Methane and ethane are the most abundant hydrocarbons in the atmosphere and they affect both atmospheric chemistry and climate. Both gases are emitted from fossil fuels and biomass burning, whereas methane (CH(4)) alone has large sources from wetlands, agriculture, landfills and waste water. Here we use measurements in firn (perennial snowpack) air from Greenland and Antarctica to reconstruct the atmospheric variability of ethane (C(2)H(6)) during the twentieth century. Ethane levels rose from early in the century until the 1980s, when the trend reversed, with a period of decline over the next 20 years. We find that this variability was primarily driven by changes in ethane emissions from fossil fuels; these emissions peaked in the 1960s and 1970s at 14-16 teragrams per year (1 Tg = 10(12) g) and dropped to 8-10 Tg  yr(-1) by the turn of the century. The reduction in fossil-fuel sources is probably related to changes in light hydrocarbon emissions associated with petroleum production and use. The ethane-based fossil-fuel emission history is strikingly different from bottom-up estimates of methane emissions from fossil-fuel use, and implies that the fossil-fuel source of methane started to decline in the 1980s and probably caused the late twentieth century slow-down in the growth rate of atmospheric methane.

Measurements of trace gases in air trapped in polar firn (unconsolidated snow) demonstrate that natural sources of chlorofluorocarbons, halons, persistent chlorocarbon solvents and sulphur hexafluoride to the atmosphere are minimal or non-existent. Atmospheric concentrations of these gases, reconstructed back to the late nineteenth century, are consistent with atmospheric histories derived from anthropogenic emission rates and known atmospheric lifetimes. The measurements confirm the predominance of human activity in the atmospheric budget of organic chlorine, and allow the estimation of atmospheric histories of halogenated gases of combined anthropogenic and natural origin. The pre-twentieth-century burden of methyl chloride was close to that at present, while the burden of methyl bromide was probably over half of today's value.