Global methane emissions from terrestrial plants

Recent measurements suggest that the terrestrial plant community may be an important source of methane with global contributions between 62 and 236 Tg CH4 y(-1). If true, terrestrial plants could rival wetlands as being the largest global source of methane forcing us to rethink the methane budget. While further measurements are needed to confirm the methane release rates from this source and their dependencies, in this work we use the preliminary measurements to assess the potential impact of the methane release from this source globally. Using novel techniques we extrapolate the initially reported chamber measurements to the global scale and calculate the global methane emissions from the terrestrial plant community to be in the range 20 to 69 Tg CH4 y(-1). The spread in emissions is largely due to the sensitivity of the global flux to the prescribed temperature dependence of the plant emission rate, which is largely unknown. The spread of calculated emissions is in good agreement with the upper limit imposed on the source during the late pre-industrial period, which we estimate to range from 25 to 54 Tg CH4 y(-1) during the years 0 to 1700 A.D. using the published atmospheric delta13CH4 record. In addition, if we assume that plant emissions have been constant at the mean value of 45 Tg CH4 y(-1), we find that the methane release from wildfires and biomass burning during the pre-industrial span 0-1000 A.D. must be near 12 Tg CH4 y(-1), which would be in better agreement with previous estimates of the pyrogenic source during this time than a methane budget missing the plant source. We conclude that methane release from the terrestrial plant community as presently understood does not require major innovations to the global methane budget.     

Methane emissions from vehicles

Methane (CH4) is an important greenhouse gas emitted by vehicles. We report results of a laboratory study of methane emissions using a standard driving cycle for 30 different cars and trucks (1995-1999 model years) from four different manufacturers. We recommend the use of an average emission factor for the U.S. on-road vehicle fleet of (g of CH/g of CO2) = (15 +/- 4) x 10(-5) and estimate that the global vehicle fleet emits 0.45 +/- 0.12 Tg of CH4 yr(-1) (0.34 +/- 0.09 Tg of C yr(-1)), which represents < 0.2% of anthropogenic CH4 emissions. This estimate includes the effects of vehicle aging, cold start, and hot running emissions. The contribution of CH4 emissions from vehicles to radiative forcing of climate change is 0.3-0.4% of that of CO2 emissions from vehicles. The environmental impact of CH4 emissions from vehicles is negligible and is likely to remain so for the foreseeable future.     

Evaluation of a biologically active cover for mitigation of landfill gas emissions

Landfills are the third largest source of anthropogenic CH4 in the United States, and there is potential for reduction in this source of greenhouse gases and other contaminants. The objective of this work was to contrast emissions of CH4 and non-methane organic compounds (NMOCs) from landfill cells covered with soil or a biologically active cover consisting of yard waste compost. On the basis of four field campaigns over 14 months, CH4 emissions from the biocover (BC) varied from -1.73 to 1.33 g m(-2) d(-1), with atmospheric uptake measured in 52% of tests. BC emissions did not increase when the gas collection system was turned off. Uptake of atmospheric CH4 was measured in 54% of tests on the soil cover (SC) when the gas collection was system active and 12% when the gas collection system was off. Many (26%) relatively high fluxes (>15 g m(-2) d(-1)) were measured from the SC as were some dramatic effects due to deactivation of the gas collection system. In tests with positive emissions, stable isotope measurements showed that the BC and SC were responsible for oxidation of 55% and 21% of the CH4 reaching the bottom of the respective cover. Seven of the highest 10 NMOC emissions were measured in the SC, and 17 of 21 fluxes for speciated organic compounds were higher in the SC. The relationship between CH4, NMOC, and individual organic compound emissions suggested a correlation between CH4 and trace organic oxidation. BCs can reduce landfill gas emissions in the absence of a gas collection system and can serve as a polishing step in the presence of an active system.     

