Stratigraphic sequence, elemental concentrations and heavy metal pollution in Holocene sediments from the Tinto-Odiel Estuary, southwestern Spain

The Holocene filling of the Tinto-Odiel Estuary comprises seven lithofacies over a Mio-Pliocene substrate. The sequence includes three system tracts: lowstand system (10000 to 8700 years BP), transgressive system (8700 to 7000 years BP), and regressive system (7000 to Recent). Twenty sediment samples from the 50-m borehole were analyzed for their major components and minor element concentrations. Two multivariate analysis methods, principal component analysis and cluster analysis, were performed in the analytical data set to help visualize the sample clusters and the element associations. Samples corresponding to unpolluted, pre-mining sediments are clearly separated by cluster analysis, mainly as a result of the low content in sulphide-associated heavy metals such as Cu, Zn, As, Ag, and Pb. So, these sediments may be utilized as a background for geochemical analysis (bulk sample) in other adjacent estuaries, both in sandy and silty-clayey sediments. As a consequence of large-scale mining and smelting operations occurred since prehistorical times on the river banks, a rapid rise in the metal pollution was found in the upper 2.5 m of the natural filling, with values exceeding up to ten times the natural background levels. In addition, since the mid-1960s, large amounts of waste and pollutant effluents have been discharged from industries located around the estuary, increasing the heavy metal content in the last 0.3 m of the natural sedimentation.