Natural and anthropogenic sources of Hg, Cd, Pb, Cu and Zn in seawater and sediment of Mljet National Park, Croatia

Abstract

Distributions of Hg, Cd, Pb, Cu and Zn in seawater and sediment from Mljet National Park, Adriatic Sea are presented for the first time. Natural and anthropogenic factors play an important role in determining resultant trace metals' concentrations in the region. We place particular emphasis on the saline “lakes” of Malo Jezero and Veliko Jezero, which have restricted flows of seawater. In Malo Jezero lake, fresh karstic spring water generated by flooding, and weathering of dolomites are the main sources of naturally elevated Cd, Pb and Zn concentrations (20.7 ± 1.6, 289 ± 19, 1260 ± 0.08 ng L −1, respectively); anthropogenic input is negligible. In Veliko Jezero lake enhanced Cu and Zn contents originate from anthropogenic input (tourism and agriculture). Distributions of the Pb and Zn in the water columns of both lakes are influenced by natural aragonite precipitation and sedimentation. Exceptionally high total Hg concentrations of 24.2 and 33.7 ng L −1 in the water column of Malo Jezero, sampled during periods of high rainfall associated with strong eastern winds, suggest an airborne input. Total Hg concentrations in waters of both lakes are elevated because of inefficient mixing. Two different metal distribution patterns exist in the sediment columns. First, Hg, Pb, Cu and Zn show elevated concentrations in recent sediments due to anthropogenic input. Second, Cd content increases with depth due to reprecipitation via a downward redox boundary shift. Described natural processes, as well as anthropogenic influence, enhance levels of trace metals. Careful study followed by suitable interpretation based on geochemical data were necessary to distinguish natural from anthropogenic sources.