Contribution of anthropogenic and natural sources to atmospheric methane variability.

Methane is an important greenhouse gas, and its atmospheric concentration has nearly tripled since pre-industrial times. The growth rate of atmospheric methane is determined by the balance between surface emissions and photochemical destruction by the hydroxyl radical, the major atmospheric oxidant. Remarkably, this growth rate has decreased markedly since the early 1990s, and the level of methane has remained relatively constant since 1999, leading to a downward revision of its projected influence on global temperatures. Large fluctuations in the growth rate of atmospheric methane are also observed from one year to the next, but their causes remain uncertain. Here we quantify the processes that controlled variations in methane emissions between 1984 and 2003 using an inversion model of atmospheric transport and chemistry. Our results indicate that wetland emissions dominated the inter-annual variability of methane sources, whereas fire emissions played a smaller role, except during the 1997-1998 El Niño event. These top-down estimates of changes in wetland and fire emissions are in good agreement with independent estimates based on remote sensing information and biogeochemical models. On longer timescales, our results show that the decrease in atmospheric methane growth during the 1990s was caused by a decline in anthropogenic emissions. Since 1999, however, they indicate that anthropogenic emissions of methane have risen again. The effect of this increase on the growth rate of atmospheric methane has been masked by a coincident decrease in wetland emissions, but atmospheric methane levels may increase in the near future if wetland emissions return to their mean 1990s levels.

High-precision continuous-flow measurement of delta13C and deltaD of atmospheric CH4.

We describe our development of a CH4 preconcentration system for use with continuous-flow gas chromatograph combustion isotope ratio mass spectrometry (GC/C/IRMS). Precision of measurement of delta13C-CH4 is 0.05/1000 (1sigma) on multiple 60-mL aliquots of the same ambient air sample. The same front-end on-line CH4 preconcentration system allows us to measure deltaD of CH4 by gas chromatography IRMS when the combustion furnace is replaced with a pyrolysis oven (GC/P/IRMS). Precision of measurement for deltaD-CH4 is 1.5/1000 (1sigma) using 120 mL of ambient air based on multiple aliquots of the same air sample. These are the first reported measurements of atmospheric CH4 using GC/P/IRMS methodology. Each isotope analysis can be made much more rapidly (30-40 min) than they could using off-line combustion of an air sample (1-6 h) followed by conventional dual-inlet IRMS measurements (12-20 min), while requiring much less total volume and retaining a comparable level of precision and accuracy. To illustrate the capabilities of our preconcentration GC/C/IRMS system, we compare the results of measurement of 24 background air samples made using both GC/C/IRMS and conventional vacuum line/dual-inlet IRMS methodology. The air samples were collected on a shipboard air sampling transect made across the Pacific Ocean in July 2000 and are part of an ongoing atmospheric CH4 research program. The average difference between the two methods of IRMS analyses on these 24 samples is 0.01 +/- 0.03/1000 (95% confidence interval) for delta3C-CH4. These are the first measurements to be reported of air samples directly intercompared for delta13C-CH4 using both GC/C/IRMS and dual-inlet IRMS measurement methodology. Measurement of deltaD-CH4 of these air samples is also presented as an illustration of the ability of this system to resolve small isotopic differences in remote air. High-precision measurement of delta13C and deltaD of atmospheric CH4 made using our coupled preconcentration GC/IRMS system will greatly improve our ability to utilize isotopic data in understanding spatial and temporal changes in atmospheric CH4 and the biogeochemistry of its sources and sinks.

Emissions of methyl halides and methane from rice paddies.

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.

Methane: Interhemispheric concentration gradient and atmospheric residence time.

The ground level concentrations of methane in the atmosphere have been measured to be in the range from 1.45 to 1.62 parts per million by volume (ppmv) of dry air in remote locations between 62 degrees N and 54 degrees S latitudes during the time period from November 1977 to July 1979. The average (+/-rms) concentration for the northern hemisphere was 1.57 +/- 0.02 ppmv in January 1978 and 1.59 +/- 0.02 in July 1979. The average concentration in the southern hemisphere was lower-1.47 +/- 0.02 in January 1978 and 1.51 +/- 0.01 in July 1979. The ratio of concentrations between the two hemispheres was 1.068 +/- 0.016 in January 1978 and 1.055 +/- 0.013 in July 1979, for an average of 1.06 +/- 0.01. The higher concentrations in the northern hemisphere require either that the sources of methane lie preferentially in the northern hemisphere or that the removal processes operate more rapidly in the southern hemisphere or both. The primary removal process for CH(4) is reaction with tropospheric OH radicals and its estimated atmospheric lifetime is 10.5 +/- 1.8 yr. The observed interhemispheric gradient is consistent with this lifetime and preferential release of methane in the northern hemisphere. Measurements taken in the Amazon basin region indicate the presence of a substantial source of methane in that area.