Heavy metal contents in water, sediment and fish in a karst aquatic ecosystem of the Plitvice Lakes National Park (Croatia)

An evaluation of the quality status of the pristine karst, tufa depositing aquatic environment of the Plitvice Lakes National Park based on the analysis of heavy (ecotoxic) metals was examined for the first time. Analyses of trace metals in water, sediment and fish (Salmo trutta, Oncorhynchus mykiss, Squalius cephalus) samples were conducted either by stripping voltammetry (Zn, Cd, Pb and Cu) or cold vapour atomic absorption spectrometry (Hg). The concentration of dissolved trace metals in water was very low revealing a pristine aquatic environment (averages were, in ng/L: 258 (Zn), 10.9 (Cd), 11.7 (Pb), 115 (Cu) and 1.22 (Hg)). Slightly enhanced concentrations of Cd (up to 50 ng/L) and Zn (up to 900 ng/L) were found in two main water springs and are considered as of natural origin. Observed downstream decrease in concentration of Cd, Zn and Cu in both water and sediments is a consequence of the self-purification process governed by the formation and settling of authigenic calcite. Anthropogenic pressure was spotted only in the Kozjak Lake: Hg concentrations in sediments were found to be up to four times higher than the baseline value, while at two locations, Pb concentrations exceeded even a probable effect concentration. The increase of Hg and Pb was not reflected on their levels in the fish tissues; however, significant correlations were found between Cd level in fish tissues (liver and muscle) and in the water/sediment compartments, while only partial correlations were estimated for Zn and Cu. A high discrepancy between values of potentially bioavailable metal fraction estimated by different modelling programs/models raised the question about the usefulness of these data as a parameter in understanding/relating the metal uptake and their levels in aquatic organism. The aquatic environment of the Plitvice Lakes National Park is characterized, in general, as a clean ecosystem.