Correlation of metals and degraded marine (micro)plastic litter in geologically similar coastal areas with different anthropogenic characteristics.

The association and statistical correlation of anthropogenically important trace metals (TM) Cd, Cu, Pb, Zn and degraded marine microplastic (MP) extracted from the bulk debris samples at two locations from two marine systems, estuarine and coastal, in the Croatian Adriatic coastal area were assessed. The abundance of MP particles at both sites were primarily defined by local wave climate, with the open coastal site containing 9-fold more microplastic particles (>4 mm) as compared to the semi-closed estuarine, or twice as much considering bulk plastics. Generally, the higher abundance of adsorbed metal on MP were observed in the more anthropogenically influenced estuary than in the open coastal site and followed the order: polystyrene > polypropylene > low density polyethylene. The amounts of adsorbed zinc were the highest on all types of plastics at both sites, while the affinity of polystyrene for metals followed: Zn > Pb ≈ Cu > Cd.

Assessing trace metal contamination and organic matter in the brackish lakes as the major source of potable water.

On small and medium karstic coastal islands in the Adriatic Sea, brackish lakes are often the only source of freshwater. Therefore, it is important to adequately evaluate the biogeochemical processes occurring in these complex water systems, as well as to determine the origin of contaminants present. In this study, the distribution and origin of trace metals (Tl, Hg, Cd, Pb, Cu, Zn, Ni, Co) and organic matter in the water column, sediment, and surrounding soil of the brackish lakes on Mljet Island, South Adriatic Sea, Croatia, were evaluated. Thallium and mercury concentrations in the lake water were up to two orders of magnitude higher compared to ranges found in the adjacent coastal sea water. Elevated thallium concentrations were of anthropogenic origin resulting from previous use of rodenticide, while elevated mercury content was naturally enhanced. Levels for the other metals were characteristic of uncontaminated water systems. Speciation modelling showed that dissolved trace metals such as Cu, Pb, and Zn were mostly associated with organic matter, while Tl, Co, and Ni were present predominantly as free ions and inorganic complexes. The presence of organic matter (OM) clearly influenced the speciation and distribution of some trace metals. OM was characterised by the determination of the complexing capacity for Cu ions (CuCC), surface active substances, and catalytically active compounds. Reduced sulphur species (glutathione and other thiols) representing significant Cu-binding ligands were determined and discussed as well.

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.

A comparison of anthropogenic mercury pollution in Kastela Bay (Croatia) with pristine estuaries in Ore (Sweden) and Krka (Croatia).

Anthropogenic mercury pollution was studied in Kastela Bay (Croatia), 10 years after chloralkaline plant (PVC) stopped production. The concentration of total mercury determined in sediments which are composed mainly of calcite and quartz, are in the range 14,280-30,400 ng/g. The values are higher than reported in the literature for Elbe and Seine estuaries and also above 25,000 ng/g used for criterion in remediation project in Minamata Bay. The concentration of methylmercury 6.05-36.74 ng/g are typical for slightly to highly contaminated estuarine sediments. The low ratio of methylmercury to total mercury found in sediments of Kastela Bay is in the range 0.04-0.18%. It can be explained that in this region predominate conditions which do not promote in-situ methylation. Sediments were found to be highly anoxic. Concentrations of total mercury in unfiltered surface waters are in the range 69-145 ng/l and in unfiltered bottom waters in the range 230-1,418 ngl(-1). High concentrations found in bottom waters suggest that either resuspension or partial dissolution of sediments takes place. An experiment performed on filtered and unfiltered waters showed that about 85% of total mercury in surface water and almost 100% in bottom water was retained on 45 microm filters. To demonstrate contrasts, two pristine estuaries from norths and south Europe were studied. Silicious sediments of Ore estuary (Sweden) and calcareous sediments of Krka estuary (Croatia) have total mercury concentrations close to accepted background level. The ratio of methylmercury to total mercury is < or = 1% in all samples with one exception. The highest observed ratio (2.70%) was in the surface sediment from E2 station in Krka estuary measured in March 2000. This location is suitable for studying methylmercury formation in pristine environment.