Atmospheric histories of halocarbons from analysis of Antarctic firn air: Major Montreal Protocol species

[1] Air samples extracted from Antarctic firn at Law Dome have been analyzed for the suite of halocarbons that contribute most of the anthropogenic chlorine and about half the anthropogenic bromine presently released into the stratosphere. The species, all included in the Montreal Protocol, are the chlorofluorocarbons (CFCs -11, -12, -113, -114, -115), hydrochlorofluorocarbons (HCFCs -22, -141b, -142b), halons (H -1211, -1301), CH3CCl3 (methyl chloroform) and CCl4 (carbon tetrachloride). The measurements were used to reconstruct the atmospheric history of these species since the 1930s, providing a record considerably predating existing in situ records or other conventional air archives, encompassing virtually the entire history of anthropogenic emissions of CFCs, HCFCs, and halons and giving early 20(th) century levels for CH3CCl3 and CCl4. Significant features of this study are (1) the narrow age spread (spectral width 5 years) of the individual firn air samples, which reveals rapid atmospheric changes, (2) the use of inversion techniques to infer past atmospheric composition with associated uncertainties, and (3) the low analytical detection limit (< 0.1 ppt), which, together with the narrow air age spread, detects early background levels and resolves the time that industrial emissions first appeared in the southern hemisphere atmosphere. Integrity of the data is demonstrated by successful intercomparison of data from independent firn sites on Law Dome with common time-series. An upper limit is given for the potential contribution to atmospheric levels of CH3CCl3 from nonindustrial sources. The atmospheric records produced from firn air are compared to calculations based on the history of their global emissions.