Oxygen isotopic ratio measurements (δ17O and δ18O) of background and volcanic sulfate preserved in South Pole snow and ice were used to investigate the impact on the oxidation state of the atmosphere by explosive volcanic eruptions. By comparing different paleovolcanic events, we observe a difference in the SO2 oxidation pathway between moderate (tens of teragrams (Tg) of SO2) and massive (hundreds of Tg) eruptions. Both isotopic data and numerical simulations suggest the shutdown of stratospheric OH chemistry and the opening of unaccounted oxidation channels for SO2, such as the reaction with O(3P) atoms when hundreds of Tg of SO2 are injected into the stratosphere. It is very likely that oxidation rates and pathways and concentrations of most traces gases are also dramatically affected, with potentially important implications for climate forcing.