We report measurements of δ13C-CH4 and δ2H-CH4 at a central station in the Black Sea. We considered the Black Sea as a "biogeochemical bucket" and the single station as a basin-wide integrator of processes affecting methane. Considering the rapid (3.6-18 yr) turnover of methane and the similarity of these stable isotope distributions to the methane concentration and oxidation rate profiles [Reeburgh, Ward, Whalen, Sandbeck, Kilpatrick, Kerkhof, 1991. Black Sea methane geochemistry. Deep-Sea Research 38, S1189-S1210], it appears that methane is being added approximately as fast as it is being oxidized. Methane can be thought of as "running in place" in the Black Sea water column. Recent reports of extensive vents on the northern side of the Black Sea suggest that they might be a methane source capable of effectively balancing the Black Sea methane budget. Unfortunately, we have limited information on basin-wide seep fluxes and cannot identify them with stable isotope measurements. Methane oxidation (and accompanying isotope fractionation) is so extensive that the water-column stable isotope measurements provide little information on methane sources. Future measurements of 14C-CH4 should permit partitioning Black Sea methane sources into fossil and recent components. © 2006 Elsevier Ltd. All rights reserved.

Methane (CH4) concentration and stable isotope (δ 2H-CH4 and δ 13C-CH4) depth distributions show large differences in the water columns of the Earth's largest CH4-containing anoxic basins, the Black Sea and Cariaco Basin. In the deep basins, the between-basin stable isotope differences are large, 83‰ for δ2H-CH4 and 9‰ for δ13C-CH4, and the distributions are mirror images of one another. The major sink in both basins, anaerobic oxidation of CH4, results in such extensive isotope fractionation that little direct information can be obtained regarding sources. Recent measurements of natural 14C-CH4 show that the CH4 geochemistry in both basins is dominated (∼64 to 98%) by inputs of fossil (radiocarbon-free) CH4 from seafloor seeps. We derive open-system kinetic isotope effect equations and use a one-dimensional (vertical) stable isotope box model that, along with isotope budgets developed using radiocarbon, permits a quantitative treatment of the stable isotope differences. We show that two main factors control the CH4 concentration and stable isotope differences: (1) the depth distributions of the input of CH4 from seafloor seeps and (2) anaerobic oxidation of CH4 under open-system steady state conditions in the Black Sea and open-system non-steady-state conditions in the Cariaco Basin. Copyright 2006 by the American Geophysical Union.

Two field experiments in California rice paddies are reported, one with a single treatment of a research plot and the other with varied treatments in a typical commercial rice field. Small total methane emissions, only 11 g CH4/m2, were measured for the entire growing season in the first experiment. in the second experiment, the addition of exogenous organic matter (rice straw), the presence or absence of vegetation, and the nitrogen fertilizer amounts were examined for their influence on methane emissions. The total methane emission over the growing season varied from 1.2 g CH4/m2 (with no added organic matter) to 58.2 g CH4/m2 (with largest organic matter treatments). Added organic matter was the major factor affecting methane emissions. Vegetation did not greatly affect total methane fluxes, but it did influence the mode and timing of release. Nitrogen fertilizer did not greatly affect the amount of methane emitted, but it influenced slightly the time course of the process. A diurnal effect in methane emission was observed during the early ontogeny of the crop. The variation of methane emission with time during the course of the growing season was very unusual in this experiment; only one peak was observed, and it was early in the season. During the period of largest emissions, δ13C values of the methane were measured to be −55.7 ±1.8‰ in plots with added organic matter. Copyright 1992 by the American Geophysical Union.

We measured emissions of methane from asphalt surfaces used in pavement for roadways. Maximum emissions were 22 mg/m2/yr for 1- to 4-week-old pavement during maximum sunlight intensity. Emissions were much smaller at low sunlight intensity and dropped off to negligible amounts at night. Smaller emissions were observed for asphalt pavement of 2.5 to 3 years approximate age under similar conditions. Companion measurements of carbon monoxide emissions resulted in maximum emissions of about 2.6 mg/m2/hr for 1-wk-old pavement. These findings indicate that emissions of CH4 and CO are a function of both sunlight and temperature. Based on our results, methane emissions from asphalt pavement cannot be a significant source of atmospheric methane. -from Authors

Methyl halide gases are important sources of atmospheric inorganic halogen compounds, which in turn are central reactants in many stratospheric and tropospheric chemical processes. By observing emissions of methyl chloride, methyl bromide, and methyl iodide from flooded California rice fields, we estimate the impact of rice agriculture on the atmospheric budgets of these gases. Factors influencing methyl halide emissions are stage of rice growth, soil organic content, halide concentrations, and field-water management. Extrapolating our data implies that about 1 percent of atmospheric methyl bromide and 5 percent of methyl iodide arise from rice fields worldwide. Unplanted flooded fields emit as much methyl chloride as planted, flooded rice fields.

