Carbon isotope ratios of methyl bromide and methyl chloride emitted from a coastal salt marsh

Methyl bromide (CH3Br) and methyl chloride (CH3Cl) play important roles in stratospheric ozone depletion, but their atmospheric budgets have large uncertainties. The analysis of stable isotope composition of methyl halides may provide useful independent information for further constraining their budgets. Here we report the first measurements of CH3Br and CH3Cl stable carbon isotope ratios emitted from a biogenic source under in situ conditions. CH3Br and CH3Cl emissions from the salt marsh plant Batis maritima showed a strong diurnal variation in δ13C, from −65‰ during the daytime to −12‰ at night. The minimum δ13C values were observed at midday, coinciding with the time of greatest emissions and ambient temperature. At night, when the emissions were much smaller, the stable carbon isotopic ratios of CH3Br and CH3Cl became enriched in 13C. The daily mean δ13C of CH3Br and CH3Cl emissions, weighted by emission rate, were −43‰ and −62‰ respectively.