increasing data availability and improvements in the surface area estimates by types. At present, the lack of sufficient data is the major limitation in the quantification of the spatial and temporal variability of CO2 fluxes in estuarine environments. Regarding future observations, there is also a need for sustained measurements to unravel inter-annual variability and long-term trends of CO2 and CH4 in estuarine environments. Indeed, due to the strong linkage with river catchements, inter-annual variability of CO2 and CH4 in estuarine environments is expected to be strong. Data used in the present synthesis were either obtained by the authors, data mined from publications or communicated by colleagues. There is a need for publicly available and quality checked data-bases for CO2 and CH4 in estuarine environments. Not only cross-system meta-analysis of data (CO2, CH4, O2, …) can be enlightening as explored in the present work, but also considering the uncertainties in the evaluation of the gas transfer velocity, there could be a need for future re-evaluations of air-water CO2 and CH4 fluxes, requiring access to the raw pCO2 and [CH4] data.

Arctic Methane: the View from Space

NASA Astrophysics Data System (ADS)

Leifer, I.; Yurganov, L.; Xiong, X.

2014-12-01

Global increase of methane that started in 2007-2008 after a decade of stability requires investigation and explanation. Recent Arctic warming has stimulated speculation about dissociation of Arctic Ocean methane hydrates providing a potentially important new climatic positive feedback. Satellite thermal infrared (TIR) data do not require sunlight, providing key advantages for Arctic data collection compared to shortwave infrared spectroscopy. The US Atmospheric IR Sounder (AIRS) has been delivering CH4 tropospheric data since 2002; NOAA CH4 retrievals from the European Infrared Atmospheric Sounding Interferometer (IASI) radiation data are available since 2008 and analyzed here since 2009. Accuracy of TIR satellite retrievals, especially for the lower troposphere, diminishes for a cold, underlying surface. In this analysis the dependence is parameterized using the Thermal Contrast (a difference between surface temperature and air temperature at the altitude of 4 km, defined THC). A correction function was applied to CH4 data based on a data-derived relationship between THC and retrieved CH4 for areas with positive THC (in other words, without temperature inversions). The seasonal cycles of the adjusted low tropospheric data are in agreement with the surface in situ measurements. Instantaneous IASI retrievals exhibit less variability than AIRS v6 data. Maximum positive deviation of methane concentration measured by IASI for the study period was found for Baffin Bay in November-December, 2013 (Figure). It was concluded that the methane anomaly could indicate both coastal and off-shore emissions. Off-shore data were spatially consistent with a hydrate dissociation mechanisms, active for water depths below the hydrate stability zone top at ~300 m. These are hypothesized to dissociate during seasonal temperature maximum in the bottom layer of the ocean, which occurs in fall. IASI data may be considered as a reliable source of information about Arctic CH4 for conditions of sufficiently high atmospheric vertical thermal contrast. Figure caption. Standard adjusted NOAA/IASI retrievals of 0-4 km mean methane concentration over areas with positive THC. Black points are for the entire Baffin Bay, red points are for locations with seawater depth below 300 m. Blue line is the all-Arctic mean.

Forest floor methane flux modelled by soil water content and ground vegetation - comparison to above canopy flux

NASA Astrophysics Data System (ADS)

Halmeenmäki, Elisa; Peltola, Olli; Haikarainen, Iikka; Ryhti, Kira; Rannik, Üllar; Pihlatie, Mari

2017-04-01

Methane (CH4) is an important and strong greenhouse gas of which atmospheric concentration is rising. While boreal forests are considered as an important sink of CH4 due to soil CH4 oxidation, the soils have also a capacity to emit CH4. Moreover, vegetation is shown to contribute to the ecosystem-atmosphere CH4 flux, and it has been estimated to be the least well known natural sources of CH4. In addition to well-known CH4 emissions from wetland plants, even boreal trees have been discovered to emit CH4. At the SMEAR (Station for Measuring Ecosystem-Atmosphere Relations) II station in Hyytiälä, southern Finland (61° 51' N, 24°17' E; 181 m asl), we have detected small CH4 emissions from above the canopy of a Scots pine (Pinus sylvestris) dominated forest. To assess the origin of the observed emissions, we conducted forest floor CH4 flux measurements with 54 soil chambers at the footprint area of the above canopy flux measurements during two growing seasons. In addition, we measured the soil volumetric water content (VWC) every time next to the forest floor chamber measurements, and estimated vegetation coverages inside the chambers. In order to model the forest floor CH4 flux at the whole footprint area, we combined lidar (light detection and ranging) data with the field measurements. To predict the soil water content and thus the potential CH4 flux, we used local elevation, slope, and ground return intensity (GRI), calculated from the lidar data (National Land Survey of Finland). We categorized the soil chambers into four classes based on the VWC so that the class with the highest VWC values includes all the soil chambers with a potential to emit CH4. Based on a statistically significant correlation between the VWC and the forest floor CH4 flux (r = 0.30, p < 0.001), we modelled the potential forest floor CH4 flux of the whole area. The results of the soil chamber measurements show a few areas of the forest floor with significant CH4 emissions. The modelled map of the potential CH4 flux is consistent with the measurements of the flux and the VWC, indicating that the wetter areas have potential for CH4 emissions, while the drier areas have potential for CH4 uptake. Preliminary results of the vegetation coverage show a positive correlation between the first year forest floor CH4 flux and the coverage of Sphagnum spp. mosses (r = 0.55, p < 0.001). Furthermore, we will include the vegetation coverage to the analysis, and compare the modelled forest floor CH4 flux with the measured above canopy flux. This ongoing research will give valuable information about the CH4 sources and dynamics in boreal forests.

Clathrate hydrate stability models for Titan: implications for a global subsurface ocean

NASA Astrophysics Data System (ADS)

Basu Sarkar, D.; Elwood Madden, M.

2013-12-01

Titan is the only planetary body in the solar system, apart from the Earth, with liquid at its surface. Titan's changing rotational period suggests that a global subsurface ocean decouples the icy crust from the interior. Several studies predict the existence of such an internal ocean below an Ice I layer, ranging in depth between a few tens of kilometers to a few hundreds of kilometers, depending on the composition of the icy crust and liquid-ocean. While the overall density of Titan is well constrained, the degree of differentiation within the interior is unclear. These uncertainties lead to poor understanding of the volatile content of the moon. However, unlike other similar large icy moons like Ganymede and Callisto, Titan has a thick nitrogen atmosphere, with methane as the second most abundant constituent - 5% near the surface. Titan's atmosphere, surface, and interior are likely home to various compounds such as C2H6, CO2, Ar, N2 and CH4, capable of forming clathrate hydrates. In addition, the moon has low temperature and low-to-high pressure conditions required for clathrate formation. Therefore the occurrence of extensive multicomponent hydrates may effect the composition of near-surface materials, the subsurface ocean, as well as the atmosphere. This work uses models of hydrate stability for a number of plausible hydrate formers including CH4, C2H6, CH4 + C2H6 and CH4 + NH3, and equilibrium geothermal gradients for probable near-surface materials to delineate the lateral and vertical extent of clathrate hydrate stability zones for Titan. By comparing geothermal gradients with clathrate stability fields for these systems we investigate possible compositions of Titan's global subsurface ocean. Preliminary model results indicate that ethane hydrates or compound hydrates of ethane and methane could be destabilized within the proposed depth range of the internal ocean, while methane/ammonia or pure methane hydrates may not be affected. Therefore, ethane or ethane-methane clathrates may be a major component of Titan's icy shell. Modeled geothermal gradients and stability fields of possible clathrate formers with three different scenarios for an internal ocean from the recent literature. Geothermal gradients obtained from thermal conductivity and density representing water ice and pure CH4-C2H6 hydrate. Clathrate stability field determined using HYDOFF and recent publications of NH3 clathrate stability.

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.

Methane oxidation in a crude oil contaminated aquifer: Delineation of aerobic reactions at the plume fringes

USGS Publications Warehouse

Amos, R.T.; Bekins, B.A.; Delin, G.N.; Cozzarelli, I.M.; Blowes, D.W.; Kirshtein, J.D.

2011-01-01

High resolution direct-push profiling over short vertical distances was used to investigate CH4 attenuation in a petroleum contaminated aquifer near Bemidji, Minnesota. The contaminant plume was delineated using dissolved gases, redox sensitive components, major ions, carbon isotope ratios in CH4 and CO2, and the presence of methanotrophic bacteria. Sharp redox gradients were observed near the water table. Shifts in ??13CCH4 from an average of - 57.6??? (?? 1.7???) in the methanogenic zone to - 39.6??? (?? 8.7???) at 105 m downgradient, strongly suggest CH4 attenuation through microbially mediated degradation. In the downgradient zone the aerobic/anaerobic transition is up to 0.5 m below the water table suggesting that transport of O2 across the water table is leading to aerobic degradation of CH4 at this interface. Dissolved N2 concentrations that exceeded those expected for water in equilibrium with the atmosphere indicated bubble entrapment followed by preferential stripping of O2 through aerobic degradation of CH4 or other hydrocarbons. Multivariate and cluster analysis were used to distinguish between areas of significant bubble entrapment and areas where other processes such as the infiltration of O 2 rich recharge water were important O2 transport mechanisms. ?? 2011 Elsevier B.V. All rights reserved.

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

USGS Publications Warehouse

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

2006-01-01

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

Methane emission by plant communities in an alpine meadow on the Qinghai-Tibetan Plateau: a new experimental study of alpine meadows and oat pasture.

PubMed

Wang, Shiping; Yang, Xiaoxia; Lin, Xingwu; Hu, Yigang; Luo, Caiyun; Xu, Guangping; Zhang, Zhenhua; Su, Ailing; Chang, Xiaofen; Chao, Zengguo; Duan, Jichuang

2009-08-23

Recently, plant-derived methane (CH(4)) emission has been questioned because limited evidence of the chemical mechanism has been identified to account for the process. We conducted an experiment with four treatments (i.e. winter-grazed, natural alpine meadow; naturally restored alpine meadow eight years after cultivation; oat pasture and bare soil without roots) during the growing seasons of 2007 and 2008 to examine the question of CH(4) emission by plant communities in the alpine meadow. Each treatment consumed CH(4) in closed, opaque chambers in the field, but two types of alpine meadow vegetation reduced CH(4) consumption compared with bare soil, whereas oat pasture increased consumption. This result could imply that meadow vegetation produces CH(4). However, measurements of soil temperature and water content showed significant differences between vegetated and bare soil and appeared to explain differences in CH(4) production between treatments. Our study strongly suggests that the apparent CH(4) production by vegetation, when compared with bare soil in some previous studies, might represent differences in soil temperature and water-filled pore space and not the true vegetation sources of CH(4).

Above- and below-ground methane fluxes and methanotrophic activity in a landfill-cover soil

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

Schroth, M.H., E-mail: martin.schroth@env.ethz.ch; Eugster, W.; Gomez, K.E.

2012-05-15

Highlights: Black-Right-Pointing-Pointer We quantify above- and below-ground CH{sub 4} fluxes in a landfill-cover soil. Black-Right-Pointing-Pointer We link methanotrophic activity to estimates of CH{sub 4} loading from the waste body. Black-Right-Pointing-Pointer Methane loading and emissions are highly variable in space and time. Black-Right-Pointing-Pointer Eddy covariance measurements yield largest estimates of CH{sub 4} emissions. Black-Right-Pointing-Pointer Potential methanotrophic activity is high at a location with substantial CH{sub 4} loading. - Abstract: Landfills are a major anthropogenic source of the greenhouse gas methane (CH{sub 4}). However, much of the CH{sub 4} produced during the anaerobic degradation of organic waste is consumed by methanotrophic microorganismsmore » during passage through the landfill-cover soil. On a section of a closed landfill near Liestal, Switzerland, we performed experiments to compare CH{sub 4} fluxes obtained by different methods at or above the cover-soil surface with below-ground fluxes, and to link methanotrophic activity to estimates of CH{sub 4} ingress (loading) from the waste body at selected locations. Fluxes of CH{sub 4} into or out of the cover soil were quantified by eddy-covariance and static flux-chamber measurements. In addition, CH{sub 4} concentrations at the soil surface were monitored using a field-portable FID detector. Near-surface CH{sub 4} fluxes and CH{sub 4} loading were estimated from soil-gas concentration profiles in conjunction with radon measurements, and gas push-pull tests (GPPTs) were performed to quantify rates of microbial CH{sub 4} oxidation. Eddy-covariance measurements yielded by far the largest and probably most representative estimates of overall CH{sub 4} emissions from the test section (daily mean up to {approx}91,500 {mu}mol m{sup -2} d{sup -1}), whereas flux-chamber measurements and CH{sub 4} concentration profiles indicated that at the majority of locations the cover soil was a net sink for atmospheric CH{sub 4} (uptake up to -380 {mu}mol m{sup -2} d{sup -1}) during the experimental period. Methane concentration profiles also indicated strong variability in CH{sub 4} loading over short distances in the cover soil, while potential methanotrophic activity derived from GPPTs was high (v{sub max} {approx} 13 mmol L{sup -1}(soil air) h{sup -1}) at a location with substantial CH{sub 4} loading. Our results provide a basis to assess spatial and temporal variability of CH{sub 4} dynamics in the complex terrain of a landfill-cover soil.« less

Using GMD Data, AIRS Measurements, and the NASA Chemistry-Climate Model to Reveal Regional and Seasonal Variation of Methane

NASA Astrophysics Data System (ADS)

Steele, K. J.; Duncan, B. N.; Warner, J. X.; Nielsen, J. E.

2010-12-01

The concentration of methane (CH4) has more than doubled in the atmosphere since the preindustrial era due to a change in source-sink interactions. Many studies have aimed to quantify CH4 source contributions, but 1) the long tropospheric lifetime of CH4, resulting in a high background concentration, 2) along with sources often having overlapping distributions, and 3) the uncertainty in the chemical sink of CH4 with the hydroxyl radical makes it difficult to constrain inputs to the CH4 budget. The purpose of this study was to use a variety of observations in conjunction with the NASA GEOS-5 climate-chemistry model (CCM) to better understand regional and seasonal variation in atmospheric CH4. Seasonal variation in surface in situ data from the NOAA ESRL Global Monitoring Division (GMD) and data from the Japanese Airlines (JAL) in the upper troposphere (UT) were compared to satellite observations recorded by the Atmospheric Infrared Sounder (AIRS) on the EOS/Aqua satellite, which is most sensitive to CH4 in the UT. There was more variability in CH4 at the GMD sites than in the JAL data or AIRS because the GMD sites are closer to the source. As the CH4 is lofted into the UT, it mixes with the background CH4 so the seasonal variation is dampened. The JAL data followed the AIRS observations as expected. There was less variability in all measurements in the Southern Hemisphere and over oceans because these areas are farther away from sources. While the observations from AIRS, JAL flights, and the GMD sites provide valuable information regarding source locations and atmospheric CH4 concentration, it is important to understand which CH4 sources have the largest contribution to CH4 emissions in different regions of the world and the influence of these sources on the global CH4 cycle. Model output from the GEOS-5 CCM was used to monitor individual CH4 sources (e.g. from rice production, wetlands, biofuel use, etc.) as they are transported from the surface to the UT. The model revealed that variation in source strength is dependent on the site location in relation to the source strength. Assessing CH4 source contributions to the UT revealed that variability is affected by seasonal variation in the sources convolved with seasonal variation in deep convection. More work is needed in order to constrain sources of atmospheric CH4. However, surface and tropospheric in situ data can be used to validate AIRS observations so that CH4 can be monitored at a global scale, and CCM output can aid in determining which sources have the largest contribution to atmospheric CH4.

Methane emissions from Alaska Arctic tundra - An assessment of local spatial variability

NASA Technical Reports Server (NTRS)

Morrissey, L. A.; Livingston, G. P.

1992-01-01

The findings of an extensive midsummer survey of CH4 emissions measurements representing the Alaska Arctic tundra are presented. Variability in rates of emissions was similar in magnitude on local and regional scales, ranging from 0 to 286.5 mg/sq m/d overall and often varying across two orders of magnitude within 0.5 m distances. Primary control on rates of emission was determined by the substrate and position of the water table relative to the surface. Emission rates in the Arctic Foothills ranged from 0.2 mg/sq m/d for tussock tundra to 55.53 mg/sq m/d over wet meadows. Plant-mediated release of CH4 to the atmosphere was directly proportional to green leaf area and represented 92-98 percent of the total emission rates over vegetated sites. The results suggest the current published emission rates may have overestimated the contribution of boreal ecosystems to the global CH4 budget by several fold.

Influence of processing parameters on the characteristics of surface layers of low temperature plasma nitrocarburized AISI 630 martensitic stainless steel

NASA Astrophysics Data System (ADS)

Lee, Insup

2017-11-01

Plasma nitrocarburizing was performed on solution-treated AISI 630 martensitic precipitation hardening stainless steel samples with a gas mixture of H2, N2, and CH4 with changing temperature, discharge voltage and amount of CH4. When nitrocarburized with increasing temperature from 380 °C to 430 °C at fixed 25% N2 and 6% CH4, the thickness of expanded martensite (α'N) layer and surface hardness increased up to 10 μm and 1323 HV0.05, respectively but the corrosion resistance decreased. Though the increase of discharge voltage from 400 V to 600 V increased α'N layer thickness and surface hardness (up to 13 μm and 1491 HV0.05, respectively), the treated samples still showed very poor corrosion behavior. Thus, to further improve the corrosion resistance, the influence of variation of the amount of CH4 in the nitrocarburizing process was investigated. Increasing the CH4 percentage aided higher corrosion resistance, although it decreased the α'N layer thickness. The most appropriate conditions for moderate α'N layer thickness, high surface hardness and better corrosion resistance than the solution-treated bare sample were established, which is plasma nitrocarburizing at 400 °C with 400 V discharge voltage and containing 25% N2 and 4% CH4.

Calculating the surface tension of binary solutions of simple fluids of comparable size

NASA Astrophysics Data System (ADS)

Zaitseva, E. S.; Tovbin, Yu. K.

2017-11-01

A molecular theory based on the lattice gas model (LGM) is used to calculate the surface tension of one- and two-component planar vapor-liquid interfaces of simple fluids. Interaction between nearest neighbors is considered in the calculations. LGM is applied as a tool of interpolation: the parameters of the model are corrected using experimental surface tension data. It is found that the average accuracy of describing the surface tension of pure substances (Ar, N2, O2, CH4) and their mixtures (Ar-O2, Ar-N2, Ar-CH4, N2-CH4) does not exceed 2%.

Chemistry, isotopic composition, and origin of a methane-hydrogen sulfide hydrate at the Cascadia subduction zone

USGS Publications Warehouse

Kastner, M.; Kvenvolden, K.A.; Lorenson, T.D.

1998-01-01

Although the presence of extensive gas hydrate on the Cascadia margin, offshore from the western U.S. and Canada, has been inferred from marine seismic records and pore water chemistry, solid gas hydrate has only been found at one location. At Ocean Drilling Program (ODP) Site 892, offshore from central Oregon, gas hydrate was recovered close to the sediment - water interface at 2-19 m below the seafloor, (mbsf) at 670 m water depth. The gas hydrate occurs as elongated platy crystals or crystal aggregates, mostly disseminated irregularly, with higher concentrations occurring in discrete zones, thin layers, and/or veinlets parallel or oblique to the bedding. A 2-to 3-cm thick massive gas hydrate layer, parallel to bedding, was recovered at ???17 mbsf. Gas from a sample of this layer was composed of both CH4 and H2S. This sample is the first mixed-gas hydrate of CH4-H2S documented in ODP; it also contains ethane and minor amounts of CO2. Measured temperature of the recovered core ranged from 2 to - 18??C and are 6 to 8 degrees lower than in-situ temperatures. These temperature anomalies were caused by the partial dissociation of the CH4-H2S hydrate during recovery without a pressure core sampler. During this dissociation, toxic levels of H2S (??34S, +27.4???) were released. The ??13C values of the CH4 in the gas hydrate, -64.5 to -67.5???(PDB), together with ??D values of - 197 to - 199???(SMOW) indicate a primarily microbial source for the CH4. The ??18O value of the hydrate H2O is +2.9???(SMOW), comparable with the experimental fractionation factor for sea-ice. The unusual composition (CH4-H2S) and depth distribution (2-19 mbsf) of this gas hydrate indicate mixing between a methane-rich fluid with a pore fluid enriched in sulfide; at this site the former is advecting along an inclined fault into the active sulfate reduction zone. The facts that the CH4-H2S hydrate is primarily confined to the present day active sulfate reduction zone (2-19 mbsf), and that from here down to the BSR depth (19-68 mbsf) the gas hydrate inferred to exist is a ???99% CH4 hydrate, suggest that the mixing of CH4 and H2S is a geologically young process. Because the existence of a mixed CH4-H2S hydrate is indicative of moderate to intense advection of a methane-rich fluid into a near surface active sulfate reduction zone, technically active (faulted) margins with organic-rich sediments and moderate to high sedimentation rates are the most likely regions of occurrence. The extension of such a mixed hydrate below the sulfate reduction zone should reflect the time-span of methane advection into the sulfate reduction zone. ?? 1998 Elsevier Science B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Estimating gas exchange of CO2 and CH4 between headwater systems and the atmosphere in Southwest Sweden

NASA Astrophysics Data System (ADS)

Somlai, Celia; Natchimuthu, Sivakiruthika; Bastviken, David; Lorke, Andreas

2015-04-01

Quantifying the role of inland water systems in terms of carbon sinks and sources and their connection to the terrestrial ecosystems and landscapes is fundamental for improving the balance approach of regional and global carbon budgets. Recent research showed that freshwater bodies emit significant amounts of CO2 and CH4 into the atmosphere. The extent of the emissions from small streams and headwaters, however, remains uncertain due to a limited availability of data. Studies have shown that headwater systems receive most of the terrestrial organic carbon, have the highest dissolved CO2 concentration and the highest gas exchange velocities and cover the largest fractional surface area within fluvial networks. The gas exchange between inland waters and the atmosphere is controlled by two factors: the difference between the dissolved gas concentration and its atmospheric equilibrium concentration, and the gas exchange velocity. The direct measurement of the dissolved gas concentration of greenhouse gases can be measured straightforwardly, for example, by gas chromatography from headspace extraction of water sample. In contrast, direct measurement of gas exchange velocity is more complex and time consuming, as simultaneous measurements with a volatile and nonvolatile inert tracer gas are needed. Here we analyze measurements of gas exchange velocities, concentrations and fluxes of dissolved CO2 and CH4, as well as loads of total organic and inorganic carbon in 10 reaches in headwater streams in Southwest Sweden. We compare the gas exchange velocities measured directly through tracer injections with those estimated through various empirical approaches, which are based on modelled and measured current velocity, stream depth and slope. Furthermore, we estimate the resulting uncertainties of the flux estimates. We also present different time series of dissolved CO2, CH4 and O2 concentration, water temperature, barometric pressure, electro conductivity, and pH values measured during the period of tracer injection.

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

Methane emission to the atmosphere from landfills in the Canary Islands

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

Transcontinental methane measurements: Part 2. Mobile surface investigation of fossil fuel industrial fugitive emissions

NASA Astrophysics Data System (ADS)

Leifer, Ira; Culling, Daniel; Schneising, Oliver; Farrell, Paige; Buchwitz, Michael; Burrows, John P.

2013-08-01

The potent greenhouse gas, methane, CH4, has a wide variety of anthropogenic and natural sources. Fall, continental-scale (Florida to California) surface CH4 data were collected to investigate the importance of fossil fuel industrial (FFI) emissions in the South US. A total of 6600 measurements along 7020-km of roadways were made by flame ion detection gas chromatography onboard a nearly continuously moving recreational vehicle in 2010. A second, winter survey in Southern California measured CH4 at 2 Hz with a cavity ring-down spectrometer in 2012. Data revealed strong and persistent FFI CH4 sources associated with refining, oil/gas production, a presumed major pipeline leak, and a coal loading plant. Nocturnal CH4 mixing ratios tended to be higher than daytime values for similar sources, sometimes significantly, which was attributed to day/night meteorological differences, primarily changes in the boundary layer height. The highest CH4 mixing ratio (39 ppm) was observed near the Kern River Oil Field, California, which uses steam reinjection. FFI CH4 plume signatures were distinguished as stronger than other sources on local scales. On large (4°) scales, the CH4 trend was better matched spatially with FFI activity than wetland spatial patterns. Qualitative comparison of surface data with SCIAMACHY and GOSAT satellite retrievals showed agreement of the large-scale CH4 spatial patterns. Comparison with inventory models and seasonal winds suggests for some seasons and some portions of the Gulf of Mexico a non-negligible underestimation of FFI emissions. For other seasons and locations, qualitative interpretation is not feasible. Unambiguous quantitative source attribution is more complex, requiring transport modeling.

Estimating regional-scale methane flux and budgets using CARVE aircraft measurements over Alaska

NASA Astrophysics Data System (ADS)

Hartery, Sean; Commane, Róisín; Lindaas, Jakob; Sweeney, Colm; Henderson, John; Mountain, Marikate; Steiner, Nicholas; McDonald, Kyle; Dinardo, Steven J.; Miller, Charles E.; Wofsy, Steven C.; Chang, Rachel Y.-W.

2018-01-01

Methane (CH4) is the second most important greenhouse gas but its emissions from northern regions are still poorly constrained. In this study, we analyze a subset of in situ CH4 aircraft observations made over Alaska during the growing seasons of 2012-2014 as part of the Carbon in Arctic Reservoirs Vulnerability Experiment (CARVE). Net surface CH4 fluxes are estimated using a Lagrangian particle dispersion model which quantitatively links surface emissions from Alaska and the western Yukon with observations of enhanced CH4 in the mixed layer. We estimate that between May and September, net CH4 emissions from the region of interest were 2.2 ± 0.5 Tg, 1.9 ± 0.4 Tg, and 2.3 ± 0.6 Tg of CH4 for 2012, 2013, and 2014, respectively. If emissions are only attributed to two biogenic eco-regions within our domain, then tundra regions were the predominant source, accounting for over half of the overall budget despite only representing 18 % of the total surface area. Boreal regions, which cover a large part of the study region, accounted for the remainder of the emissions. Simple multiple linear regression analysis revealed that, overall, CH4 fluxes were largely driven by soil temperature and elevation. In regions specifically dominated by wetlands, soil temperature and moisture at 10 cm depth were important explanatory variables while in regions that were not wetlands, soil temperature and moisture at 40 cm depth were more important, suggesting deeper methanogenesis in drier soils. Although similar environmental drivers have been found in the past to control CH4 emissions at local scales, this study shows that they can be used to generate a statistical model to estimate the regional-scale net CH4 budget.

Gas-phase nitrosation of ethylene and related events in the C2H4NO+ landscape.

PubMed

Gerbaux, Pascal; Dechamps, Noemie; Flammang, Robert; Nam, Pham Cam; Nguyen, Minh Tho; Djazi, Fayçal; Berruyer, Florence; Bouchoux, Guy

2008-06-19

The C2H4NO(+) system has been examined by means of quantum chemical calculations using the G2 and G3B3 approaches and tandem mass spectrometry experiments. Theoretical investigation of the C2H4NO(+) potential-energy surface includes 19 stable C2H4NO(+) structures and a large set of their possible interconnections. These computations provide insights for the understanding of the (i) addition of the nitrosonium cation NO(+) to the ethylene molecule, (ii) skeletal rearrangements evidenced in previous experimental studies on comparable systems, and (iii) experimental identification of new C2H4NO(+) structures. It is predicted from computation that gas-phase nitrosation of ethylene may produce C2H4(*)NO(+) adducts, the most stable structure of which is a pi-complex, 1, stabilized by ca. 65 kJ/mol with respect to its separated components. This complex was produced in the gas phase by a transnitrosation process involving as reactant a complex between water and NO(+) (H2O.NO(+)) and the ethylene molecule and fully characterized by collisional experiments. Among the other C 2H 4NO (+) structures predicted by theory to be protected against dissociation or isomerization by significant energy barriers, five were also experimentally identified. These finding include structures CH3CHNO(+) (5), CH 3CNOH (+) ( 8), CH3NHCO(+) (18), CH3NCOH(+) (19), and an ion/neutral complex CH2O...HCNH(+) (12).

Annual greenhouse gas budget for a bog ecosystem undergoing restoration by rewetting

NASA Astrophysics Data System (ADS)

Lee, Sung-Ching; Christen, Andreas; Black, Andrew T.; Johnson, Mark S.; Jassal, Rachhpal S.; Ketler, Rick; Nesic, Zoran; Merkens, Markus

2017-06-01

Many peatlands have been drained and harvested for peat mining, agriculture, and other purposes, which has turned them from carbon (C) sinks into C emitters. Rewetting of disturbed peatlands facilitates their ecological recovery and may help them revert to carbon dioxide (CO2) sinks. However, rewetting may also cause substantial emissions of the more potent greenhouse gas (GHG) methane (CH4). Our knowledge of the exchange of CO2 and CH4 following rewetting during restoration of disturbed peatlands is currently limited. This study quantifies annual fluxes of CO2 and CH4 in a disturbed and rewetted area located in the Burns Bog Ecological Conservancy Area in Delta, BC, Canada. Burns Bog is recognized as the largest raised bog ecosystem on North America's west coast. Burns Bog was substantially reduced in size and degraded by peat mining and agriculture. Since 2005, the bog has been declared a conservancy area, with restoration efforts focusing on rewetting disturbed ecosystems to recover Sphagnum and suppress fires. Using the eddy covariance (EC) technique, we measured year-round (16 June 2015 to 15 June 2016) turbulent fluxes of CO2 and CH4 from a tower platform in an area rewetted for the last 8 years. The study area, dominated by sedges and Sphagnum, experienced a varying water table position that ranged between 7.7 (inundation) and -26.5 cm from the surface during the study year. The annual CO2 budget of the rewetted area was -179 ± 26.2 g CO2-C m-2 yr-1 (CO2 sink) and the annual CH4 budget was 17 ± 1.0 g CH4-C m-2 yr-1 (CH4 source). Gross ecosystem productivity (GEP) exceeded ecosystem respiration (Re) during summer months (June-August), causing a net CO2 uptake. In summer, high CH4 emissions (121 mg CH4-C m-2 day-1) were measured. In winter (December-February), while roughly equal magnitudes of GEP and Re made the study area CO2 neutral, very low CH4 emissions (9 mg CH4-C m-2 day-1) were observed. The key environmental factors controlling the seasonality of these exchanges were downwelling photosynthetically active radiation and 5 cm soil temperature. It appears that the high water table caused by ditch blocking suppressed Re. With low temperatures in winter, CH4 emissions were more suppressed than Re. Annual net GHG flux from CO2 and CH4 expressed in terms of CO2 equivalents (CO2 eq.) during the study period totalled -22 ± 103.1 g CO2 eq. m-2 yr-1 (net CO2 eq. sink) and 1248 ± 147.6 g CO2 eq. m-2 yr-1 (net CO2 eq. source) by using 100- and 20-year global warming potential values, respectively. Consequently, the ecosystem was almost CO2 eq. neutral during the study period expressed on a 100-year time horizon but was a significant CO2 eq. source on a 20-year time horizon.

Process-based approach for the detection of deep gas invading the surface

DOEpatents

Romanak, Katherine; Bennett, Philip C.

2017-05-09

The present invention includes a method for determining the level of deep gas in a near surface formation that includes: measuring CO.sub.2, O.sub.2, CH.sub.4, and N.sub.2 levels in percent by volume from one or more surface or near surface geological samples; adding the water vapor content to the measured CO.sub.2, O.sub.2, CH.sub.4, and N.sub.2 levels in percent by volume; normalizing the gas mixture to 100% by volume or 1 atmospheric total pressure; and determining the ratios of: O.sub.2 versus CO.sub.2 to distinguish in-situ vadose zone CO.sub.2 from exogenous deep leakage CO.sub.2; CO.sub.2 versus N.sub.2 to distinguish whether CO.sub.2 is being removed from the near surface formation or CO.sub.2 is added from an exogenous deep leakage input; or CO.sub.2 versus N.sub.2/O.sub.2 to determine the degree of oxygen influx, consumption, or both; wherein the ratios are indicative of natural in situ CO.sub.2 or CO.sub.2 from the exogenous deep leakage input.

