Nutrient fluxes and sulfur cycling in the organic-rich sediment of Makirina Bay (Central Dalmatia, Croatia).

Fluxes of dissolved nutrients in the organic-rich sediment of Makirina Bay (Croatia) were estimated in in-situ incubation experiments and compared to those calculated from a diagenetic model based on the concentration vs. depth profiles in the pore water extracted from a sediment core at the same sampling site. Benthic fluxes observed in the in-situ experiment were strongly influenced by the decomposition of sedimentary organic matter by bacterial sulfate reduction and precipitation of authigenic pyrite and calcite. Assimilation of dissolved nitrate and ammonia within the sediment resulted in peculiar nitrate and ammonia concentration profiles. Differences between the benthic and diffusive fluxes indicated that the effects of bioturbation and irrigation, which were not taken into account in the model calculation of diffusive fluxes, should not be considered as negligible. They are, however, extremely difficult to estimate because of the heterogeneity of the sediment. Sulfate reduction in the pore water could not be detected, although it was obvious from pyrite precipitation and the isotopic compositions of different sedimentary sulfur species. It is suggested that reoxidation of sulfide and upward diffusion of sulfate from the sediment layer accumulated during past salt production can account for the scattered sulfate vs. depth profile. The distribution and stable isotope compositions of sedimentary sulfur species were studied in more detail. The influx of sulfate was explained by rapid sulfate reduction in the sediment. The sulfate reduction rate was highest in the upper part of the sediment column, as concluded from delta(34)S values. In lower horizons, the concentration of organic sulfur increased, while concentrations of sulfide decreased. The mirror-imaged concentration vs. depth profiles of sulfide and organic sulfur, as well as their stable isotopic compositions, show that they were formed simultaneously, most probably in competitive processes.

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.