Spatial heterogeneity of methane ebullition in a large tropical reservoir

Tropical reservoirs have been identified as important methane (CH(4)) sources to the atmosphere, primarily through turbine and downstream degassing. However, the importance of ebullition (gas bubbling) remains unclear. We hypothesized that ebullition is a disproportionately large CH(4) source from reservoirs with dendritic littoral zones because of ebullition hot spots occurring where rivers supply allochthonous organic material. We explored this hypothesis in Lake Kariba (Zambia/Zimbabwe; surface area >5000 km(2)) by surveying ebullition in bays with and without river inputs using an echosounder and traditional surface chambers. The two techniques yielded similar results, and revealed substantially higher fluxes in river deltas (～10(3) mg CH(4) m(-2) d(-1)) compared to nonriver bays (<100 mg CH(4) m(-2) d(-1)). Hydroacoustic measurements resolved at 5 m intervals showed that flux events varied over several orders of magnitude (up to 10(5) mg CH(4) m(-2) d(-1)), and also identified strong differences in ebullition frequency. Both factors contributed to emission differences between all sites. A CH(4) mass balance for the deepest basin of Lake Kariba indicated that hot spot ebullition was the largest atmospheric emission pathway, suggesting that future greenhouse gas budgets for tropical reservoirs should include a spatially well-resolved analysis of ebullition hot spots.     

Life-cycle greenhouse gas emissions of shale gas, natural gas, coal, and petroleum

The technologies and practices that have enabled the recent boom in shale gas production have also brought attention to the environmental impacts of its use. It has been debated whether the fugitive methane emissions during natural gas production and transmission outweigh the lower carbon dioxide emissions during combustion when compared to coal and petroleum. Using the current state of knowledge of methane emissions from shale gas, conventional natural gas, coal, and petroleum, we estimated up-to-date life-cycle greenhouse gas emissions. In addition, we developed distribution functions for key parameters in each pathway to examine uncertainty and identify data gaps such as methane emissions from shale gas well completions and conventional natural gas liquid unloadings that need to be further addressed. Our base case results show that shale gas life-cycle emissions are 6% lower than conventional natural gas, 23% lower than gasoline, and 33% lower than coal. However, the range in values for shale and conventional gas overlap, so there is a statistical uncertainty whether shale gas emissions are indeed lower than conventional gas. Moreover, this life-cycle analysis, among other work in this area, provides insight on critical stages that the natural gas industry and government agencies can work together on to reduce the greenhouse gas footprint of natural gas.     

Biofiltration for mitigation of methane emission from animal husbandry

Removal of methane from exhaust air of animal houses and manure storage has a large potential for the reduction of greenhouse gas emissions from animal husbandry. The aim of this study was to design a biofilter for methane removal at a full-scale livestock production facility. Air from the headspace of a covered 6 m3 liquid manure storage (air flow: 0.75-8.5 m3 m(-3) h(-1); CH4: 500-5500 mg m(-3)) was treated in an experimental biofilter (160 L). The filterbed, a mixture of compost and perlite in a 40:60 (v/v) ratio, was inoculated with activated sludge that had shown a good methane oxidation rate as compared to pure cultures in preceding laboratory tests. Methane removal up to 85% could be achieved in the experimental biofilter. The methane removal (g m(-3) h(-1)) appeared to be proportional to the concentration (g m(-3)) with k = 2.5 h(-1). Relatively low methane concentrations and high air flows, as reported for the exhaust air of animal houses, would require very large biofilter sizes. Extrapolation of the results showed that treatment of air from a 1000 m3 liquid manure storage with a methane concentration of 22 g m(-3) would require a 20 m3 biofilter for a desired emission reduction of 50%. The costs for such a biofilter are USD 26 per t of CO2 equiv reduction.     

Linking soil O2, CO2, and CH4 concentrations in a Wetland soil: implications for CO2 and CH4 fluxes

Oxygen (O(2)) availability and diffusivity in wetlands are controlling factors for the production and consumption of both carbon dioxide (CO(2)) and methane (CH(4)) in the subsoil and thereby potential emission of these greenhouse gases to the atmosphere. To examine the linkage between high-resolution spatiotemporal trends in O(2) availability and CH(4)/CO(2) dynamics in situ, we compare high-resolution subsurface O(2) concentrations, weekly measurements of subsurface CH(4)/CO(2) concentrations and near continuous flux measurements of CO(2) and CH(4). Detailed 2-D distributions of O(2) concentrations and depth-profiles of CO(2) and CH(4) were measured in the laboratory during flooding of soil columns using a combination of planar O(2) optodes and membrane inlet mass spectrometry. Microsensors were used to assess apparent diffusivity under both field and laboratory conditions. Gas concentration profiles were analyzed with a diffusion-reaction model for quantifying production/consumption profiles of O(2), CO(2), and CH(4). In drained conditions, O(2) consumption exceeded CO(2) production, indicating CO(2) dissolution in the remaining water-filled pockets. CH(4) emissions were negligible when the oxic zone was >40 cm and CH(4) was presumably consumed below the depth of detectable O(2). In flooded conditions, O(2) was transported by other mechanisms than simple diffusion in the aqueous phase. This work demonstrates the importance of changes in near-surface apparent diffusivity, microscale O(2) dynamics, as well as gas transport via aerenchymous plants tissue on soil gas dynamics and greenhouse gas emissions following marked changes in water level.     