CH4 emissions from two floodplain fens of differing nutrient status

NASA Astrophysics Data System (ADS)

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

2014-05-01

Floodplain fens emit large amounts of CH4 in comparison with ombrotrophic bogs. Little is known about the effect of fluvial nitrogen (N) and phosphorus (P) on CH4 dynamics in fens, although N and P affect carbon (C) dynamics indirectly in other environments by controlling plant growth and root exudate release, as well as by altering microbial biomass and decomposition rates. This study aimed to compare CH4 emissions from two floodplain fen sites which differ in nutrient status, Sutton Fen (52°45'N 001°30'E) and Strumpshaw Fen (52°36'N 001°27'E), in the Norfolk Broadland of England. Sutton and Strumpshaw Fen are under conservation management and both sites have water levels that vary within a few decimetres above and below the surface. The sites are dominated by reed (Phragmites australis). Areas within the fens where the reed was cut in 2009 were chosen for this study. Average plant height and mean aboveground biomass were significantly greater at Strumpshaw (107.2 ± 7.8 cm and 1578 ± 169 g m-2, respectively) than Sutton (56.5 ± 5.1 cm and 435 ± 42 g m-2) as were mean foliar N and P contents (21.8 ± 1.5 g kg-1 and 2.0 ± 0.2 g kg-1 at Strumpshaw, versus 16.3 ± 1.5 g kg-1 and 1.1 ± 0.1 g kg-1 at Sutton). Foliar NPK ratios showed Strumpshaw to be N limited, whereas Sutton was both N and P limited, depending on microsite. Surface peat N and P contents were also greater at Strumpshaw (28.3 ± 0.35 g kg-1 and 0.78 ± 0.02 g kg-1, respectively) than Sutton (18.32 ± 0.87 g kg-1 and 0.43 ± 0.1 g kg-1). These results indicate clear differences in nutrient status between the two sites despite their geographical proximity and other similarities. CH4 emissions were monitored monthly between 19th June 2012 and 2nd September 2013 using tall static chambers and glass funnel-traps, the latter for ebullition. Steady fluxes did not follow a clear seasonal pattern; however, emission was greatest in the summer months. Strumpshaw had a greater range in efflux (0.25 to 134.2 mg CH4 m-2 h-1) than Sutton (0.17 to 29.82 mg CH4 m-2 h-1). Ebullition was generally greater at Sutton throughout the study period, with rates ranging from 0 to 62.09 mg CH4 m-2 h-1 and 0 to 19.30 mg CH4 m-2 h-1 for Sutton and Strumpshaw, respectively. Fluxes were generally within the range of values reported in the literature for ebullition (0 to 466 mg CH4 m-2 h-1) and steady fluxes (0 to 76.83 mg CH4 m-2 h-1). Results show the importance of floodplain fens for CH4 emission, and more research needs to be undertaken to fully understand the factors controlling CH4 fluxes from these systems.

Seasonal variability and degradation investigation of iodocarbons in a coastal fjord

NASA Astrophysics Data System (ADS)

Shi, Qiang; Wallace, Douglas

2016-04-01

Methyl iodide (CH3I) is considered an important carrier of iodine atoms from sea to air. The importance of other volatile iodinated compounds, such as very short-lived iodocarbons (e.g. CH2ClI, CH2I2), has also been demonstrated [McFiggans, 2005; O'Dowd and Hoffmann, 2005; Carpenter et al., 2013]. The production pathways of iodocarbons, and controls on their sea-to-air flux can be investigated by in-situ studies (e.g. surface layer mass balance from time-series studies) and by incubation experiments. Shi et al., [2014] reported previously unrecognised large, night-time losses of CH3I observed during incubation experiments with coastal waters. These losses were significant for controlling the sea-to-air flux but are not yet understood. As part of a study to further investigate sources and sinks of CH3I and other iodocarbons in coastal waters, samples have been analysed weekly since April 2015 at 4 depths (5 to 60 m) in the Bedford Basin, Halifax, Canada. The time-series study was part of a broader study that included measurement of other, potentially related parameters (temperature, salinity, Chlorophyll a etc.). A set of repeated degradation experiments was conducted, in the context of this time-series, including incubations within a solar simulator using 13C labelled CH3I. Results of the time-series sampling and incubation experiments will be presented.

Thermophysical properties of aqueous solution of ammonium-based ionic liquids.

PubMed

Umapathi, Reddicherla; Attri, Pankaj; Venkatesu, Pannuru

2014-06-05

Experimental densities (ρ), ultrasonic sound velocities (u), viscosities (η), and refractive indices (n(D)) of binary mixtures of ammonium-based ionic liquids (ILs) such as diethylammonium acetate (DEAA) [(CH3CH2)2NH][CH3COO], triethylammonium acetate (TEAA) [(CH3CH2)3NH][CH3COO], diethylammonium hydrogen sulfate (DEAS) [(CH3CH2)2NH][HSO4], triethylammonium hydrogen sulfate (TEAS) [(CH3CH2)3NH][HSO4], trimethylammonium acetate (TMAA) [(CH3)3NH][CH3COO], and trimethylammonium hydrogen sulfate (TMAS) [(CH3)3NH][HSO4] with water are reported over the wide composition range at 25 °C under atmospheric pressure. The excess molar volumes (V(E)), deviation in isentropic compressibilities (Δκ(s)), deviation in viscosities (Δη) and deviation in refractive indices (Δn(D)) are calculated from experimental values and are correlated by Redlich-Kister polynomial equations. The V(E) and Δκ(s) values for the aforesaid systems are negative over the entire composition range while the Δη and Δn(D) values are positive under the same experimental conditions. The intermolecular interactions and structural effects were analyzed on the basis of measured and derived properties. A qualitative analysis of the results is discussed in terms of the ion-dipole, ion-pair interactions and hydrogen bonding between ILs and water. Furthermore, the hydrogen bonding features between ILs with water were analyzed by using a molecular modeling program with the help of HyperChem7.

Direct Conversion of Methane to Methanol on Ni-Ceria Surfaces: Metal-Support Interactions and Water-enabled Catalytic Conversion by Site Blocking

DOE PAGES

Lustemberg, Pablo G.; Palomino, Robert M.; Gutierrez, Ramon A.; ...

2018-05-28

The transformation of methane into methanol or higher alcohols at moderate temperature and pressure conditions is of great environmental interest and remains a challenge despite many efforts. Extended surfaces of metallic nickel are inactive for a direct CH 4 → CH 3OH conversion. This experimental and computational study provides clear evidence that low Ni loadings on a CeO 2(111) support can perform a direct catalytic cycle for the generation of methanol at low temperature using oxygen and water as reactants, with a higher selectivity than ever reported for ceria-based catalysts. On the basis of ambient pressure X-ray photoemission spectroscopy andmore » density functional theory calculations, we demonstrate that water plays a crucial role in blocking catalyst sites where methyl species could fully decompose, an essential factor for diminishing the production of CO and CO 2, and in generating sites on which methoxy species and ultimately methanol can form. In addition to water-site blocking, one needs the effects of metal-support interactions to bind and activate methane and water. Lastly, these findings should be considered when designing metal/oxide catalysts for converting methane to value-added chemicals and fuels.« less

Direct Conversion of Methane to Methanol on Ni-Ceria Surfaces: Metal-Support Interactions and Water-enabled Catalytic Conversion by Site Blocking

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

Lustemberg, Pablo G.; Palomino, Robert M.; Gutierrez, Ramon A.

The transformation of methane into methanol or higher alcohols at moderate temperature and pressure conditions is of great environmental interest and remains a challenge despite many efforts. Extended surfaces of metallic nickel are inactive for a direct CH 4 → CH 3OH conversion. This experimental and computational study provides clear evidence that low Ni loadings on a CeO 2(111) support can perform a direct catalytic cycle for the generation of methanol at low temperature using oxygen and water as reactants, with a higher selectivity than ever reported for ceria-based catalysts. On the basis of ambient pressure X-ray photoemission spectroscopy andmore » density functional theory calculations, we demonstrate that water plays a crucial role in blocking catalyst sites where methyl species could fully decompose, an essential factor for diminishing the production of CO and CO 2, and in generating sites on which methoxy species and ultimately methanol can form. In addition to water-site blocking, one needs the effects of metal-support interactions to bind and activate methane and water. Lastly, these findings should be considered when designing metal/oxide catalysts for converting methane to value-added chemicals and fuels.« less

Methane and carbon dioxide fluxes over a lake: comparison between eddy covariance, floating chambers and boundary layer method

NASA Astrophysics Data System (ADS)

Erkkilä, Kukka-Maaria; Ojala, Anne; Bastviken, David; Biermann, Tobias; Heiskanen, Jouni J.; Lindroth, Anders; Peltola, Olli; Rantakari, Miitta; Vesala, Timo; Mammarella, Ivan

2018-01-01

Freshwaters bring a notable contribution to the global carbon budget by emitting both carbon dioxide (CO2) and methane (CH4) to the atmosphere. Global estimates of freshwater emissions traditionally use a wind-speed-based gas transfer velocity, kCC (introduced by Cole and Caraco, 1998), for calculating diffusive flux with the boundary layer method (BLM). We compared CH4 and CO2 fluxes from BLM with kCC and two other gas transfer velocities (kTE and kHE), which include the effects of water-side cooling to the gas transfer besides shear-induced turbulence, with simultaneous eddy covariance (EC) and floating chamber (FC) fluxes during a 16-day measurement campaign in September 2014 at Lake Kuivajärvi in Finland. The measurements included both lake stratification and water column mixing periods. Results show that BLM fluxes were mainly lower than EC, with the more recent model kTE giving the best fit with EC fluxes, whereas FC measurements resulted in higher fluxes than simultaneous EC measurements. We highly recommend using up-to-date gas transfer models, instead of kCC, for better flux estimates. BLM CO2 flux measurements had clear differences between daytime and night-time fluxes with all gas transfer models during both stratified and mixing periods, whereas EC measurements did not show a diurnal behaviour in CO2 flux. CH4 flux had higher values in daytime than night-time during lake mixing period according to EC measurements, with highest fluxes detected just before sunset. In addition, we found clear differences in daytime and night-time concentration difference between the air and surface water for both CH4 and CO2. This might lead to biased flux estimates, if only daytime values are used in BLM upscaling and flux measurements in general. FC measurements did not detect spatial variation in either CH4 or CO2 flux over Lake Kuivajärvi. EC measurements, on the other hand, did not show any spatial variation in CH4 fluxes but did show a clear difference between CO2 fluxes from shallower and deeper areas. We highlight that while all flux measurement methods have their pros and cons, it is important to carefully think about the chosen method and measurement interval, as well as their effects on the resulting flux.

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.

Temperature, productivity and sediment characteristics as drivers of seasonal and spatial variations of dissolved methane in the near-shore coastal areas (Belgian coastal zone, North Sea)

NASA Astrophysics Data System (ADS)

Borges, Alberto V.; Speeckaert, Gaëlle; Champenois, Willy; Scranton, Mary I.; Gypens, Nathalie

2017-04-01

The open ocean is a modest source of CH4 to the atmosphere compared to other natural and anthropogenic CH4 emissions. Coastal regions are more intense sources of CH4 to the atmosphere than open oceanic waters, in particular estuarine zones. The CH4 emission to the atmosphere from coastal areas is sustained by riverine inputs and methanogenesis in the sediments due to high organic matter (OM) deposition. Additionally, natural gas seeps are sources of CH4 to bottom waters leading to high dissolved CH4 concentrations in bottom waters (from tenths of nmol L-1 up to several µmol L-1). We report a data set of dissolved CH4 concentrations obtained at nine fixed stations in the Belgian coastal zone (Southern North Sea), during one yearly cycle, with a bi-monthly frequency in spring, and a monthly frequency during the rest of the year. This is a coastal area with multiple possible sources of CH4 such as from rivers and gassy sediments, and where intense phytoplankton blooms are dominated by the high dimethylsulfoniopropionate (DMSP) producing micro-algae Phaeocystis globosa, leading to DMSP and dimethylsulfide (DMS) concentrations. Furthermore, the BCZ is a site of important OM sedimentation and accumulation unlike the rest of the North Sea. Spatial variations of dissolved CH4 concentrations were very marked with a minimum yearly average of 9 nmol L-1 in one of the most off-shore stations and maximum yearly average of 139 nmol L-1 at one of the most near-shore stations. The spatial variations of dissolved CH4 concentrations were related to the organic matter (OM) content of sediments, although the highest concentrations seemed to also be related to inputs of CH4 from gassy sediments associated to submerged peat. In the near-shore stations with fine sand or muddy sediments with a high OM content, the seasonal cycle of dissolved CH4 concentration closely followed the seasonal cycle of water temperature, suggesting the control of methanogenesis by temperature in these OM replete sediments. In the off-shore stations with permeable sediments with a low OM content, the seasonal cycle of dissolved CH4 concentration showed a yearly peak following the chlorophyll-a spring peak. This suggests that in these OM poor sediments, methanogenesis depended on the delivery to the sediments of freshly produced OM. In both types of sediments, the seasonal cycle of dissolved CH4 concentrations was unrelated the seasonal cycles of DMS, and DMSP, despite the fact that these quantities were very high during the spring Phaeocystis globosa bloom. This suggests that in this shallow coastal environment CH4 production is overwhelmingly related to benthic processes and unrelated to DMS(P) transformations in the water column as recently suggested in several open ocean regions. The annual average CH4 emission was 41 mmol m-2 yr-1 in the most near-shore stations ( 4 km from the coast) and 10 mmol m-2 yr-1 in the most off-shore stations ( 23 km from the coast), 410-100 times higher than the average value in the open ocean (0.1 mmol m-2 yr-1). The strong control of CH4 concentrations by sediment OM content and by temperature suggests that marine coastal CH4 emissions, in particular shallow coastal areas, should respond in future to eutrophication and warming of climate. This is confirmed by the comparison of CH4 concentrations at five stations obtained in March in years 1990 and 2016, showing a decreasing trend consistent with alleviation of eutrophication in the area.

One-step surface modification of poly(dimethylsiloxane) by undecylenic acid

NASA Astrophysics Data System (ADS)

Zhou, Jinwen; McInnes, Steven J. P.; Md Jani, Abdul Mutalib; Ellis, Amanda V.; Voelcker, Nicolas H.

2008-12-01

Poly(dimethylsiloxane) (PDMS) is a popular material for microfluidic devices due to its relatively low cost, ease of fabrication, oxygen permeability and optical transmission characteristics. However, its highly hydrophobic surface is still the main factor limiting its wide application, in particular as a material for biointerfaces. A simple and rapid method to form a relatively stable hydrophilised PDMS surface is reported in this paper. The PDMS surface was treated with pure undecylenic acid (UDA) for 10 min, 1 h and 1 day at 80 °C in a sealed container. The effects of the surface modification were investigated using water contact angle (WCA) measurements, Fourier transform infrared spectroscopy in attenuated total reflection mode (FTIR-ATR), and streaming zeta-potential analysis. The water contact angle of 1 day UDAmodified PDMS was found to decrease from that of native PDMS (110 °) to 75 °, demonstrating an increase in wettability of the surface. A distinctive peak at 1715 cm-1 in the FTIR-ATR spectra after UDA treatment was representative of carboxylation of the PDMS surface. The measured zeta-potential (ζ) at pH 4 changed from -27 mV for pure PDMS to -19 mV after UDA treatment. In order to confirm carboxylation of the surface visually, Lucifer Yellow CH fluorescence dye was reacted via a condensation reaction to the 1 day UDA modified PDMS surface. Fluorescent microscopy showed Lucifer Yellow CH fluorescence on the carboxylated surface, but not on the pure PDMS surface. Stability experiments were also performed showing that 1 day modified UDA samples were stable in both MilliQ water at 50 °C for 17 h, and in a desiccator at room temperature for 19.5 h.

Hydrogeology, chemical and microbial activity measurement through deep permafrost

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

Stotler, R.L.; Frape, S.K.; Freifeld, B.M.

2010-04-01

Little is known about hydrogeochemical conditions beneath thick permafrost, particularly in fractured crystalline rock, due to difficulty in accessing this environment. The purpose of this investigation was to develop methods to obtain physical, chemical, and microbial information about the subpermafrost environment from a surface-drilled borehole. Using a U-tube, gas and water samples were collected, along with temperature, pressure, and hydraulic conductivity measurements, 420 m below ground surface, within a 535 m long, angled borehole at High Lake, Nunavut, Canada, in an area with 460-m-thick permafrost. Piezometric head was well above the base of the permafrost, near land surface. Initial watermore » samples were contaminated with drill fluid, with later samples <40% drill fluid. The salinity of the non-drill fluid component was <20,000 mg/L, had a Ca/Na ratio above 1, with {delta}{sup 18}O values {approx}5{per_thousand} lower than the local surface water. The fluid isotopic composition was affected by the permafrost-formation process. Nonbacteriogenic CH{sub 4} was present and the sample location was within methane hydrate stability field. Sampling lines froze before uncontaminated samples from the subpermafrost environment could be obtained, yet the available time to obtain water samples was extended compared to previous studies. Temperature measurements collected from a distributed temperature sensor indicated that this issue can be overcome easily in the future. The lack of methanogenic CH{sub 4} is consistent with the high sulfate concentrations observed in cores. The combined surface-drilled borehole/U-tube approach can provide a large amount of physical, chemical, and microbial data from the subpermafrost environment with few, controllable, sources of contamination.« less

Year-round CH4 and CO2 flux dynamics in two contrasting freshwater ecosystems of the subarctic

NASA Astrophysics Data System (ADS)

Jammet, Mathilde; Dengel, Sigrid; Kettner, Ernesto; Parmentier, Frans-Jan W.; Wik, Martin; Crill, Patrick; Friborg, Thomas

2017-11-01

Lakes and wetlands, common ecosystems of the high northern latitudes, exchange large amounts of the climate-forcing gases methane (CH4) and carbon dioxide (CO2) with the atmosphere. The magnitudes of these fluxes and the processes driving them are still uncertain, particularly for subarctic and Arctic lakes where direct measurements of CH4 and CO2 emissions are often of low temporal resolution and are rarely sustained throughout the entire year. Using the eddy covariance method, we measured surface-atmosphere exchange of CH4 and CO2 during 2.5 years in a thawed fen and a shallow lake of a subarctic peatland complex. Gas exchange at the fen exhibited the expected seasonality of a subarctic wetland with maximum CH4 emissions and CO2 uptake in summer, as well as low but continuous emissions of CH4 and CO2 throughout the snow-covered winter. The seasonality of lake fluxes differed, with maximum CO2 and CH4 flux rates recorded at spring thaw. During the ice-free seasons, we could identify surface CH4 emissions as mostly ebullition events with a seasonal trend in the magnitude of the release, while a net CO2 flux indicated photosynthetic activity. We found correlations between surface CH4 emissions and surface sediment temperature, as well as between diel CO2 uptake and diel solar input. During spring, the breakdown of thermal stratification following ice thaw triggered the degassing of both CH4 and CO2. This spring burst was observed in 2 consecutive years for both gases, with a large inter-annual variability in the magnitude of the CH4 degassing. On the annual scale, spring emissions converted the lake from a small CO2 sink to a CO2 source: 80 % of total annual carbon emissions from the lake were emitted as CO2. The annual total carbon exchange per unit area was highest at the fen, which was an annual sink of carbon with respect to the atmosphere. Continuous respiration during the winter partly counteracted the fen summer sink by accounting for, as both CH4 and CO2, 33 % of annual carbon exchange. Our study shows (1) the importance of overturn periods (spring or fall) for the annual CH4 and CO2 emissions of northern lakes, (2) the significance of lakes as atmospheric carbon sources in subarctic landscapes while fens can be a strong carbon sink, and (3) the potential for ecosystem-scale eddy covariance measurements to improve the understanding of short-term processes driving lake-atmosphere exchange of CH4 and CO2.

Factors Influencing Greenhouse Gas Emissions from Three Gorges Reservoir of China

NASA Astrophysics Data System (ADS)

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

2013-05-01

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

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.

Energy from aquatic plant wastewater treatment systems

NASA Technical Reports Server (NTRS)

Wolverton, B. C.; Mcdonald, R. C.

1979-01-01

Water hyacinth (Eichhornia crassipes), duckweed (Spirodela sp. and Lemma sp.), water pennywort (Hydrocotyle ranunculoides), and kudzu (Pueraria lobata) were anaerobically fermented using an anaerobic filter technique that reduced the total digestion time from 90 days to an average of 23 days and produced 0.14-0.28 cu m CH4/kg (dry weight) (2.3-4.5 cu ft/lb) from mature filters. The anaerobic filter provided a large surface area for the anaerobic bacteria to establish and maintain an optimum balance of facultative, acid-forming, and methane-producing bacteria. Consequently the efficiency of the process was greatly improved over prior batch fermentations.

Surface restructuring behavior of various types of poly(dimethylsiloxane) in water detected by SFG.

PubMed

Chen, Chunyan; Wang, Jie; Chen, Zhan

2004-11-09

Surface structures of several different poly(dimethylsiloxane) (PDMS) materials, tetraethoxysilane-cured hydroxy-terminated PDMS (TEOS-PDMS), platinum-cured vinyl-terminated PDMS (Pt-PDMS), platinum-cured vinyl-terminated poly(diphenylsiloxane)-co-poly(dimethylsiloxane) (PDPS-co-PDMS), and PDMS-co-polystyrene (PDMS-co-PS) copolymer in air and water have been investigated by sum frequency generation (SFG) vibrational spectroscopy. The SFG spectra collected from all PDMS surfaces in both air and water are dominated by methyl group stretches, indicating that all the surfaces are mainly covered by methyl groups. Other than surface-dominating methyl groups, some -Si-CH2-CH2- moieties on the Pt-PDMS surface have also been detected in air, which are present at cross-linking points. Information about the average orientation angle and angle distribution of the methyl groups on the PDMS surface has been evaluated. Surface restructuring of the methyl groups has been observed for all PDMS surfaces in water. Upon contacting water, the methyl groups on all PDMS surfaces tilt more toward the surface. The detailed restructuring behaviors of several PDMS surfaces in water and the effects of molecular weight on restructuring behaviors have been investigated. For comparison, in addition to air and water, surface structures of PDMS materials mentioned above in a nonpolar solvent, FC-75, have also been studied. By comparing the different response of phenyl groups to water on both PDPS-co-PDMS and PS-co-PDMS surfaces, we have demonstrated how the restructuring behaviors of surface phenyl groups are affected by the structural flexibility of the molecular chains where they are attached.

Derivation of scaled surface reflectances from AVIRIS data

NASA Technical Reports Server (NTRS)

Gao, Bo-Cai; Heidebrecht, Kathleen B.; Goetz, Alexander F. H.

1993-01-01

A method for retrieving 'scaled surface reflectances' assuming horizontal surfaces having Lambertian reflectances from spectral data collected by Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) is presented here. In this method, the integrated water vapor amount on a pixel by pixel basis is derived from the 0.94 micron and 1.14 micron water vapor absorption features. The transmission spectra of H2O, CO2, O3, N2O, CO, CH4, and O2 in the 0.4-2.5 micron region are simulated. The scattering effect due to atmospheric molecules and aerosols is modeled with the 5S computer code. The AVIRIS radiances are divided by solar irradiances above the atmosphere to obtain the apparent reflectances. The scaled surface reflectances are derived from the apparent reflectances using the simulated atmospheric gaseous transmittances and the simulated molecular and aerosol scattering data. The scaled surface reflectances differ from the real surface reflectances by a multiplicative factor. In order to convert the scaled surface reflectances into real surface reflectances, the slopes and aspects of the surfaces must be known.

Prediction of future methane emission from irrigated rice paddies in central Thailand under different water management practices.

PubMed

Minamikawa, Kazunori; Fumoto, Tamon; Iizumi, Toshichika; Cha-Un, Nittaya; Pimple, Uday; Nishimori, Motoki; Ishigooka, Yasushi; Kuwagata, Tsuneo

2016-10-01

There is concern about positive feedbacks between climate change and methane (CH4) emission from rice paddies. However, appropriate water management may mitigate the problem. We tested this hypothesis at six field sites in central Thailand, where the irrigated area is rapidly increasing. We used DNDC-Rice, a process-based biogeochemistry model adjusted based on rice growth data at each site to simulate CH4 emission from a rice-rice double cropping system from 2001 to 2060. Future climate change scenarios consisting of four representative concentration pathways (RCPs) and seven global climate models were generated by statistical downscaling. We then simulated CH4 emission in three water management practices: continuous flooding (CF), single aeration (SA), and multiple aeration (MA). The adjusted model reproduced the observed rice yield and CH4 emission well at each site. The simulated CH4 emissions in CF from 2051 to 2060 were 5.3 to 7.8%, 9.6 to 16.0%, 7.3 to 18.0%, and 13.6 to 19.0% higher than those from 2001 to 2010 in RCPs 2.6, 4.5, 6.0, and 8.5, respectively, at the six sites. Regionally, SA and MA mitigated CH4 emission by 21.9 to 22.9% and 53.5 to 55.2%, respectively, relative to CF among the four RCPs. These mitigation potentials by SA and MA were comparable to those from 2001 to 2010. Our results indicate that climate change in the next several decades will not attenuate the quantitative effect of water management practices on mitigating CH4 emission from irrigated rice paddies in central Thailand. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

Drivers of atmospheric methane uptake by montane forest soils in the southern Peruvian Andes

NASA Astrophysics Data System (ADS)

Jones, Sam P.; Diem, Torsten; Huaraca Quispe, Lidia P.; Cahuana, Adan J.; Reay, Dave S.; Meir, Patrick; Arn Teh, Yit

2016-07-01

The soils of tropical montane forests can act as sources or sinks of atmospheric methane (CH4). Understanding this activity is important in regional atmospheric CH4 budgets given that these ecosystems account for substantial portions of the landscape in mountainous areas like the Andes. We investigated the drivers of net CH4 fluxes from premontane, lower and upper montane forests, experiencing a seasonal climate, in south-eastern Peru. Between February 2011 and June 2013, these soils all functioned as net sinks for atmospheric CH4. Mean (standard error) net CH4 fluxes for the dry and wet season were -1.6 (0.1) and -1.1 (0.1) mg CH4-C m-2 d-1 in the upper montane forest, -1.1 (0.1) and -1.0 (0.1) mg CH4-C m-2 d-1 in the lower montane forest, and -0.2 (0.1) and -0.1 (0.1) mg CH4-C m-2 d-1 in the premontane forest. Seasonality in CH4 exchange varied among forest types with increased dry season CH4 uptake only apparent in the upper montane forest. Variation across these forests was best explained by available nitrate and water-filled pore space indicating that nitrate inhibition of oxidation or diffusional constraints imposed by changes in water-filled pore space on methanotrophic communities may represent important controls on soil-atmosphere CH4 exchange. Net CH4 flux was inversely related to elevation; a pattern that differs to that observed in Ecuador, the only other extant study site of soil-atmosphere CH4 exchange in the tropical Andes. This may result from differences in rainfall patterns between the regions, suggesting that attention should be paid to the role of rainfall and soil moisture dynamics in modulating CH4 uptake by the organic-rich soils typical of high-elevation tropical forests.

Disinfection of water with new chitosan-modified hybrid clay composite adsorbent.

PubMed

Unuabonah, Emmanuel I; Adewuyi, Adewale; Kolawole, Matthew O; Omorogie, Martins O; Olatunde, Olalekan C; Fayemi, Scott O; Günter, Christina; Okoli, Chukwunonso P; Agunbiade, Foluso O; Taubert, Andreas

2017-08-01

Hybrid clay composites were prepared from Kaolinite clay and Carica papaya seeds via modification with chitosan, Alum, NaOH, and ZnCl 2 in different ratios, using solvothermal and surface modification techniques. Several composite adsorbents were prepared, and the most efficient of them for the removal of gram negative enteric bacteria was the hybrid clay composite that was surface-modified with chitosan, Ch-nHYCA 1:5 (Chitosan: nHYCA = 1:5). This composite adsorbent had a maximum adsorption removal value of 4.07 × 10 6 cfu/mL for V. cholerae after 120 min, 1.95 × 10 6 cfu/mL for E. coli after ∼180 min and 3.25 × 10 6 cfu/mL for S. typhi after 270 min. The Brouers-Sotolongo model was found to better predict the maximum adsorption capacity ( q max ) of Ch-nHYCA 1:5 composite adsorbent for the removal of E. coli with a q max of 103.07 mg/g (7.93 × 10 7 cfu/mL) and V. cholerae with a q max of 154.18 mg/g (1.19 × 10 8 cfu/mL) while the Sips model best described S. typhi adsorption by Ch-nHYCA 1:5 composite with an estimated q max of 83.65 mg/g (6.43 × 10 7 cfu/mL). These efficiencies do far exceed the alert/action levels of ca. 500 cfu/mL in drinking water for these bacteria. The simplicity of the composite preparation process and the availability of raw materials used for its preparation underscore the potential of this low-cost chitosan-modified composite adsorbent (Ch-nHYCA 1:5 ) for water treatment.

On the state of methane and nitrogen ice on Pluto and Triton: Implications of the binary phase diagram

NASA Astrophysics Data System (ADS)

Trafton, Laurence M.

2015-01-01

Compositional analyses of Pluto's surface ice in the literature typically include large areas on the body where CH4 and other volatiles are segregated in the pure form from the solid solution N2:CH4 in which CH4 is diluted. However, the existence of continent-size areas of pure CH4 are in conflict with both of the alternative models that successfully explain the enhancement of CH4 in Pluto's atmosphere, the Detailed Balancing thermal equilibrium model and the Hot Methane Patch model. Pluto's spectrum includes an apparently unshifted CH4 component while Triton's does not, and 93% of the concentration range of the binary phase diagram at 38 K shows that these species exist as a mixture of two saturated solid solution phases. Recognizing this, we propose that both of these saturated phases are present on Pluto and the CH4-rich phase of the mixture, CH4:N2, is the source of the relatively unshifted CH4 spectrum attributed to pure CH4. We also propose that CH4 is less abundant in Triton's ice to the point where either the ice is not saturated or the saturated CH4:N2 phase has not been detected. In this scenario, the partial vapor pressures do not change when the relative proportions of these saturated phases are varied in the mixture. Thus, the partial vapor pressures are independent of N2-CH4 concentrations if both saturated phases are present. Accordingly, the longitudinal and seasonal variations of CH4 and N2 features in Pluto's spectrum would be attributed to spatial variations in the relative proportions of these species. This may occur during volatile transport in the sublimation wind through extensive influences. The lower, unsaturated, values of the mole fraction of CH4 in the ice reported by Owen et al. (Owen et al. [1993]. Science 261, 745-748) and Cruikshank et al. (Cruikshank, D.P., Rush, T.L., Owen, T.C., Quirico, E., de Bergh, C. [1998]. The surface compositions of Triton, Pluto, and Charon. In: Solar System Ices. Astrophysics and Space Science Library Series, vol. 227. Kluwer Academic Publishers, Dordrecht), and by Doute et al. (Doute, S., Schmitt, B., Quirico, E., Owen, T.C., Cruikshank, D.P., de Bergh, C., Geballe, T.R., Roush, T.L. [1999]. Icarus 142, 421-444) based on a compositional analysis of Pluto's surface, were not obtained using optical constants for components consistent with the constraints of the phase diagram.

Flux and distribution of methane (CH4) in the Gunsan Basin of the southeastern Yellow Sea, off the Western Korea.

PubMed

Lee, Jun-Ho; Woo, Han Jun; Son, Seung-Kyu; Kim, Moonkoo; Lee, Dong-Hun; Tsunogai, Urumu; Jeong, Kap-Sik

2018-04-16

The flux and distribution of methane (CH 4 ) was investigated in the seawater column at 14 stations in the Gunsan Basin, the southeastern part of Yellow Sea from 2013 to 2015. Here CH 4 is concentrated 2.4-4.7 (3.4 ± 0.7) nM in the surface and 2.5-7.4 (5.2 ± 1.7) nM in the bottom layer. The CH 4 saturation ratios ranged from 65.5% to 295.5% (162.6 ± 68.7), comprising the mean sea-to-air CH 4 flux of 3.8 to 25.3 (15.6 ± 5.5) µM m -2 d -1 . Methane concentration was largely different in the upper and the lower seawater layers that is separated by the thermocline of which depth is variable (20-60 m) depending on the time of sampling. The concentration of seawater dissolved CH 4 is high between the bottom surface of the thermocline layer and the sea floor. Generally it tends to decrease from the south-westernmost part of the basin toward the west coast of Korea. This distribution pattern of CH 4 seems to result from the CH 4 supply by decomposition of organic matters produced in the upper seawater layer that is superimposed by the larger supply from the underlying sediment layer especially beneath the thermocline. The latter is manifested by ubiquitous CH 4 seeps from the seafloor sediments.

