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The results of δ13C measurements of several types of major sources of atmospheric methane are as follows: rice paddies, −67‰; the peat bogs of the Lake Agassiz region of northern Minnesota, −67±5‰; swamps of the Florida Everglades, −55±3‰ and biomass burning, −24 to −32‰. In addition, results are presented of a study of the δ13C of CH4 released from a slough, compared to the CH4 in the bottom sediment. These isotopic values are used, together with previously published data, to make up a tentative budget of the fluxes of the major sources for atmospheric methane with an average isotopic composition matching the measured value for atmospheric CH4, taking into account the fractionation effect of the sink processes. This budget requires the existence of a significant flux from an anthropogenic source of heavy CH4, calculated to be 45±15 Tg yr−1 if attributed to CH4 from biomass burning, with δC = −25‰.

Recent measurements of the carbon isotopic abundance of atmospheric methane give a value of δ(13C/12C) = −47.0 ± 0.3‰, which is significantly different from earlier values measured by others between 1950 and 1970. The isotopic composition of various sources and the possibility of a temporal trend are discussed. The average methane concentration measured was 1.66 ppm, which is in accord with the increase in concentration since 1965–1970 observed in other studies.

The kinetic isotope effect (KIE) for carbon and oxygen in the reaction CO + OH has been measured over a range of pressures of air and at 0.2 and 1.0 atm of oxygen, argon, and helium. The reaction was carried out with 21-86% conversion under static conditions, utilizing the photolysis of HzOz as a source of OH radicals. The value of the KIE for carbon varies with pressure and the kind of ambient gas; for air the ratio of the reaction rates 12k/13k has the value 1.007 at 1.00 atm and decreases to 0.997 at 0.2 atm; for oxygen and argon over the same pressure range the values are 1.002-0.994 and 1.000-0.991, respectively. The value of the KIE for the CO oxygen atom is l6k/l*k = 0.990 over the pressure range 0.2-1.0 atm and is independent of the kind of ambient gas. No exchange of the oxygen atoms in the activated complex, followed by decomposition to the starting molecules, was observed. From the mechanistic standpoint the normal KIE observed for carbon at the high pressure is attributed to the initial formation of the activated HOCO radical, whereas the inverse KIE observed at low pressures is a result of the KIE for the reverse reaction HOCOt -CO + OH being greater than that for the forward reaction HOCOt -+ COz'+ H. The derived isotopic equilibrium constant for HOCO s CO favors the enrichment of 13C in the more strongly bound HOCO.