Comparative oxidation and net emissions of methane and selected non-methane organic compounds in landfill cover soils

The surface emissions of methane (CH4) and non-methane organic compounds (NMOCs) were determined at two different areas at a French landfill: a permanently covered and fully vegetated area (40 cm coarse sand + 80 cm of loam) and a temporarily covered area (40 cm of coarse sand). The 37 NMOCs quantified in the landfill gas samples included alkanes (C1-C10), alkenes (C1-C4), halogenated hydrocarbons (including (H)CFCs), and aromatic hydrocarbons. Both positive and negative CH4 fluxes ranging from -0.01 to 0.008 g m(-2) d(-1) were measured from the permanently covered cell. However, high spatial variation was observed, and a hot spot with a high flux (10 g m(-2) d(-1)) was identified. A higher CH4 emission occurred from the temporarily covered cell (CH4 flux of 49.9 g m(-2) d(-1)) as compared to the permanently covered cell. The NMOC fluxes from the permanently covered zone were all very small with both positive and negative fluxes in the order of 10(-7) to 10(-5) g m(-2) d(-1). Higher and mainly positive NMOC fluxes in the order of 10(-5) to 10(-4) g m(-2) d(-1) were obtained from the temporarily covered zone. The lower emission from the permanently covered and fully vegetated cell was attributable to the thicker soil layer, which functions as microbial habitat for methanotrophic bacteria. The NMOC oxidation capacity was investigated in soil microcosms incubated with CH4. Maximal oxidation rates for the halogenated aliphatic compounds varied between 0.06 and 8.56 microg (g of soil)(-1) d(-1). Fully substituted hydrocarbons (tetrachloromethane, perchloroethylene, CFC-11, CFC-12, and CFC-113) were not degraded in the presence of CH4 and O2. Benzene and toluene were rapidly degraded, giving very high maximal oxidation rates (28 and 39 microg (g of soil)(-1) d(-1)). On the basis of the emission measurements and the batch experiments conducted, a general pattern was observed between emissions and biodegradability of various NMOCs. The emissions mainly consisted of compounds that were not degradable or slowly degradable, while an uptake of easily degradable compounds was registered. As an example, perchloroethylene, trichloromethane, CFC-11, and CFC-12 were emitted, while atmospheric consumption of aromatic hydrocarbons and lower chlorinated hydrocarbons such as vinyl chloride, dichloromethane, and chloromethane was observed. This study demonstrates that landfill soil covers show a significant potential for CH4 oxidation and co-oxidation of NMOCs. Under certain conditions, landfills may even function as sinks for CH4 and selected NMOCs, like aromatic hydrocarbons and lower chlorinated compounds.     

Micrometeorological measurements of methane and carbon dioxide fluxes at a municipal landfill

Continuous and area-integrating monitoring of methane (CH4) and carbon dioxide (CO2) emissions was performed for 6 and 9 months, respectively, at a municipal landfill in Finland with the micrometeorological eddy covariance (EC) method. The mean CH4 emission from June to December was 0.53 mg m(-2) s(-1), while the CO2 emission between February and December averaged 1.78 mg m(-2) s(-1). The CH4 emissions from the summit area of the landfill, where active waste deposition was going on, were 1.7 times as high as from the slope area with a better surface cover. The variation in emissions over the source area of the measurement was high. Significant seasonal variation, linked to air and soil temperature, was only seen in the CO2 release rates. Results obtained with the EC method were comparable to those measured with closed static chambers. According to the EC measurements, the gas recovery system decreased CH4 fluxes by 69-79%. The ratio of the measured CH4 and CO2 emissions roughly indicated the route of the landfill gas emission, resembling the ratio of the gases measured in the gas wells (1.24) when the emission originated from the area with no oxidizing cover layer and being smaller when CH4 oxidation had taken place.     