Increased CO2 selectivity of asphalt-derived porous carbon through introduction of water into pore space

NASA Astrophysics Data System (ADS)

Jalilov, Almaz S.; Li, Yilun; Kittrell, Carter; Tour, James M.

2017-12-01

The development of inexpensive porous solid sorbents, such as porous carbons, that can selectively capture carbon dioxide (CO2) from natural gas wells is essential to reduce emission of CO2 to the atmosphere. However, at higher pressures, the selectivity for CO2 over that for methane (CH4) remains poor. Here we show that H2O can be imbibed within asphalt-derived porous carbon, with a surface area of 4,200 m2 g-1, to generate a hydrated powder material. While maintaining a high CO2 uptake capacity of 48 mmol g-1 (211 wt%), the molar selectivity for CO2 over CH4 increases to >200:1 and the H2O remains within the pores on repeated cycling. To mimic realistic natural gas wells, we used a 90% CH4 and 10% CO2 gas mixture and showed selective CO2 separation at 20 bar. Furthermore, in situ vibrational spectroscopy reveals the formation of an ordered matrix within the pores consisting of gas hydrates.

Soil methane and CO2 fluxes in rainforest and rubber plantations

NASA Astrophysics Data System (ADS)

Lang, Rong; Blagodatsky, Sergey; Goldberg, Stefanie; Xu, Jianchu

2017-04-01

Expansion of rubber plantations in South-East Asia has been a land use transformation trend leading to losses of natural forest cover in the region. Besides impact on ecosystem carbon stocks, this conversion influences the dynamics of greenhouse gas fluxes from soil driven by microbial activity, which has been insufficiently studied. Aimed to understand how land use change affects the soil CO2 and CH4 fluxes, we measured surface gas fluxes, gas concentration gradient, and 13C signature in CH4 and soil organic matter in profiles in a transect in Xishuangbanna, including a rainforest site and three rubber plantation sites with age gradient. Gas fluxes were measured by static chamber method and open chamber respiration system. Soil gases were sampled from installed gas samplers at 5, 10, 30, and 75cm depth at representative time in dry and rainy season. The soil CO2 flux was comparable in rainforest and old rubber plantations, while young rubber plantation had the lowest rate. Total carbon content in the surface soil well explained the difference of soil CO2 flux between sites. All sites were CH4 sinks in dry season and uptake decreased in the order of rainforest, old rubber plantations and young rubber plantation. From dry season to rainy season, CH4 consumption decreased with increasing CH4 concentration in the soil profile at all depths. The enrichment of methane by 13CH4 shifted towards to lowerδ13C, being the evidence of enhanced CH4 production process while net surface methane flux reflected the consumption in wet condition. Increment of CH4 concentration in the profile from dry to rainy season was higher in old rubber plantation compared to rainforest, while the shifting of δ13CH4 was larger in rainforest than rubber sites. Turnover rates of soil CO2 and CH4 suggested that the 0-5 cm surface soil was the most active layer for gaseous carbon exchange. δ13C in soil organic matter and soil moisture increased from rainforest, young rubber plantation to old rubber plantations. Conversion the forest into rubber plantation decreased soil respiration in young plantation and it recovered during rubber development. However, the CH4consumption by tropical upland forest soil decreased in converted rubber plantations of all ages, with more decrement in old plantation. Change forest into rubber plantations weakened the soil function as CH4 sink.

Activated adsorption of methane on clean and oxygen-modified Pt?111? and Pd?110?

NASA Astrophysics Data System (ADS)

Valden, M.; Pere, J.; Hirsimäki, M.; Suhonen, S.; Pessa, M.

1997-04-01

Activated adsorption of CH 4 on clean and oxygen modified Pt{111} and Pd{110} has been studied using molecular beam surface scattering. The absolute dissociation probability of CH 4 was measured as a function of the incident normal energy ( E) and the surface temperature ( Ts). The results from clean Pt{111} and Pd{110} are consistent with a direct dissociation mechanism. The dissociative chemisorption dynamics of CH 4 is addressed by using quantum mechanical and statistical models. The influence of adsorbed oxygen on the dissociative adsorption of CH 4 on both Pt{111} and Pd{110} shows that the dissociation probability decreases linearly with increasing oxygen coverage.

The Destabilization of Protected Soil Organic Carbon Following Experimental Drought at the Pore and Core scale

NASA Astrophysics Data System (ADS)

Smith, A. P.; Bond-Lamberty, B. P.; Tfaily, M. M.; Todd-Brown, K. E.; Bailey, V. L.

2015-12-01

The movement of water and solutes through the pore matrix controls the distribution and transformation of carbon (C) in soils. Thus, a change in the hydrologic connectivity, such as increased saturation, disturbance or drought, may alter C mineralization and greenhouse gas (GHG) fluxes to the atmosphere. While these processes occur at the pore scale, they are often investigated at coarser scale. This project investigates pore- and core-scale soil C dynamics with varying hydrologic factors (simulated precipitation, groundwater-led saturation, and drought) to assess how climate-change induced shifts in hydrologic connectivity influences the destabilization of protected C in soils. Surface soil cores (0-15 cm depth) were collected from the Disney Wilderness Preserve, Florida, USA where water dynamics, particularly water table rise and fall, appear to exert a strong control on the emissions of GHGs and the persistence of soil organic matter in these soils. We measured CO2 and CH4 from soils allowed to freely imbibe water from below to a steady state starting from either field moist conditions or following experimental drought. Parallel treatments included the addition of similar quantities of water from above to simulate precipitation. Overall respiration increased in soil cores subjected to drought compared to field moist cores independent of wetting type. Cumulative CH4 production was higher in drought-induced soils, especially in the soils subjected to experimental groundwater-led saturation. Overall, the more C (from CO2 and CH4) was lost in drought-induced soils compared to field moist cores. Our results indicate that future drought events could have profound effects on the destabilization of protected C, especially in groundwater-fed soils. Our next steps focus on how to accurately capture drought-induced C destabilization mechanisms in earth system models.

Enhanced methane emissions from tropical wetlands during the 2011 La Niña

PubMed Central

Pandey, Sudhanshu; Houweling, Sander; Krol, Maarten; Aben, Ilse; Monteil, Guillaume; Nechita-Banda, Narcisa; Dlugokencky, Edward J.; Detmers, Rob; Hasekamp, Otto; Xu, Xiyan; Riley, William J.; Poulter, Benjamin; Zhang, Zhen; McDonald, Kyle C.; White, James W. C.; Bousquet, Philippe; Röckmann, Thomas

2017-01-01

Year-to-year variations in the atmospheric methane (CH4) growth rate show significant correlation with climatic drivers. The second half of 2010 and the first half of 2011 experienced the strongest La Niña since the early 1980s, when global surface networks started monitoring atmospheric CH4 mole fractions. We use these surface measurements, retrievals of column-averaged CH4 mole fractions from GOSAT, new wetland inundation estimates, and atmospheric δ13C-CH4 measurements to estimate the impact of this strong La Niña on the global atmospheric CH4 budget. By performing atmospheric inversions, we find evidence of an increase in tropical CH4 emissions of ∼6–9 TgCH4 yr−1 during this event. Stable isotope data suggest that biogenic sources are the cause of this emission increase. We find a simultaneous expansion of wetland area, driven by the excess precipitation over the Tropical continents during the La Niña. Two process-based wetland models predict increases in wetland area consistent with observationally-constrained values, but substantially smaller per-area CH4 emissions, highlighting the need for improvements in such models. Overall, tropical wetland emissions during the strong La Niña were at least by 5% larger than the long-term mean. PMID:28393869

Langmuir and Langmuir-Blodgett films of multifunctional, amphiphilic polyethers with cholesterol moieties.

PubMed

Reuter, Sascha; Hofmann, Anna M; Busse, Karsten; Frey, Holger; Kressler, Jörg

2011-03-01

Langmuir films of multifunctional, hydrophilic polyethers containing a hydrophobic cholesterol group (Ch) were studied by surface pressure-mean molecular area (π-mmA) measurements and Brewster angle microscopy (BAM). The polyethers were either homopolymers or diblock copolymers of linear poly(glycerol) (lPG), linear poly(glyceryl glycidyl ether) (lPGG), linear poly(ethylene glycol) (lPEG), or hyperbranched poly(glycerol) (hbPG). Surface pressure measurements revealed that the homopolymers lPG and hbPG did not stay at the water surface after spreading and solvent evaporation, in contrast to lPEG. Because of the incorporation of the Ch group in the polymer structure, stable Langmuir films were formed by Ch-lPG(n), Ch-lPGG(n), and Ch-hbPG(n). The Ch-hbPG(n), Ch-lPEG(n), Ch-lPEG(n)-b-lPG(m), Ch-lPEG(n)-b-lPGG(m), and Ch-lPEG(n)-b-hbPG(m) systems showed an extended plateau region assigned to a phase transition involving the Ch groups. Typical hierarchically ordered morphologies of the LB films on hydrophilic substrates were observed for all Ch-initiated polymers. All LB films showed that Ch of the Ch-initiated homopolymers is able to crystallize. This strong tendency of self-aggregation then triggers further dewetting effects of the respective polyether entities. Fingerlike morphologies are observed for Ch-lPEG(69), since the lPEG(69) entity is able to undergo crystallization after transfer onto the silicon substrate.

Diurnal variation of CO2, CH4, and N2O emission fluxes continuously monitored in-situ in three environmental habitats in a subtropical estuarine wetland.

PubMed

Yang, Wen-Bin; Yuan, Chung-Shin; Tong, Chuan; Yang, Pin; Yang, Lei; Huang, Bang-Qin

2017-06-15

Wetlands play a crucial role in modulating atmospheric concentrations of greenhouse gases (GHGs) such as carbon dioxide (CO 2 ), methane (CH 4 ), and nitrous oxide (N 2 O). The key factors controlling GHG emission from subtropical estuarine wetlands were investigated in this study, which continuously monitored the uptake/emission of GHGs (CO 2 , CH 4 , and N 2 O) by/from a subtropical estuarine wetland located in the Minjiang estuary in the coastal region of southeastern China. A self-designed floating chamber was used to collect air samples on-site at three environmental habitats (Phragmites australis marsh, mudflats, and river water). The CO 2 , CH 4 , and N 2 O concentrations were then measured using an automated nondispersive infrared analyzer. The magnitudes of the CO 2 and N 2 O emission fluxes at the three habitats were ordered as river water>P. australis>mudflats. P. australis emitted GHGs through photosynthesis and respiration processes. Emissions of CH 4 from P. australis and the mudflats were revealed to be slightly higher than those from the river water. The total GHG emission fluxes at the three environmental habitats were quite similar (4.68-4.78gm -2 h -1 ). However, when the total carbon dioxide equivalent fluxes (CO 2 -e) were considered, the river water was discovered to emit the most CO 2 -e compared with P. australis and the mudflats. Based on its potential to increase global warming, N 2 O was the main contributor to the total GHG emission, with that emitted from the river water being the most considerable. Tidal water carried onto the marsh had its own GHG content and thus has acted as a source or sink of GHGs. However, water quality had a large effect on GHG emissions from the river water whereas the tidal water height did not. Both high salinity and large amounts of sulfates in the wetlands explicitly inhibited the activity of CH 4 -producing bacteria, particularly at nighttime. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effect of air composition (N2, O2, Ar, and H2O) on CO2 and CH4 measurement by wavelength-scanned cavity ring-down spectroscopy: calibration and measurement strategy

NASA Astrophysics Data System (ADS)

Nara, H.; Tanimoto, H.; Tohjima, Y.; Mukai, H.; Nojiri, Y.; Katsumata, K.; Rella, C. W.

2012-11-01

We examined potential interferences from water vapor and atmospheric background gases (N2, O2, and Ar), and biases by isotopologues of target species, on accurate measurement of atmospheric CO2 and CH4 by means of wavelength-scanned cavity ring-down spectroscopy (WS-CRDS). Changes of the background gas mole fractions in the sample air substantially impacted the CO2 and CH4 measurements: variation of CO2 and CH4 due to relative increase of each background gas increased as Ar < O2 < N2, suggesting similar relation for the pressure-broadening effects (PBEs) among the background gas. The pressure-broadening coefficients due to variations in O2 and Ar for CO2 and CH4 are empirically determined from these experimental results. Calculated PBEs using the pressure-broadening coefficients are linearly correlated with the differences between the mole fractions of O2 and Ar and their ambient abundances. Although the PBEs calculation showed that impact of natural variation of O2 is negligible on the CO2 and CH4 measurements, significant bias was inferred for the measurement of synthetic standard gases. For gas standards balanced with purified air, the PBEs were estimated to be marginal (up to 0.05 ppm for CO2 and 0.01 ppb for CH4) although the PBEs were substantial (up to 0.87 ppm for CO2 and 1.4 ppb for CH4) for standards balanced with synthetic air. For isotopic biases on CO2 measurements, we compared experimental results and theoretical calculations, which showed excellent agreement within their uncertainty. We derived instrument-specific water correction functions empirically for three WS-CRDS instruments (Picarro EnviroSense 3000i, G-1301, and G-2301), and evaluated the transferability of the water correction function from G-1301 among these instruments. Although the transferability was not proven, no significant difference was found in the water vapor correction function for the investigated WS-CRDS instruments as well as the instruments reported in the past studies within the typical analytical precision at sufficiently low water concentrations (<0.7% for CO2 and <0.6% for CH4). For accurate measurements of CO2 and CH4 in ambient air, we concluded that WS-CRDS measurements should be performed under complete dehumidification of air samples, or moderate dehumidification followed by application of a water vapor correction function, along with calibration by natural air-based standard gases or purified air-balanced synthetic standard gases with the isotopic correction.

From Layered Structures to Cubic Frameworks. Expanding the Structural Diversity of Uranyl Carboxyphosphonates via the Incorporation of Cobalt

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

Alsobrook, Andrea N.; Hauser, Brad G.; Hupp, Joseph T.

2011-02-08

Five heterobimetallic U(VI)/Co(II) carboxyphosphonates have been synthesized under mild hydrothermal conditions by reacting UO 3, Co(CH 3CO 2) 2·4H 2O, and triethyl phosphonoacetate. These compounds, Co(H 2O) 4[(UO 2) 2(PO 3CH 2CO 2) 2(H 2O) 2] (CoUPAA-1), [Co(H 2O) 6][UO 2(PO 3CH 2CO 2)] 2·8H 2O (CoUPAA-2), Co(H 2O) 4[UO 2(PO 3CH 2CO 2)] 2·4H 2O (CoUPAA-3), Co(H 2O) 4[(UO 2) 62CH 2CO 2) 2O 2(OH) 3(H 2O) 3] 2·3H 2O (CoUPAA-4), and Co 2(UO 2) 6(PO 3CH 2CO 2) 3O 3(OH)(H 2O) 2·16H 2O (CoUPAA-5), range from two- to three-dimensional structures. CoUPAA-1 to CoUPAA-3 all possess uranyl carboxyphosphonate layersmore » that are separated by the Co(II) cation with varying degrees of hydration. CoUPAA-4 contains both UO 7 pentagonal bipyramids and UO 8 hexagonal bipyramids within the uranyl carboxyphosphonate plane. Unlike the first four low-symmetry compounds, CoUPAA-5 is a cubic, three-dimensional network with large cavities approximately 16 Å in diameter that are filled with cocrystallized water molecules. Differential gas absorption measurements performed on CoUPAA-5 displayed a surface area uptake for CO 2 of 40 m 2 g -1 at 273 K, and no uptake for N 2 at 77 K.« less

Export of Dissolved Methane and Carbon Dioxide with Effluents from Municipal Wastewater Treatment Plants.

PubMed

Alshboul, Zeyad; Encinas-Fernández, Jorge; Hofmann, Hilmar; Lorke, Andreas

2016-06-07

Inland waters play an important role for regional and global scale carbon cycling and are significant sources of the atmospheric greenhouse gases methane (CH4) and carbon dioxide (CO2). Although most studies considered the input of terrestrially derived organic and inorganic carbon as the main sources for these emissions, anthropogenic sources have rarely been investigated. Municipal wastewater treatment plants (WWTPs) could be additional sources of carbon by discharging the treated wastewater into the surrounding aquatic ecosystems. Here we analyze seasonally resolved measurements of dissolved CH4 and CO2 concentrations in effluents and receiving streams at nine WWTPs in Germany. We found that effluent addition significantly altered the physicochemical properties of the streamwater. Downstream of the WWTPs, the concentrations of dissolved CH4 and CO2 were enhanced and the atmospheric fluxes of both gases increased by a factor of 1.2 and 8.6, respectively. The CH4 exported with discharged effluent, however, accounted for only a negligible fraction (0.02%) of the estimated total CH4 emissions during the treatment process. The CH4 concentration in the effluent water was linearly related to the organic load of the wastewater, which can provide an empirical basis for future attempts to add WWTPs inputs to regional-scale models for inland water-carbon fluxes.

Nitrogen losses and greenhouse gas emissions under different N and water management in a subtropical double-season rice cropping system.

PubMed

Liang, Kaiming; Zhong, Xuhua; Huang, Nongrong; Lampayan, Rubenito M; Liu, Yanzhuo; Pan, Junfeng; Peng, Bilin; Hu, Xiangyu; Fu, Youqiang

2017-12-31

Nitrogen non-point pollution and greenhouse gas (GHG) emission are major challenges in rice production. This study examined options for both economic and environmental sustainability through optimizing water and N management. Field experiments were conducted to examine the crop yields, N use efficiency (NUE), greenhouse gas emissions, N losses under different N and water management. There were four treatments: zero N input with farmer's water management (N0), farmer's N and water management (FP), optimized N management with farmer's water management (OPT N ) and optimized N management with alternate wetting and drying irrigation (OPT N +AWD). Grain yields in OPT N and OPT N +AWD treatments increased by 13.0-17.3% compared with FP. Ammonia volatilization (AV) was the primary pathway for N loss for all treatments and accounted for over 50% of the total losses. N losses mainly occurred before mid-tillering. N losses through AV, leaching and surface runoff in OPT N were reduced by 18.9-51.6% compared with FP. OPT N +AWD further reduced N losses from surface runoff and leaching by 39.1% and 6.2% in early rice season, and by 46.7% and 23.5% in late rice season, respectively, compared with OPT N . The CH 4 emissions in OPT N +AWD were 20.4-45.4% lower than in OPT N and FP. Total global warming potential of CH 4 and N 2 O was the lowest in OPT N +AWD. On-farm comparison confirmed that N loss through runoff in OPT N +AWD was reduced by over 40% as compared with FP. OPT N and OPT N +AWD significantly increased grain yield by 6.7-13.9%. These results indicated that optimizing water and N management can be a simple and effective approach for enhancing yield with reduced environmental footprints. Copyright © 2017. Published by Elsevier B.V.

Proposed Trace Gas Measurements Over the Western United States for TROPOMI Validation

NASA Technical Reports Server (NTRS)

Parworth, Caroline L.; Marrero, Josette E.; Yates, Emma L.; Ryoo, Ju-Mee; Iraci, Laura T.

2018-01-01

The Alpha Jet Atmospheric eXperiment (AJAX), located in the Bay Area of California, is a joint effort between NASA Ames Research Center and H211, LCC. AJAX makes in-situ airborne measurements of trace gases 2-4 times per month, resulting in over 216 flights since 2011. Current measurements include ozone (O3), carbon dioxide (CO2), methane (CH4), water (H2O), formaldehyde (HCHO), and meteorological measurements (i.e., ambient pressure, temperature, and 3D winds). Currently, the AJAX team is working to incorporate nitrogen dioxide (NO2) measurements with a Cavity Attenuated Phase Shift Spectrometer (CAPS). Successful science flights coincident with satellite overpasses have been performed since 2011 by the Alpha Jet, with more than 40 flights under the Greenhouse Observing SATellite (GOSAT) and several flights under the Orbiting Carbon Observatory-2 (OCO-2). Results from these flights, which have covered a range of different surfaces and seasonal conditions, will be presented. In-situ vertical profiles of O3, CO2, CH4, H2O, HCHO, and NO2 from the surface to 28,000 feet made by AJAX will also be valuable for satellite validation of data products obtained from the TROPOspheric Montoring Instrument (TROPOMI). TROPOMI is on board the Copernicus Sentinel-5 precursor (S5p) satellite, with level 2 products including O3, CO, CH4, HCHO, NO2, and aerosols.

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.

Generation of Hydrogen and Methane during Experimental Low-Temperature Reaction of Ultramafic Rocks with Water.

PubMed

McCollom, Thomas M; Donaldson, Christopher

2016-06-01

Serpentinization of ultramafic rocks is widely recognized as a source of molecular hydrogen (H2) and methane (CH4) to support microbial activity, but the extent and rates of formation of these compounds in low-temperature, near-surface environments are poorly understood. Laboratory experiments were conducted to examine the production of H2 and CH4 during low-temperature reaction of water with ultramafic rocks and minerals. Experiments were performed by heating olivine or harzburgite with aqueous solutions at 90°C for up to 213 days in glass bottles sealed with butyl rubber stoppers. Although H2 and CH4 increased steadily throughout the experiments, the levels were very similar to those found in mineral-free controls, indicating that the rubber stoppers were the predominant source of these compounds. Levels of H2 above background were observed only during the first few days of reaction of harzburgite when CO2 was added to the headspace, with no detectable production of H2 or CH4 above background during further heating of the harzburgite or in experiments with other mineral reactants. Consequently, our results indicate that production of H2 and CH4 during low-temperature alteration of ultramafic rocks may be much more limited than some recent experimental studies have suggested. We also found no evidence to support a recent report suggesting that spinels in ultramafic rocks may stimulate H2 production. While secondary silicates were observed to precipitate during the experiments, formation of these deposits was dominated by Si released by dissolution of the glass bottles, and reaction of the primary silicate minerals appeared to be very limited. While use of glass bottles and rubber stoppers has become commonplace in experiments intended to study processes that occur during serpentinization of ultramafic rocks at low temperatures, the high levels of H2, CH4, and SiO2 released during heating indicate that these reactor materials are unsuitable for this purpose. Serpentinization-Hydrogen generation-Abiotic methane synthesis. Astrobiology 16, 389-406.

Constraining the sources of CH4 emissions during past abrupt climate change using CH4 triple isotopes mass balance from the ice core records

NASA Astrophysics Data System (ADS)

Dyonisius, M.; Petrenko, V. V.; Smith, A. W.; Hmiel, B.; Beck, J.; Seth, B.; Bock, M.; Hua, Q.; Yang, B.; Harth, C. M.; Beaudette, R.; Lee, J.; Erhardt, T.; Schmitt, J.; Brook, E.; Weiss, R. F.; Fischer, H.; Severinghaus, J. P.

2017-12-01

Methane (CH4) is the third most important greenhouse gas in the atmosphere after water vapor and CO2. Understanding how the natural CH4 budget has changed in response to changing climate in the past can provide insights on the sensitivity of the natural CH4 emissions to the current anthropogenic warming. CH4 isotopes (Δ14CH4, δ13C-CH4, and δD-CH4) from ice cores can be used to fingerprint the sources of CH4 increases in the past. We have successfully extracted 6 large volume (>1000kg) ice core samples from Taylor Glacier, Antarctica spanning the Oldest Dryas-Bølling transition ( 14.7ka) - the first abrupt warming and CH4 rise since the Last Glacial Maximum. Among the CH4 isotopes, our Δ 14CH4 data are unique in their ability to unambiguously distinguish between "old" CH4 sources (e.g. marine clathrate, geologic sources, old permafrost) and "modern" CH4 sources (e.g. tropical and boreal wetlands). Our Δ14CH4 data unambiguously rule out marine clathrate and old permafrost as the sources of the abrupt CH4 rise. Preliminary CH4 stable isotopes box modeling combined with interpolar CH4 concentration gradient from existing ice core records suggest that tropical wetlands were the dominant driver for the Oldest Dryas-Bølling CH4 rise.

Husbandry Trace Gas Emissions from a Dairy Complex By Mobile in Situ and Airborne and Spaceborne Remote Sensing: A Comex Campaign Focus

NASA Astrophysics Data System (ADS)

Leifer, I.; Tratt, D. M.; Bovensmann, H.; Buckland, K. N.; Burrows, J. P.; Frash, J.; Gerilowski, K.; Iraci, L. T.; Johnson, P. D.; Kolyer, R.; Krautwurst, S.; Krings, T.; Leen, J. B.; Hu, C.; Melton, C.; Vigil, S. A.; Yates, E. L.; Zhang, M.

2014-12-01

Recent field study reviews on the greenhouse gas methane (CH4) found significant underestimation from fossil fuel industry and husbandry. The 2014 COMEX campaign seeks to develop methods to derive CH4 and carbon dioxide (CO2) from remote sensing data by combining hyperspectral imaging (HSI) and non-imaging spectroscopy (NIS) with in situ airborne and surface data. COMEX leverages synergies between high spatial resolution HSI column abundance maps and moderate spectral/spatial resolution NIS. Airborne husbandry data were collected for the Chino dairy complex (East Los Angeles Basin) by NIS-MAMAP, HSI-Mako thermal-infrared (TIR); AVIRIS NG shortwave IR (SWIR), with in situ surface mobile-AMOG Surveyor (AutoMObile greenhouse Gas)-and airborne in situ from a Twin Otter and the AlphaJet. AMOG Surveyor uses in situ Integrated Cavity Off Axis Spectroscopy (OA-ICOS) to measure CH4, CO2, H2O, H2S and NH3 at 5-10 Hz, 2D winds, and thermal anomaly in an adapted commuter car. OA-ICOS provides high precision and accuracy with excellent stability. NH3 and CH4 emissions were correlated at dairy size-scales but not sub-dairy scales in surface and Mako data, showing fine-scale structure and large variations between the numerous dairies in the complex (herd ~200,000-250,000) embedded in an urban setting. Emissions hotspots were consistent between surface and airborne surveys. In June, surface and MAMAP data showed a weak overall plume, while surface and Mako data showed a stronger plume in late (hotter) July. Multiple surface plume transects using NH3 fingerprinting showed East and then NE advection out of the LA Basin consistent with airborne data. Long-term trends were investigated in satellite data. This study shows the value of synergistically combined NH3 and CH4 remote sensing data to the task of CH4 source attribution using airborne and space-based remote sensing (IASI for NH3) and top of atmosphere sensitivity calculations for Sentinel V and Carbon Sat (CH4).

Monitoring the Thermal Regime at Hot Creek and Vicinity, Long Valley Caldera, Eastern California

NASA Astrophysics Data System (ADS)

Clor, L. E.; Hurwitz, S.; Howle, J.

2015-12-01

Hot Creek Gorge contains the most obvious surface expression of the hydrothermal system in Long Valley Caldera, California, discharging 200-300 L/s of thermal water according to USGS measurements made since 1988. Formerly, Hot Creek was a popular public swimming area, but it was closed in 2006 due to unpredictable temperature fluctuations and sporadic geysering of thermal water within the creek (Farrar et al. USGS Fact Sheet2007-3045). The USGS has monitored the thermal regime in the area since the mid-1980s, including a long-term series of studies 0.6 km away at well CH-10b. Temperature measurements in the ~100 m deep well, which have been performed on an intermittent basis since it was drilled in 1983, reveal a complex temperature profile. Temperatures increase with depth to a maximum at about 45 meters below the ground surface, and then decrease steadily to the bottom of the well. The depth of the temperature maximum in the well (~45 m) corresponds to an elevation of ~2,120 m, roughly equivalent to the elevation of Hot Creek, and appears to sample the same hydrothermal flow system that supplies thermal features at the surface in the gorge. Starting in the early 1990s, the maximum temperature in CH-10b rose from 93.4°C to its peak in 2007 at 101.0°C. A cooling trend was observed beginning in 2009 and continues to present (99.3°C in June 2015). As the input into CH-10b is at the elevation of the creek, it exhibits the potential for response to thermal events at Hot Creek, and could provide a useful tool for monitoring future hazards. On short timescales, CH-10b also responds to large global earthquakes, greater than ~M7. These responses are captured with continuously logged high-frequency data (5s), and are usually characterized by a co-seismic water level drop of up to ten centimeters. Water levels tend to recover to pre-earthquake levels within a few hours to days.

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.

Surface Forcing from CH4 at the North Slope of Alaska and Southern Great Plains Sites

NASA Astrophysics Data System (ADS)

Collins, W.; Feldman, D.; Turner, D. D.

2014-12-01

Recent increases in atmospheric CH4 have been spatially heterogeneous as indicated by in situ flask measurements and space-borne remote-sensing retrievals from the AIRS instrument, potentially leading to increased radiative forcing. We present detailed, specialized measurements at the DOE ARM North Slope of Alaska (NSA) and Southern Great Plains (SGP) sites to derive the time-series of both CH4 atmospheric concentrations and associated radiative implications at highly-contrasting natural and anthropogenic sources. Using a combination of spectroscopic measurements, in situ observations, and ancillary data for the atmospheric thermodynamic state from radiosondes and cloud-clearing from active sounders, we can separate out the contribution of CH4 to clear-sky downwelling radiance spectra and its infrared surface forcing. The time-series indicates year-to-year variation in shoulder season increases of CH4 concentration and forcing at NSA and large signals from anthropogenic activity at SGP.

Methanogenesis, Mesospheric Clouds, and Global Habitability

NASA Technical Reports Server (NTRS)

Pueschel, Rudolf F.; Condon, Estelle P. (Technical Monitor)

2000-01-01

Hyperthermophilic methanogens can exist in a deep hot biosphere up to 110 C, or 10 km deep. Methane (CH4) itself is thermodynamically stable to depths of 300 km. Geologic (microbial plus abiogenic thermal) methane is transported upward, attested to by its association with helium, to form petroleum pools. Near or at the surface, geologic CH4 mixes with other natural and with anthropogenic CH4 yielding annual emissions into the atmosphere of 500 Tg, of which 200 Tg are natural and 300 Tg are man-made. The atmospheric lifetime of CH4, a greenhouse gas 20 times more effective than CO2 in raising global temperatures, is approximately 10 years. It is removed from the atmosphere mainly by reactions with hydroxyl radical (OH) to form CO2, but also by dry soil and by conversion to H2O in the stratosphere and middle atmosphere. A sudden rise in atmospheric temperatures by 9-12 C some 55 million years ago has been explained by the release in a few thousand years of three trillion tons of CH4 out of 15 trillion tons that had formed beneath the sea floor. What prevented this CH4-induced greenhouse effect from running away? An analog to the CH4-burp of 55 million years ago is the CH4-doubling over the past century which resulted in a increase in upper level H2O from 4.3 ppmv to 6 ppmv. This 30% increase in H2O vapor yielded a tenfold increase in brightness of polar mesospheric clouds because of a strong dependence of the ice particle nucleation rate on the water saturation ratios. Models show that at a given temperature the optical depth of mesospheric clouds scales as [H2O]beta with beta varying between 4 and 8. Radiative transfer tools applied to mesospheric particles suggest that an optical depth of approximately one, or 1000 times the current mesospheric cloud optical depth, would result in tropospheric cooling of about 10 K. Assuming beta=6, a thousandfold increase in optical thickness would require a three-fold increase of H2O, or a 20-fold increase of CH4. At the current rate of anthropogenic emissions this is expected to occur within the next 1000 years. This timescale is also commensurate with what has been assumed for the CH4- burp 55 million years ago.

Neotropical peatland methane emissions along a vegetation and biogeochemical gradient.

PubMed

Winton, R Scott; Flanagan, Neal; Richardson, Curtis J

2017-01-01

Tropical wetlands are thought to be the most important source of interannual variability in atmospheric methane (CH4) concentrations, yet sparse data prevents them from being incorporated into Earth system models. This problem is particularly pronounced in the neotropics where bottom-up models based on water table depth are incongruent with top-down inversion models suggesting unaccounted sinks or sources of CH4. The newly documented vast areas of peatlands in the Amazon basin may account for an important unrecognized CH4 source, but the hydrologic and biogeochemical controls of CH4 dynamics from these systems remain poorly understood. We studied three zones of a peatland in Madre de Dios, Peru, to test whether CH4 emissions and pore water concentrations varied with vegetation community, soil chemistry and proximity to groundwater sources. We found that the open-canopy herbaceous zone emitted roughly one-third as much CH4 as the Mauritia flexuosa palm-dominated areas (4.7 ± 0.9 and 14.0 ± 2.4 mg CH4 m-2 h-1, respectively). Emissions decreased with distance from groundwater discharge across the three sampling sites, and tracked changes in soil carbon chemistry, especially increased soil phenolics. Based on all available data, we calculate that neotropical peatlands contribute emissions of 43 ± 11.9 Tg CH4 y-1, however this estimate is subject to geographic bias and will need revision once additional studies are published.

