Spatial distribution of trace metals in the Krka River, Croatia: an example of the self-purification

The spatial distribution of dissolved and total trace metals (Zn, Cd, Pb and Cu) in the Krka River (partly located in the Krka National Park) has been studied using a "clean" sampling, handling and analysis technique. Differential pulse anodic stripping voltammetry (DPASV) with a hanging mercury drop electrode (HMDE) has been used for trace metal analysis. The Krka River has been divided into the upper and lower flow region with respect to the metals concentration and main physico-chemical parameters. A significant increase in trace metal concentration as the result of the untreated waste water discharge downstream of Knin Town has been registered in the upper flow region. Due to a specific characteristic of the Krka, the so-called self-purification process, a decrease in the elevated trace metals concentration from the water column takes place at numerous small lakes formed by tufa barriers (at the end of the upper flow region). The clean groundwater input at the beginning of the lower flow region additionally contributes to the observed decrease in trace metals concentration in the Krka, maintaining them at a very low level in the remaining region of fresh-water flow. The determined median total concentrations were zinc 120-7400 ng l(-1), cadmium 3-8 ng l(-1), lead 11-250 ng l(-1) and copper 110-440 ng l(-1). Karst rivers, such as the Krka River, with extremely low natural concentrations of trace metals are highly sensitive to the anthropogenic influence. Therefore, such aquatic systems require implementation of strict protection regimes in the entire catchments area.     

Biomonitoring of heavy metals in fish from the Danube River

The Croatian part of the Danube River extends over 188 km and comprises 58 % of the country’s overall area used for commercial freshwater fishing. To date, the heavy metal contamination of fish in the Croatian part of the Danube has not been studied. The main purpose of this study was to determine heavy metal levels in muscle tissue of sampled fish species and to analyze the measured values according to feeding habits of particular groups. Lead ranged from 0.015 μg^?1 dry weight in planktivorous to 0.039 μg^?1 dry weight in herbivorous fish, cadmium from 0.013 μg^?1 dry weight in herbivorous to 0.018 μg^?1 dry weight in piscivorous fish, mercury from 0.191 μg^?1 dry weight in omnivorous to 0.441 μg^?1 dry weight in planktivorous fish and arsenic from 0.018 μg^?1 dry weight in planktivorous to 0.039 μg^?1 dry weight in omnivorous fish. Among the analyzed metals in muscle tissue of sampled fish, only mercury exceeded the maximal level (0.5 mg kg^?1) permitted according to the national and EU regulations determining maximum levels for certain contaminants in foodstuffs, indicating a hazard for consumers of fish from the Danube River.     

Controlling factors of phytoplankton seasonal succession in oligotrophic Mali Ston Bay (south-eastern Adriatic)

Fine spatial and temporal phytoplankton variability in Mali Ston Bay has been observed for the first time based on physicochemical properties and small herbivorous zooplankton. Extensive year-through research was conducted during 2002 at Usko station which is traditionally an area of intensive shellfish farming. The Neretva River inflow, submarine springs (“vruljas”) and precipitation are additional sources of nutrients in the bay. Temperature and salinity, combined with total inorganic nitrogen (TIN) were observed to be the most important environmental factors driving the succession of phytoplankton communities. Orthophosphate was a potential limiting factor for phytoplankton development. The nanophytoplankton abundances, as well as the microphytoplankton diatoms are controlled by herbivorous zooplankton grazing (‘top-down’ control) more than other groups of microphytoplankton. Nanophytoplankton dominated phytoplankton abundance and its most intensive development was recorded in winter and spring, while increase in microphytoplankton abundance occurred in spring and autumn. Diatoms dominated microphytoplankton abundance mostly in winter and autumn, while dinoflagellates dominated in spring and summer. Considering the number of taxa and abundance, dinoflagellates were the dominant microphytoplankton group during the year and were the main component of the spring blooms. At that time, in conditions of elevated temperature (>16 °C), decreased salinity (34–36) and increased concentrations of TIN, blooms of harmful dinoflagellate Prorocentrum minimum were recorded for the first time in the bay. The results showed a significant difference in environmental conditions, as well as in the annual phytoplankton succession and community structure, as compared with studies carried out more than 20 years ago in this area.     

Transfer of natural and anthropogenic radionuclides to ants, bryophytes and lichen in a semi-natural ecosystem

Few data are available to quantify the transfer of both natural and anthropogenic radionuclides to detritivorous invertebrates to facilitate estimation of the internal dose to such biota in models used to assess radiation exposure. To enhance the available data, activity concentrations of ¹³⁷Cs, ⁴⁰K, ⁹⁰Sr, ^239?+?240Pu, ²⁴¹Am, ²³⁵U and ²³⁸U were measured in ants (Formicidae) and corresponding undisturbed soil collected from the Zlatibor mountain in Serbia and ant/soil concentration ratios (CR) calculated. The ²⁴¹Am concentration ratios for ants were fourfold higher than those calculated for ants in a previous study whereas they are similar to the more numerous data previously reported for a range of detritivorous invertebrates in other studies. CR values for ¹³⁷Cs in ants were similar to the few other reported values and slightly lower than those for a range of detritivorous invertebrates. Those for ^239?+?240Pu were slightly higher than those for ants in two other studies but they were close to upper limit of a range of data reported for detritivorous invertebrates. All the CR values will be included in a future revision of the ERICA Tool database and will particularly improve the information available for uranium.     