Atmospheric trends and radiative forcings of CF4 and C2F6 inferred from firn air

The atmospheric histories of two potent greenhouse gases, tetrafluoromethane (CF4) and hexafluoroethane (C2F6), have been reconstructed for the 20th century based on firn air measurements from both hemispheres. The reconstructed atmospheric trends show that the mixing ratios of both CF4 and C2F6 have increased during the 20th century by factors of approximately 2 and approximately 10, respectively. Initially, the increasing mixing ratios coincided with the rise in primary aluminum production. However, a slower atmospheric growth rate for CF4 appears to be evident during the 1990s, which supports recent aluminum industry reports of reduced CF4 emissions. This work illustrates the changing relationship between CF4 and C2F6 that is likely to be largely the result of both reduced emissions from the aluminum industry and faster growing emissions of C2F6 from the semiconductor industry. Measurements of C2F6 in the older firn air indicate a natural background mixing ratio of <0.3 parts per trillion (ppt), demonstrating that natural sources of this gas are negligible. However, CF4 was deduced to have a preindustrial mixing ratio of 34 -1 ppt (-50% of contemporary levels). This is in good agreement with the previous work of Harnisch et al. (18) and provides independent confirmation of their results. As a result of the large global warming potentials of CF4 and C2F6, these results have important implications for radiative forcing calculations. The radiative forcings of CF4 and C2F6 are shown to have increased over the past 50 years to values in 2001 of 4.1 x 10(-3) Wm(-2) and 7.5 x 10(-4) Wm(-2), respectively, relative to preindustrial concentrations. These forcings are small compared to present day forcings due to the major greenhouse gases but, if the current trends continue, they will continue to increase since both gases have essentially infinite lifetimes. There is, therefore, a large incentive to reduce perfluorocarbon emissions such that through the implementation of the Kyoto Protocol, the atmospheric growth rates may decline in the future.     

Atmospheric chemistry of perfluoroalkanesulfonamides: kinetic and product studies of the OH radical and Cl atom initiated oxidation of N-ethyl perfluorobutanesulfonamide

Perfluorooctanesulfonamides [C8F17SO2N(R1)(R2)] are present in the atmosphere and may, via atmospheric transport and oxidation, contribute to perfluorocarboxylates (PFCA) and perfluorooctanesulfonate (PFOS) pollution in remote locations. Smog chamber experiments with the perfluorobutanesulfonyl analogue N-ethyl perfluorobutanesulfonamide [NEtFBSA; C4F9SO2N(H)CH2CH3] were performed to assess this possibility. By use of relative rate methods, rate constants for reactions of NEtFBSA with chlorine atoms (296 K) and OH radicals (301 K) were determined to be kCL) = (8.37 +/- 1.44) x 10(-12) and kOH = (3.74 +/- 0.77) x 10(-13) cm3 molecule(-1) s(-1), indicating OH reactions will be dominant in the troposphere. Simple modeling exercises suggestthat reaction with OH radicals will dominate removal of perfluoroalkanesulfonamides from the gas phase (wet and dry deposition will not be important) and that the atmospheric lifetime of NEtFBSA in the gas phase will be 20-50 days, thus allowing substantial long-range atmospheric transport. Liquid chromatography/tandem mass spectrometry (LC/MS/MS) analysis showed that the primary products of chlorine atom initiated oxidation were the ketone C4F9SO2N(H)COCH3; aldehyde 1, C4F9SO2N(H)CH2CHO; and a product identified as C4F9SO2N(C2H5O)- by high-resolution MS but whose structure remains tentative. Another reaction product, aldehyde 2, C4F9SO2N(H)CHO, was also observed and was presumed to be a secondary oxidation product of aldehyde 1. Perfluorobutanesulfonate was not detected above the level of the blank in any sample; however, three perfluoroalkanecarboxylates (C3F7CO2-, C2F5CO2-, and CF3CO2-) were detected in all samples. Taken together, results suggest a plausible route by which perfluorooctanesulfonamides may serve as atmospheric sources of PFCAs, including perfluorooctanoic acid.     