Role of meteorology in simulating methane seasonal cycle and growth rate

NASA Astrophysics Data System (ADS)

Ghosh, A.; Patra, P. K.; Ishijima, K.; Morimoto, S.; Aoki, S.; Nakazawa, T.

2012-12-01

Methane (CH4) is the second most important anthropogenically produced greenhouse gas whose radiative effect is comparable to that of carbon dioxide since the preindustrial time. Methane also contributes to formation of tropospheric ozone and water vapor in the stratosphere, further increasing its importance to the Earth's radiative balance. In the present study, model simulation of CH4 for three different emission scenarios has been conducted using the CCSR/NIES/FRCGC Atmospheric General Circulation Model (AGCM) based Chemistry Transport Model (ACTM) with and without nudging of meteorological parameters for the period of 1981-2011. The model simulations are compared with measurements at monthly timescale at surface monitoring stations. We show the overall trends in CH4 growth rate and seasonal cycle at most measurement sites can be fairly successfully modeled by using existing knowledge of CH4 flux trends and seasonality. Detailed analysis reveals the model simulation without nudging has greater seasonal cycle amplitude compared to observation as well as the model simulation with nudging. The growth rate is slightly overestimated for the model simulation without nudging. For better representation of regional/global flux distribution pattern and strength in the future, we are exploring various dynamical and chemical aspects in the forward model with and without nudging.

Fall season atypically warm weather event leads to substantial CH4 loss in Arctic ecosystems?

NASA Astrophysics Data System (ADS)

Zona, Donatella; Moreaux, Virginie; Liljedahl, Anna; Losacco, Salvatore; Murphy, Patrick; Oechel, Walter

2014-05-01

In the last century (during 1875-2008) high-latitudes are warming at a rate of 1.360C century-1, almost 2 times faster than the Northern Hemisphere trend (Bekryaev et al., 2010). This warming has been more intense outside of the summer season, with anomalies of 1.09, 1.59, 1.730C in the fall, winter, and spring season respectively (Bekryaev et al., 2010). This substantial temperature anomalies have the potential to increase the emission of greenhouse gas (CO2 and CH4) fluxes from arctic tundra ecosystems. In particular, CH4 emissions, which are primarily controlled by temperature (in addition to water table), can steeply increase with warming. Despite the potential relevance of CH4 emissions, very few measurements have been performed outside of the growing season across the entire Arctic, due to logistic constrains. Importantly, no flux measurements achieved a temporal and spatial data coverage sufficient to estimate with confidence an annual CH4 emissions from tundra ecosystem in Alaska, and its sensitivity to warming. Fall 2013 was unusually warm in central and northern Alaska. Following a relatively warm summer with dramatically above-average rainfall, the October mean monthly temperatures was the 4th and top warmest in Barrow (1949-2013) and Ivotuk (1998-2013), respectively. As we just upgraded several eddy covariance towers to measure CO2 and CH4 fluxes year-round, the atypical weather conditions of fall 2013 represented a unique chance for testing the sensitivity of CH4 loss to these atypically warm temperatures. All our sites across a latitudinal gradient (from the northern site, Barrow, to the southern site, Ivotuk), presented substantial CH4 loss in the fall. Importantly, in two of these sites (Barrow, Ivotuk) where the fall weather was substantially warmer than the long term trend, fall CH4 emission represented between 44-63% of the June-November cumulative emission. Surprisingly, in the southernmost site (Ivotuk), when the temperature anomaly was the highest, cumulative fall CH4 emission outpaced even the summer emission. This shows the sensitivity of CH4 loss to abnormal conditions, and the importance of fall periods for the annual CH4 budget in these Arctic ecosystems. Bekryaev, R. V., I. V. Polyakov, and V. A. Alexeev. 2010. Role of polar amplification in long-term surface air temperature variations and modern Arctic warming. Journal of Climate 23(14):3888-3906.

Irrigation with oxygen-nanobubble water can reduce methane emission and arsenic dissolution in a flooded rice paddy

NASA Astrophysics Data System (ADS)

Minamikawa, Kazunori; Takahashi, Masayoshi; Makino, Tomoyuki; Tago, Kanako; Hayatsu, Masahito

2015-08-01

A remarkable feature of nanobubbles (<10-6 m in diameter) is their long lifetime in water. Supplying oxygen-nanobubbles (NBs) to continuously flooded paddy soil may retard the development of reductive conditions, thereby reducing the emission of methane (CH4), a potent greenhouse gas, and dissolution of arsenic, an environmental load. We tested this hypothesis by performing a pot experiment and measuring redox-related variables. The NBs were introduced into control water (with properties similar to those of river water) using a commercially available generator. Rice (Oryza sativa L.) growth did not differ between plants irrigated with NB water and those irrigated with control water, but NB water significantly (p < 0.05) reduced cumulative CH4 emission during the rice-growing season by 21%. The amounts of iron, manganese, and arsenic that leached into the drainage water before full rice heading were also reduced by the NB water. Regardless of the water type, weekly-measured CH4 flux was linearly correlated with the leached iron concentration during the rice-growing season (r = 0.74, p < 0.001). At the end of the experiment, the NB water significantly lowered the soil pH in the 0-5 cm layer, probably because of the raised redox potential. The population of methanogenic Archaea (mcrA copy number) in the 0-5 cm layer was significantly increased by the NB water, but we found no correlation between the mcrA copy number and the cumulative CH4 emission (r = -0.08, p = 0.85). In pots without rice plants, soil reduction was not enhanced, regardless of the water type. The results indicate that NB water reduced CH4 emission and arsenic dissolution through an oxidative shift of the redox conditions in the flooded soil. We propose the use of NB water as a tool for controlling redox conditions in flooded paddy soils.

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.

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.

Ammonia and Methane Dairy Emission Plumes in the San Joaquin Valley of California from Individual Feedlot to Regional Scales

NASA Technical Reports Server (NTRS)

Miller, David J.; Sun, Kang; Pan, Da; Zondlo, Mark A.; Nowak, John B.; Liu, Zhen; Diskin, Glenn; Sachse, Glen; Beyersdorf, Andreas; Ferrare, Richard;

Ammonia and methane dairy emissions in the San Joaquin Valley of California from individual feedlot to regional scale

DOE PAGES

Miller, David J.; Sun, Kang; Tao, Lei; ...

2015-09-27

Agricultural ammonia (NH 3) emissions are highly uncertain, with high spatiotemporal variability and a lack of widespread in situ measurements. Regional NH 3 emission estimates using mass balance or emission ratio approaches are uncertain due to variable NH 3 sources and sinks as well as unknown plume correlations with other dairy source tracers. We characterize the spatial distributions of NH 3 and methane (CH 4) dairy plumes using in situ surface and airborne measurements in the Tulare dairy feedlot region of the San Joaquin Valley, California, during the NASA Deriving Information on Surface conditions from Column and Vertically Resolved Observationsmore » Relevant to Air Quality 2013 field campaign. Surface NH 3 and CH 4 mixing ratios exhibit large variability with maxima localized downwind of individual dairy feedlots. The geometric mean NH 3:CH 4 enhancement ratio derived from surface measurements is 0.15 ± 0.03 ppmv ppmv –1. Individual dairy feedlots with spatially distinct NH 3 and CH 4 source pathways led to statistically significant correlations between NH 3 and CH 4 in 68% of the 69 downwind plumes sampled. At longer sampling distances, the NH 3:CH 4 enhancement ratio decreases 20–30%, suggesting the potential for NH 3 deposition as a loss term for plumes within a few kilometers downwind of feedlots. Aircraft boundary layer transect measurements directly above surface mobile measurements in the dairy region show comparable gradients and geometric mean enhancement ratios within measurement uncertainties, even when including NH 3 partitioning to submicron particles. Individual NH 3 and CH 4 plumes sampled at close proximity where losses are minimal are not necessarily correlated due to lack of mixing and distinct source pathways. As a result, our analyses have important implications for constraining NH 3 sink and plume variability influences on regional NH 3 emission estimates and for improving NH 3 emission inventory spatial allocations.« less

Atomic and molecular adsorption on Fe(110)

DOE PAGES

Xu, Lang; Kirvassilis, Demetrios; Bai, Yunhai; ...

2017-09-12

Iron is the principal catalyst for the ammonia synthesis process and the Fischer–Tropsch process, as well as many other heterogeneously catalyzed reactions. It is thus of fundamental importance to understand the interactions between the iron surface and various reaction intermediates. Here in this paper, we present a systematic study of atomic and molecular adsorption behavior over Fe(110) using periodic, self-consistent density functional theory (DFT-GGA) calculations. The preferred binding sites, binding energies, and the corresponding surface deformation energies of five atomic species (H, C, N, O, and S), six molecular species (NH 3, CH 4, N 2, CO, HCN, and NO),more » and eleven molecular fragments (CH, CH 2, CH 3, NH, NH 2, OH, CN, COH, HCO, NOH, and HNO) were determined on the Fe(110) surface at a coverage of 0.25 monolayer. The binding strengths calculated using the PW91 functional decreased in the following order: C> CH > N > O > S > NH > COH > CN > CH2 > NOH > OH > HNO > HCO > NH2 > H > NO > HCN > CH 3 > CO > N 2 > NH 3. No stable binding structures were observed for CH 4. The estimated diffusion barriers and pathways, as well as the adsorbate-surface and intramolecular vibrational modes of all the adsorbates at their preferred binding sites, were identified. Using the calculated adsorption energetics, we constructed the potential energy surfaces for a few surface reactions including the decomposition of methane, ammonia, dinitrogen, carbon monoxide, and nitric oxide. These potential energy surfaces provide valuable insight into the ability of Fe(110) to catalyze common elementary steps.« less

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.

Second-Year Results from the Circumarctic Lakes Observation Network (CALON) Project

NASA Astrophysics Data System (ADS)

Hinkel, K. M.; Arp, C. D.; Beck, R. A.; Eisner, W. R.; Frey, K. E.; Gaglioti, B.; Grosse, G.; Jones, B. M.; Kim, C.; Lenters, J. D.; Liu, H.; Townsend-Small, A.

2013-12-01

Beginning in April 2012, over 55 lakes in northern Alaska were instrumented as the initial phase of CALON, a project designed to document landscape-scale variability in physical and biogeochemical processes of Arctic lakes developed atop permafrost. The current network has nine observation nodes along two latitudinal transects that extend from the Arctic Ocean south 200 km to the foothills of the Brooks Range. At each node, six representative lakes of differing area and depth were instrumented at different intensity levels, and a suite of instruments were deployed to collect field measurements on lake physiochemistry, lake-surface and terrestrial climatology, and lake bed and permafrost temperature. Each April, sensors measuring water temperature and water depth are deployed through the ice and water samples are collected. Sensors are downloaded from lakes and meteorological stations in August, recording a timeline of lake regimes and events from ice decay to the summertime energy and water balance. In general, lake ice thickness increased with latitude. In 2012, ice on deeper (>2 m) lakes was about 1.4 m thick in the Arctic Foothills and 1.7 m thick near the Arctic Ocean coast. Lake ice thickness was about 20 cm thicker in winter 2013 although winter temperatures were several degrees warmer than the previous year; this is likely due to a thinner snow cover in 2013. Lake ice elevations agree with this general trend, showing higher absolute elevation in April 2013 compared to 2012 for most of the surveyed lakes. Regionally, ice-off occurs 2-4 weeks later on lakes near the coast, although there is significant inter-lake variability related to lake depth. Following ice-off, rapid lake warming occurs and water temperature varies synchronously in response to synoptic weather variations and associated changes in net radiation and turbulent heat fluxes. Average mid-summer (July) lake temperatures spanned a relatively wide range in 2012 from 7°C to 18°C, with higher temperatures in small shallow lakes and more southern latitudes. Most lakes are well-mixed and largely isothermal, with short periods of thermal stratification occurring in deeper lakes during calm, sunny periods. Over the ice-free season, the majority of the available energy from net radiation goes into evaporation, followed by sensible heat flux and warming of bottom sediments. Thermal bands of MODIS and Landsat imagery were fused using a spatio-temporal cokriging method to generate daily surface temperature estimates at Landsat spatial resolution. The close correspondence between satellite-derived and in situ measured near-surface lake temperature suggests that this approach yields viable results. Biogeochemical and inorganic geochemical constituents measured include dissolved greenhouse gas concentrations (CO2, CH4, and N2O), inorganic N, DON and DOC, alkalinity, chlorophyll-a, major ions, and CDOM. The greatest difference in the dissolved CH4:CO2 ratio in summer was longitudinal, with several lakes in western Alaskan Arctic exhibiting CH4 concentrations hundreds of times more supersaturated than air. Stable isotope analyses of CH4 (δ13C and δ2H) show that several of these lakes have natural gas methane sources. Methane concentrations under ice (April) were several thousand times higher than in open-water conditions (August). Data collected during this 4-year project are archived at A-CADIS.

Investigation of Wyoming Bentonite Hydration in Dry to Water-Saturated Supercritical CH4 and CH4/CO2 Mixtures: Implications for CO2-Enhanced Gas Production

NASA Astrophysics Data System (ADS)

Loring, J.; Thompson, C.; Ilton, E. S.; McGrail, B. P.; Schaef, T.

2014-12-01

Injection of CO2 into low permeability shale formations leads to additional gas recovery and reduces the flux of CO2 into the atmosphere, thus combining a strong economic incentive with a permanent storage option for CO2. Reduced formation transmissivity due to clay swelling is a concern in CO2 -enhanced gas production. Clay minerals partly determine the physical (i.e. permeability, brittleness) and certain chemical properties (i.e. wetting ability, gas adsorption) of shales, and montmorillonites are of particular interest because they swell by the uptake of species in their interlayer. In this study, the hydration and expansion of a Na-saturated montmorillonite (Na-SWy-2) in high-pressure (90 bar) and moderate temperature (50 °C) methane and mixtures of methane and carbon dioxide were investigated usingCH4 IR spectroscopic titrations andCH4 XRD. The goals were to (1) determine if the hydration/expansion behavior of the clay in supercritical methane is different than in supercritical CO2, (2) determine if methane intercalates the clay, and (3) probe the effects of increasing CO2 concentrations. IR spectra were collected as Na-SWy-2 was titrated with water under several fluid exposures: pure methane, 25, 50, and 75 mole% CO2 in methane, and pure CO2. ComplementaryCH4 XRD experiments were conducted in the same fluids at discrete dissolved water concentrations to measure the d001 values of the clay and thus its volume change on hydration and CH4 and/or CO2 intercalation. In pure methane, no direct evidence of CH4 intercalation was detected in CH bending or stretching regions of the IR spectra. Similarly, in situ XRD indicated the montmorillonite structure was stable in the presence of CH4 and no measurable changes to the basal spacing were observed. However, under low water conditions where the montmorillonite structure was partially expanded (~sub 1W), the IR data indicated a rapid intercalation of CO2 into the interlayer, even with fluid mixtures containing the lowest concentrations of CO2. Likewise,CH4 XRD showed indirect evidence of CO2 intercalation from an increase in the basal spacing from 11.8 to 12.3 under identical conditions. These findings demonstrate that water and CO2 intercalation processes could lead to permeability changes that directly impact methane transmissivity in shales.

Transfer of Fas (CD95) protein from the cell surface to the surface of polystyrene beads coated with anti-Fas antibody clone CH-11

PubMed Central

Sawai, H.; Domae, N.

2010-01-01

Mouse monoclonal anti-Fas (CD95) antibody clone CH-11 has been widely used in research on apoptosis. CH-11 has the ability to bind to Fas protein on cell surface and induce apoptosis. Here, we used polystyrene beads coated with CH-11 to investigate the role of lipid rafts in Fas-mediated apoptosis in SKW6.4 cells. Unexpectedly, by treatment of the cells with CH-11-coated beads Fas protein was detached from cell surface and transferred to the surface of CH-11-coated beads. Western blot analysis showed that Fas protein containing both extracellular and intracellular domains was attached to the beads. Fas protein was not transferred from the cells to the surface of the beads coated with other anti-Fas antibodies or Fas ligand. Similar phenomenon was observed in Jurkat T cells. Furthermore, CH-11-induced apoptosis was suppressed by pretreatment with CH-11-coated beads in Jurkat cells. These results suggest that CH-11 might possess distinct properties on Fas protein compared with other anti-Fas antibodies or Fas ligand, and also suggest that caution should be needed to use polystyrene beads coated with antibodies such as CH-11. PMID:20353915

More CH4 is emitted during the fallow than during the growing season in a Mediterranean rice agrosystems

NASA Astrophysics Data System (ADS)

Martínez-Eixarch, Maite; Ibàñez, Carles; Alcaraz, Carles; Viñas, Marc; Aranda, Xavier; Saldaña, J. Antonio

2017-04-01

Paddy rice fields are an important source of greenhouse gas emissions (GHG) as they contribute 5 to 20 % of the global anthropogenic CH4 emissions. The Ebre Delta (Catalonia, NE Spain) is one of the most important wetland complexes in the Western Mediterranean with 65 % of its area covered by rice fields. The results herein presented assess the annual pattern of CH4 emissions from paddy rice in Ebre Delta, including the growing and fallow seasons as well as the major environmental variables modulating such emissions. Fifteen rice fields covering the geo-physical variability of the Ebre Delta were selected for GHG monitoring. Common agronomic management was practiced: water direct-seeding, permanent flooding and moderate mineral fertilization during the growing season and straw incorporation, progressive drainage of the fields after the harvest. Fields are left fallow during the winter. GHG were monthly sampled, from May to December in 2015. In each field, three closed chambers were used; from each of these, four gas samples were taken over a 30-minute period. Simultaneously, hydrological regime, soil physic-chemical parameters and plant cover were measured. GHG were analysed by gas chromatography. A Generalized linear model analysis (GLM) was performed to assess the most important influencing factors on CH4 emissions. An information-theoretic approach was used to find the best approximating models. Overall, the CH4 emissions showed a bi-modal pattern, with peaks in July-August and in October. Emissions rates ranged from 2.1 ± 0.5 to 7.5 ± 1.4 mg C-CH4 m-2 h-1 in the growing season (May to September) and from 25.0 ± 5.7 to 20.1 ± 3.3 mg C-CH4 m-2 h-1 at post-harvest (October to December). In total, 314 kg C-CH4 ha-1 were emitted from Ebre Delta rice fields, of which 70 % during post-harvest. Larger off-season emissions were likely induced by straw incorporation. The results of the GLM-IT analysis revealed that during the growing season, soil Eh and water level were the most important factors influencing CH4 emissions, followed by soil temperature and plant cover, with similar degree of importance. During the fallow season, soil redox and water level were also the most important factors, along with air temperature. Throughout the growing and fallow seasons, soil Eh was negatively related to CH4 emissions whereas temperature and plant cover positively. Interestingly, water level showed a contrasting effect on CH4 emissions: positive during the growing season and negative the fallow. Traditionally, most of the research on GHG mitigation options in paddy rice has been focused on the rice growing period and less attention has been paid to the post-harvest season. The higher contribution of the fallow season to the total annual CH4 emissions evidenced in our study suggests that more effort should be made on this season when aiming at mitigating CH4 emissions, being water and straw management the key factors. Accordingly, we also recommend the inclusion of the fallow season for GHG inventories from paddy rice, usually neglected, to avoid CH4 emissions underestimations.

Forest ecosystem changes from annual methane source to sink depending on late summer water balance

Treesearch

Julie K. Shoemaker; Trevor F. Keenan; David Y. Hollinger; Andrew D. Richardson

2014-01-01

Forests dominate the global carbon cycle, but their role in methane (CH4) biogeochemistry remains uncertain. We analyzed whole-ecosystem CH4 fluxes from 2 years, obtained over a lowland evergreen forest in Maine, USA. Gross primary productivity provided the strongest correlation with the CH4 flux in...

CO2 CH4 flux Air temperature Soil temperature and Soil moisture, Barrow, Alaska 2013 ver. 1

DOE Data Explorer

Margaret Torn

2015-01-14

This dataset consists of field measurements of CO2 and CH4 flux, as well as soil properties made during 2013 in Areas A-D of Intensive Site 1 at the Next-Generation Ecosystem Experiments (NGEE) Arctic site near Barrow, Alaska. Included are i) measurements of CO2 and CH4 flux made from June to September (ii) Calculation of corresponding Gross Primary Productivity (GPP) and CH4 exchange (transparent minus opaque) between atmosphere and the ecosystem (ii) Measurements of Los Gatos Research (LGR) chamber air temperature made from June to September (ii) measurements of surface layer depth, type of surface layer, soil temperature and soil moisture from June to September.

Integral emission factors for methane determined using urban flux measurements and local-scale inverse models

NASA Astrophysics Data System (ADS)

Christen, Andreas; Johnson, Mark; Molodovskaya, Marina; Ketler, Rick; Nesic, Zoran; Crawford, Ben; Giometto, Marco; van der Laan, Mike

2013-04-01

The most important long-lived greenhouse gas (LLGHG) emitted during combustion of fuels is carbon dioxide (CO2), however also traces of the LLGHGs methane (CH4) and nitrous oxide (N2O) are released, the quantities of which depend largely on the conditions of the combustion process. Emission factors determine the mass of LLGHGs emitted per energy used (or kilometre driven for cars) and are key inputs for bottom-up emission modelling. Emission factors for CH4 are typically determined in the laboratory or on a test stand for a given combustion system using a small number of samples (vehicles, furnaces), yet associated with larger uncertainties when scaled to entire fleets. We propose an alternative, different approach - Can integrated emission factors be independently determined using direct micrometeorological flux measurements over an urban surface? If so, do emission factors determined from flux measurements (top-down) agree with up-scaled emission factors of relevant combustion systems (heating, vehicles) in the source area of the flux measurement? Direct flux measurements of CH4 were carried out between February and May, 2012 over a relatively densely populated, urban surface in Vancouver, Canada by means of eddy covariance (EC). The EC-system consisted of an ultrasonic anemometer (CSAT-3, Campbell Scientific Inc.) and two open-path infrared gas analyzers (Li7500 and Li7700, Licor Inc.) on a tower at 30m above the surface. The source area of the EC system is characterised by a relative homogeneous morphometry (5.3m average building height), but spatially and temporally varying emission sources, including two major intersecting arterial roads (70.000 cars drive through the 50% source area per day) and seasonal heating in predominantly single-family houses (natural gas). An inverse dispersion model (turbulent source area model), validated against large eddy simulations (LES) of the urban roughness sublayer, allows the determination of the spatial area that contributes to each measurement interval (30 min), which varies with wind direction and stability. A detailed geographic information system of the urban surface combined with traffic counts and building energy models makes it possible to statistically relate fluxes to vehicle density (km driven) and buildings (gas heated volume) - and ultimately quantify the contribution of space heating, transport sector and fugitive emissions to the total emitted CH4 from an urban environment. The measured fluxes of CH4 over the selected urban environment averaged to 22.8 mg CH4 m-2 day-1 during the study period. Compared with the simultaneously measured CO2 emissions, the contribution of CH4, however, accounts for only about 3% of the total LLGHG emissions from this particular urban surface. Traffic contributed 8.8 mg CH4 m-2 day-1, equivalent to 39% of the total CH4 flux. The determined emission factor for the typical fleet composition is 0.062 g CH4 per km driven which is higher than upscaled fleet emission factors (EPA) by a factor of two. This discrepancy can be partially explained through the slower city traffic with frequent idling (traffic congestion), fleet composition and cold starts. Emissions of CH4 by domestic space heating (55% of the total CH4 flux or 12.7 mg CH4 m-2 day-1) are also higher than estimated from upscaled emission factors. There is no evidence of substantial unknown sources such as soil processes, combustion of wood, and leakages from gas distribution pipes (residual: 6% or 1.3 mg CH4 m-2 day-1). The presented study is among the first direct measurements of CH4 emissions over an urban surface and demonstrates that flux measurements of greenhouse gases can be used to determine sources and emission factors in complex urban situations.

Ab initio studies of methane and carbon dioxide affinity to carbon compounds and minerals

NASA Astrophysics Data System (ADS)

Wlazlo, Mateusz; Siklitskaya, Alexandra; Majewski, Jacek

2017-04-01

Understanding of physico-chemistry of capture and storage of carbon dioxide and methane might be crucial for development of the novel technologies meant: (i) to deal with the global warming process through the reduction of the CO2 atmospheric concentration by sequestration, and (ii) to enhance oil recovery, on the other hand. The accurate description of CO2 and CH4 adsorption to minerals and carbonaceous systems (which constitute the main component of sedimentary rocks) is essential to reach this goal. We have employed the ab initio molecular dynamics AIMD) based on the density functional theory (DFT) to study the affinity of CO2 and CH4 from gaseous phase, also at elevated temperatures and hydrostatic pressure, to pristine and defected graphene, spiral carbon nanoparticles (spiroids), calcite rocks (represented by the most stable (10-14) surface of CaCoO3), CaO, MgO, illite, and kaolonite. In the case of kaolonite that exhibits layered crystallographic structure, we have also studied the intercalation of CO2. These studies provide valuable quantitative predictions and shed light on physical mechanisms governing the processes of chemisorption and physisorption of the CO2 and CH4 molecules, revealing also the essential role of Van der Waals interaction. In particular, we find out that CO2 molecules in supercritical gaseous phase (i.e. at temperature of order 60oC and moderate hydrostatic pressure of 20-30 MPa) change their shape from linear one to the water like bended V-shape with angle between C-O chemical bonds smaller than 180 degrees. This shape change of CO2 molecules facilitates the CO2 adsorption. Therefore, in the temperature-pressure conditions of shale deposits, the adsorption probability of CO2 can be enhanced in comparison to the ambient conditions. It turns out that the carbon atoms in the surrounding of characteristic Stone-Wales (or 5-7) defects in graphene are more reactive towards adsorption of CO2 and CH4 molecules. In the case of CO2 adsorption to the most stable (10-14) surface of CaCO3, the AIMD studies demonstrate that the carbon atom of CO2 is attracted to calcium atoms at the (10-14) calcite surface. The performed studies also show that CH4 molecule can be accumulated at the calcite surface in parallel to CO3 groups at low temperatures, and even it can induce reconfiguration of the surface by dehydrogenation process with the increase of temperature.

Does shortwave absorption by methane influence its effectiveness?

NASA Astrophysics Data System (ADS)

Modak, Angshuman; Bala, Govindasamy; Caldeira, Ken; Cao, Long

2018-01-01

In this study, using idealized step-forcing simulations, we examine the effective radiative forcing of CH4 relative to that of CO2 and compare the effects of CH4 and CO2 forcing on the climate system. A tenfold increase in CH4 concentration in the NCAR CAM5 climate model produces similar long term global mean surface warming ( 1.7 K) as a one-third increase in CO2 concentration. However, the radiative forcing estimated for CO2 using the prescribed-SST method is 81% that of CH4, indicating that the efficacy of CH4 forcing is 0.81. This estimate is nearly unchanged when the CO2 physiological effect is included in our simulations. Further, for the same long-term global mean surface warming, we simulate a smaller precipitation increase in the CH4 case compared to the CO2 case. This is because of the fast adjustment processes—precipitation reduction in the CH4 case is larger than that of the CO2 case. This is associated with a relatively more stable atmosphere and larger atmospheric radiative forcing in the CH4 case which occurs because of near-infrared absorption by CH4 in the upper troposphere and lower stratosphere. Within a month after an increase in CH4, this shortwave heating results in a temperature increase of 0.8 K in the lower stratosphere and upper troposphere. In contrast, within a month after a CO2 increase, longwave cooling results in a temperature decrease of 3 K in the stratosphere and a small change in the upper troposphere. These fast adjustments in the lower stratospheric and upper tropospheric temperature, along with the adjustments in clouds in the troposphere, influence the effective radiative forcing and the fast precipitation response. These differences in fast climate adjustments also produce differences in the climate states from which the slow response begins to evolve and hence they are likely associated with differing feedbacks. We also find that the tropics and subtropics are relatively warmer in the CH4 case for the same global mean surface warming because of a larger longwave clear-sky and shortwave cloud forcing over these regions in the CH4 case. Further investigation using a multi-model intercomparison framework would permit an assessment of the robustness of our results.

Structure of water at zwitterionic copolymer film-liquid water interfaces as examined by the sum frequency generation method.

PubMed

Kondo, Takuya; Nomura, Kouji; Gemmei-Ide, Makoto; Kitano, Hiromi; Noguchi, Hidenori; Uosaki, Kohei; Saruwatari, Yoshiyuki

2014-01-01

A copolymer film composed of zwitterionic carboxymethylbetaine (CMB) and n-butyl methacrylate (BMA), Poly(CMB-r-BMA), was cast on a flat plane of an octadecyltrichlorosilane (ODS)-modified fused quartz prism with a semi-cylindrical shape. CH stretching of the polymer film and O-H stretching of water at the surface of the film were examined using the sum frequency generation (SFG) technique. The C-H stretching band of the cast film, indicating a gauche defect of the film, was affected by the contact medium including dry nitrogen, water vapor-saturated nitrogen and liquid water. In contrast, the C-H stretching of an octadecyl group introduced onto the quartz prism for stable attachment of the cast film was not significantly changed by the contact medium. The O-H stretching band indicated that water molecules at the surface of the Poly(CMB-r-BMA) film in contact with liquid water were not greatly oriented in comparison with those at the surfaces of a bare prism, an ODS SAM-modified prism, and a prism covered with a PolyBMA film or a copolymer film of BMA and methacrylic acid or 2-(dimethylamino)ethyl methacrylate. A similar small perturbation of the structure of water was previously observed in the vicinity of water-soluble zwitterionic polymers and zwitterionic copolymer films using Raman and attenuated total reflection infrared spectroscopies, respectively. A distinct effect of charge neutralization to diminish the perturbation of the structure of interfacial water around polymer materials was suggested. Copyright © 2013 Elsevier B.V. All rights reserved.

Methane production as key to the greenhouse gas budget of thawing permafrost on climate relevant time scales

NASA Astrophysics Data System (ADS)

Knoblauch, C.; Beer, C.; Liebner, S.; Schütt, A.; Grigoriev, M.; Pfeiffer, E. M.

2017-12-01

Permafrost in circum-arctic soils stores as much carbon as the global atmosphere. Permafrost thaw liberates organic matter, which is mineralized by microorganisms to carbon dioxide (CO2) and methane (CH4). The release of these greenhouse gases (GHGs) may form a positive feedback to atmospheric CO2 and CH4 concentrations and accelerate climate change. The microbial formation of CH4, which has 28 to 45 times the global warming potential (GWP) of CO2 (100 years time scale), requires anoxic conditions. Current studies indicate that permafrost thaw at the bottom of well drained (oxic) soils cause a higher formation of GHGs than in water saturated (anoxic) soils since more CO2 is formed under oxic conditions and only small amounts of CH4 are formed from permafrost organic matter under anoxic conditions. Here we show through 7-year laboratory incubations and molecular analysis of Siberian permafrost that low CH4 production from permafrost organic matter is due to the lack of active methanogens. Equal amounts of permafrost organic carbon are mineralized to CO2 and CH4 under anoxic conditions after an active methanogenic community has established. Field measurements demonstrate that recently thawed permafrost organic matter is a substantial source for CH4 if primed with surface soil. An organic carbon decomposition model, calibrated with the collected long-term incubation data, predicts a higher loss of permafrost carbon under oxic conditions but a twice as high production of CO2-C equivalents under anoxic conditions when considering a GWP of 28 for CH4. Combining these model results with observed permafrost carbon profile data, up-scaled carbon stocks and thaw depth projections suggests a global formation of 3 - 10 Pg CO2-C from thawing permafrost in oxic soils compared to 0.2 - 0.6 Pg CO2-C and 0.2- 0.8 Pg CH4-C in anoxic soils until 2100. However, based on CO2-C equivalents the GHG production in anoxic soils (2 - 9 Pg CO2-C equivalents) is similar to those in oxic soils. These findings challenge the view of a stronger permafrost carbon-climate feedback from drained soils and emphasize the importance of CH4 production in thawing permafrost.