Cancer risk assessment after exposure from natural radionuclides in soil using Monte Carlo techniques

Purpose  

The purpose of this paper is to assess fatal cancer risk after external and internal (inhalation and ingestion) exposure from natural radionuclides in soil like ²³⁸U, ²³²Th, ⁴⁰K, and ²²⁶Ra on the territory of Bela Crkva, Serbia. Although receiving doses are low from sources like natural radionuclides in soil, because of stochastic effects of ionizing radiation, risk for developing cancer exists and can be quantified.     

Monitoring of nitrates in drinking water from agricultural and residential areas of Podravina and Prigorje (Croatia)

Nitrates are the most common chemical pollutant of groundwater in agricultural and suburban areas. Croatia must comply with the Nitrate Directive (91/676/EEC) whose aim is to reduce water pollution by nitrates originating from agriculture and to prevent further pollution. Podravina and Prigorje are the areas with a relatively high degree of agricultural activity. Therefore, the aim of this study was, by monitoring nitrates, to determine the distribution of nitrates in two different areas, Podravina and Prigorje (Croatia), to determine sources of contamination as well as annual and seasonal trends. The nitrate concentrations were measured in 30 wells (N?=?382 samples) in Prigorje and in 19 wells (N?=?174 samples) in Podravina from 2002 to 2007. In Podravina, the nitrate content was 24.9 mg/l and 6 % of the samples were above the maximum available value (MAV), and in Prigorje the content was 53.9 mg/l and 38 % of the samples above MAV. The wells were classified as correct, occasionally incorrect and incorrect. In the group of occasionally incorrect and incorrect wells, the point sources were within 10 m of the well. There is no statistically significant difference over the years or seasons within the year, but the interaction between locations and years was significant. Nitrate concentrations’ trend was not significant during the monitoring. These results are a prerequisite for the adjustment of Croatian standards to those of the EU and will contribute to the implementation of the Nitrate Directive and the Directives on Environmental Protection in Croatia and the EU.     

Effect of water matrices on removal of veterinary pharmaceuticals by nanofiltration and reverse osmosis membranes

This study explored the removal of five veterinary pharmaceuticals (VPs) (sulfamethoxazole (SMETOX), trimethoprim (TMP), ciprofloxacin (CIPRO), dexamethasone (DEXA) and febantel (FEBA)) from different water matrices (Milli-Q water, model water, tap water and real pharmaceutical wastewater using four types of nanofiltration (NF) membranes (NF90, NF270, NF and HL) and two reverse osmosis (RO) membranes (LFC-1 and XLE). All VPs were added to different water matrices at a concentration of 10 mg/L. Rejections of VPs and water flux were measured. The rejection increased with increase of molecular weight. The highest rejections were obtained with RO membranes (LFC-1, XLE) and tight NF (NF90) membrane. In general, the rejection of VPs was higher in model water and tap water than in Milli-Q water, but the water flux was lower. This was mainly explained by ion adsorption inside the membranes pores. Narrower pore size counteracted the effect of presence of low concentration of natural organic matter (NOM) in tap water. The NOM was assumed to enhance the adsorption of VPs onto membrane surface, increased the size exclusion and electrostatic repulsion also appeared during the transport. Investigated water matrices had influence on water flux decline due to their complexity.     

On vertical distribution of tintinnines (Ciliata,Oligotrichida, Tintinnina) in the open waters of the South Adriatic

The vertical distribution of tintinnines was studied in the open sea of the South Adriatic at a station near the city of Dubrovnik (Station 12) in the period from 1979–1980 as well as at 11 stations during a cruise in January 1980. Samples were taken with the 53-m Nansen type net equipped with a closing system. The hauls were taken in 7 vertical layers. In the area investigated 72 species of tintinnines were observed. Six dominating species contributed from 30 to 93%, an average of 63% of the total numerical abundance of tintinnines. Based on the occurrence of the majority of the population of individual species going from the surface towards the sea bottom, the tintinnines have been divided into 5 groups. Most of the species (42), presenting more than 90% of the population, were found in the layer between the surface and a depth of 100 m. Other species were found in deeper layers (rarely or almost never at the surface).     

Ex situ bioremediation of a soil contaminated by mazut (heavy residual fuel oil)--a field experiment

Mazut (heavy residual fuel oil)-polluted soil was exposed to bioremediation in an ex situ field-scale (600 m(3)) study. Re-inoculation was performed periodically with biomasses of microbial consortia isolated from the mazut-contaminated soil. Biostimulation was conducted by adding nutritional elements (N, P and K). The biopile (depth 0.4m) was comprised of mechanically mixed polluted soil with softwood sawdust and crude river sand. Aeration was improved by systematic mixing. The biopile was protected from direct external influences by a polyethylene cover. Part (10 m(3)) of the material prepared for bioremediation was set aside uninoculated, and maintained as an untreated control pile (CP). Biostimulation and re-inoculation with zymogenous microorganisms increased the number of hydrocarbon degraders after 50 d by more than 20 times in the treated soil. During the 5 months, the total petroleum hydrocarbon (TPH) content of the contaminated soil was reduced to 6% of the initial value, from 5.2 to 0.3 g kg(-1) dry matter, while TPH reduced to only 90% of the initial value in the CP. After 150 d there were 96%, 97% and 83% reductions for the aliphatic, aromatic, and nitrogen-sulphur-oxygen and asphaltene fractions, respectively. The isoprenoids, pristane and phytane, were more than 55% biodegraded, which indicated that they are not suitable biomarkers for following bioremediation. According to the available data, this is the first field-scale study of the bioremediation of mazut and mazut sediment-polluted soil, and the efficiency achieved was far above that described in the literature to date for heavy fuel oil.