This study was carried on Upper Mazowe River in Zimbabwe which connects with Luenha River in Mozambique, which is a tributary of the Zambezi River. Zambezi River is the fourth longest river in Africa flowing into the Indian Ocean, which makes the study of regional and global interest. Heavy metal aqueous speciation has received relatively little attention compared to sediment speciation in the Upper Mazowe River, and yet heavy metal behaviour and fate in surface waters are greatly affected by the heavy metal chemical form in solution. The aim of the study was to determine the elemental composition and speciation of heavy metal(oid)s. This study focused on water and sediment speciation of Al, As, Cu, Hg, Mn, Fe, and Pb using Visual MINTEQ Version 3.1 computer modelling and sequential extraction techniques. Twenty-eight different water column elemental species, comprising 3, 2, 3, 1, 7, 7 and 5 species each, and 35 sediment phase elemental species, comprising 6, 6, 6, 2, 6, 5, and 4 species each for Al, As, Cu, Hg, Mn, Fe, and Pb respectively, were identified. Of note is the fact that Hg, mainly derived from artisanal gold mining activities, exists entirely as the fulvic acid complex, FA2Hg (aq), and As exists as H3AsO3 and H2AsO3− in the water phase. Exchange equilibrium reactions across the water-sediment interface were observed for Mn2+, Fe2+, Cu2+, and Pb2+. Reactions leading to the formation of the species were identified. Species interactions within the water column and sediment phase and species interrelationships with physicochemical parameters are discussed. H3AsO3 formation is predicted to be temperature sensitive and the aluminium hydroxide-fulvic acid complex /FA2(AlOH) (aq) is oxic favourable.
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