The fine-grained character of volcanic ash generated in the long-lived eruption of the Soufrière Hills volcano, Montserrat, West Indies, raises the issue of its possible health hazards. Surface- and free-radical production has been closely linked to bioreactivity of dusts within the lung. In this study, electron paramagnetic resonance (EPR) techniques have been used, for the first time, on volcanic ash to measure the production of radicals from the surface of particles. Results show that concentrations of hydroxyl radicals (HO*) in respirable ash are two to three times higher than a toxic quartz standard. The dome-collapse ash contains cristobalite, a crystalline silica polymorph that may cause adverse health effects. EPR experiments indicate, however, that cristobalite in the ash does not contribute to HO* generation. Our results show that the main cause of reactivity is removable divalent iron (Fe2+), which is present in abundance on the surfaces of the particles and is very reactive in the lung. Our analyses show that fresh ash generates more HO* than weathered ash (which has undergone progressive oxidation and leaching of iron from exposed surfaces), an effect replicated experimentally by incubating fresh ash in dilute acid. HO* production experiments also indicate that iron-rich silicate minerals are responsible for surface reactivity in the Soufrière Hills ash.