The relationship between whole effluent toxicity (WET) and chemical-based effluent quality assessment in Vojvodina (Serbia)

The relationship between whole effluent toxicity (WET) and chemical-based effluent quality assessment across a range of effluent types was examined for the first time in Serbia. WET was determined by Daphnia magna acute tests, while chemical-based toxicity was taken as theoretical for concentrations of priority chemicals and effluent quality assessment based on the valid Serbian regulations. A poor correlation was found between WET and chemical-based effluent quality assessment: positive toxicity tests were found, in general, in cases where samples satisfied the requirements of mandatory effluent monitoring. Statistically insignificant correlation between the predicted and observed toxicity indicated that the presence of priority substances accounted to the overall toxicity only to a certain degree, most probably due to a rather short list of priority pollutants regularly analysed in effluents. Current monitoring requirements neglect hazards that derive from potentially present toxicants and unpredictable toxicity of complex mixtures, which led to poor correlation between the WET and chemical-based results in this study.     

Seasonal Differences in the Levels of Gaseous Air Pollutants in the Vicinity of a Waste Dump

Hydrogen sulphide, ammonia, nitrogen dioxide, mercaptans and sulphur dioxide (H₂S, NH₃, NO₂, R-SH, SO₂) concentrations were measured at the location in the vicinity of the waste dump to determine the air pollution level of these pollutants prior to the operation of the Mobile Thermal Treatment Plant. Samples were collected over one year period. Seasonal differences, and the influence of meteorological parameters (temperature, relative humidity, pressure and wind direction) on the air pollution levels were studied. Results show relatively low concentrations of H₂S, NO₂, R-SH and SO₂, while NH₃ levels were higher compared to the guideline values. Good weather conditions (high air pressure and low relative humidity) are connected to long range transport of NO₂, while higher temperatures result in elevated NH₃ and R-SH concentrations. Because of the predominant northeast wind direction (the same as the waste dump direction), the contribution of air pollution from the direction of the waste dump at the measuring site is significant, but that does not necessarily mean that the pollutants originated from that source.     

Heavy metal concentration in fish tissues inhabiting waters of “Buško Blato” reservoar (Bosnia and Herzegovina)

Heavy metals concentration (mercury, lead, cadmium, arsenic, copper, zinc and chromium) in tissues (muscles, liver, kidney and gonads) of Dalmatian barbelgudgeon, the nase, the souffie and brown trout, inhabiting waters of Busko Blato reservoir in Bosnia and Herzegovina, has been determined by atomic absorption spectrophotometry. The meat of the tested fish sorts does not contain elevated concentration of most analyzed heavy metals with exception of lead (higher than MAC in Italy, Germany and Denmark) and mercury (in muscles of brown trout higher than MAC in most countries). The lowest level of all heavy metals is always detected in gonads, with higher values in fry compared to milt for copper, zinc, chromium and arsenic. The highest copper concentration is observed in the liver from the souffie which is suggested as a suitable biomonitor for copper intoxication. In muscles of all fish sorts, lead was always present in much higher concentration than cadmium, while in kidneys of most fish sorts, lead and cadmium concentrations were similar. We showed that bioaccumulation of some heavy metals in the fish sorts analyzed is tissue and sex dependent. Also, we concluded that the small water exchange in reversible shallow reservoir does not induce elevated concentration of heavy metals in fish tissues inhabiting Busko Blato.     

Mate sampling behaviour of black grouse females (Tetrao tetrix)

We studied female mate sampling behaviour in lekking black grouse (Tetrao tetrix). Females mainly visited males occupying territories in the centre of the lek with relatively large territories. They were also more likely to visit males that had high attendance. The same factors were also correlated with male mating success. A multiple regression model including these factors explained more of the variance in female visits per male (53%) than in mating success (33%). The pattern of female sampling conformed with a pool comparison (best-of-n) tactic. Such a tactic is expected if the costs of sampling are low. Females of high body mass visited more males than lighter females, however, which indicates that females may vary in their search tactics and suggests that there may be search costs. The existence of costs is further suggested by the fact that if the mate from a previous year was still present, females always mated with the same male in the following year. Though search costs were not measured directly, our findings suggest that some costs are negligible (e.g. energetic exhaustion or predation) whereas others (timing of mating) may be more important.     

