Seasonal drives on potentially toxic elements dynamics in a tropical estuary impacted by mine tailings.

ABSTRACT

This study investigates the impact of seasonality on estuarine soil geochemistry, focusing on redox-sensitive elements, particularly Fe, in a tropical estuary affected by Fe-rich mine tailings. We analyzed soil samples for variations in particle size, pH, redox potential (Eh), and the content of Fe, Mn, Cr, Cu, Ni, and Pb. Additionally, sequential extraction was employed to understand the fate of these elements. Results revealed dynamic changes in the soil geochemical environment, transitioning between near-neutral and suboxic/anoxic conditions in the wet season and slightly acidic to suboxic/oxic conditions in the dry season. During the wet season, fine particle deposition (83%) rich in Fe (50 g kg-1), primarily comprising crystalline Fe oxides, occurred significantly. Conversely, short-range ordered Fe oxides dominated during the dry season. Over consecutive wet/dry seasons, substantial losses of Fe (-55%), Mn (-41%), and other potentially toxic elements (Cr -44%, Cu -31%, Ni -25%, Pb -9%) were observed. Despite lower pseudo-total PTE contents, exchangeable PTEs associated with carbonate content increased over time (Cu +188%, Ni +557%, Pb +99%). Modeling indicated climatic variables and short-range oxides substantially influenced PTE bioavailability, emphasizing the ephemeral Fe oxide control during the wet season and heightened ecological and health risks during the dry seasons.