CH4 dehydrogenation on Cu(1 1 1), Cu@Cu(1 1 1), Rh@Cu(1 1 1) and RhCu(1 1 1) surfaces: A comparison studies of catalytic activity

NASA Astrophysics Data System (ADS)

Zhang, Riguang; Duan, Tian; Ling, Lixia; Wang, Baojun

2015-06-01

In the CVD growth of graphene, the reaction barriers of the dehydrogenation for hydrocarbon molecules directly decide the graphene CVD growth temperature. In this study, density functional theory method has been employed to comparatively probe into CH4 dehydrogenation on four types of Cu(1 1 1) surface, including the flat Cu(1 1 1) surface (labeled as Cu(1 1 1)) and the Cu(1 1 1) surface with one surface Cu atom substituted by one Rh atom (labeled as RhCu(1 1 1)), as well as the Cu(1 1 1) surface with one Cu or Rh adatom (labeled as Cu@Cu(1 1 1) and Rh@Cu(1 1 1), respectively). Our results show that the highest barrier of the whole CH4 dehydrogenation process is remarkably reduced from 448.7 and 418.4 kJ mol-1 on the flat Cu(1 1 1) and Cu@Cu(1 1 1) surfaces to 258.9 kJ mol-1 on RhCu(1 1 1) surface, and to 180.0 kJ mol-1 on Rh@Cu(1 1 1) surface, indicating that the adsorbed or substituted Rh atom on Cu catalyst can exhibit better catalytic activity for CH4 complete dehydrogenation; meanwhile, since the differences for the highest barrier between Cu@Cu(1 1 1) and Cu(1 1 1) surfaces are smaller, the catalytic behaviors of Cu@Cu(1 1 1) surface are very close to the flat Cu(1 1 1) surface, suggesting that the morphology of Cu substrate does not obviously affect the dehydrogenation of CH4, which accords with the reported experimental observations. As a result, the adsorbed or substituted Rh atom on Cu catalyst exhibit a better catalytic activity for CH4 dehydrogenation compared to the pure Cu catalyst, especially on Rh-adsorbed Cu catalyst, we can conclude that the potential of synthesizing high-quality graphene with the help of Rh on Cu foils may be carried out at relatively low temperatures. Meanwhile, the adsorbed Rh atom is the reaction active center, namely, the CVD growth can be controlled by manipulating the graphene nucleation position.

Universal Strategy for Ultrathin Pt-M (M = Fe, Co, Ni) Nanowires for Efficient Catalytic Hydrogen Generation.

PubMed

Bai, Shuxing; Huang, Bolong; Shao, Qi; Huang, Xiaoqing

2018-06-25

Methanol (CH 3 OH) reformation with water (H 2 O) to in situ release hydrogen (H 2 ) is regarded as a hopeful H 2 production approach for polymer electrolyte membrane fuel cells, while developing highly efficient CH 3 OH reformation catalysts still remains a great challenge. Herein, a series of Pt-based ultrafine nanowires (UNWs) with high surface atom ratio are used as highly active and stable catalysts for CH 3 OH reformation to H 2 . By tuning Pt 3 M (M = Fe, Co, Ni), support and the composition of the Pt x Fe UNWs, the optimized Pt 4 Fe UNWs/Al 2 O 3 exhibits excellent catalytic behaviors with the high H 2 turnover frequency reaching to 2035.8 h -1 , more than 4 times higher than that of Pt UNWs/Al 2 O 3 . The reaction mechanism investigated by diffuse reflectance infrared Fourier transform spectroscopy turns out that the production of H 2 undergoes the CH 3 OH decomposition to *CO and gas-shift reaction of *CO with H 2 O. Combing with the XPS result and the density functional theory calculations, the high CH 3 OH reformation activity of Pt 4 Fe UNWs/Al 2 O 3 is attributable to synergism between Pt and Fe, which facilitates H 2 desorption and intermediate HCOO* and *COO formations via the reaction between *CO and OH - .

CO2 and CH4 Surface Flux, Soil Profile Concentrations, and Stable Isotope Composition, Barrow, Alaska, 2012-2013

DOE Data Explorer

Curtis, J.B.; Vaughn, L.S.; Torn, M.S.; Conrad, M.S.; Chafe, O.; Bill, M.

2015-12-31

In August-October 2012 and June-October 2013, co-located measurements were made of surface CH4 and CO2 flux, soil pore space concentrations and stable isotope compositions of CH4 and CO2, and subsurface temperature and soil moisture. Measurements were made in intensive study site 1 areas A, B, and C, and from the site 0 and AB transects, from high-centered, flat-centered, and low-centered polygons, from the center, edge, and trough of each polygon.

Anisotropic contribution to the van der Waals and the Casimir-Polder energies for CO2 and CH4 molecules near surfaces and thin films

NASA Astrophysics Data System (ADS)

Thiyam, Priyadarshini; Parashar, Prachi; Shajesh, K. V.; Persson, Clas; Schaden, Martin; Brevik, Iver; Parsons, Drew F.; Milton, Kimball A.; Malyi, Oleksandr I.; Boström, Mathias

2015-11-01

In order to understand why carbon dioxide (CO2) and methane (CH4) molecules interact differently with surfaces, we investigate the Casimir-Polder energy of a linearly polarizable CO2 molecule and an isotropically polarizable CH4 molecule in front of an atomically thin gold film and an amorphous silica slab. We quantitatively analyze how the anisotropy in the polarizability of the molecule influences the van der Waals contribution to the binding energy of the molecule.

Radiolytic Gas-Driven Cryovolcanism in the Outer Solar System

NASA Technical Reports Server (NTRS)

Cooper, John F.; Cooper, Paul D.; Sittler, Edward C.; Sturner, Steven J.; Rymer, Abigail M.; Hill, Matthew E.

2007-01-01

Water ices in surface crusts of Europa, Enceladus, Saturn's main rings, and Kuiper Belt Objects can become heavily oxidized from radiolytic chemical alteration of near-surface water ice by space environment irradiation. Oxidant accumulations and gas production are manifested in part through observed H2O2 on Europa. tentatively also on Enceladus, and found elsewhere in gaseous or condensed phases at moons and rings of Jupiter and Saturn. On subsequent chemical contact in sub-surface environments with significant concentrations of primordially abundant reductants such as NH3 and CH4, oxidants of radiolytic origin can react exothermically to power gas-driven cryovolcanism. The gas-piston effect enormously amplifies the mass flow output in the case of gas formation at basal thermal margins of incompressible fluid reservoirs. Surface irradiation, H2O2 production, NH3 oxidation, and resultant heat, gas, and gas-driven mass flow rates are computed in the fluid reservoir case for selected bodies. At Enceladus the oxidant power inputs are comparable to limits on nonthermal kinetic power for the south polar plumes. Total heat output and plume gas abundance may be accounted for at Enceladus if plume activity is cyclic in high and low "Old Faithful" phases, so that oxidants can accumulate during low activity phases. Interior upwelling of primordially abundant NH3 and CH4 hydrates is assumed to resupply the reductant fuels. Much lower irradiation fluxes on Kuiper Belt Objects require correspondingly larger times for accumulation of oxidants to produce comparable resurfacing, but brightness and surface composition of some objects suggest that such activity may be ongoing.

Chemical identifications of possible martian hot spots

NASA Astrophysics Data System (ADS)

Wong, A. S.; Atreya, S. K.; Renno, N. O.

2003-04-01

If the interpretation of certain Mars Global Surveyor images indicating recent ground water seepage and surface runoff (1) is correct, it may imply that Mars can still be active internally in some places from time to time, and outgassing of certain molecules from the interior could occur with or without the water seepage. Although there is no evidence of active volcanism on Mars today, ``localized'' outgassing sources, the ``hot spots'', may not be ruled out. If outgassing does occur somewhere on Mars, water, carbon dioxide, sulfur species, methane, and to a lesser extent, halogens, would be the likely molecules of outgassing, based on the terrestrial analogs. The sulfur species, methane and halogens have not been detected in the ``global'' observations of Mars. Considering the possibility of outgassing from some localized hot spots, we have developed a one-dimensional photochemical model (2) that includes methane (CH_4), sulfur dioxide (SO_2) and hydrogen sulfide (H_2S), starting with their current ``global average'' upper limits of, respectively, 0.02, 0.1 and 0.1 ppm at the surface, and then progressively increasing their abundances above possible hot spots. Halogens are neglected as they are a minor product of the terrestrial outgassing sources. We find that the introduction of methane into the martian atmosphere results in the formation of mainly formaldehyde, methyl alcohol (CH_3OH) and ethane (C_2H_6), whereas the introduction of the sulfur species produces mainly sulfur monoxide (SO) and sulfuric acid (H_2SO_4). In a relatively short time of an hour, ordinary convective processes alone can reduce the mixing ratios of outgassed species by factors of 10^4 -- 10^5 approximately 50 km from the source, and the time for spreading the source material more or less uniformly over the planet (with corresponding dilution factor of ˜10^8) would be approximately one year. Depending upon the flux of the outgassed molecules from possible hot spots, some of these species, especially CH_4, SO_2, H_2S, and perhaps CH_2O, may be detectable locally, either by remote sensing or in situ measurements. References: (1) Malin, M. C. and K. S. Edgett, Science 288, 2330, 2000; (2) Wong, A. S., S. K. Atreya, and Th. Encrenaz, J. Geophys. Res., in press, 2003.

Increased importance of methane reduction for a 1.5 degree target

NASA Astrophysics Data System (ADS)

Collins, William J.; Webber, Christopher P.; Cox, Peter M.; Huntingford, Chris; Lowe, Jason; Sitch, Stephen; Chadburn, Sarah E.; Comyn-Platt, Edward; Harper, Anna B.; Hayman, Garry; Powell, Tom

2018-04-01

To understand the importance of methane on the levels of carbon emission reductions required to achieve temperature goals, a processed-based approach is necessary rather than reliance on the transient climate response to emissions. We show that plausible levels of methane (CH4) mitigation can make a substantial difference to the feasibility of achieving the Paris climate targets through increasing the allowable carbon emissions. This benefit is enhanced by the indirect effects of CH4 on ozone (O3). Here the differing effects of CH4 and CO2 on land carbon storage, including the effects of surface O3, lead to an additional increase in the allowable carbon emissions with CH4 mitigation. We find a simple robust relationship between the change in the 2100 CH4 concentration and the extra allowable cumulative carbon emissions between now and 2100 (0.27 ± 0.05 GtC per ppb CH4). This relationship is independent of modelled climate sensitivity and precise temperature target, although later mitigation of CH4 reduces its value and thus methane reduction effectiveness. Up to 12% of this increase in allowable emissions is due to the effect of surface ozone. We conclude early mitigation of CH4 emissions would significantly increase the feasibility of stabilising global warming below 1.5 °C, alongside having co-benefits for human and ecosystem health.

Dual stable isotopes of CH 4 from Yellowstone hot-springs suggest hydrothermal processes involving magmatic CO 2

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

Moran, James J.; Whitmore, Laura M.; Jay, Zackary J.

Volcanism and post-magmatism contribute significant annual methane (CH 4) fluxes to the atmosphere (on par with other natural sources such as forest fire and wild animal emissions) and have been implicated in past climate-change events. The Yellowstone hot spot is one of the largest volcanic systems on Earth and is known to emit CH 4 (as well as carbon dioxide (CO 2) and other gases), but the ultimate sources of this CH 4 flux have not been elucidated. In this paper, we use dual stable isotope analysis (δ 2H and δ 13C) of CH 4 sampled from ten high-temperature geothermalmore » pools in Yellowstone National Park along with other isotopic and gas analyses to evaluate potential sources of methane. The average δ 13C and δ 2H values of CH 4 emitted from hot springs ( 26.7 (± 2.4) and - 236.9 (± 12.0) ‰, respectively) are inconsistent with microbial methanogenesis but do not allow distinction between thermogenic and abiotic sources. Correlation between δ 13C CH4 and δ 13C of dissolved inorganic C (DIC) is consistent with DIC as the parent C source for the observed CH 4, or with equilibration of CH 4 and DIC. Methane formation temperatures estimated by isotopic geothermometry based on δ 13C CH4 and δ 13C CO2 ranged from ~ 250–350 °C, which is just below previous temperature estimates for the hydrothermal reservoir. Further, the δ 2H H2O of the thermal springs and the measured δ 2H CH4 values are consistent with equilibration between the source water and the CH 4 at the formation temperatures. Though the ultimate origin of the CH 4 could be attributed to either abiotic of themorgenic processes with subsequent isotopic equilibration, the C 1/C 2+ composition of the gases is more consistent with abiotic origins for most of the samples. Finally, our data support the hypothesis that subsurface rock-water interactions are responsible for at least a significant fraction of the CH 4 flux from the Yellowstone National Park volcanic system.« less

Dual stable isotopes of CH 4 from Yellowstone hot-springs suggest hydrothermal processes involving magmatic CO 2

DOE PAGES

Moran, James J.; Whitmore, Laura M.; Jay, Zackary J.; ...

2017-05-16

Volcanism and post-magmatism contribute significant annual methane (CH 4) fluxes to the atmosphere (on par with other natural sources such as forest fire and wild animal emissions) and have been implicated in past climate-change events. The Yellowstone hot spot is one of the largest volcanic systems on Earth and is known to emit CH 4 (as well as carbon dioxide (CO 2) and other gases), but the ultimate sources of this CH 4 flux have not been elucidated. In this paper, we use dual stable isotope analysis (δ 2H and δ 13C) of CH 4 sampled from ten high-temperature geothermalmore » pools in Yellowstone National Park along with other isotopic and gas analyses to evaluate potential sources of methane. The average δ 13C and δ 2H values of CH 4 emitted from hot springs ( 26.7 (± 2.4) and - 236.9 (± 12.0) ‰, respectively) are inconsistent with microbial methanogenesis but do not allow distinction between thermogenic and abiotic sources. Correlation between δ 13C CH4 and δ 13C of dissolved inorganic C (DIC) is consistent with DIC as the parent C source for the observed CH 4, or with equilibration of CH 4 and DIC. Methane formation temperatures estimated by isotopic geothermometry based on δ 13C CH4 and δ 13C CO2 ranged from ~ 250–350 °C, which is just below previous temperature estimates for the hydrothermal reservoir. Further, the δ 2H H2O of the thermal springs and the measured δ 2H CH4 values are consistent with equilibration between the source water and the CH 4 at the formation temperatures. Though the ultimate origin of the CH 4 could be attributed to either abiotic of themorgenic processes with subsequent isotopic equilibration, the C 1/C 2+ composition of the gases is more consistent with abiotic origins for most of the samples. Finally, our data support the hypothesis that subsurface rock-water interactions are responsible for at least a significant fraction of the CH 4 flux from the Yellowstone National Park volcanic system.« less

Saturn's satellites: Predictions for Cassini

NASA Astrophysics Data System (ADS)

Delitsky, M. L.; Hibbitts, C. A.

2004-11-01

Saturn's satellites are subjected to a variety of energy inputs (from photons, magnetospheric and solar ions and electrons) which will affect their surface composition. The Saturn magnetosphere contains an assortment of ions, including O+ and H+ from sputtering of water ice on the inner satellites and N+ from sputtering of Titan's atmosphere. Implantation of these ions onto the surfaces of the satellites may produce compounds possibly detectable by Cassini instruments. The satellites contain water ice and carbon dioxide ice (and possibly organics, on Phoebe). In Delitsky and Lane (2002), chemistry resulting from nitrogen ion implantation into water ice and carbon dioxide ice was outlined. From deposition of N+ ions into H2O/CO2, a complicated C-H-N-O chemistry may result, including formation of isocyanates, nitriles, nitrogen oxides and amino acids. Upon irradiation, H2O/CO2 mixtures will yield esters, ketones, alcohols, carboxylic acids and other interesting compounds. Cassini's infrared instruments CIRS and VIMS have spectral ranges that can detect many bands of these compounds. VIMS spectral range is 0.35 - 5.1 microns; CIRS covers the spectral range 7 - 100 microns, although its Mid-IR interferometer portion (7 -16 microns) is where organic materials are particularly spectrally active. Weak features are present in the short IR for NO (1.91 microns), NO2 (1.95), NH3 (2.00, 2.24), CH3OH (2.27, 2.34), and CO2 (1.965, 2.01) [Quirico et al.,1999]. Some molecules have stronger absorption features at these wavelengths: [CO2: 4.25 - 4.27 microns; NH3: 3 microns and 9.2 microns (important because the 3 micron band can be masked by water); H2CO3: 3.88 microns (weak); HCOOH: 8.2 microns; O2: 9.7 microns]. These molecules may exist as ices, or as molecules trapped in the surface. CH- and CN-containing molecules absorb at 3.2 - 3.4 microns, and 4.6 microns, respectively. H2O2, detected on Europa by its 3.5 micron band, may exist in the icy surfaces of the Saturn satellites as well.

Four-year measurement of methane flux over a temperate forest with a relaxed eddy accumulation method

NASA Astrophysics Data System (ADS)

Sakabe, A.; Kosugi, Y.; Ueyama, M.; Hamotani, K.; Takahashi, K.; Iwata, H.; Itoh, M.

2013-12-01

Forests are generally assumed to be an atmospheric methane (CH4) sink (Le Mer and Roger, 2001). However, under Asian monsoon climate, forests are subject to wide spatiotemporal range in soil water status, where forest soils often became water-saturated condition heterogeneously. In such warm and humid conditions, forests may act as a CH4 source and/or sink with considerable spatiotemporal variations. Micrometeorological methods such as eddy covariance (EC) method continuously measure spatially-representative flux at a canopy scale without artificial disturbance. In this study, we measured CH4 fluxes over a temperate forest during four-year period using a CH4 analyzer based on tunable diode laser spectroscopy detection with a relaxed eddy accumulation (REA) method (Hamotani et al., 1996, 2001). We revealed the amplitude and seasonal variations of canopy-scale CH4 fluxes. The REA method is the attractive alternative to the EC method to measure trace-gas flux because it allows the use of analyzers with an optimal integration time. We also conducted continuous chamber measurements on forest floor to reveal spatial variations in soil CH4 fluxes and its controlling processes. The observations were made in an evergreen coniferous forest in central Japan. The site has a warm temperate monsoon climate with wet summer. Some wetlands were located in riparian zones along streams within the flux footprint area. For the REA method, the sonic anemometer (SAT-550, Kaijo) was mounted on top of the 29-m-tall tower and air was sampled from just below the sonic anemometer to reservoirs according to the direction of vertical wind velocity (w). After accumulating air for 30 minutes, the air in the reservoirs was pulled into a CO2/H2O gas analyzer (LI-840, Li-Cor) and a CH4 analyzer (FMA-200, Los Gatos Research). Before entering the analyzers, the sampled air was dried using a gas dryer (PD-50 T-48; Perma Pure Inc.). The REA flux is obtained from the difference in the mean concentrations of the reservoirs. In the chamber method, automated dynamic-closed chambers were located at three points of water-unsaturated forest floor. Soil CO2 and CH4 fluxes were measured using the same analyzers with the REA method. CH4 fluxes showed seasonal variations at both canopy and plot scales. Based on the chamber measurements, water-unsaturated forest floor mostly consumed CH4 throughout a year. In contrast, canopy-scale CH4 fluxes by the REA method seasonally fluctuated between emission and absorption. The seasonal variation of canopy-scale CH4 fluxes varied at years to years. Every year, no notable emission nor absorption was observed during winter when daily average air temperature was less than about 10°C. In this forest, the canopy-scale CH4 fluxes could be determined by a balance between sources by methanogens and sinks by methanotrophs. Since these two processes were influenced by soil conditions (e.g., soil temperature and soil moisture), canopy-scale CH4 fluxes were influenced by CH4 fluxes from wetlands within the forest, because magnitude of wetland emission was a few order larger than those of absorption. We will discuss the factors of interannual variation of the canopy- and plot-scale CH4 fluxes in terms of precipitation patterns.

Inherent substrate-dependent growth initiation and selective-area atomic layer deposition of TiO{sub 2} using “water-free” metal-halide/metal alkoxide reactants

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

Atanasov, Sarah E.; Kalanyan, Berç; Parsons, Gregory N., E-mail: gnp@ncsu.edu

2016-01-15

Titanium dioxide atomic layer deposition (ALD) is shown to proceed selectively on oxidized surfaces with minimal deposition on hydrogen-terminated silicon using titanium tetrachloride (TiCl{sub 4}) and titanium tetra-isopropoxide [Ti(OCH(CH{sub 3}){sub 2}){sub 4}, TTIP] precursors. Ex situ x-ray photoelectron spectroscopy shows a more rapid ALD nucleation rate on both Si–OH and Si–H surfaces when water is the oxygen source. Eliminating water delays the oxidation of the hydrogen-terminated silicon, thereby impeding TiO{sub 2} film growth. For deposition at 170 °C, the authors achieve ∼2 nm of TiO{sub 2} on SiO{sub 2} before substantial growth takes place on Si–H. On both Si–H and Si–OH, themore » surface reactions proceed during the first few TiCl{sub 4}/TTIP ALD exposure steps where the resulting products act to impede subsequent growth, especially on Si–H surfaces. Insight from this work helps expand understanding of “inherent” substrate selective ALD, where native differences in substrate surface reaction chemistry are used to promote desired selective-area growth.« less

Formation of interstellar methanol ice prior to the heavy CO freeze-out stage

NASA Astrophysics Data System (ADS)

Qasim, D.; Chuang, K.-J.; Fedoseev, G.; Ioppolo, S.; Boogert, A. C. A.; Linnartz, H.

2018-04-01

Context. The formation of methanol (CH3OH) on icy grain mantles during the star formation cycle is mainly associated with the CO freeze-out stage. Yet there are reasons to believe that CH3OH also can form at an earlier period of interstellar ice evolution in CO-poor and H2O-rich ices. Aims: This work focuses on CH3OH formation in a H2O-rich interstellar ice environment following the OH-mediated H-abstraction in the reaction, CH4 + OH. Experimental conditions are systematically varied to constrain the CH3OH formation yield at astronomically relevant temperatures. Methods: CH4, O2, and hydrogen atoms are co-deposited in an ultrahigh vacuum chamber at 10-20 K. OH radicals are generated by the H + O2 surface reaction. Temperature programmed desorption - quadrupole mass spectrometry (TPD-QMS) is used to characterize CH3OH formation, and is complemented with reflection absorption infrared spectroscopy (RAIRS) for CH3OH characterization and quantitation. Results: CH3OH formation is shown to be possible by the sequential surface reaction chain, CH4 + OH → CH3 + H2O and CH3 + OH → CH3OH at 10-20 K. This reaction is enhanced by tunneling, as noted in a recent theoretical investigation Lamberts et al. (2017, A&A, 599, A132). The CH3OH formation yield via the CH4 + OH route versus the CO + H route is approximately 20 times smaller for the laboratory settings studied. The astronomical relevance of the new formation channel investigated here is discussed.

Agricultural peatlands: towards a greenhouse gas sink - a synthesis of a Dutch landscape study

NASA Astrophysics Data System (ADS)

Schrier-Uijl, A. P.; Kroon, P. S.; Hendriks, D. M. D.; Hensen, A.; Van Huissteden, J.; Berendse, F.; Veenendaal, E. M.

2014-08-01

It is generally known that managed, drained peatlands act as carbon (C) sources. In this study we examined how mitigation through the reduction of the intensity of land management and through rewetting may affect the greenhouse gas (GHG) emission and the C balance of intensively managed, drained, agricultural peatlands. Carbon and GHG balances were determined for three peatlands in the western part of the Netherlands from 2005 to 2008 by considering spatial and temporal variability of emissions (CO2, CH4 and N2O). One area (Oukoop) is an intensively managed grass-on-peatland area, including a dairy farm, with the ground water level at an average annual depth of 0.55 (±0.37) m below the soil surface. The second area (Stein) is an extensively managed grass-on-peatland area, formerly intensively managed, with a dynamic ground water level at an average annual depth of 0.45 (±0.35) m below the soil surface. The third area is a (since 1998) rewetted former agricultural peatland (Horstermeer), close to Oukoop and Stein, with the average annual ground water level at a depth of 0.2 (±0.20) m below the soil surface. During the measurement campaigns we found that both agriculturally managed sites acted as C and GHG sources and the rewetted former agricultural peatland acted as a C and GHG sink. The ecosystem (fields and ditches) total GHG balance, including CO2, CH4 and N2O, amounted to 3.9 (±0.4), 1.3 (±0.5) and -1.7 (±1.8) g CO2-eq m-2 d-1 for Oukoop, Stein and Horstermeer, respectively. Adding the farm-based emissions to Oukoop and Stein resulted in a total GHG emission of 8.3 (±1.0) and 6.6 (±1.3) g CO2-eq m-2 d-1, respectively. For Horstermeer the GHG balance remained the same since no farm-based emissions exist. Considering the C balance (uncertainty range 40-60%), the total C release in Oukoop and Stein is 5270 and 6258 kg C ha-1 yr-1, respectively (including ecosystem and management fluxes), and the total C uptake in Horstermeer is 3538 kg C ha-1 yr-1. Water bodies contributed significantly to the terrestrial GHG balance because of a high release of CH4. Overall, this study suggests that managed peatlands are large sources of GHGs and C, but, if appropriate measures are taken, they can be turned back into GHG and C sinks within 15 years of abandonment and rewetting. The shift from an intensively managed grass-on-peat area (Oukoop) to an extensively managed one (Stein) reduced the GHG emissions mainly because N2O emission and farm-based CH4 emissions decreased.

Neotropical peatland methane emissions along a vegetation and biogeochemical gradient

PubMed Central

Flanagan, Neal; Richardson, Curtis J.

2017-01-01

Tropical wetlands are thought to be the most important source of interannual variability in atmospheric methane (CH4) concentrations, yet sparse data prevents them from being incorporated into Earth system models. This problem is particularly pronounced in the neotropics where bottom-up models based on water table depth are incongruent with top-down inversion models suggesting unaccounted sinks or sources of CH4. The newly documented vast areas of peatlands in the Amazon basin may account for an important unrecognized CH4 source, but the hydrologic and biogeochemical controls of CH4 dynamics from these systems remain poorly understood. We studied three zones of a peatland in Madre de Dios, Peru, to test whether CH4 emissions and pore water concentrations varied with vegetation community, soil chemistry and proximity to groundwater sources. We found that the open-canopy herbaceous zone emitted roughly one-third as much CH4 as the Mauritia flexuosa palm-dominated areas (4.7 ± 0.9 and 14.0 ± 2.4 mg CH4 m-2 h-1, respectively). Emissions decreased with distance from groundwater discharge across the three sampling sites, and tracked changes in soil carbon chemistry, especially increased soil phenolics. Based on all available data, we calculate that neotropical peatlands contribute emissions of 43 ± 11.9 Tg CH4 y-1, however this estimate is subject to geographic bias and will need revision once additional studies are published. PMID:29053738

Spatial and temporal variability of greenhouse gas emissions from a small and shallow temperate lake

NASA Astrophysics Data System (ADS)

Praetzel, Leandra; Schmiedeskamp, Marcel; Broder, Tanja; Hüttemann, Caroline; Jansen, Laura; Metzelder, Ulrike; Wallis, Ronya; Knorr, Klaus-Holger; Blodau, Christian

2017-04-01

Small inland waters (< 1 km2) have recently been discovered as significant sources and sinks in the global carbon cycle because they cover larger areas than previously assumed and exhibit a higher metabolic activity than larger lakes. They are further expected to be susceptible to changing climate conditions. So far, little is known about the spatial and temporal variability of carbon dioxide (CO2) and methane (CH4) emissions and in-lake dynamics of CH4 production and oxidation in small, epilimnetic lakes in the temperate zone. Of particular interest is the potential occurrence of "hot spots" and "hot moments" that could contribute significantly to total emissions. To address this knowledge gap, we determined CO2 and CH4 emissions and dynamics to identify their controlling environmental factors in a polymictic small (1.4 ha) and shallow (max. depth approx. 1.5 m) crater lake ("Windsborn") in the Eifel uplands in south-west Germany. As Lake Windsborn has a small catchment area (8 ha) and no surficial inflows, it serves well as a model system for the identification of factors and processes controlling emissions. In 2015, 2016 and 2017 we measured CO2 and CH4 gas fluxes with different techniques across the sediment/water and water/atmosphere interface. Atmospheric exchange was measured using mini-chambers equipped with CO2 sensors and with an infra-red greenhouse gas analyzer for high temporal resolution flux measurements. Ebullition of CH4 was quantified with funnel traps. Sediment properties were examined using pore-water peepers. All measurements were carried out along a transect covering both littoral and central parts of the lake. Moreover, a weather station on a floating platform in the center of the lake recorded meteorological data as well as CO2 concentration in different depths of the water column. So far, Lake Windsborn seems to be a source for both CO2 and CH4 on an annual scale. CO2 emissions generally increased from spring to summer. Even though CO2 uptake could be observed during some periods in spring and fall, CO2 emissions in the summer exceeded the uptake. CO2 and CH4 emissions also appeared to be spatially variable between littoral areas and the inner lake. Shallow areas turned out to be "hot spots" of CO2 emissions whereas CH4 emissions were - against our expectations - highest in the center of the lake. Moreover, CH4 ebullition contributed substantially to total CH4 emissions. Our results show the importance of spatially and temporally highly resolved long-term measurements of greenhouse gas emissions and of potential controlling factors to address diurnal, seasonal and inter-annual variability as well as possible feedbacks to climate change.

Trapping of Methanol, Hydrogen Cyanide, and n-Hexane in Water Ice, above Its Transformation Temperature to the Crystalline Form

NASA Astrophysics Data System (ADS)

Notesco, G.; Bar-Nun, A.

1997-04-01

HCN and n-C 6H 14were found experimentally to be trapped in water ice, when codeposited with water vapor on a cold plate, at 140 K and CH 3OH even at 160 K. At these temperatures at least part of the water ice is cystalline. These three gases have relatively high sublimation temperatures, whereas the gases studied earlier, Ar, Kr, Xe, CO, CH 4, and N 2, which have lower sublimination temperatures, are trapped only in amorphous water ice, up to ˜100 K. It seems that the major factor determining the efficiency of gas trapping by water ice, during codeposition of a gas-water vapor mixture on a cold plate, is the sublimation temperatures of the gases to be trapped. Those with a high sublimation temperature remain, during codeposition, longer in the pores of the water ice which are open to the surface, until they are covered by additional ice layers. Only methanol seems to form a clathrate hydrate, in agreement with the experimental results of D. Blake et al.(1991), Science254, 548-551), which points to the importance of the interaction of the gas molecules with the water molecules in the ice. Consequently, comets and icy satellites that were formed in the Jupiter-Saturn region and their subnebulae could trap CH 3OH, HCN, and heavy hydrocarbons, whereas comets and icy satellites that were formed in the Uranus-Neptune region, at the outskirts of the Saturnian subnebulae (Titan), and beyond the planets in the Kuiper belt could trap also gases having lower sublimation temperatures.

Rising plant-mediated methane emissions from arctic wetlands

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

Andresen, Christian G.; Lara, Mark J.; Tweedie, Craig E.

Plant-mediated CH 4 flux is an important pathway for land–atmosphere CH 4 emissions, but the magnitude, timing, and environmental controls, spanning scales of space and time, remain poorly understood in arctic tundra wetlands, particularly under the long-term effects of climate change. CH 4 fluxes were measured in situ during peak growing season for the dominant aquatic emergent plants in the Alaskan arctic coastal plain, Carex aquatilis and Arctophila fulva, to assess the magnitude and species-specific controls on CH 4 flux. Plant biomass was a strong predictor of A. fulva CH 4 flux while water depth and thaw depth were copredictorsmore » for C. aquatilis CH 4 flux. Here, we used plant and environmental data from 1971 to 1972 from the historic International Biological Program (IBP) research site near Barrow, Alaska, which we resampled in 2010–2013, to quantify changes in plant biomass and thaw depth, and used these to estimate species-specific decadal-scale changes in CH 4 fluxes. A ~60% increase in CH 4 flux was estimated from the observed plant biomass and thaw depth increases in tundra ponds over the past 40 years. In spite of our covering only ~5% of the landscape, we estimate that aquatic C. aquatilis and A. fulva account for two-thirds of the total regional CH 4 flux of the Barrow Peninsula. The regionally observed increases in plant biomass and active layer thickening over the past 40 years not only have major implications for energy and water balance, but also have significantly altered land–atmosphere CH 4 emissions for this region, potentially acting as a positive feedback to climate warming.« less

Rising plant-mediated methane emissions from arctic wetlands

DOE PAGES

Andresen, Christian G.; Lara, Mark J.; Tweedie, Craig E.; ...

