Volcanoes have only recently been recognized as a potentially major source of reactive bromine species to the atmosphere, following from the detection of bromine monoxide (BrO) in the plume emitted by Soufriere Hills Volcano, Montserrat. However, BrO is not expected to be emitted in significant quantity from magma, presenting a puzzle regarding its formation. We report here new field measurements of the tropospheric plume emitted by Mt. Etna, Italy, which provide the first direct evidence of fast oxidation of halogen species in a volcanic plume, and lead to an explanation of how BrO is generated from magmatic HBr emissions. We show that the timescale of BrO formation (a few minutes after emission into the atmosphere) is consistent with rapid heterogeneous halogen chemistry involving sulphate aerosol in the plume. The model highlights considerable complexity to the oxidative chemistry of volcanic plumes.