The initial kinetics of sulphurous acid leaching of well characterised synthetic pure goethite (G–O) and goethites containing cobalt in sorption [G---Co(S)] and co-precipitation [G---Co(C)] modes have been studied. The interfacial reaction controlled nature of iron dissolution from different samples is indicated by the activation energy of about 65 kJ/mol. The rates of iron and cobalt dissolution from different samples showed a stronger dependence on the concentration of SO2(aq.) compared with other solution species such as HSO3− and H+. The particles were found to be non-uniformly attacked, preferentially on multi-domain grain boundaries. The results of infra-red (IR) spectroscopy on leach liquors indicated that SO42− is the major species ...