2016-09-14

Plant-mediated CH 4 flux is an important pathway for land–atmosphere CH 4 emissions, but the magnitude, timing, and environmental controls, spanning scales of space and time, remain poorly understood in arctic tundra wetlands, particularly under the long-term effects of climate change. CH 4 fluxes were measured in situ during peak growing season for the dominant aquatic emergent plants in the Alaskan arctic coastal plain, Carex aquatilis and Arctophila fulva, to assess the magnitude and species-specific controls on CH 4 flux. Plant biomass was a strong predictor of A. fulva CH 4 flux while water depth and thaw depth were copredictorsmore » for C. aquatilis CH 4 flux. Here, we used plant and environmental data from 1971 to 1972 from the historic International Biological Program (IBP) research site near Barrow, Alaska, which we resampled in 2010–2013, to quantify changes in plant biomass and thaw depth, and used these to estimate species-specific decadal-scale changes in CH 4 fluxes. A ~60% increase in CH 4 flux was estimated from the observed plant biomass and thaw depth increases in tundra ponds over the past 40 years. In spite of our covering only ~5% of the landscape, we estimate that aquatic C. aquatilis and A. fulva account for two-thirds of the total regional CH 4 flux of the Barrow Peninsula. The regionally observed increases in plant biomass and active layer thickening over the past 40 years not only have major implications for energy and water balance, but also have significantly altered land–atmosphere CH 4 emissions for this region, potentially acting as a positive feedback to climate warming.« less

Photosynthates as dominant source of CH4 and CO2 in soil water and CH4 emitted to the atmosphere from paddy fields

NASA Astrophysics Data System (ADS)

Minoda, Tomomi; Kimura, Mamoto; Wada, Eitaro

1996-09-01

Emission rates of CH4 from paddy soil with and without rice straw applications were measured with pot experiments to estimate the contribution of rice straw to the total CH4 emission during the growth period of rice plants. The CH4 derived from rice straw was calculated to be 44% of the total emission. 13CO2 uptake experiments were also carried out four times from June 30 to September 13, 1994, to estimate the contribution of photosynthesized carbon to CH4 emission. The contribution percentages of photosynthesized carbon to the total CH4 emitted to the atmosphere were 3.8% around June 30, 31% around July 25, 30% around August 19, and 14% around September 13 in the treatment with rice straw applications, and 52% around July 25, 28% around August 19, and 15% around September 13 in the treatment without rice straw applications. They were calculated to be 22% and 29% for the entire growth period in the treatments with and without rice straw applications, respectively. The contribution percentages of photosynthesized carbon to the total CH4 and inorganic carbon (Σ CO2) dissolved in soil water were 1.3%, 30%, 29%, and 34% for dissolved CH4 and 3.0%, 36%, 30% and 28% for dissolved inorganic carbon around June 30, July 25, August l9, and September 13, respectively, in the treatment with rice straw applications. They were 70%, 23%, and 32% for dissolved CH4 and 31%, 16%, and 19% for dissolved inorganic carbon around July 25, August 19, and September 13, respectively, in the treatment without rice straw applications.

Methane and CO2 emissions from China's hydroelectric reservoirs: a new quantitative synthesis.

PubMed

Li, Siyue; Zhang, Quanfa; Bush, Richard T; Sullivan, Leigh A

2015-04-01

Controversy surrounds the green credentials of hydroelectricity because of the potentially large emission of greenhouse gases (GHG) from associated reservoirs. However, limited and patchy data particularly for China is constraining the current global assessment of GHG releases from hydroelectric reservoirs. This study provides the first evaluation of the CO2 and CH4 emissions from China's hydroelectric reservoirs by considering the reservoir water surface and drawdown areas, and downstream sources (including spillways and turbines, as well as river downstream). The total emission of 29.6 Tg CO2/year and 0.47 Tg CH4/year from hydroelectric reservoirs in China, expressed as CO2 equivalents (eq), corresponds to 45.6 Tg CO2eq/year, which is 2-fold higher than the current GHG emission (ca. 23 Tg CO2eq/year) from global temperate hydropower reservoirs. China's average emission of 70 g CO2eq/kWh from hydropower amounts to 7% of the emissions from coal-fired plant alternatives. China's hydroelectric reservoirs thus currently mitigate GHG emission when compared to the main alternative source of electricity with potentially far great reductions in GHG emissions and benefits possible through relatively minor changes to reservoir management and design. On average, the sum of drawdown and downstream emission including river reaches below dams and turbines, which is overlooked by most studies, represents the equivalent of 42% of the CO2 and 92% of CH4 that emit from hydroelectric reservoirs in China. Main drivers on GHG emission rates are summarized and highlight that water depth and stratification control CH4 flux, and CO2 flux shows significant negative relationships with pH, DO, and Chl-a. Based on our finding, a substantial revision of the global carbon emissions from hydroelectric reservoirs is warranted.

On-site isotopic analysis of dissolved inorganic carbon using an isotope ratio infrared spectrometer

NASA Astrophysics Data System (ADS)

Stoltmann, Tim; Mandic, Magda; Stöbener, Nils; Wapelhorst, Eric; Aepfler, Rebecca; Hinrichs, Kai-Uwe; Taubner, Heidi; Jost, Hj; Elvert, Marcus

2016-04-01

An Isotope Ratio Infrared Spectrometer (IRIS) has been adapted to perform measurements of δ13C of dissolved inorganic carbon (DIC) in marine pore waters. The resulting prototype allowed highly automated analysis of δ13C isotopic ratios and CO2 concentration. We achieved a throughput of up to 70 samples per day with DIC contents as low as 1.7 μmol C. We achieved an internal precision of 0.066 ‰ and an external precision of 0.16 ‰, which is comparable to values given for Isotope Ratio Mass Spectrometers (IRMS). The prototype instrument is field deployable, suitable for shipboard analysis of deep sea core pore waters. However, the validation of the prototype was centered around a field campaign in Eckernförde Bay, NW- Baltic Sea. As a proof of concept, a shallow site within an area of submarine groundwater discharge (SGD) and a site outside this area was investigated. We present profiles of δ13C of DIC over 50 cm exhibiting well understood methane turnover processes (anaerobic oxidation of methane). At the lowest point below the seafloor, microbial reduction of CO2 to CH4 dominates. 12CO2 is reduced preferentially over 13CO2, leading to more positive δ13C values in the remaining DIC pool; in layers closer to the surface, the oxidation of CH4 to CO2 becomes more prominent. Since the CH4 pool is enriched in 12C a shift to more negative δ13C can be observed in the DIC pool. In the upper 15 cm, the pore water DIC mixes with the sea water DIC, increasing δ13C again. Finally, we will present recent developments to further improve performance and future plans for deployments on research cruises.

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Spatial variability in plant species composition and peatland carbon exchange

NASA Astrophysics Data System (ADS)

Goud, E.; Moore, T. R.; Roulet, N. T.

2015-12-01

Plant species shifts in response to global change will have significant impacts on ecosystem carbon (C) exchange and storage arising from changes in hydrology. Spatial variation in peatland C fluxes have largely been attributed to the spatial distribution of microhabitats that arise from variation in surface topography and water table depth, but little is known about how plant species composition impacts peatland C cycling or how these impacts will be influenced by changing environmental conditions. We quantified the effect of species composition and environmental variables on carbon dioxide (CO2) and methane (CH4) fluxes over 2 years in a temperate peatland for four plant communities situated along a water table gradient from ombrotrophic bog to beaver pond. We hypothesized that (i) spatial heterogeneity in species composition would drive predictable spatial heterogeneity in C fluxes due to variation in plant traits and ecological tolerances, and (ii) increases in peat temperature would increase C fluxes. Species had different effects on C fluxes primarily due to differences in leaf traits. Differences in ecological tolerances among communities resulted in different rates of CO2 exchange in response to changes in water table depth. There was an overall reduction in ecosystem respiration (ER), gross primary productivity (GPP) and CH4 flux in response to colder peat temperatures in the second year, and the additive effects of a deeper water table in the bog margin and pond sites further reduced flux rates in these areas. These results demonstrate that different plant species can increase or decrease the flux of C into and out of peatlands based on differences in leaf traits and ecological tolerances, and that CO2 and CH4 fluxes are sensitive to changes in soil temperature, especially when coupled with changes in moisture availability.

Evaluation of constructed wetlands by wastewater purification ability and greenhouse gas emissions.

PubMed

Gui, P; Inamori, R; Matsumura, M; Inamori, Y

2007-01-01

Domestic wastewater is a significant source of nitrogen and phosphorus, which cause lake eutrophication. Among the wastewater treatment technologies, constructed wetlands are a promising low-cost means of treating point and diffuse sources of domestic wastewater in rural areas. However, the sustainable operation of constructed wetland treatment systems depends upon a high rate conversion of organic and nitrogenous loading into their metabolic gaseous end products, such as N2O and CH4. In this study, we examined and compared the performance of three typical types of constructed wetlands: Free Water Surface (FWS), Subsurface Flow (SF) and Vertical Flow (VF) wetlands. Pollutant removal efficiency and N2O and CH4 emissions were assessed as measures of performance. We found that the pollutant removal rates and gas emissions measured in the wetlands exhibited clear seasonal changes, and these changes were closely associated with plant growth. VF wetlands exhibited stable removal of organic pollutants and NH3-N throughout the experiment regardless of season and showed great potential for CH4 adsorption. SF wetlands showed preferable T-N removal performance and a lower risk of greenhouse gas emissions than FWS wetlands. Soil oxidation reduction potential (ORP) analysis revealed that water flow structure and plant growth influenced constructed wetland oxygen transfer, and these variations resulted in seasonal changes of ORP distribution inside wetlands that were accompanied by fluctuations in pollutant removal and greenhouse gas emissions.

Pluto's surface composition and atmosphere

NASA Astrophysics Data System (ADS)

Young, L. A.; Gladstone, R.; Summers, M. E.; Strobel, D. F.; Kammer, J.; Hinson, D. P.; Grundy, W. M.; Cruikshank, D. P.; Protopapa, S.; Schmitt, B.; Stern, A.; Weaver, H. A., Jr.; Olkin, C.; Ennico Smith, K.

2017-12-01

New Horizons studied Pluto's N2-dominated neutral atmosphere through radio (at 4.2 cm with the REX radio experiment), solar and stellar occultations and airglow (at 52-187 nm with the Alice ultraviolet spectrograph), and imaging (with the LORRI and MVIC visible-wavelength cameras). It studied the plasma environment and solar wind interaction with in situ instruments (PEPPSI and SWAP). Contemporaneous observations of Pluto's atmosphere from Earth included a ground-based stellar occultation and ALMA observations of gaseous CO and HCN. Joint analysis of these datasets reveal a variable boundary layer; a stable lower atmosphere; radiative heating and cooling; haze production and hydrocarbon chemistry; diffusive equilibrium; and slower-than-expected escape. New Horizons studied Pluto's surface composition with the LEISA near-infrared spectral imager from 1.25 to 2.5 micron. Additional compositional information at higher spatial resolution came from the MVIC 4-channel color imager, which included a channel centered at 0.89 micron specifically designed to detect solid CH4. These instruments allow mapping of the volatiles N2, CO, and CH4, the surface expression of the H2O bedrock, and the dark, reddish material presumed to be tholins. These observations reveal a large equatorial basin (informally named Sptunik Planitia), filled with N2 ice with minor amounts of CO and CH4, surrounded by hills of CH4 and H2O ice. Broadly speaking, composition outside of Sptunik Planitia follows latitudinal banding, with dark, mainly volatile free terrains near the equator, with N2, CO, and CH4 at mid-northern latitudes, and mainly CH4 at high northern latitudes. Deviations from these broad trends are seen, and point to complex surface-atmosphere interactions at diurnal, seasonal, perennial, and million-year timescales.

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

NASA Technical Reports Server (NTRS)

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

1992-01-01

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

Global Scale Methane Emissions from On-Site Wastewater Management

NASA Astrophysics Data System (ADS)

Reid, M. C.; Guan, K.; Mauzerall, D. L.

2013-12-01

Pit latrines and other on-site sanitation methods are important forms of wastewater management at the global scale, providing hygienic and low-cost sanitation for more than 1.7 billion people in developing and middle-income regions. Latrines have also been identified as major sources of the greenhouse gas methane (CH4) from the anaerobic decomposition of organic waste in pits. Understanding the greenhouse gas footprint of different wastewater systems is essential for sustainable water resource development and management. Despite this importance, CH4 emissions from decentralized wastewater treatment have received little attention in the scientific literature, and the rough calculations underlying government inventories and integrated assessment models do not accurately capture variations in emissions within and between countries. In this study, we improve upon earlier efforts and develop the first spatially explicit approach to quantifying latrine CH4 emissions, combining a high-resolution geospatial analysis of population, urbanization, and water table (as an indicator of anaerobic decomposition pathways) with CH4 emissions factors from the 2006 IPCC Guidelines for National Greenhouse Gas Inventories. Country-level health and sanitation surveys were used to determine latrine utilization in 2000 and predict usage in 2015. 18 representative countries in Asia, Africa, and Latin America were selected for this analysis to illustrate regional variations in CH4 emissions and to include the greatest emitting nations. Our analysis confirms that pit latrines are a globally significant anthropogenic CH4 source, emitting 4.7 Tg CH4 yr-1 in the countries considered here. This total is projected to decrease ~25% by 2015, however, driven largely by rapid urbanization in China and decreased reliance on latrines in favor of flush toilets. India has the greatest potential for large growth in emissions in the post-2015 period, since public health campaigns to end open defecation, which is currently practiced by more than 600 million people in India, will rely heavily on latrines. Our results emphasize that decisions regarding water and sanitation can significantly influence anthropogenic CH4 emissions, and that discussions around sustainable water resources policy should give full consideration to the greenhouse gas impacts of decentralized sanitation systems like latrines. We conclude with a brief discussion of household biogas and composting toilets as CH4 mitigation options which also allow for harvesting of renewable energy and/or nutrients from wastewater.

Tropical rainforest methane consumption during the El Niño of 2015-16

NASA Astrophysics Data System (ADS)

Aronson, E. L.; Dierick, D.; Botthoff, J.; Swanson, A. C.; Allen, M. F.

2016-12-01

Tropical forests sequester up to 40% of the anthropogenic and natural carbon exchanged with the atmosphere. Even though soils are the largest pool of terrestrial carbon, relatively little is known about the methane consumption capacity of tropical forest soils. Under high water, low oxygen (anaerobic) conditions, carbon decomposed is respired as methane (CH4) by methanogen microorganisms. During dry seasons, deeper rainforest soils remain wet, but dry at the surface. Since molecule for molecule the global warming potential of CH4 is two orders of magnitude greater than CO2, the relative production and sequestration of CO2 versus CH4 in tropical rainforests has a large impact on global climate trends. In 2015-16, the globe experienced an unusually strong ENSO event, which impacted the tropics. Atypical ENSO climatic events such as this include drought in tropical forests of Central America. We hypothesized that ENSO controls much of the year-to-year variability in the global CH4 cycle, primarily by turning the tropical forest from a strong annual source for CH4 during the La Niña or normal rainy season, to a year-round sink for CH4 during El Niño events. Further, we hypothesized that during a strong El Niño event, the unusually dry conditions of the tropical rainy season lead to the methanotrophs in these soils consuming large amounts of CH4. In order to investigate these predictions, CH4 flux was measured in three campaigns in March, during peak ENSO impact, as well as May and July 2016, at the La Selva Biological Station, Costa Rica. Fluxes were measured in eight paired plots, each with four collars. The collars measure 20 cm diameter by 12 cm in length, inserted into the soil, with a collar height of around 8 cm, in February 2016, a month before the first field campaign. Air samples were injected into pre-evacuated exetainers, and analyzed by gas chromatograph within 72 h. We found an average CH4 sink of -0.018 mg m-2 h-1. This flux is roughly four times lower than the average forest consumption rate, however most forest CH4 flux data is from temperate and boreal forests. While differences in flux magnitude between months were not significant, CH4 consumption was greatest in May, at -0.025 mg m-2 h-1, and lowest in March, at -0.011 mg m-2 h-1. These data help to fill the gap in knowledge of tropical forest methane flux.

Natural Gas Evolution in a Gas Hydrate Melt: Effect of Thermodynamic Hydrate Inhibitors.

PubMed

Sujith, K S; Ramachandran, C N

2017-01-12

Natural gas extraction from gas hydrate sediments by injection of hydrate inhibitors involves the decomposition of hydrates. The evolution of dissolved gas from the hydrate melt is an important step in the extraction process. Using classical molecular dynamics simulations, we study the evolution of dissolved methane from its hydrate melt in the presence of two thermodynamic hydrate inhibitors, NaCl and CH 3 OH. An increase in the concentration of hydrate inhibitors is found to promote the nucleation of methane nanobubbles in the hydrate melt. Whereas NaCl promotes bubble formation by enhancing the hydrophobic interaction between aqueous CH 4 molecules, CH 3 OH molecules assist bubble formation by stabilizing CH 4 bubble nuclei formed in the solution. The CH 3 OH molecules accumulate around the nuclei leading to a decrease in the surface tension at their interface with water. The nanobubbles formed are found to be highly dynamic with frequent exchange of CH 4 molecules between the bubble and the surrounding liquid. A quantitative analysis of the dynamic behavior of the bubble is performed by introducing a unit step function whose value depends on the location of CH 4 molecules with respect to the bubble. It is observed that an increase in the concentration of thermodynamic hydrate inhibitors reduces the exchange process, making the bubble less dynamic. It is also found that for a given concentration of the inhibitor, larger bubbles are less dynamic compared to smaller ones. The dependence of the dynamic nature of nanobubbles on bubble size and inhibitor concentration is correlated with the solubility of CH 4 and the Laplace pressure within the bubble. The effect of CO 2 on the formation of nanobubble in the CH 4 -CO 2 mixed gas hydrate melt in the presence of inhibitors is also examined. The simulations show that the presence of CO 2 molecules significantly reduces the induction time for methane nanobubble nucleation. The role of CO 2 in the early nucleation of bubble is explained based on the interaction between the bubble and the dissolved CO 2 molecules.

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

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

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Controls on northern wetland methane emissions: insights from regional synthesis studies and the Alaska Peatland Experiment (APEX)

NASA Astrophysics Data System (ADS)

Turetsky, M. R.; Euskirchen, E. S.; Czimczik, C. I.; Waldrop, M. P.; Olefeldt, D.; Fan, Z.; Kane, E. S.; McGuire, A. D.; Harden, J. W.

2014-12-01

Wetlands are the largest natural source of atmospheric methane. Static chambers have been used to quantify variation in wetland CH4 flux for many decades. Regional to global scale synthesis studies of static chamber measurements show that relationships between temperature, water availability and CH4 emissions depend on wetland type (bog, fen, swamp), region (tropical, temperate, arctic) and disturbance. For example, while water table position and temperature serve as the dominant controls on bog and swamp CH4 flux, vegetation is an important control on emissions from fens. These studies highlight the fact that wetland types have distinct controls on CH4 emissions; however, it is unlikely that modeling of wetland CH4 flux will improve without a better mechanistic understanding of the processes underlying CH4 production, transport, and oxidation. At the Alaska Peatland Experiment, we are quantifying CH4 emission using static chambers, automated chambers, and towers. Our sites vary in permafrost regime, including groundwater fens without permafrost, forested peat plateaus with intact permafrost, and collapse scar bogs formed through permafrost thaw. Experimental studies that examine plant and microbial responses to altered water table position and soil temperature are complemented by a gradient approach, where we use a space-for-time substitutions to examine the consequences of thaw on time-scales of decades to centuries. Our results thus far have documented the importance of soil rewetting in governing large CH4 fluxes from northern wetland soils. Accounting for CH4, our collapse scar bog significantly contributed to the global warming potential of the landscape. A major objective of our work is to explore the role of permafrost C release in greenhouse gas fluxes from wetland soils, which we are assessing using radiocarbon as a natural tracer. We have shown, for example, that ebullition of CH4 is dominated by recently fixed C, but a significant fraction of CH4 in bubbles is derived from old C released during thaw. The APEX time series datasets are being used in a variety of modeling studies, from small-scale soil pore and microbial controls on gas production and transport to regional scale assessments of how carbon cycle feedbacks to climate vary with wetland type and abundance.

Large CO2 and CH4 release from a flooded formerly drained fen

NASA Astrophysics Data System (ADS)

Sachs, T.; Franz, D.; Koebsch, F.; Larmanou, E.; Augustin, J.

2016-12-01

Drained peatlands are usually strong carbon dioxide (CO2) sources. In Germany, up to 4.5 % of the national CO2 emissions are estimated to be released from agriculturally used peatlands and for some peatland-rich northern states, such as Mecklenburg-Western Pomerania, this share increases to about 20%. Reducing this CO2 source and restoring the peatlands' natural carbon sink is one objective of large-scale nature protection and restoration measures, in which 37.000 ha of drained and degraded peatlands in Mecklenburg-Western Pomerania are slated for rewetting. It is well known, however, that in the initial phase of rewetting, a reduction of the CO2 source strength is usually accompanied by an increase in CH4 emissions. Thus, whether and when the intended effects of rewetting with regard to greenhouse gases are achieved, depends on the balance of CO2 and CH4 fluxes and on the duration of the initial CH4 emission phase. In 2013, a new Fluxnet site went online at a flooded formerly drained river valley fen site near Zarnekow, NE Germany (DE-Zrk), to investigate the combined CO2 and CH4 dynamics at such a heavily degraded and rewetted peatland. The site is dominated by open water with submerged and floating vegetation and surrounding Typha latifolia.Nine year after rewetting, we found large CH4 emissions of 53 g CH4 m-2 a-1 from the open water area, which are 4-fold higher than from the surrounding vegetation zone (13 g CH4 m-2 a-1). Surprisingly, both the open water and the vegetated area were net CO2 sources of 158 and 750 g CO2 m-2 a-1, respectively. Unusual meteorological conditions with a warm and dry summer and a mild winter might have facilitated high respiration rates, particularly from temporally non-inundated organic mud in the vegetation zone.

Adsorption of methane and CO2 onto olivine surfaces in Martian dust conditions

NASA Astrophysics Data System (ADS)

Escamilla-Roa, Elizabeth; Martin-Torres, Javier; Sainz-Díaz, C. Ignacio

2018-04-01

Methane has been detected on all planets of our Solar System, and most of the larger moons, as well as in dwarf-planets like Pluto and Eric. The presence of this molecule in rocky planets is very interesting because its presence in the Earth's atmosphere is mainly related to biotic processes. Space instrumentation in orbiters around Mars has detected olivine on the Martian soil and dust. On the other hand the measurements of methane from the Curiosity rover report detection of background levels of atmospheric methane with abundance that is lower than model estimates of ultraviolet degradation of accreted interplanetary dust particles or carbonaceous chondrite material. Additionally, elevated levels of methane about this background have been observed implying that Mars is episodically producing methane from an additional unknown source, making the reasons of these temporal fluctuations of methane a hot topic in planetary research. The goal of this study is to investigate at atomic level the interactions during the adsorption processes of methane and other Mars atmospheric species (CO2, H2O) on forsterite surfaces, through electronic structure calculations based on the Density Functional Theory (DFT). We propose two models to simulate the interaction of adsorbates with the surface of dust mineral, such as binary mixtures (5CH4+5H2O/5CH4+5CO2) and as a semi-clathrate adsorption. We have obtained interesting results of the adsorption process in the mixture 5CH4+5CO2. Associative and dissociative adsorptions were observed for water and CO2 molecules. The methane molecules were only trapped and held by water or CO2 molecules. In the dipolar surface, the adsorption of CO2 molecules produced new species: one CO from a CO2 dissociation, and, two CO2 molecules chemisorbed to mineral surface forming in one case a carbonate group. Our results suggest that CO2 has a strong interaction with the mineral surface when methane is present. These results could be confirmed after the analysis of the data from the upcoming remote and in-situ observations on Mars, as those to be performed by instruments on the ESA's ExoMars Trace Gas Orbiter and ExoMars rover.

How does whole ecosystem warming of a peatland affect methane production and consumption?

NASA Astrophysics Data System (ADS)

Hopple, A.; Brunik, K.; Keller, J.; Pfeifer-Meister, L.; Woerndle, G.; Zalman, C.; Hanson, P.; Bridgham, S. D.

2017-12-01

Peatlands are among Earth's most important terrestrial ecosystems due to their massive soil carbon (C) stores and significant release of methane (CH4) into the atmosphere. Methane has a sustained-flux global warming potential 45-times greater than carbon dioxide (CO2), and the accuracy of Earth system model projections relies on our mechanistic understanding of peatland CH4 cycling in the context of environmental change. The objective of this study was to determine, under in situ conditions, how heating of the peat profile affects ecosystem-level anaerobic C cycling. We assessed the response of CO2 and CH4 production, as well as the anaerobic oxidation of CH4 (AOM), in a boreal peatland following 13 months of deep peat heating (DPH) and 16 months of subsequent whole-ecosystem warming (surface and deep heating; WEW) as part of the Spruce and Peatland Responses Under Changing Environments (SPRUCE) project in northern Minnesota, USA. The study uses a regression-based experimental design including 5 temperature treatments that warmed the entire 2 m peat profile from 0 to +9 °C above ambient temperature. Soil cores were collected at multiple depths (25-200 cm) from each experimental chamber at the SPRUCE site and anaerobically incubated at in situ temperatures for 1-2 weeks. Methane and CO2 production in surface peat were positively correlated with elevated temperature, but no consistent temperature response was found at depth (75-200 cm) following DPH. However, during WEW, we observed significant increases in both surface and deep peat methanogenesis with increasing temperature. Surface peat had greater CH4 production rates than deeper peat, implying that the increased CH4 emissions observed in the field were largely driven by surface peat warming. The CO2:CH4 ratio was inversely correlated with temperature across all depths following 16 months of WEW, indicating that the entire peat profile is becoming more methanogenic with warming. We also observed AOM throughout the whole peat profile, with the highest rates observed at the surface and initial data suggesting a positive correlation with increasing temperature. While SPRUCE will continue for many years, our initial results suggest that the vast C stores at depth in peatlands are minimally responsive to warming and any response will be driven largely by surface peat.

Electronic spectroscopy and photodissociation dynamics of Co(2+)-methanol clusters: Co2+ (CH3OH)n (n = 4-7).

PubMed

Thompson, Christopher J; Faherty, Kieron P; Stringer, Kay L; Metz, Ricardo B

2005-03-07

Solvated cluster ions Co2+ (CH3OH)n (n = 4-7) have been produced by electrospray and studied using photofragment spectroscopy. There are notable differences between the photodissociation spectra of these complexes and the analogous water complexes. Co2+ (CH3OH)6 absorbs significantly more strongly than Co2+ (H2O)6. The photodissociation spectra of Co2+ (CH3OH)n (n = 4, 5 and 6) are very similar, which suggests that they share the Co2+ (CH3OH)4 chromophore, with additional solvent molecules in the second shell. In contrast, our earlier studies indicate that Co2+ (H2O)6 is six coordinate, and its spectrum is significantly different from that of Co2+ (H2O)4. The larger clusters Co2+ (CH3OH)n (n = 5-7) dissociate by simple loss of one or more solvent molecules. Larger clusters tend to lose more solvent molecules, especially at higher photon energies. As with the corresponding water cluster, Co2+ (CH3OH)4 photodissociates by proton transfer through a salt-bridge intermediate. This is accompanied by a modest kinetic energy release of 170 kJ mol(-1) and occurs with a lifetime of 145 ns.

Global methane emission estimates for 2000-2012 from CarbonTracker Europe-CH4 v1.0

NASA Astrophysics Data System (ADS)

Tsuruta, Aki; Aalto, Tuula; Backman, Leif; Hakkarainen, Janne; van der Laan-Luijkx, Ingrid T.; Krol, Maarten C.; Spahni, Renato; Houweling, Sander; Laine, Marko; Dlugokencky, Ed; Gomez-Pelaez, Angel J.; van der Schoot, Marcel; Langenfelds, Ray; Ellul, Raymond; Arduini, Jgor; Apadula, Francesco; Gerbig, Christoph; Feist, Dietrich G.; Kivi, Rigel; Yoshida, Yukio; Peters, Wouter

2017-03-01

We present a global distribution of surface methane (CH4) emission estimates for 2000-2012 derived using the CarbonTracker Europe-CH4 (CTE-CH4) data assimilation system. In CTE-CH4, anthropogenic and biospheric CH4 emissions are simultaneously estimated based on constraints of global atmospheric in situ CH4 observations. The system was configured to either estimate only anthropogenic or biospheric sources per region, or to estimate both categories simultaneously. The latter increased the number of optimizable parameters from 62 to 78. In addition, the differences between two numerical schemes available to perform turbulent vertical mixing in the atmospheric transport model TM5 were examined. Together, the system configurations encompass important axes of uncertainty in inversions and allow us to examine the robustness of the flux estimates. The posterior emission estimates are further evaluated by comparing simulated atmospheric CH4 to surface in situ observations, vertical profiles of CH4 made by aircraft, remotely sensed dry-air total column-averaged mole fraction (XCH4) from the Total Carbon Column Observing Network (TCCON), and XCH4 from the Greenhouse gases Observing Satellite (GOSAT). The evaluation with non-assimilated observations shows that posterior XCH4 is better matched with the retrievals when the vertical mixing scheme with faster interhemispheric exchange is used. Estimated posterior mean total global emissions during 2000-2012 are 516 ± 51 Tg CH4 yr-1, with an increase of 18 Tg CH4 yr-1 from 2000-2006 to 2007-2012. The increase is mainly driven by an increase in emissions from South American temperate, Asian temperate and Asian tropical TransCom regions. In addition, the increase is hardly sensitive to different model configurations ( < 2 Tg CH4 yr-1 difference), and much smaller than suggested by EDGAR v4.2 FT2010 inventory (33 Tg CH4 yr-1), which was used for prior anthropogenic emission estimates. The result is in good agreement with other published estimates from inverse modelling studies (16-20 Tg CH4 yr-1). However, this study could not conclusively separate a small trend in biospheric emissions (-5 to +6.9 Tg CH4 yr-1) from the much larger trend in anthropogenic emissions (15-27 Tg CH4 yr-1). Finally, we find that the global and North American CH4 balance could be closed over this time period without the previously suggested need to strongly increase anthropogenic CH4 emissions in the United States. With further developments, especially on the treatment of the atmospheric CH4 sink, we expect the data assimilation system presented here will be able to contribute to the ongoing interpretation of changes in this important greenhouse gas budget.

Sulfur Metabolizing Microbes Dominate Microbial Communities in Andesite-Hosted Shallow-Sea Hydrothermal Systems

PubMed Central

Zhang, Yao; Zhao, Zihao; Chen, Chen-Tung Arthur; Tang, Kai; Su, Jianqiang; Jiao, Nianzhi

2012-01-01

To determine microbial community composition, community spatial structure and possible key microbial processes in the shallow-sea hydrothermal vent systems off NE Taiwan’s coast, we examined the bacterial and archaeal communities of four samples collected from the water column extending over a redoxocline gradient of a yellow and four from a white hydrothermal vent. Ribosomal tag pyrosequencing based on DNA and RNA showed statistically significant differences between the bacterial and archaeal communities of the different hydrothermal plumes. The bacterial and archaeal communities from the white hydrothermal plume were dominated by sulfur-reducing Nautilia and Thermococcus, whereas the yellow hydrothermal plume and the surface water were dominated by sulfide-oxidizing Thiomicrospira and Euryarchaeota Marine Group II, respectively. Canonical correspondence analyses indicate that methane (CH4) concentration was the only statistically significant variable that explains all community cluster patterns. However, the results of pyrosequencing showed an essential absence of methanogens and methanotrophs at the two vent fields, suggesting that CH4 was less tied to microbial processes in this shallow-sea hydrothermal system. We speculated that mixing between hydrothermal fluids and the sea or meteoric water leads to distinctly different CH4 concentrations and redox niches between the yellow and white vents, consequently influencing the distribution patterns of the free-living Bacteria and Archaea. We concluded that sulfur-reducing and sulfide-oxidizing chemolithoautotrophs accounted for most of the primary biomass synthesis and that microbial sulfur metabolism fueled microbial energy flow and element cycling in the shallow hydrothermal systems off the coast of NE Taiwan. PMID:22970260

Sulfur metabolizing microbes dominate microbial communities in Andesite-hosted shallow-sea hydrothermal systems.