Multiple kinetic Langmuir modeling to predict the environmental behaviour of As(v) in soils

A soil with a relatively high Fe content (2.82% [w/w]) was loaded for up to one year with As(v) by equilibrating it with a solution containing 1000 mg l(-1) As(v) at a soil mass-to-solution ratio of 0.1 kg l(-1). The incorporation of As(v) into the soil and its distribution over the soil phases were monitored by sampling at strategic time intervals using an operationally defined five-step sequential extraction procedure (Wenzel et al., Anal. Chim. Acta, 2001, 436, 309) and subsequent As measurement. A multiple kinetic Langmuir model was developed to retrieve the dynamic parameters (adsorption and desorption rate constants, capacities and Langmuir equilibrium constants) for each of the soil phases by numerical fitting of the experimental adsorption data to the model. Under the equilibration conditions used the adsorption rate constants for all five operationally defined soil phases were very similar but the desorption rate constants decreased by a factor of ca. 150 from soil phase 1 (non-specifically sorbed As) to 5 (residual phases). This implies that As(v) incorporation "deeper" into the soil leads to stronger binding which is associated with the Langmuir equilibrium constants (adsorption rate constants/desorption rate constants). Equilibration of the soil with As(v) was complete in ca. 10 days with As(v) predominantly bound to soil phase 2 (specifically sorbed As) and soil phase 3 (amorphous and poorly crystalline hydrous oxides). X-Ray absorption spectroscopy techniques revealed that these binding characteristics may be related to adsorption of As(v) on Si- and/or Al-containing structures and natural hydrous iron oxide (HFO) surface sites, respectively. Since the model is independent of the initial As(v) concentration in the solution and the soil mass-to-solution ratio, the behaviour of the thus characterized soil-As(v) system can be predicted for a range of conditions. Simulations showed that in an accidental As(v) spill the soil studied would actively scavenge As(v) by instantaneous adsorption onto all soil phases followed by redistribution of As(v) from weaker binding sites to stronger ones over time.     

Chemical dynamics of the Sava riverine system

Presented here is a study of the geochemical dynamics of the entire River Sava watershed, a major tributary of the River Danube which has not previously been investigated. The sampling was performed at 33 selected locations along the main channel of the stream and at its largest tributaries during three sampling seasons (fall 2005, spring 2006 and fall 2006), going from headwater locations to the mouth near the confluence with the Danube. Almost 80% of the solutes are derived from carbonate mineral weathering and represent over 50% of specific HCO(3)(-) flux normalized to unit basin area at the mouth of the Danube. Statistical analysis indicates that agricultural and industrial sources contribute significantly to increased Na(+), K(+), Cl(-), SO(4)(2-) and NO(3)(-) concentrations in tributary waters. Different processes control the water chemistry along the course of the Sava's drainage-the upper reaches are largely regulated by contributions from carbonate mineral weathering, the middle reaches are influenced by agricultural activity and biological processes related to eutrophication, while the lower reaches tend to have more pronounced parameters related to the industrial processing along with leakages from municipal sanitary systems of these higher population density areas.     

A complex investigation of the extent of pollution in sediments of the Sava River. Part 1: Selected elements

The Sava River is the biggest tributary to the Danube River. As a part of the 6th FW EU project, Sava River Basin: Sustainable Use, Management and Protection of Resources (SARIB), ecological status of sediments was investigated. In order to assess the geographical distribution in sediment contamination of the Sava River, inorganic and persistent organic pollutants were analyzed in sediments at 20 selected sampling sites along the Sava River from its spring to its outfall into the Danube River. For comparability of data to other river basins the sediment fraction below 63 μm was studied. Due to complexity of the work performed, the results are published separately (“Part I: Selected elements” and “Part II: Persistent organic pollutants”). In the present study, the extent of pollution was estimated by determination of the total element concentrations and by the identification of the most hazardous highly mobile element fractions and anthropogenic inputs of elements to sediments. To assess the mobile metal fraction extraction in 0.11 mol L^???1, acetic acid was performed (first step of the Community Bureau of Reference extraction procedure), while anthropogenic inputs of elements were estimated on the basis of normalization to aluminum (Al) concentration. According to the Water Framework Directive, the following elements were investigated in sediments: cadmium (Cd), lead (Pb), nickel (Ni), and mercury (Hg). Furthermore, copper (Cu), zinc (Zn), chromium (Cr), arsenic (As), and phosphorous (P) were determined. The analyses of sediments demonstrated slightly elevated values for Hg, Cr, and Ni in industrially exposed sites (concentrations up to 0.6, 380, and 210 mg kg^???1, respectively). However, the latter two elements exist in sparingly soluble forms and therefore do not represent an environmental burden. P concentrations were found in elevated concentrations at agricultural areas and big cities (up to 1,000 mg kg^???1).     

Acid dissolution methods for heavy metals determination in pine needles

Microwave digestion procedures using HNO₃, HNO₃+H₂O₂, HNO₃+HClO₄, HF mixtures and dry ashing with HF were investigated for heavy metals analysis by either inductively coupled plasma-optical emission spectroscopy (ICP-OES) or ICP-mass spectrometry (ICP-MS) in pine needles. The HF digestion procedures gave about 1.5 times higher values than a mixture of HNO₃+H₂O₂ alone. For Ti determination in needles, the HF procedure using dry ashing is thus recommended. The mean concentrations amounted to 900 mg/kg for Fe and 21.8 mg/kg for Ti in needles collected at an area polluted by a stainless steel works. Those concentrations were 10.6 and 4.3 times higher than in needles collected at an area nearby a pulp mill complex (84.5 mg/kg Fe and 5.0 mg/kg Ti).