Control of trace metal distribution and variability in an interdunal wetland

Trace elements are serious pollutants in the natural environment and are of increasing concern due to the adverse effects at global scale. To refine the current understanding of trace metal distribution and variability in natural environments, concentrations of dissolved trace metals (Ag, Al, As, B, Ba, Be, Co, Cr, Cd, Cu, Fe, Hg, Mo, Ni, Pb, Sb, Se, Th,Tl, U, V, Mn, Zn), major ions, inorganic nutrients (NO₃, PO₄), TOC and stable isotopes of water were determined in water samples from rainwater, seven piezometers and a pond in the coastal Doñana wetland during four sampling campaigns between 2017 and 2019. Results show clear evaporation signatures of stable isotopes in the pond but not in the groundwater. Hydrochemical analyses yield significant, systematic changes in groundwater trace metal and nutrient composition along the flowpath from the dune belt to the pond, controlled by organic matter in the sediments. Whereas major ions reached maximum concentrations in the pond due to evapoconcentration, most trace metals showed highest concentrations at sites with lower redox levels, except for B, As and U, which showed very high concentrations in the pond. Cu, Zn, Ni, Sb and Tl yielded higher median concentrations in rainwater than in most of the groundwater points and in case of Cu and Zn higher even than in surface water which points to an atmospheric input source of these elements. Temporal variability of trace metals was related to lower hydraulic heads after an elongated dry period which led to lower redox levels and higher concentrations of most of the trace elements whereas major ions showed more constant concentration levels. This is of special concern regarding climate change and the predicted higher frequency of prolonged dry periods, which could modify the natural hydrochemical patterns in undisturbed wetlands systems.