Estuarine sediments commonly form major sinks for contaminants released during industrial activity. Many industrial processes lead to the release of metals initially in solution, which can then be adsorbed on to, for example, Fe hydroxides or clay minerals. However, in the mining industry, there are two major contaminant waste streams: (1) metals discharged in solution via mine drainage; and (2) particulate grains of the ore-forming or related minerals released after ore processing. The release of particulate waste can have a major long-term impact on environmental geochemistry. In this study, we have mapped the distribution of arsenic, copper, tin and zinc within the surficial sediments of the Fal Estuary, Cornwall, UK, an area that drains a historically important polymetallic mining district. There are clear spatial variations in the contaminants, with the highest levels (> 2800 p.p.m. As, > 5000 p.p.m. Cu, > 3000 p.p.m. Sn and > 6000 p.p.m. Zn) within Restronguet Creek on the western side of the estuary. Mineralogical studies show that small (<20 μm) grains of detrital arsenopyrite, chalcopyrite, cassiterite and sphalerite are very abundant within the surface sediments. Most of the sulphide grains are fractured, but mineralogically unaltered, although some grains show alteration rims caused by oxidation of the sulphides. The geochemistry and mineralogy are indicative of sediment supply from the discharge of particulate waste into the estuary during historical mining activity. Subsequently, this particulate waste has been largely physically and biologically reworked within the surface sediments. Although considerable effort has been made to minimize contaminants released via mine drainage into the estuary, the potential flux of contaminants present within the intertidal and subtidal sediments has not been addressed. Benthic invertebrates living within the area have adapted to be metal tolerant, and it is likely that the dominant source of bioavailable metals is a result of alteration of the particulate mine waste present within the intertidal and subtidal sediments.