PubMed

Zhang, Yao; Zhao, Zihao; Chen, Chen-Tung Arthur; Tang, Kai; Su, Jianqiang; Jiao, Nianzhi

2012-01-01

To determine microbial community composition, community spatial structure and possible key microbial processes in the shallow-sea hydrothermal vent systems off NE Taiwan's coast, we examined the bacterial and archaeal communities of four samples collected from the water column extending over a redoxocline gradient of a yellow and four from a white hydrothermal vent. Ribosomal tag pyrosequencing based on DNA and RNA showed statistically significant differences between the bacterial and archaeal communities of the different hydrothermal plumes. The bacterial and archaeal communities from the white hydrothermal plume were dominated by sulfur-reducing Nautilia and Thermococcus, whereas the yellow hydrothermal plume and the surface water were dominated by sulfide-oxidizing Thiomicrospira and Euryarchaeota Marine Group II, respectively. Canonical correspondence analyses indicate that methane (CH(4)) concentration was the only statistically significant variable that explains all community cluster patterns. However, the results of pyrosequencing showed an essential absence of methanogens and methanotrophs at the two vent fields, suggesting that CH(4) was less tied to microbial processes in this shallow-sea hydrothermal system. We speculated that mixing between hydrothermal fluids and the sea or meteoric water leads to distinctly different CH(4) concentrations and redox niches between the yellow and white vents, consequently influencing the distribution patterns of the free-living Bacteria and Archaea. We concluded that sulfur-reducing and sulfide-oxidizing chemolithoautotrophs accounted for most of the primary biomass synthesis and that microbial sulfur metabolism fueled microbial energy flow and element cycling in the shallow hydrothermal systems off the coast of NE Taiwan.

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).

Evaluation of column-averaged methane in models and TCCON with a focus on the stratosphere

DOE PAGES

Ostler, Andreas; Sussmann, Ralf; Patra, Prabir K.; ...

2016-09-28

The distribution of methane (CH 4) in the stratosphere can be a major driver of spatial variability in the dry-air column-averaged CH 4 mixing ratio (XCH 4), which is being measured increasingly for the assessment of CH 4 surface emissions. Chemistry-transport models (CTMs) therefore need to simulate the tropospheric and stratospheric fractional columns of XCH 4 accurately for estimating surface emissions from XCH 4. Simulations from three CTMs are tested against XCH 4 observations from the Total Carbon Column Network (TCCON). We analyze how the model–TCCON agreement in XCH 4 depends on the model representation of stratospheric CH 4 distributions.more » Model equivalents of TCCON XCH 4 are computed with stratospheric CH 4 fields from both the model simulations and from satellite-based CH 4 distributions from MIPAS (Michelson Interferometer for Passive Atmospheric Sounding) and MIPAS CH 4 fields adjusted to ACE-FTS (Atmospheric Chemistry Experiment Fourier Transform Spectrometer) observations. Using MIPAS-based stratospheric CH 4 fields in place of model simulations improves the model–TCCON XCH 4 agreement for all models. For the Atmospheric Chemistry Transport Model (ACTM) the average XCH 4 bias is significantly reduced from 38.1 to 13.7 ppb, whereas small improvements are found for the models TM5 (Transport Model, version 5; from 8.7 to 4.3 ppb) and LMDz (Laboratoire de Météorologie Dynamique model with zooming capability; from 6.8 to 4.3 ppb). Replacing model simulations with MIPAS stratospheric CH 4 fields adjusted to ACE-FTS reduces the average XCH 4 bias for ACTM (3.3 ppb), but increases the average XCH 4 bias for TM5 (10.8 ppb) and LMDz (20.0 ppb). These findings imply that model errors in simulating stratospheric CH 4 contribute to model biases. Current satellite instruments cannot definitively measure stratospheric CH 4 to sufficient accuracy to eliminate these biases. Applying transport diagnostics to the models indicates that model-to-model differences in the simulation of stratospheric transport, notably the age of stratospheric air, can largely explain the inter-model spread in stratospheric CH 4 and, hence, its contribution to XCH 4. Furthermore, it would be worthwhile to analyze how individual model components (e.g., physical parameterization, meteorological data sets, model horizontal/vertical resolution) impact the simulation of stratospheric CH 4 and XCH 4.« less

Evaluation of column-averaged methane in models and TCCON with a focus on the stratosphere

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

Ostler, Andreas; Sussmann, Ralf; Patra, Prabir K.

The distribution of methane (CH 4) in the stratosphere can be a major driver of spatial variability in the dry-air column-averaged CH 4 mixing ratio (XCH 4), which is being measured increasingly for the assessment of CH 4 surface emissions. Chemistry-transport models (CTMs) therefore need to simulate the tropospheric and stratospheric fractional columns of XCH 4 accurately for estimating surface emissions from XCH 4. Simulations from three CTMs are tested against XCH 4 observations from the Total Carbon Column Network (TCCON). We analyze how the model–TCCON agreement in XCH 4 depends on the model representation of stratospheric CH 4 distributions.more » Model equivalents of TCCON XCH 4 are computed with stratospheric CH 4 fields from both the model simulations and from satellite-based CH 4 distributions from MIPAS (Michelson Interferometer for Passive Atmospheric Sounding) and MIPAS CH 4 fields adjusted to ACE-FTS (Atmospheric Chemistry Experiment Fourier Transform Spectrometer) observations. Using MIPAS-based stratospheric CH 4 fields in place of model simulations improves the model–TCCON XCH 4 agreement for all models. For the Atmospheric Chemistry Transport Model (ACTM) the average XCH 4 bias is significantly reduced from 38.1 to 13.7 ppb, whereas small improvements are found for the models TM5 (Transport Model, version 5; from 8.7 to 4.3 ppb) and LMDz (Laboratoire de Météorologie Dynamique model with zooming capability; from 6.8 to 4.3 ppb). Replacing model simulations with MIPAS stratospheric CH 4 fields adjusted to ACE-FTS reduces the average XCH 4 bias for ACTM (3.3 ppb), but increases the average XCH 4 bias for TM5 (10.8 ppb) and LMDz (20.0 ppb). These findings imply that model errors in simulating stratospheric CH 4 contribute to model biases. Current satellite instruments cannot definitively measure stratospheric CH 4 to sufficient accuracy to eliminate these biases. Applying transport diagnostics to the models indicates that model-to-model differences in the simulation of stratospheric transport, notably the age of stratospheric air, can largely explain the inter-model spread in stratospheric CH 4 and, hence, its contribution to XCH 4. Furthermore, it would be worthwhile to analyze how individual model components (e.g., physical parameterization, meteorological data sets, model horizontal/vertical resolution) impact the simulation of stratospheric CH 4 and XCH 4.« less

Evaluation of column-averaged methane in models and TCCON with a focus on the stratosphere

NASA Astrophysics Data System (ADS)

Ostler, Andreas; Sussmann, Ralf; Patra, Prabir K.; Houweling, Sander; De Bruine, Marko; Stiller, Gabriele P.; Haenel, Florian J.; Plieninger, Johannes; Bousquet, Philippe; Yin, Yi; Saunois, Marielle; Walker, Kaley A.; Deutscher, Nicholas M.; Griffith, David W. T.; Blumenstock, Thomas; Hase, Frank; Warneke, Thorsten; Wang, Zhiting; Kivi, Rigel; Robinson, John

2016-09-01

The distribution of methane (CH4) in the stratosphere can be a major driver of spatial variability in the dry-air column-averaged CH4 mixing ratio (XCH4), which is being measured increasingly for the assessment of CH4 surface emissions. Chemistry-transport models (CTMs) therefore need to simulate the tropospheric and stratospheric fractional columns of XCH4 accurately for estimating surface emissions from XCH4. Simulations from three CTMs are tested against XCH4 observations from the Total Carbon Column Network (TCCON). We analyze how the model-TCCON agreement in XCH4 depends on the model representation of stratospheric CH4 distributions. Model equivalents of TCCON XCH4 are computed with stratospheric CH4 fields from both the model simulations and from satellite-based CH4 distributions from MIPAS (Michelson Interferometer for Passive Atmospheric Sounding) and MIPAS CH4 fields adjusted to ACE-FTS (Atmospheric Chemistry Experiment Fourier Transform Spectrometer) observations. Using MIPAS-based stratospheric CH4 fields in place of model simulations improves the model-TCCON XCH4 agreement for all models. For the Atmospheric Chemistry Transport Model (ACTM) the average XCH4 bias is significantly reduced from 38.1 to 13.7 ppb, whereas small improvements are found for the models TM5 (Transport Model, version 5; from 8.7 to 4.3 ppb) and LMDz (Laboratoire de Météorologie Dynamique model with zooming capability; from 6.8 to 4.3 ppb). Replacing model simulations with MIPAS stratospheric CH4 fields adjusted to ACE-FTS reduces the average XCH4 bias for ACTM (3.3 ppb), but increases the average XCH4 bias for TM5 (10.8 ppb) and LMDz (20.0 ppb). These findings imply that model errors in simulating stratospheric CH4 contribute to model biases. Current satellite instruments cannot definitively measure stratospheric CH4 to sufficient accuracy to eliminate these biases. Applying transport diagnostics to the models indicates that model-to-model differences in the simulation of stratospheric transport, notably the age of stratospheric air, can largely explain the inter-model spread in stratospheric CH4 and, hence, its contribution to XCH4. Therefore, it would be worthwhile to analyze how individual model components (e.g., physical parameterization, meteorological data sets, model horizontal/vertical resolution) impact the simulation of stratospheric CH4 and XCH4.

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.

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

NASA Astrophysics Data System (ADS)

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

2013-04-01

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

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

NASA Astrophysics Data System (ADS)

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

2012-12-01

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

Variations in the methane budget over the last two millennia

NASA Astrophysics Data System (ADS)

Sapart, C. J.

2012-06-01

Methane (CH4) is a strong greenhouse gas and even though its atmospheric abundance is lower than carbon dioxide (CO2), CH4 has a global warming potential twenty-five times larger than CO2 and its atmospheric abundance has drastically increased since 1800. Understanding the evolution of the CH4 atmospheric abundance is complex, because it is controlled by multiple sources (e.g. wetlands, biomass burning, ruminants, rice paddies and fossil fuel) and sinks, and large uncertainties exist on how sensitive those sources and sinks are to climate variability. The aim of this research is to understand the influence of climate variability and anthropogenic activity on the CH4 budget, i.e. the balance between the different sources and sinks, during the last two millennia. For this purpose a technique was developed to analyze the CH4 isotopic composition of air in ice cores. Analysis of the isotopic composition of CH4 preserved in ice cores provides evidence for the environmental drivers of variations in CH4 mixing ratios, because different sources and sinks affect the isotopic composition of CH4 uniquely. Our main results from air trapped in Greenland ice cores shows that the carbon isotopic composition (d13C) of CH4 underwent pronounced centennial-scale variations between 200 BC and 1600 AD without clear corresponding changes in CH4 mixing ratios. Two-box model calculations suggest that those centennial-scale variations in isotope ratios are due to changes in biomass burning and biogenic sources (e.g. wetlands, agriculture), which are correlated with both natural climate variability, including the Medieval Climate Anomaly and with changes in human population, land-use and important events in history as the expansion of the Roman Empire, the fall of the Han dynasty and the Medieval period. This shows that human activity had an impact on the methane budget already two thousand years ago and is likely responsible for the atmospheric methane increase in the atmosphere during this period. Also the more recent CH4 budget has been investigated by measuring the isotope composition of CH4 in air trapped in the surface layer of the ice sheet (called firn). Several processes involving isotopic fractionation occur in the firn, hence corrections need to be apply to the isotope data in order to reconstruct the atmospheric history. Those corrections were carried out with a firn air transport model and the best-estimate scenario shows an enrichment in d13C of CH4 over the last 50 years very likely caused by enhanced fossil fuel production and consumption during this period. The role of wetlands, the main natural CH4 source, has also been investigated using measurements of d13C from air trapped in ice covering Arctic lakes in the winter. Those data showed that during the winter and in presence of ice cover, CH4, which is produced in the lake sediment, is partly removed by oxidation in the water column. Therefore, shorter is the period of ice cover on Arctic lakes, more CH4 will reach the atmosphere. This process may be of major importance in a future changing climate.

Chemical markers of possible hot spots on Mars

NASA Astrophysics Data System (ADS)

Wong, Ah-San; Atreya, Sushil K.; Encrenaz, Thérèse

2003-04-01

Although there is no evidence of active volcanism on Mars today, ``localized'' outgassing sources, the hot spots, may not be ruled out. If outgassing does occur somewhere on Mars, water, carbon dioxide, sulfur species, methane, and to a lesser extent, halogens would be the likely molecules of outgassing, based on terrestrial analogs. The sulfur species, methane, and halogens have not been detected in the Martian atmosphere, but the observations were averaged over large areas, which could result in substantial dilution in abundances. If the interpretation of certain Mars Global Surveyor images indicating recent ground water seepage and surface runoff [Malin and Edgett, 2000] is correct, it may imply that Mars could still be active internally in some places from time to time, and outgassing of the abovementioned species may occur with or without the water seepage. Moreover, if the tentative detection of formaldehyde (CH2O) in the equatorial region of Mars [Korablev et al., 1993] is confirmed by future observations, it would imply at least local outgassing of methane, whose oxidation results in the formation of CH2O. Considering the possibility of outgassing from some localized hot spots, we have developed a one-dimensional photochemical model that includes methane (CH4), sulfur dioxide (SO2), and hydrogen sulfide (H2S), starting with their current ``global average'' upper limits of 0.02, 0.1, and 0.1 ppm at the surface, respectively, and then progressively increasing their abundances above possible hot spots. We find that the introduction of methane into the Martian atmosphere results in the formation of mainly formaldehyde, methyl alcohol (CH3OH), and ethane (C2H6), whereas the introduction of the sulfur species produces mainly sulfur monoxide (SO) and sulfuric acid (H2SO4). The effect of outgassed halogens on the Martian atmosphere is found to be negligible. Depending upon the flux of outgassed molecules from possible hot spots, some of these species and the resulting new molecules may be detectable locally, either by remote sensing or in situ measurements.

Effects of seasonality, transport pathway, and spatial structure on greenhouse gas fluxes in a restored wetland.

PubMed

McNicol, Gavin; Sturtevant, Cove S; Knox, Sara H; Dronova, Iryna; Baldocchi, Dennis D; Silver, Whendee L

2017-07-01

Wetlands can influence global climate via greenhouse gas (GHG) exchange of carbon dioxide (CO 2 ), methane (CH 4 ), and nitrous oxide (N 2 O). Few studies have quantified the full GHG budget of wetlands due to the high spatial and temporal variability of fluxes. We report annual open-water diffusion and ebullition fluxes of CO 2 , CH 4 , and N 2 O from a restored emergent marsh ecosystem. We combined these data with concurrent eddy-covariance measurements of whole-ecosystem CO 2 and CH 4 exchange to estimate GHG fluxes and associated radiative forcing effects for the whole wetland, and separately for open-water and vegetated cover types. Annual open-water CO 2 , CH 4 , and N 2 O emissions were 915 ± 95 g C-CO 2  m -2  yr -1 , 2.9 ± 0.5 g C-CH 4  m -2  yr -1 , and 62 ± 17 mg N-N 2 O m -2  yr -1 , respectively. Diffusion dominated open-water GHG transport, accounting for >99% of CO 2 and N 2 O emissions, and ~71% of CH 4 emissions. Seasonality was minor for CO 2 emissions, whereas CH 4 and N 2 O fluxes displayed strong and asynchronous seasonal dynamics. Notably, the overall radiative forcing of open-water fluxes (3.5 ± 0.3 kg CO 2 -eq m -2  yr -1 ) exceeded that of vegetated zones (1.4 ± 0.4 kg CO 2 -eq m -2  yr -1 ) due to high ecosystem respiration. After scaling results to the entire wetland using object-based cover classification of remote sensing imagery, net uptake of CO 2 (-1.4 ± 0.6 kt CO 2 -eq yr -1 ) did not offset CH 4 emission (3.7 ± 0.03 kt CO 2 -eq yr -1 ), producing an overall positive radiative forcing effect of 2.4 ± 0.3 kt CO 2 -eq yr -1 . These results demonstrate clear effects of seasonality, spatial structure, and transport pathway on the magnitude and composition of wetland GHG emissions, and the efficacy of multiscale flux measurement to overcome challenges of wetland heterogeneity. © 2017 John Wiley & Sons Ltd.

Vacuum Ultraviolet Photoabsorption Spectra of Nitrile Ices for their Identification on Pluto

NASA Astrophysics Data System (ADS)

Sivaraman, B.; Pavithraa, S.; Lo, J.-I.; Raja Sekhar, B. N.; Hill, H.; Cheng, B.-M.; Mason, N. J.

2016-07-01

Icy bodies, such as Pluto, are known to harbor simple and complex molecules. The recent New Horizons flyby of Pluto has revealed a complex surface composed of bright and dark ice surfaces, indicating a rich chemistry based on nitrogen (N2), methane (CH4), and carbon monoxide (CO). Nitrile (CN) containing molecules such as acetonitrile (CH3CN), propionitrile (CH3CH2CN), butyronitrile (CH3CH2CH2CN), and isobutyronitrile ((CH3)2CHCN) are some of the nitrile molecules that are known to be synthesized by radiative processing of such simple ices. Through the provision of a spectral atlas for such compounds we propose that such nitriles may be identified from the ALICE payload on board New Horizons.

Annual dynamics of N2O, CH4 and CO2 fluxes from the agricultural irrigation watersheds in southeast China

NASA Astrophysics Data System (ADS)

Wu, S.; Zou, J.; Liu, S.; Chen, J.; Kong, D.; Geng, Y.

2017-12-01

Agricultural irrigation watershed covers a large area in southeast of China and is a potentially important source of carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O). However, the flux magnitudes contribution to the overall catchment greenhouse gas (GHGs) fluxes and their drivers of seasonal variability are limited in agricultural irrigation watersheds. An in-situ observation was performed to measure annual CO2, CH4 and N2O fluxes from an agricultural irrigation watershed in southeast of China from September 2014 to September 2016. GHGs fluxes were measured using floating chambers and a gas exchange model was also used to predict CH4 and N2O fluxes. All GHGs showed varied seasonally with highest fluxes in early summer (July) and lowest in winter. Estimated seasonal CH4-C fluxes (11.5-97.6 mg m-2 hr-1) and N2O-N fluxes (2.8-80.8μg m-2 hr-1) were in relative agreement with measured CH4-C fluxes (0.05-74.9mg m-2 hr-1) and N2O-N fluxes (3.9-68.7μg m-2 hr-1) fluxes using floating chambers. Both CH4 and N2O fluxes were positively related to water temperature. The CH4 fluxes were negatively related to water dissolved oxygen (DO) concentration but positively related to sediment dissolved organic carbon (DOC). The N2O fluxes were positively related to water NH4+ and NO3-. The calculated EF5-r value in this study (mean = 0.0016; range = 0.0013-0.0018) was below the current IPCC (2006) default value of 0.0025. This implied that IPCC methodology may over estimates of N2O emissions associated with nitrogen leaching and runoff from agriculture.

Satellite microwave detection of contrasting changes in surface inundation across pan-Arctic permafrost zones

NASA Astrophysics Data System (ADS)

Watts, J.; Kimball, J. S.; Jones, L. A.; Schroeder, R.; McDonald, K. C.

2012-12-01

Surface water inundation in the Arctic is concomitant with soil permafrost and strongly influences land-atmosphere water, energy and carbon (CO2, CH4) exchange, and plant community structure. We examine recent (2003-2010) surface water inundation patterns across the pan-Arctic (≥ 50 deg.N) and within major permafrost zones using satellite passive microwave remote sensing retrievals of fractional open water extent (Fw) derived from Advanced Microwave Scanning Radiometer for EOS (AMSR-E) 18.7 and 23.8 GHz brightness temperatures. The AMSR-E Fw retrievals are insensitive to atmosphere contamination and solar illumination effects, enabling daily Fw monitoring across the Arctic. The Fw retrievals are sensitive to sub-grid scale open water inundation area, including lakes and wetlands, within the relatively coarse (~25-km resolution) satellite footprint. A forward model error sensitivity analysis indicates that total Fw retrieval uncertainty is within ±4.1% (RMSE), and AMSR-E Fw compares favorably (0.71 < R2 < 0.84) with alternative static open water maps derived from finer scale (30-m to 250-m resolution) Landsat, MODIS and SRTM radar-based products. The Fw retrievals also show dynamic seasonal and annual variability in surface inundation that corresponds (0.71 < R < 0.87) with regional wet/dry cycles inferred from basin discharge records, including Yukon, Mackenzie, Ob, Yenisei, and Lena basins. A regional change analysis of the 8-yr AMSR-E record shows no significant trend in pan-Arctic wide Fw, and instead reveals contrasting inundation changes within permafrost zones. Widespread Fw wetting is observed within continuous (92% of grid cells with significant trend show wetting; p < 0.1) and discontinuous (82%) permafrost zones, while areas with sporadic/isolated permafrost show widespread (71%) Fw drying. These results are consistent with previous studies showing evidence of changes in regional surface hydrology influenced by permafrost degradation under recent climate warming. Changes in Fw may also be linked to shifts in regional precipitation patterns and a lengthening non-frozen season. Regional changes observed in the AMSR-E Fw record compliment finer-scale permafrost monitoring efforts and documented variability in surface inundation extent may help constrain pan-Arctic lake and wetland CO2, CH4 emission estimates. This work was supported under the Jet Propulsion Laboratory, California Institute of Technology under contract to the National Aeronautics and Space Administration, NASA Making Earth System Data Records for Use in Research Environments (MEaSUREs) programs.

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.

Structural requirements and reaction pathways in dimethyl ether combustion catalyzed by supported Pt clusters.

PubMed

Ishikawa, Akio; Neurock, Matthew; Iglesia, Enrique

2007-10-31

The identity and reversibility of the elementary steps required for catalytic combustion of dimethyl ether (DME) on Pt clusters were determined by combining isotopic and kinetic analyses with density functional theory estimates of reaction energies and activation barriers to probe the lowest energy paths. Reaction rates are limited by C-H bond activation in DME molecules adsorbed on surfaces of Pt clusters containing chemisorbed oxygen atoms at near-saturation coverages. Reaction energies and activation barriers for C-H bond activation in DME to form methoxymethyl and hydroxyl surface intermediates show that this step is more favorable than the activation of C-O bonds to form two methoxides, consistent with measured rates and kinetic isotope effects. This kinetic preference is driven by the greater stability of the CH3OCH2* and OH* intermediates relative to chemisorbed methoxides. Experimental activation barriers on Pt clusters agree with density functional theory (DFT)-derived barriers on oxygen-covered Pt(111). Measured DME turnover rates increased with increasing DME pressure, but decreased as the O2 pressure increased, because vacancies (*) on Pt surfaces nearly saturated with chemisorbed oxygen are required for DME chemisorption. DFT calculations show that although these surface vacancies are required, higher oxygen coverages lead to lower C-H activation barriers, because the basicity of oxygen adatoms increases with coverage and they become more effective in hydrogen abstraction from DME. Water inhibits reaction rates via quasi-equilibrated adsorption on vacancy sites, consistent with DFT results indicating that water binds more strongly than DME on vacancies. These conclusions are consistent with the measured kinetic response of combustion rates to DME, O2, and H2O, with H/D kinetic isotope effects, and with the absence of isotopic scrambling in reactants containing isotopic mixtures of 18O2-16O2 or 12CH3O12CH3-13CH3O13CH3. Turnover rates increased with Pt cluster size, because small clusters, with more coordinatively unsaturated surface atoms, bind oxygen atoms more strongly than larger clusters and exhibit lower steady-state vacancy concentrations and a consequently smaller number of adsorbed DME intermediates involved in kinetically relevant steps. These effects of cluster size and metal-oxygen bond energies on reactivity are ubiquitous in oxidation reactions requiring vacancies on surfaces nearly saturated with intermediates derived from O2.

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

SFG and SPR Study of Sodium Dodecyl Sulfate Film Assembly on Positively Charged Surfaces

NASA Astrophysics Data System (ADS)

Song, Sanghun; Weidner, Tobias; Wagner, Matthew; Castner, David

2012-02-01

This study uses sum frequency generation (SFG) vibrational spectroscopy and surface plasmon resonance (SPR) sensing to investigate the structure of sodium dodecyl sulfate (SDS) films formed on positively charged and hydrophilic surfaces. The SPR signals show a good surface coverage suggesting that full monolayer coverage is reached at 1 mM. SFG spectra of SDS adsorbed exhibits well resolved CH3 peaks and OH peaks. At both 0.2 mM and 1 mM SDS concentration the intensity of both the CH3 and OH peaks decreased close to background levels. We found that the loss of SFG signal at 0.2 mM occurs at this concentration independent of surface charge density. It is more likely that the loss of signal is related to structural inhomogeneity induced by a striped phase - stand-up phase transition. This is supported by a distinct change of the relative SFG phase between CH3/OH near 0.2 mM. The second intensity minimum might be related to charge compensation effects. We observed a substrate dependence for the high concentration transition. We also observed distinct SFG signal phase changes for water molecules associated with SDS layers at different SDS solution concentrations indicating that the orientation of bound water changed with SDS surface structure.

Measurements and Interpretation of Surface Mixing Ratios of CH4 and CO and δ 13C and δ D of CH4 in Air from Pacific Ocean Transects Between Auckland, New Zealand and Los Angeles, California

NASA Astrophysics Data System (ADS)

Ajie, H. O.; Tyler, S. C.; Gotoh, A. A.; McMillan, A. M.; Rice, A. L.; Lowe, D. C.

2003-12-01

We report on measurements of atmospheric CH4 and CO mixing ratios and δ 13C of CH4 from air samples collected every 2.5 to 5° latitude along a transect over the Pacific Ocean using container ships of P&O Nedlloyd (formerly Blue Star) shipping line. Data presented here begins in June 1996 and extends to January 2002. Scientists from the National Institute of Water and Atmospheric Research in New Zealand and from University of California, Irvine alternate sampling trips so that a transect between Auckland, New Zealand (35° S) and Los Angeles, California (35° N) can be sampled over a period of ˜15 days approximately every four months. Data sets from the two laboratories are intercalibrated through a sample exchange program. The data provide detail on the spatial and seasonal variation of CH4 and CO mixing ratios and stable isotope ratios of CH4 over the Pacific equatorial region, including the Intertropical Convergence Zone (ITCZ) and both northern and southern temperate zones to about 30° latitude, including the South Pacific Convergence Zone (SPCZ). Data from 18 transect samplings so far clearly show that δ 13C in the mid latitudes of both hemispheres are ˜6 months out of phase. In June, a minimum in δ 13C CH4 in the southern hemisphere (SH) coincides approximately with the maximum in the northern hemisphere (NH) seasonal cycle. Because the NH is less enriched in 13C than the SH this situation results in a remarkably flat gradient between 30° N and 30° S. In November the opposite situation occurs with the SH mid latitude maximum coinciding with the minimum in the NH cycle, leading to a relatively large gradient of ˜0.5‰ between the hemispheres. We discuss how CH4 and CO mixing ratios are related to the changing positions and strengths of the ITCZ and SPCZ and how this data can be used in multi-dimensional models of atmospheric chemistry and transport to better define CH4 sources and sinks both temporally and spatially.

Technical note: Comparison of methane ebullition modelling approaches used in terrestrial wetland models

NASA Astrophysics Data System (ADS)

Peltola, Olli; Raivonen, Maarit; Li, Xuefei; Vesala, Timo

2018-02-01

Emission via bubbling, i.e. ebullition, is one of the main methane (CH4) emission pathways from wetlands to the atmosphere. Direct measurement of gas bubble formation, growth and release in the peat-water matrix is challenging and in consequence these processes are relatively unknown and are coarsely represented in current wetland CH4 emission models. In this study we aimed to evaluate three ebullition modelling approaches and their effect on model performance. This was achieved by implementing the three approaches in one process-based CH4 emission model. All the approaches were based on some kind of threshold: either on CH4 pore water concentration (ECT), pressure (EPT) or free-phase gas volume (EBG) threshold. The model was run using 4 years of data from a boreal sedge fen and the results were compared with eddy covariance measurements of CH4 fluxes.

Modelled annual CH4 emissions were largely unaffected by the different ebullition modelling approaches; however, temporal variability in CH4 emissions varied an order of magnitude between the approaches. Hence the ebullition modelling approach drives the temporal variability in modelled CH4 emissions and therefore significantly impacts, for instance, high-frequency (daily scale) model comparison and calibration against measurements. The modelling approach based on the most recent knowledge of the ebullition process (volume threshold, EBG) agreed the best with the measured fluxes (R2 = 0.63) and hence produced the most reasonable results, although there was a scale mismatch between the measurements (ecosystem scale with heterogeneous ebullition locations) and model results (single horizontally homogeneous peat column). The approach should be favoured over the two other more widely used ebullition modelling approaches and researchers are encouraged to implement it into their CH4 emission models.

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.

Tunneling Rate Constants for H2CO+H on Amorphous Solid Water Surfaces

NASA Astrophysics Data System (ADS)

Song, Lei; Kästner, Johannes

2017-12-01

Formaldehyde (H2CO) is one of the most abundant molecules observed in the icy mantle covering interstellar grains. Studying its evolution can contribute to our understanding of the formation of complex organic molecules in various interstellar environments. In this work, we investigated the hydrogenation reactions of H2CO yielding CH3O, CH2OH, and the hydrogen abstraction resulting in H2+HCO on an amorphous solid water (ASW) surface using a quantum mechanics/molecular mechanics (QM/MM) model. The binding energies of H2CO on the ASW surface vary broadly, from 1000 to 9370 K. No correlation was found between binding energies and activation energies of hydrogenation reactions. Combining instanton theory with QM/MM modeling, we calculated rate constants for the Langmuir-Hinshelwood and the Eley-Rideal mechanisms for the three product channels of H+H2CO surface reactions down to 59 K. We found that the channel producing CH2OH can be ignored, owing to its high activation barrier leading to significantly lower rates than the other two channels. The ASW surface influences the reactivity in favor of formation of CH3O (branching ratio ˜80%) and hinders the H2CO dissociation into H2+HCO. In addition, kinetic isotope effects are strong in all reaction channels and vary strongly between the channels. Finally, we provide fits of the rate constants to be used in astrochemical models.

Differentiating biotic from abiotic methane genesis in hydrothermally active planetary surfaces

PubMed Central

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

2012-01-01

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

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

PubMed

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

2012-06-19

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

Coloration and darkening of methane clathrate and other ices by charged particle irradiation - Applications to the outer solar system

NASA Technical Reports Server (NTRS)

Thompson, W. Reid; Murray, B. G. J. P. T.; Khare, B. N.; Sagan, Carl

1987-01-01

The results of laboratory experiments simulating the irradiation of hydrocarbon-H2O or hydrocarbon-H2O/NH3 clathrates by charged particles in the outer solar system are reported. Ices produced by condensing and boiling liquid CH4 on an H2O frost surface at 100 K or by cocondensing frosts from gaseous mixtures were exposed to coronal-discharge electron irradiation at 77 K, and the spectral properties of the irradiated surfaces were determined. Significant darkening of the initially white ices was observed at doses of 1 Gerg/sq cm, corresponding to 8-500 yrs of irradiation by Uranian magnetospheric electrons on the surfaces of the principal Uranian satellites, or to total destruction of CH4 in the upper 1 mm of the satellite surfaces after 0.05-3.0 Myr. It is estimated that 10 m or more of icy satellite or comet surfaces would be radiation-hardened to a CH4-free ice-tholin mixture over 4 Gyr.

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.

Relationship between gas exchange, wind speed, and radar backscatter in a large wind-wave tank

NASA Technical Reports Server (NTRS)

Wanninkhof, Richard H.; Bliven, L. F.

1991-01-01

The relationships between the gas exchange, wind speed, friction velocity, and radar backscatter from the water surface was investigated using data obtained in a large water tank in the Delft (Netherlands) wind-wave tunnel, filled with water supersaturated with SF6, N2O, and CH4. Results indicate that the gas-transfer velocities of these substances were related to the wind speed with a power law dependence. Microwave backscatter from water surface was found to be related to gas transfer velocities by a relationship in the form k(gas) = a 10 exp (b A0), where k is the gas transfer velocity for the particular gas, the values of a and b are obtained from a least squares fit of the average backscatter cross section and gas transfer at 80 m, and A0 is the directional (azimuthal) averaged return.

