A size partitioning of several trace metals (Zn, Cd, Pb, Cu, Ni, Co, Mn, Fe and Al) between five size fractions (5 µm) was studied in the vertical salinity gradient of the highly stratified Krka River estuary. The results indicated a dominant river source for Zn, Co, Mn, Fe and Al and a diluting effect on Cd, Pb and Ni. The truly dissolved fraction (5 µm particles. Pb, Mn, Fe and Al were closely related, showing a precipitation and colloidal aggregation in the surface layers and dissolution in the seawater layer. The highest percentage (30–37%) of colloids (3 kDa–0.1 µm) in the dissolved pool was found for Pb, Cu, Fe and Al. Differences in size distribution between low and high river flow periods revealed that Zn, Pb, Co, Mn, Fe and Al are introduced by the river mostly in the 3 kDa–5 µm size range. Therefore, a low percentage of colloidally bound metals compared to other coastal areas can be explained by a limited riverine input of terrigenous material, characteristic for this estuary. Correlation with PARAFAC components revealed associations of Cu with protein-like substances and Co with humic-like substances. The accumulation of Cu at the freshwater-seawater interface coupled with an increase of its colloidal fraction was observed, apparently governed by biologically produced organic ligands.

To evaluate the level of contamination and predict the potential toxicity risk, selected metal concentrations (Cd, Pb, Cr, Mn, Co, Ni, Cu, Zn, and As) were determined in 40 surface sediment samples from the stratified karstic Krka River estuary (Croatia). In addition, diffusive gradients in thin films (DGT) probes were deployed in situ to understand the mobilization mechanisms and bioavailability of metals in the sediment. The results show significant spatial differences between the upper and lower estuary, with the latter being more affected by anthropogenic pollution. The pollution assessment using the enrichment factor (EF), the geoaccumulation index (Igeo), and the pollution load index (PLI) showed a strong enrichment of metals in the lower part of the estuary, especially of Mn, Cu, Zn, Pb, and As. The statistical analysis (PCA) revealed the former ferromanganese factory and the port as major sources of pollution in the area. Nickel, Co, and Cr, although slightly elevated, may be attributed to the natural origin. The metal mobility in the estuarine sediment was primarily governed by early diagenetic processes (aerobic organic matter mineralization, Fe and Mn oxyhydroxide reduction), which caused the release of metals from the sediment into the pore water and subsequently into the overlying water column.