Numerous methane-emitting bottom features, such as seeps, methane clathrate hydrates (clathrates), and mud volcanoes, have been identified recently in the Black Sea. The fluxes of methane from these sources averaged over large spatial scales are unknown. Here we take advantage of the fact that the Black Sea is a semi-enclosed basin with restricted deep water circulation to establish first-order estimates of basin-wide fluxes of methane from these sources to the water column and atmosphere. First, we measured the natural radiocarbon content of methane (14C-CH4) dissolved in the water column and emitted from seeps. The 14C-CH4 results showed that the dominant source of methane to the water column is emitted from seeps and a smaller source is diagenetically produced in relatively modern sediments. The 14C-CH4 results were then used to partition a basin-wide total methane budget; this analysis estimated the basin-wide flux of methane from seeps and clathrates to the water column to be 3.60 to 4.28 Tg yr-1. Second, a geochemical box model was used to calculate possible distributions of methane inputs from seeps and clathrates as well as provide additional estimates of the basin-wide flux of methane from seeps and clathrates to the water column (4.95 to 5.65 Tg yr-1). © 2006 Elsevier B.V. All rights reserved.

Methane (CH4) in the subsurface ocean is often supersaturated compared to equilibrium with the modern atmosphere. In order to investigate sources of CH4 to the subsurface ocean, isotope surveys (14C-CH4, δ13 C-CH4, δ2 H-CH4) were conducted at five locations: Skan Bay (SB), Santa Barbara Basin (SBB), Santa Monica Basin (SMB), Cariaco Basin (CB), and the Guaymas Basin (GB). Depth distributions of CH4 concentration and isotopic abundance were determined for both the sediment and water column at the SB, SBB, SMB, and CB sites; CH4 emitted from seeps on the continental shelf adjacent to the SBB as well as seeps and decomposing clathrate hydrates in the GB was also collected, purified, and analyzed. Methane isotope distributions in the sediments were consistent with known methanogenic and methanotrophic activity; seep- and clathrate-hydrate-derived CH4 was found to be depleted in radiocarbon. However, surprising results were obtained in the water column at all sites investigated. In SB the radiocarbon content of the subsurface CH4 concentration maximum was on average 41% less than its suspected sediment CH4 source, suggesting CH4 seepage in the bay. In the SBB, SMB, and CB, the 14C-CH4 contents in the subsurface ocean were 1.2 to 3.6 times greater than modem carbon quantities suggesting a source of 14C from atmospheric nuclear weapons testing, nuclear power plant effluents, or cosmogenic isotope production. Copyright 2008 by the American Geophysical Union.

High-resolution in situ CO2 measurements were conducted aboard the NASA DC-8 aircraft during the ARCTAS/POLARCAT field campaign, a component of the wider 2007-2008 International Polar Year activities. Data were recorded during large-scale surveys spanning the North American sub-Arctic to the North Pole from 0.04 to 12 km altitude in spring and summer of 2008. Influences on the observed CO2 concentrations were investigated using coincident CO, black carbon, CH3CN, HCN, O3, C2Cl4, and Δ14CO2 data, and the FLEXPART model. In spring, the CO2 spatial distribution from 55̊N to 90̊N was largely determined by the long-range transport of air masses laden with Asian anthropogenic pollution intermingled with Eurasian fire emissions evidenced by the greater variability in the mid-to-upper troposphere. At the receptor site, the enhancement ratios of CO2 to CO in pollution plumes ranged from 27 to 80 ppmv ppmv-1 with the highest anthropogenic content registered in plumes sampled poleward of 80̊N. In summer, the CO2 signal largely reflected emissions from lightning-ignited wildfires within the boreal forests of northern Saskatchewan juxtaposed with uptake by the terrestrial biosphere. Measurements within fresh fire plumes yielded CO2 to CO emission ratios of 4 to 16 ppmv ppmv-1 and a mean CO2 emission factor of 1698 ± 280 g kg-1 dry matter. From the 14C in CO2 content of 48 whole air samples, mean spring (46.6 ± 4.4%) and summer (51.5 ± 5%) D14CO2 values indicate a 5%seasonal difference. Although the northern midlatitudes were identified as the emissions source regions for the majority of the spring samples, depleted Δ14CO2 values were observed in <1% of the data set. Rather, ARCTAS Δ14CO2 observations (54%) revealed predominately a pattern of positive disequilibrium (1-7%) with respect to background regardless of season owing to both heterotrophic respiration and fire-induced combustion of biomass. Anomalously enriched Δ14CO2 values (101-262%) measured in emissions from Lake Athabasca and Eurasian fires speak to biomass burning as an increasingly important contributor to the mass excess in Δ14CO2 observations in a warming Arctic, representing an additional source of uncertainty in the quantification of fossil fuel CO2.