Dover AFB, Delaware Revised Uniform Summary of Surface Weather Observations (RUSSWO) Parts A-F.

DTIC Science & Technology

1981-10-16

NUMIU OF OSSVATOWS 93C USAFETAC "A0-0-5 (OL-A) PSVIOUS EDITIONS OF THIS ROM ANS OBSOLETE£ AK $ I * LJAL CLIMATOLOLY iRA", CH SURFACE WINDS A .,EATH. R...Mvious IolOns of TmS POW ARE OSSOITI A; 5 C -. .-- ~ .. z.__.4 ,Lu AL CLTMAT0L06Y bRA ’ CH • E SURFACE WINDS Al EATHI-k, SERVICE/MAC PERCENTAGE FREQUENCY...USAFETAC o.e0-5 (OL-A) mvous goiTioNS OF Tis FO@M ASS OBoU TI i I 4A A AL CLTtOTOL0bY 3qA’., CH , ,ETAC SURFACE WINDS A 7 -ATH r< SEPVICE/iAC PERCENTAGE

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.

A first-principles study of CO hydrogenation into methane on molybdenum carbides catalysts

NASA Astrophysics Data System (ADS)

Qi, Ke-Zhen; Wang, Gui-Chang; Zheng, Wen-Jun

2013-08-01

The reaction mechanisms for the CO hydrogenation to produce CH4 on both fcc-Mo2C (100) and hcp-Mo2C (101) surfaces are investigated using density functional theory calculations with the periodic slab model. Through systematic calculations for the mechanisms of the CO hydrogenation on the two surfaces, we found that the reaction mechanisms are the same on both fcc and hcp Mo2C catalysts, that is, CO → HCO → H2CO → H2COH → CH2 → CH3 → CH4. The activation energy of the rate-determining step (CH3 + H → CH4) on fcc-Mo2C (100) (0.84 eV) is lower than that on hcp-Mo2C (101) (1.20 eV), and that is why catalytic activity of fcc-Mo2C is higher than hcp-Mo2C for CO hydrogenation. Our calculated results are consistent with the experimental observations. The activity difference of these two surfaces mainly comes from the co-adsorption energy difference between initial state (IS) and transition state (TS), that is, the co-adsorption energy difference between IS and TS is - 0.04 eV on fcc Mo2C (100), while it is as high as 0.68 eV on hcp Mo2C (101), and thus leading to the lower activation barrier for the reaction of CH3 + H → CH4 on fcc-Mo2C (100) compared to that of hcp-Mo2C (101).

Methane emissions to the atmosphere through aquatic plants

NASA Technical Reports Server (NTRS)

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

1985-01-01

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

Fluxes of CO2, CH4 and N2O at two European beech forests: linking soil gas production profiles with soil and stem fluxes

NASA Astrophysics Data System (ADS)

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

2016-04-01

Soil and plant surfaces are known to exchange greenhouse gases with the atmosphere. Some gases like nitrous oxide (N2O) and methane (CH4) can be produced and re-consumed in different soil depths and soil compartments, so that elevated concentrations of CH4 or N2O in the soil do not necessarily mean a net efflux from the soil into the atmosphere. Soil aeration, and thus the oxygen status can underlay a large spatial variability within the soil on the plot and profile scale, but also within soil aggregates. Thus, conditions suitable for production and consumption of CH4 and N2O can vary on different scales in the soil. Plant surfaces can also emit or take up CH4 and N2O, and these fluxes can significantly contribute to the net ecosystem exchange. Since roots usually have large intercellular spaces or aerenchyma they may represent preferential transport ways for soil gases, linking possibly elevated soil gas concentrations in the subsoil in a "shortcut" to the atmosphere. We tested the hypothesis that the spatial variability of the soil-atmosphere fluxes of CO2, CH4 and N2O is caused by the heterogeneity in soil properties. Therefore, we measured soil-atmosphere gas fluxes, soil gas concentrations and soil diffusivity profiles and did a small scale field assessment of soil profiles on the measurments plots. We further tried to link vertical profiles of soil gas concentrations and diffusivity to derive the production and consumption profiles, and to link these profiles to the stem-atmosphere flux rates of individual trees. Measurements were conducted in two mountain beech forests with different geographical and climatic conditions (White Carpathians, Czech Republic; Black Forest, Germany). Gas fluxes at stem and soil levels were measured simultaneously using static chamber systems and chromatographic and continuous laser analyses. Monitoring simultaneously vertical soil gas profiles allowed to assess the within-soil gas fluxes, and thus to localize the production and consumption sites of soil gases in the adjacent soil. Soils at both sites took up CH4 and N2O and emitted CO2. Soil gas profiles at the Black Forest showed only CH4 and N2O consumption. CH4 uptake was much larger by the well aerated Black Forest soil than by the loamy-clay soil in the White Carpathians. Here, it was possible to stratify the apparently homogenous site into two plots, one having redoximorphic features in the soil profiles, the other plot without. It seemed that CH4 and N2O were mainly produced in the deeper soil at the plot with temporarily reducing conditions. Beech stems mostly took up N2O from the atmosphere at both sites, whereas CH4 was emitted. The stem CH4 flux was higher for the White Carpathians than for the Black Forest site. Thus, the tree and soil flux of CH4 seems to be affected by soil structure, soil water content and the redox potential in the rooting space. We conclude from our results that trees might provide preferential pathways for greenhouse gases produced in the subsoil thereby enhancing the release of greenhouse gases. Acknowledgement This research was financially supported by the Czech Academy of Sciences and the German Academic Exchange Service within the project "Methane (CH4) and nitrous oxide (N2O) emissions from Fagus sylvatica trees" (DAAD-15-03), National Programme for Sustainability I (LO1415) and project DFG (MA 5826/2-1). We would like to thank Marek Jakubik for technical support and Sinikka Paulus for help by field measurements.

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.

C-H and H-H Activation in Transition Metal Complexes and on Surfaces.

DTIC Science & Technology

1983-01-01

IEEIIIIIEEEEI EEEIIEIIIIIII EEIIIEIIIEIII IIIEEEIIEIIII La.𔃻 m41. 12.2 1.4o 12.0 1.25 111.4 11. MICROCOP RE SOO TESTCHAR NATIONA BUREA OfSANAD 16m ~4 OFFICE...ML4 plane, bringing a C-H bond in proximity to the metal. The compounds will minimize M. . C-H re- -27 - pulsion by bringing the H atom into an axial...h) C-H activation has been shown also with organolanthanides and organo- actinide compounds : Watson, P.L. J.Chem.Soc. Chem.Commun. 1983, 176-177

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

PubMed

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

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

[Key pathway of methane production and characteristics of stable carbon isotope of the Tuojia River waterbody.

PubMed

Zhao, Qiang; Lyu, Cheng Wen; Qin, Xiao Bo; Wu, Hong Bao; Wan, Yun Fan; Liao, Yu Lin; Lu, Yan Hong; Wang, Bin; Li, Yong

2018-05-01

This study aimed at exploring the key pathway of methane production and clarifying the composition and distribution of carbon (C) isotopes in the Tuojia River waterbody in Hunan Pro-vince. We estimated CH 4 concentrations and fluxes of four reaches (S 1 , S 2 , S 3 and S 4 ) by a two-layer diffusion model and gas chromatography. The spatial and temporal distribution of CH 4 flux and its relationship with environmental factors were examined. The key pathway of CH 4 production was investigated by stable C isotope method to analyze the distribution characteristics of 13 C isotope (δ 13 C) of water dissolved CH 4 and seston/benthic organic matter. There was significant seasonal variability in water pH, with mean value of (7.27±0.03). The concentration of dissolved oxygen (DO) showed strong seasonal and spatial variations, with the range of 0.43-13.99 mg·L -1 . The maximum value of DO occurred in S 1 and differed significantly in summer and autumin. In addition, DO differed significantly in winter and other seasons in S 2 , S 3 and S 4 . The concentration of dissolved organic carbon (DOC) showed a gradual increasing trend from source to estuary. The highest concentration of DOC (8.32 mg·L -1 ) was found in S 2 , while the lowest was observed in S 1 (0.34 mg·L -1 ). The electrical conductivity (EC) and oxidation-reduction potential (ORP) of water ranged from 17 to 436 μS·cm -1 and from -52.30 to 674.10 mV, respectively, which were significantly different among the four reaches (P＜0.05). Water ammonium nitrogen (NH 4 + -N) and nitrate nitrogen (NO 3 - -N) concentrations were in the ranges of 0.30-1.35 (averaged 0.90±0.10) mg·L -1 and 0.82-2.45 (averaged 1.62±0.16) mg·L -1 , respectively. The dissolved concentration and diffusion flux of CH 4 ranged from 0 to 5.28 μmol·L -1 and from -0.34 to 619.72 μg C·m -2 ·h -1 , respectively, with significant temporal and spatial variations. They showed a similar trend among reaches. Their values were highest in spring, followed by in winter and lowest in summer and autumn. Spatially, the CH 4 concentration and flux followed the order of S 2 >S 3 >S 4 >S 1 . The correlation analysis showed that CH 4 flux was positively correlated with NH 4 + -N and DOC. The pathway of CH 4 production of all reaches was dominated by acetic acid fermentation, while there were obvious differences among the four reaches. The contribution of CH 4 from acetic acid fermentation was greatest (87%) in S 1 , followed by S 4 (81%), S 2 (78%) and S 3 (76%). The mean value of the δ 13 C for dissolved CH 4 , seston organic matter and benthic organic matter was -41.64‰±1.91‰, -14.07‰±1.06‰ and -26.20‰±1.02‰, respectively. There was a positive correlation between the δ 13 C of dissolved CH 4 and benthic organic matter, whereas the δ 13 C value of dissolved CH 4 was negatively correlated with CH 4 flux.

What controls the atmospheric methane seasonal variability over India?

NASA Astrophysics Data System (ADS)

Guha, Tania; Tiwari, Yogesh K.; Valsala, Vinu; Lin, Xin; Ramonet, Michel; Mahajan, Anoop; Datye, Amey; Kumar, K. Ravi

2018-02-01

Atmospheric CH4 observations from two ground-based stations within Indian subcontinent, namely, Sinhagad (SNG) and Cape Rama station (CRI) showed a strong seasonality with a minima (∼1800 ± 20 ppb) during southwest monsoon (SWM; i.e. June-September, JJAS) and a maxima (2000 ± 30 ppb) during northeast monsoon (NEM i.e. December-February, DJF) with a peak-to-peak seasonality close to 200 ppb. The Indian summer (winter) monsoon is characterized with strong southwesterly (northeasterly) winds of oceanic (land) origin at the surface level and strong easterly (westerly) jet streams aloft. The monsoon dynamics has pronounced impact on CH4 variability over India and is analyzed with winds, Lagrangian trajectories, and 3-dimentional distributions of CH4 simulated by a general circulation model. The model simulations suggest a consistent annual vertical structure (mean and sub-seasonal uncertainty) of CH4 over India with a stark contrast in concentration from summer to winter at surface levels (below 750 mb) in confirmation with what is identified by the ground-based observations. During SWM (NEM) the air with comparatively lower (higher) CH4 concentrations from southern (northern) hemisphere reduces the CH4 over India by 1814 ± 26 ppb (enhances by 1950 ± 51 ppb). The contribution of local fluxes to this seasonality appears to be albeit weak as the synthesized CH4 fluxes (from EDGAR dataset) of the Indian peninsula itself show a peak in summer and a dip in winter. Similar property of CH4 is also common to nearby oceanic region (i.e. over Arabian Sea, 1765 ± 10 ppb during summer) suggesting the role of monsoon dynamics as the controlling factor. Further the mixing and convection carries the CH4 to the upper atmosphere and advect inward or outward aloft according the seasonal monsoon dynamics.

Tin(II) alkoxide hydrolysis products for use as base catalysts

DOEpatents

Boyle, Timothy J.

2002-01-01

Tin alkoxide compounds are provided with accessible electrons. The compounds are a polymeric tin alkoxide, [Sn(OCH.sub.2 C(CH.sub.3).sub.3).sub.2 ].sub.n, and the hydrolysis products Sn.sub.6 O.sub.4 (OCH.sub.2 C(CH.sub.3).sub.3).sub.4 and Sn.sub.5 O.sub.2 (OCH.sub.2 C(CH.sub.3).sub.3).sub.6. The hydrolysis products are formed by hydrolyzing the [Sn(OCH.sub.2 C(CH.sub.3).sub.3).sub.2 ].sub.n in a solvent with controlled amounts of water, between 0.1 and 2 moles of water per mole of the polymeric tin alkoxide.

Growing season CH4 and N2O fluxes from a subarctic landscape in northern Finland; from chamber to landscape scale

NASA Astrophysics Data System (ADS)

Dinsmore, Kerry J.; Drewer, Julia; Levy, Peter E.; George, Charles; Lohila, Annalea; Aurela, Mika; Skiba, Ute M.

2017-02-01

Subarctic and boreal emissions of CH4 are important contributors to the atmospheric greenhouse gas (GHG) balance and subsequently the global radiative forcing. Whilst N2O emissions may be lower, the much greater radiative forcing they produce justifies their inclusion in GHG studies. In addition to the quantification of flux magnitude, it is essential that we understand the drivers of emissions to be able to accurately predict climate-driven changes and potential feedback mechanisms. Hence this study aims to increase our understanding of what drives fluxes of CH4 and N2O in a subarctic forest/wetland landscape during peak summer conditions and into the shoulder season, exploring both spatial and temporal variability, and uses satellite-derived spectral data to extrapolate from chamber-scale fluxes to a 2 km × 2 km landscape area.From static chamber measurements made during summer and autumn campaigns in 2012 in the Sodankylä region of northern Finland, we concluded that wetlands represent a significant source of CH4 (3.35 ± 0.44 mg C m-2 h-1 during the summer campaign and 0.62 ± 0.09 mg C m-2 h-1 during the autumn campaign), whilst the surrounding forests represent a small sink (-0.06 ± < 0.01 mg C m-2 h-1 during the summer campaign and -0.03 ± < 0.01 mg C m-2 h-1 during the autumn campaign). N2O fluxes were near-zero across both ecosystems.We found a weak negative relationship between CH4 emissions and water table depth in the wetland, with emissions decreasing as the water table approached and flooded the soil surface and a positive relationship between CH4 emissions and the presence of Sphagnum mosses. Temperature was also an important driver of CH4 with emissions increasing to a peak at approximately 12 °C. Little could be determined about the drivers of N2O emissions given the small magnitude of the fluxes.A multiple regression modelling approach was used to describe CH4 emissions based on spectral data from PLEIADES PA1 satellite imagery across a 2 km × 2 km landscape. When applied across the whole image domain we calculated a CH4 source of 2.05 ± 0.61 mg C m-2 h-1. This was significantly higher than landscape estimates based on either a simple mean or weighted by forest/wetland proportion (0.99 ± 0.16, 0.93 ± 0.12 mg C m-2 h-1, respectively). Hence we conclude that ignoring the detailed spatial variability in CH4 emissions within a landscape leads to a potentially significant underestimation of landscape-scale fluxes. Given the small magnitude of measured N2O fluxes a similar level of detailed upscaling was not needed; we conclude that N2O fluxes do not currently comprise an important component of the landscape-scale GHG budget at this site.

Resolving Some Paradoxes in the Thermal Decomposition Mechanism of Acetaldehyde

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

Sivaramakrishnan, Raghu; Michael, Joe V.; Harding, Lawrence B.

2015-07-16

The mechanism for the thermal decomposition of acetaldehyde has been revisited with an analysis of literature kinetics experiments using theoretical kinetics. The present modeling study was motivated by recent observations, with very sensitive diagnostics, of some unexpected products in high temperature micro-tubular reactor experiments on the thermal decomposition of CH3CHO and its deuterated analogs, CH3CDO, CD3CHO, and CD3CDO. The observations of these products prompted the authors of these studies to suggest that the enol tautomer, CH2CHOH (vinyl alcohol), is a primary intermediate in the thermal decomposition of acetaldehyde. The present modeling efforts on acetaldehyde decomposition incorporate a master equation re-analysismore » of the CH3CHO potential energy surface (PES). The lowest energy process on this PES is an isomerization of CH3CHO to CH2CHOH. However, the subsequent product channels for CH2CHOH are substantially higher in energy, and the only unimolecular process that can be thermally accessed is a re-isomerization to CH3CHO. The incorporation of these new theoretical kinetics predictions into models for selected literature experiments on CH3CHO thermal decomposition confirms our earlier experiment and theory based conclusions that the dominant decomposition process in CH3CHO at high temperatures is C-C bond fission with a minor contribution (~10-20%) from the roaming mechanism to form CH4 and CO. The present modeling efforts also incorporate a master-equation analysis of the H + CH2CHOH potential energy surface. This bimolecular reaction is the primary mechanism for removal of CH2CHOH, which can accumulate to minor amounts at high temperatures, T > 1000 K, in most lab-scale experiments that use large initial concentrations of CH3CHO. Our modeling efforts indicate that the observation of ketene, water and acetylene in the recent micro-tubular experiments are primarily due to bimolecular reactions of CH3CHO and CH2CHOH with H-atoms, and have no bearing on the unimolecular decomposition mechanism of CH3CHO. The present simulations also indicate that experiments using these micro-tubular reactors when interpreted with the aid of high-level theoretical calculations and kinetics modeling can offer insights into the chemistry of elusive intermediates in high temperature pyrolysis of organic molecules.« less

Stoichiometry and temperature sensitivity of methanogenesis and CO2 production from saturated polygonal tundra in Barrow, Alaska.

PubMed

Roy Chowdhury, Taniya; Herndon, Elizabeth M; Phelps, Tommy J; Elias, Dwayne A; Gu, Baohua; Liang, Liyuan; Wullschleger, Stan D; Graham, David E

2015-02-01

Arctic permafrost ecosystems store ~50% of global belowground carbon (C) that is vulnerable to increased microbial degradation with warmer active layer temperatures and thawing of the near surface permafrost. We used anoxic laboratory incubations to estimate anaerobic CO2 production and methanogenesis in active layer (organic and mineral soil horizons) and permafrost samples from center, ridge and trough positions of water-saturated low-centered polygon in Barrow Environmental Observatory, Barrow AK, USA. Methane (CH4 ) and CO2 production rates and concentrations were determined at -2, +4, or +8 °C for 60 day incubation period. Temporal dynamics of CO2 production and methanogenesis at -2 °C showed evidence of fundamentally different mechanisms of substrate limitation and inhibited microbial growth at soil water freezing points compared to warmer temperatures. Nonlinear regression better modeled the initial rates and estimates of Q10 values for CO2 that showed higher sensitivity in the organic-rich soils of polygon center and trough than the relatively drier ridge soils. Methanogenesis generally exhibited a lag phase in the mineral soils that was significantly longer at -2 °C in all horizons. Such discontinuity in CH4 production between -2 °C and the elevated temperatures (+4 and +8 °C) indicated the insufficient representation of methanogenesis on the basis of Q10 values estimated from both linear and nonlinear models. Production rates for both CH4 and CO2 were substantially higher in organic horizons (20% to 40% wt. C) at all temperatures relative to mineral horizons (<20% wt. C). Permafrost horizon (~12% wt. C) produced ~5-fold less CO2 than the active layer and negligible CH4 . High concentrations of initial exchangeable Fe(II) and increasing accumulation rates signified the role of iron as terminal electron acceptors for anaerobic C degradation in the mineral horizons. Published 2014. This article is a U.S. Government work and is in the public domain in the USA.

Stoichiometry and temperature sensitivity of methanogenesis and CO 2 production from saturated polygonal tundra in Barrow, Alaska

DOE PAGES

Roy Chowdhury, Taniya; Herndon, Elizabeth M.; Phelps, Tommy J.; ...

2014-11-26

Arctic permafrost ecosystems store ~50% of global belowground carbon (C) that is vulnerable to increased microbial degradation with warmer active layer temperatures and thawing of the near surface permafrost. We used anoxic laboratory incubations to estimate anaerobic CO2 production and methanogenesis in active layer (organic and mineral soil horizons) and permafrost samples from center, ridge and trough positions of water-saturated low-centered polygon in Barrow Environmental Observatory, Barrow AK, USA. Methane (CH4) and CO2 production rates and concentrations were determined at 2, +4, or +8 C for 60 day incubation period. Temporal dynamics of CO2 production and methanogenesis at 2 Cmore » showed evidence of fundamentally different mechanisms of substrate limitation and inhibited microbial growth at soil water freezing points compared to warmer temperatures. Nonlinear regression better modeled the initial rates and estimates of Q10 values for CO2 that showed higher sensitivity in the organic-rich soils of polygon center and trough than the relatively drier ridge soils. Methanogenesis generally exhibited a lag phase in the mineral soils that was significantly longer at 2 C in all horizons. Such discontinuity in CH4 production between 2 C and the elevated temperatures (+4 and +8 C) indicated the insufficient representation of methanogenesis on the basis of Q10 values estimated from both linear and nonlinear models. Production rates for both CH4 and CO2 were substantially higher in organic horizons (20% to 40% wt. C) at all temperatures relative to mineral horizons (<20% wt. C). Permafrost horizon (~12% wt. C) produced ~5-fold less CO2 than the active layer and negligible CH4. High concentrations of initial exchangeable Fe(II) and increasing accumulation rates signified the role of iron as terminal electron acceptors for anaerobic C degradation in the mineral horizons.« less

Impact Delivery of Reduced Greenhouse Gases on Early MARS

NASA Technical Reports Server (NTRS)

Haberle, R. M.; Zahnle, K.

2017-01-01

While there is abundant evidence for flowing liquid water on the ancient Martian surface, a widely accepted greenhouse mechanism for explaining this in the presence of a faint young sun has yet to emerge. Gases such as NH3, CO2 alone, SO2, clouds, and CH4, have sustainability issues or limited greenhouse power. Recently, Ramirez et al. proposed that CO2-H2 atmospheres, through collision induced absorptions (CIA), could solve the problem if large amounts are present (1.3-4 bars of CO2, 50-20% H2). However, they had to estimate the strength of the H2- CO2 interaction from the measured strength of the H2- N2 interaction. Recent ab initio calculations show that the strength of CO2-H2 CIA is greater than Ramirez et al. assumed. Wordsworth et al. also calculated the absorption coefficients for CO2-CH4 CIA and show that on early Mars a 0.5 bar CO2 atmosphere with percent levels of H2 or CH4 can raise mean annual temperatures by tens of degrees Kelvin. Freezing temperatures can be reached in atmospheres containing 1-2 bars of CO2 and 2-10% H2 and CH4. The new work demonstrates that less CO2 and reduced gases are needed than Ramirez et al. originally proposed, which improves prospects for their hypothesis. If thick weakly reducing atmospheres are the solution to the faint young sun paradox, then plausible mechanisms must be found to generate and sustain the required concentrations of H2 and CH4. Possible sources of reducing gases include volcanic outgassing, serpentinization, and impact delivery; sinks include photolysis, oxidation, and hydrogen escape. The viability of the reduced greenhouse hypothesis depends, therefore, on the strength of these sources and sinks.

First-principles calculation of adsorption of shale gas on CaCO3 (100) surfaces.

PubMed

Luo, Qiang; Pan, Yikun; Guo, Ping; Wang, Zhouhua; Wei, Na; Sun, Pengfei; Liu, Yuxiao

2017-06-16

To demonstrate the adsorption strength of shale gas to calcium carbonate in shale matrix, the adsorption of shale gas on CaCO3 (100) surfaces was studied using the first-principles method, which is based on the density functional theory (DFT). The structures and electronic properties of CH4, C2H6, CO2 and N2 molecules were calculated by the generalized gradient approximation (GGA), for a coverage of 1 monolayer (ML). Under the same conditions, the density of states (DOS) of CaCO3 (100) surfaces before and after the adsorption of shale gas molecules at high-symmetry adsorption sites were compared. The results showed that the adsorption energies of CH4, C2H6, CO2 and N2 on CaCO3 (100) surfaces were between 0.2683 eV and -0.7388 eV. When a CH4 molecule was adsorbed at a hollow site and its 2 hydrogen atoms were parallel to the long diagonal (H3) on the CaCO3 (100) surface, it had the most stable adsorption, and the adsorption energy was only -0.4160 eV. The change of adsorption energy of CH4 was no more than 0.0535 eV. Compared with the DOS distribution of CH4 before adsorption, it shifted to the left overall after adsorption. At the same time, the partial density of states (PDOS) curves of CaCO3 (100) surfaces before and after adsorption basically overlapped. This work showed that the adsorption effect of shale gas on calcium carbonate is very weak, and the adsorption is physisorption at the molecular level.

The Drivers of the CH4 Seasonal Cycle in the Arctic and What Long-Term Observations of CH4 Imply About Trends in Arctic CH4 Fluxes

NASA Astrophysics Data System (ADS)

Sweeney, C.; Karion, A.; Bruhwiler, L.; Miller, J. B.; Wofsy, S. C.; Miller, C. E.; Chang, R. Y.; Dlugokencky, E. J.; Daube, B.; Pittman, J. V.; Dinardo, S. J.

2012-12-01

The large seasonal change in the atmospheric column for CH4 in the Arctic is driven by two dominant processes: transport of CH4 from low latitudes and surface emissions throughout the Arctic region. The NOAA ESRL Carbon Cycle Group Aircraft Program along with the NASA funded Carbon in Arctic Reservoirs Vulnerability Experiment (CARVE) have initiated an effort to better understand the factors controlling the seasonal changes in the mole fraction of CH4 in the Arctic with a multi-scale aircraft observing network in Alaska. The backbone of this network is multi-species flask sampling from 500 to 8000 masl that has been conducted every two weeks for the last 10 years over Poker Flat, AK. In addition regular profiles at the interior Alaska site at Poker Flat, NOAA has teamed up with the United States Coast Guard to make profiling flights with continuous observations of CO2, CO, CH4 and Ozone between Kodiak and Barrow every 2 weeks. More recently, CARVE has significantly added to this observational network with targeted flights focused on exploring the variability of CO2, CH4 and CO in the boundary layer both in the interior and the North Slope regions of Alaska. Taken together with the profiling of HIAPER Pole-to-Pole Observations (HIPPO), ground sites at Barrow and a new CARVE interior Alaska surface site just north of Fairbanks, AK, we now have the ability to investigate the full evolution of the seasonal cycle in the Arctic using both the multi-scale sampling offered by the different aircraft platforms as well as the multi-species sampling offered by in-situ and flask sampling. The flasks also provide a valuable tie-point between different platforms so that spatial and temporal gradients can be properly interpreted. In the context of the seasonal cycle observed by the aircraft platforms we will look at long term ground observations over the last 20 years to assess changes in Arctic CH4 emissions which have occurred as a result of 0.6C/decade changes in mean surface temperatures.

Effect of ocean acidification and elevated fCO2 on trace gas production by a Baltic Sea summer phytoplankton community

NASA Astrophysics Data System (ADS)

Webb, Alison L.; Leedham-Elvidge, Emma; Hughes, Claire; Hopkins, Frances E.; Malin, Gill; Bach, Lennart T.; Schulz, Kai; Crawfurd, Kate; Brussaard, Corina P. D.; Stuhr, Annegret; Riebesell, Ulf; Liss, Peter S.

2016-08-01

The Baltic Sea is a unique environment as the largest body of brackish water in the world. Acidification of the surface oceans due to absorption of anthropogenic CO2 emissions is an additional stressor facing the pelagic community of the already challenging Baltic Sea. To investigate its impact on trace gas biogeochemistry, a large-scale mesocosm experiment was performed off Tvärminne Research Station, Finland, in summer 2012. During the second half of the experiment, dimethylsulfide (DMS) concentrations in the highest-fCO2 mesocosms (1075-1333 µatm) were 34 % lower than at ambient CO2 (350 µatm). However, the net production (as measured by concentration change) of seven halocarbons analysed was not significantly affected by even the highest CO2 levels after 5 weeks' exposure. Methyl iodide (CH3I) and diiodomethane (CH2I2) showed 15 and 57 % increases in mean mesocosm concentration (3.8 ± 0.6 increasing to 4.3 ± 0.4 pmol L-1 and 87.4 ± 14.9 increasing to 134.4 ± 24.1 pmol L-1 respectively) during Phase II of the experiment, which were unrelated to CO2 and corresponded to 30 % lower Chl a concentrations compared to Phase I. No other iodocarbons increased or showed a peak, with mean chloroiodomethane (CH2ClI) concentrations measured at 5.3 (±0.9) pmol L-1 and iodoethane (C2H5I) at 0.5 (±0.1) pmol L-1. Of the concentrations of bromoform (CHBr3; mean 88.1 ± 13.2 pmol L-1), dibromomethane (CH2Br2; mean 5.3 ± 0.8 pmol L-1), and dibromochloromethane (CHBr2Cl, mean 3.0 ± 0.5 pmol L-1), only CH2Br2 showed a decrease of 17 % between Phases I and II, with CHBr3 and CHBr2Cl showing similar mean concentrations in both phases. Outside the mesocosms, an upwelling event was responsible for bringing colder, high-CO2, low-pH water to the surface starting on day t16 of the experiment; this variable CO2 system with frequent upwelling events implies that the community of the Baltic Sea is acclimated to regular significant declines in pH caused by up to 800 µatm fCO2. After this upwelling, DMS concentrations declined, but halocarbon concentrations remained similar or increased compared to measurements prior to the change in conditions. Based on our findings, with future acidification of Baltic Sea waters, biogenic halocarbon emissions are likely to remain at similar values to today; however, emissions of biogenic sulfur could significantly decrease in this region.

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

Smalley, John F.

In this study, we demonstrate how small and rapid temperature perturbations (produced by the indirect laser-induced temperature jump (ILIT) technique) of solid metal electrode|electrolyte solution interfaces may be used to determine the potential of zero (total) charge (E pzc) and its temperature derivativemore » $$\\left(\\frac{dEpzc}{dT}\\right)$$ of Au(111) electrode surfaces modified by alkanethiol self-assembled monolayers in contact with high ionic strength (i.e., 1.0 M) aqueous electrolyte solutions. The E pzc’s measured for two different types of SAMs (made from either HS(CH 2) n-1CH 3 (5 ≤ n ≤ 12, E pzc = -(0.99 ± 0.12) V vs SSCE) or HS(CH 2) nOH (3 ≤ n ≤ 16, E pzc = (0.46 ± 0.22) V vs SSCE)) are considerably different than those measured previously at much lower electrolyte solution ionic strengths. For mixed monolayers made from both HS(CH 2) n-1CH 3 and HS(CH 2) nFc (where Fc refers to ferrocene), the difference in Epzc decreases as a function of the surface concentration of the Fc moiety (i.e., [Fc]), and it completely disappears at a surprisingly small [Fc] (~4.0 × 10 –11 mol cm –2). These observations for the Au(111)|hydrophobic (neat and mixed) SAM|aqueous electrolyte solution interfaces, along with the surface potentials (g Sml(dip)) evaluated for the contacting electrolyte solution surfaces of these interfaces, are consistent with a structure for the water molecule components of these surfaces where there is a net orientation of the dipoles of these molecules. Accordingly, the negative (oxygen) ends of these molecules point toward the SAM surface. The positive values of g Sml(dip) evaluated for hydrophilic SAM (e.g., made from HS(CH 2) nOH)|aqueous electrolyte solution interfaces) also indicate that the structure of these interfaces is similar to that of the hydrophobic interfaces. However, g Sml(dip) decreases with increasing ionic strength for the hydrophilic interfaces, while it increases with increasing ionic strength for the hydrophobic interfaces. The data (and calculations) reported in the present work and other studies of hydrophobic (and hydrophilic)|aqueous solution interfaces are as yet insufficient to support a complete explanation for the effects of ionic strength observed in the present study. Nevertheless, an analysis based upon the value of $$\\left(\\frac{dEpzc}{dT}\\right)$$ (= (0.51 ± 0.12) mV/K, essentially the same for SAMs made from both HS(CH 2) n-1CH 3 and HS(CH 2) nOH), determined in the present study provides a further indication that upon formation of the SAM there is a partial charge transfer of electrons from the relevant gold atoms on the Au(111) surface to the sulfur atoms of the alkanethiols.« less