Nitryl chloride and molecular chlorine in the coastal marine boundary layer

The magnitude and sources of chlorine atoms in marine air remain highly uncertain but have potentially important consequences for air quality in polluted coastal regions. We made continuous measurements of ambient ClNO(2) and Cl(2) concentrations from May 15 to June 8 aboard the Research Vessel Atlantis during the CalNex 2010 field study. In the Los Angeles region, ClNO(2) was more ubiquitous than Cl(2) during most nights of the study period. ClNO(2) and Cl(2) ranged from detection limits at midday to campaign maximum values at night reaching 2100 and 200 pptv, respectively. The maxima were observed in Santa Monica Bay when sampling the Los Angeles urban plume. Cl(2) at times appeared well correlated with ClNO(2), but at other times, there was little to no correlation implying distinct and varying sources. Well-confined Cl(2) plumes were observed, largely independent of ClNO(2), providing support for localized industrial emissions of reactive chlorine. Observations of ClNO(2), Cl(2), and HCl are used to constrain a simple box model that predicts their relative importance as chlorine atom sources in the polluted marine boundary layer. In contrast to the emphasis in previous studies, ClNO(2) and HCl are dominant primary chlorine atom sources for the Los Angeles basin.     

Real-time measurements of SO2, H2CO, and CH4 emissions from in-use curbside passenger buses in New York City using a chase vehicle

The Aerodyne Mobile Laboratory "chased" in-use curbside passenger buses operated by various operators in New York City. With the cooperation of New York State's Metropolitan Transit Authority, the relationships between the emissions of the several gas-phase species and particulate loadings were investigated across several bus technologies, bus types, and fuels (diesel, ultralow sulfur diesel, and compressed natural gas, CNG). The CNG buses followed did not employ an oxidation catalyst. The buses characterized were not prescreened in any fashion and were measured while deployed on their normal in-service routes. This paper focuses on the fuel-based mass emissions of SO2, H2CO, and CH4, measured using tunable infrared laser differential absorption spectroscopy. Sulfur dioxide emissions from buses known to be burning ultralow sulfur diesel (<30 ppm(m) S) were 16 times lower than those from buses burning normal commercial diesel fuel, nominally less than 300 ppm(m) sulfur. Emissions of formaldehyde and methane from in-use CNG buses were approximately 15 times greater than those from diesel powered buses.     

Emission changes resulting from the San Pedro Bay, California Ports Truck Retirement Program

Recent U.S. Environmental Protection Agency emissions regulations have resulted in lower emissions of particulate matter and oxides of nitrogen from heavy-duty diesel trucks. To accelerate fleet turnover the State of California in 2008 along with the Ports of Los Angeles and Long Beach (San Pedro Bay Ports) in 2006 passed regulations establishing timelines forcing the retirement of older diesel trucks. On-road emissions measurements of heavy-duty diesel trucks were collected over a three-year period, beginning in 2008, at a Port of Los Angeles location and an inland weigh station on the Riverside freeway (CA SR91). At the Port location the mean fleet age decreased from 12.7 years in April of 2008 to 2.5 years in May of 2010 with significant reductions in carbon monoxide (30%), oxides of nitrogen (48%) and infrared opacity (a measure of particulate matter, 54%). We also observed a 20-fold increase in ammonia emissions as a result of new, stoichiometrically combusted, liquefied natural gas powered trucks. These results compare with changes at our inland site where the average ages were 7.9 years in April of 2008 and 8.3 years in April of 2010, with only small reductions in oxides of nitrogen (10%) being statistically significant. Both locations have experienced significant increases in nitrogen dioxide emissions from new trucks equipped with diesel particle filters; raising the mean nitrogen dioxide to oxides of nitrogen ratios from less than 10% to more than 30% at the Riverside freeway location.     

Accuracy of noninvasive breath methane measurements using Fourier transform infrared methods on individual cows

Individual methane (CH(4)) production was recorded repeatedly on 93 dairy cows during milking in an automatic milking system (AMS), with the aim of estimating individual cow differences in CH(4) production. Methane and CO(2) were measured with a portable air sampler and analyzer unit based on Fourier transform infrared (FTIR) detection. The cows were 50 Holsteins and 43 Jerseys from mixed parities and at all stages of lactation (mean=156 d in milk). Breath was captured by the FTIR unit inlet nozzle, which was placed in front of the cow's head in each of the 2 AMS as an admixture to normal barn air. The FTIR unit was running continuously for 3 d in each of 2 AMS units, 1 with Holstein and another with Jersey cows. Air was analyzed every 20 s. From each visit of a cow to the AMS, CH(4) and CO(2) records were summarized into the mean, median, 75, and 90% quantiles. Furthermore, the ratio between CH(4) and CO(2) was used as a derived measure with the idea of using CO(2) in breath as a tracer gas to quantify the production of methane. Methane production records were analyzed with a mixed model, containing cow as random effect. Fixed effects of milk yield and daily intake of the total mixed ration and concentrates were also estimated. The repeatability of the CH(4)-to-CO(2) ratio was 0.39 for Holsteins and 0.34 for Jerseys. Both concentrate intake and total mixed ration intake were positively related to CH(4) production, whereas milk production level was not correlated with CH(4) production. In conclusion, the results from this study suggest that the CH(4)-to-CO(2) ratio measured using the noninvasive method is an asset of the individual cow and may be useful in both management and genetic evaluations.     

