Flood-related contaminant (As, Cd, Cu, Pb, Zn) remobilisation, dispersal and storage in the Río Guadiamar was investigated following the 1998 Aznalcóllar tailings dam failure, along with records of floodplain contaminant loading in the decades preceding the tailings release. A series of post-spill floods resulted in the transfer of vast quantities of sediment-borne heavy metals and As towards the lower reaches of the Guadiamar and the borders of the Doñana National Park, but over-bank flood deposits collected between May 1999 and March 2002 show a systematic fall in contaminant concentrations following successive flood events. Geochemical improvements can largely be attributed to sediment mixing of contaminated and ‘clean’ material derived from calcareous catchment soils. Longer-term contaminant patterns in floodplain sediment cores show higher heavy metal and As loading rates operating before the opening of the Aznalcóllar pit in 1979 and in some instances pre-dating 1954. The remobilization and dispersal of historically contaminated alluvium in the upper Guadiamar means that the post-clean-up contaminant signature in flood-transported sediments largely reflects chronic, long-term metal mining in the Guadiamar catchment, rather than the acute effects of the Aznalcóllar spill. Generally results present a cautiously optimistic prognosis for the sensitive wetlands of Doñana, but high dissolved (aqueous) heavy metal (especially Cu and Zn) concentrations in the upper Guadiamar emphasise the need for addressing contaminant ‘hotspots’ in the region and for maintaining flow requirements for aquatic ecosystems. This study illustrates the importance of establishing antecedent geomorphological–geochemical conditions in a spill-impacted river system, both for assessing the impacts of a single catastrophic pollution event and for developing appropriate strategies for remediation.