Geochemical signature as paleoenvironmental markers in Holocene sediments of the Tinto River estuary (Southwestern Spain)

High absolute concentrations of metals associated to sulfide deposits located at the river source (Fe, Cu, Zn, Pb, Cd, and As) have been determined from the study of major and trace element concentrations in sediment samples obtained in two vibracores in the Tinto River estuary. In most cases, the enrichment factor (EF) for these metals is over 2. Cu, Zn and As have much higher EF, over 10 in surficial samples. Fe oxy-hydroxide precipitation in high-chlorinity zones and its scavenging effect on metals is the main control process on the chemical composition of sediment. Vertical evolution of the sedimentary and geochemical characteristics of the cores show that the estuary has undergone a process of progressive shallowness and a relative increase in acidic river water volume with respect to seawater. This effect has originated a downstream displacement of acid mixing processes affecting the estuary, which is reflected in higher metal concentrations in sediments of the outer zones of the system.