Air quality model evaluation data for organics. 6. C3-C24 organic acids

The atmospheric concentrations of 47 carboxylic acids in the semivolatile and particle phases are quantified in the Los Angeles area, as part of a larger study of the vapor-phase, semivolatile, and particle-phase organic compounds. Variations in the spatial and temporal distributions of acid concentrations are analyzed to determine whether atmospheric formation or primary emissions are responsible for the observed levels. Relatively low molecular weight aliphatic dicarboxylic acids (e.g., butanedioic acid, hexanedioic acid, and propanedioic acid) and some n-alkanoic acids (e.g., n-octanoic acid and n-nonanoic acid) are found at an offshore sampling location at levels comparable to urban area concentrations indicating that these compounds or their atmospheric precursors may be derived from long-range transport or natural background sources. Some aromatic carboxylic acids (e.g., benzoic acid and 1,2-benzenedicarboxylic acid) have spatial and temporal distributions suggesting that formation from anthropogenic emissions of gaseous precursors dominates their atmospheric concentrations. Additionally, the distributions of aliphatic carboxylic acid concentrations known to be emitted from primary sources (e.g., hexadecanoic acid and octadecanoic acid) are consistent with direct emissions as the dominant source of these compounds.     

Climate and health relevant emissions from in-use Indian three-wheelers fueled by natural gas and gasoline

Auto-rickshaws in India use different fuels and engine technologies, with varying emissions and implications for air quality and climate change. Chassis dynamometer emission testing was conducted on 30 in-use auto-rickshaws to quantify the impact of switching from gasoline to compressed natural gas (CNG) in spark-ignition engines. Thirteen test vehicles had two-stroke CNG engines (CNG-2S) and 17 had four-stroke CNG engines (CNG-4S), of which 11 were dual-fuel and operable on a back-up gasoline (petrol) system (PET-4S). Fuel-based emission factors were determined for gaseous pollutants (CO(2), CH(4), NO(X), THC, and CO) and fine particulate matter (PM(2.5)). Intervehicle variability was high, and for most pollutants there was no significant difference (95% confidence level) between "old" (1998-2001) and "new" (2007-2009) age-groups within a given fuel-technology class. Mean fuel-based PM(2.5) emission factor (mean (95% confidence interval)) for CNG-2S (14.2 g kg(-1) (6.2-26.7)) was almost 30 times higher than for CNG-4S (0.5 g kg(-1) (0.3-0.9)) and 12 times higher than for PET-4S (1.2 g kg(-1) (0.8-1.7)). Global warming commitment associated with emissions from CNG-2S was more than twice that from CNG-4S or PET-4S, due mostly to CH(4) emissions. Comprehensive measurements and data should drive policy interventions rather than assumptions about the impacts of clean fuels.     

Methane, carbon dioxide, and nitrous oxide emissions from septic tank systems

Emissions of CH4, CO2, and N2O from conventional septic tank systems are known to occur, but there is a dearth of information as to the extent. Mass emission rates of CH4, CO2, and N2O, as measured with a modified flux chamber approach in eight septic tank systems, were determined to be 11, 33.3, and 0.005 g capita(-1) day(-1), respectively, in this research. Existing greenhouse gas (GHG) emission models based on BOD (biochemical oxygen demand) loading have estimated methane emissions to be as high as 27.1 g CH4 capita(-1) day(-1), more than twice the value measured in our study, and concluded that septic tanks are potentially significant sources of GHGs due to the large number of systems currently in use. Based on the measured CH4 emission value, a revised CH4 conversion factor of 0.22 (compared to 0.5) for use in the emissions models is suggested. Emission rates of CH4, CO2, and N2O were also determined from measurements of gas concentrations and flow rates in the septic vent system and were found to be 10.7, 335, and 0.2 g capita(-1)day(-1), respectively. The excellent agreement in the CH4 emission rates between the flux chamber and the vent values indicates the dominant CH4 source is the septic tank.     

An experimental and kinetic modeling study of the reaction of CHF3 with methane

The gas-phase reaction of CHF3 with CH4 has been studied experimentally and computationally. The motivation behind the study is that reaction of CHF3 with CH4 provides a possible route for synthesis of CH2=CF2 (C2H2F2). Experiments are carried out in a plug flow, isothermal alpha-alumina reactor at atmospheric pressure over the temperature range of 973-1173 K. To assist in understanding the reaction mechanism and the role of the reactor material involved in the reaction of CHF3 with CH4, the reaction of CHF3 with CH4, pyrolysis of CH4, and pyrolysis of CHCIF2 have been studied in the presence of alpha-alumina or alpha-AIF3 particles under various conditions. Under all conditions studied for the reaction of CHF3 and CH4, the major products are C2F4, C2H2F2, and HF. Minor products include C2H2, C2H4, C2H3F, C2HF3, C3F6, CO2, and H2. C2H6, CH2F2, and CHF2CHF2 are detected in trace amounts. The initial step is the gas-phase unimolecular decomposition of CHF3, producing CF2 and HF. It is proposed that CF2 decomposes on the surface of alpha-alumina, producing F radicals that are responsible for the activation of CH4. A reaction scheme developed on the basis of the existing NIST HFC and GRI-Mech 3.0 mechanisms is used to model the reaction of CHF3 with CH4. Generally satisfactory agreement between experimental and modeling results is obtained on the conversion levels of CHF3 and CH4 and rates of formation of major products. Using the software package AURORA, the reaction pathways leading to the formation of major products are elucidated.     

Enteric methane emissions and lactational performance of Holstein cows fed different concentrations of coconut oil

To determine if dietary medium-chain fatty acids (FA; C(8) to C(14)) may mitigate enteric methane emissions, 24 cows were blocked by body size (n=2) and randomly assigned to 1 sequence of dietary treatments. Diets were fed for 35 d each in 2 consecutive periods. Diets differed in concentrations of coconut oil (CNO; ~75% medium-chain FA): 0.0 (control) or 1.3, 2.7, or 3.3% CNO, dry matter basis. The control diet contained 50% forage (74% from corn silage), 16.5% crude protein (60% from rumen-degradable protein), 34% neutral detergent fiber (NDF; 71% from forage), and 28% starch, dry matter basis. Data and sample collections were from d 29 to 35 in environmentally controlled rooms to measure methane (CH(4)) production. Methane emitted was computed from the difference in concentrations of inlet and outlet air and flux as measured 8 times per day. Control cows emitted 464 g of CH(4)/d, consumed 22.9 kg of DM/d, and produced 34.8 kg of solids-corrected milk/d and 1.3 kg of milk fat/d. Treatment with 1.3, 2.7, or 3.3% dietary CNO reduced CH(4) (449, 291, and 253 g/d, respectively), but concomitantly depressed dry matter intake (21.4, 17.9, and 16.2 kg/d, respectively), solids-corrected milk yield (36.3, 28.4, and 26.8 kg/d, respectively), and milk fat yield (1.4, 0.9, and 0.9 kg/d, respectively). The amount of NDF digested in the total tract decreased with increased dietary CNO concentrations; thus, CH(4) emitted per unit of NDF digested rose from 118 to 128, 153, and 166 g/kg across CNO treatments. Dietary CNO did not significantly affect apparent digestibility of CP but increased apparent starch digestibility from 92 to 95%. No FA C(10) or shorter were detected in feces, and apparent digestibility decreased with increasing FA chain length. Coconut oil concentrations of 2.7 or 3.3% decreased yields of milk FA C(14). The highest milk fat concentration (3.69%; 1.3% CNO) was due to the greatest yields of C(12) to C(16) milk FA. Milk FA concentrations of C(18:2 trans-10,cis-12) were related to increased dietary CNO concentrations and presumably to depressed ruminal NDF digestion. Moderate dietary CNO concentrations (e.g., 1.3%) may benefit lactational performance; however, CNO concentrations greater than or equal to 2.7% depressed dry matter intake, milk yield, milk fat yield, and NDF utilization. If mitigation of enteric CH(4) emissions is due to decreased digestion of dietary NDF, then this will lessen a major advantage of ruminants compared with nonruminants in food-production systems. Thus, CNO has limited use for enteric CH(4) mitigation in lactating dairy cows.