Water Quality of Medium Size Watercourse Under Baseflow Conditions: The Case Study of River Sutla in Croatia

The study on medium size river Sutla in Croatia indicated considerable water contamination at specific sites during the baseflow period, probably associated to low flow-rate (0.73-68.8 m3 s(-1)), and consequently low dilution capacity of this river. Various aspects of contamination were observed: increased conductivity to 1,000 microS cm(-1), decreased dissolved oxygen level to 50%, 4-5 degrees C increased water temperature, increased concentrations of several dissolved trace elements (e.g., maximal values of Li: 45.4 microg l(-1); Rb: 10.4 microg l(-1); Mo: 20.1 microg l(-1); Cd: 0.31 microg l(-1); Sn: 30.2 microg l(-1); Sb: 11.8 microg l(-1); Pb: 1.18 microg l(-1); Ti: 1.03 microg l(-1); Mn: 261.1 microg l(-1); and Fe: 80.5 microg l(-1)) and macro elements (e.g., maximal values of Na: 107.5 mg l(-1); and K: 17.3 mg l(-1)), as well as moderate or even critical fecal (E. coli: 4,888 MPN/100 ml; total coliforms: 45,307 MPN/100 ml; enterococci: 1,303 MPN/100 ml) and organic pollution (heterotrophic bacteria: 94,000 cfu/ml). Although metal concentrations still have not exceeded the limits considered as hazardous for aquatic life or eventually for human health, the observed prominent increases of both metal concentrations and bacterial counts in the river water should be considered as a warning and incentive to protect the small and medium size rivers from the future deterioration, as recommended by EU Water Framework Directive.     

Toxicity of analytically cleaned pentabromodiphenylether after prolonged exposure in estuarine European flounder (Platichthys flesus), and partial life-cycle exposure in fresh water zebrafish (Danio rerio)

Residues of polybrominated diphenylethers (PBDEs), extensively applied as flame retardants, are widely spread in the aquatic environment and biota. The present study investigates effects of the environmentally relevant lower brominated diphenylethers in two fish species in vivo under controlled laboratory conditions. Euryhaline flounder (Platichthys flesus) and freshwater zebrafish (Danio rerio) were exposed to a range of concentrations of a commercial pentabromodiphenylether mixture, DE-71. Chemical analysis of exposed fish showed a pattern of PBDE congeners that was very similar to that in wild fish. The resulting range included environmentally relevant, as well as higher levels. Animals were investigated histopathologically with emphasis on endocrine and reproductive organs. In zebrafish, hatching of embryos and larval development were assessed. Biochemical parameters were investigated in flounder as markers for suggested dioxin-like activity (ethoxyresorufin-O-deethylase=EROD), and activation of endogenous estrogen synthesis (gonad aromatase activity). Thyroid hormones were analyzed in plasma in both species. Benchmark analysis using internal PBDE concentrations showed a mild dose-dependent decrease of hepatic EROD and ovarian aromatase activities, and plasma thyroxin levels in flounder, and an increase of plasma thyroid hormone levels in zebrafish. These trends did not result in statistically significant differences from control fish, and major histopathological changes were not observed. Reproduction in zebrafish appeared to be the most sensitive parameter with statistically significantly reduced larval survival and non-significant indications for decreased egg production at internal levels that were more than 55 times the highest environmental recordings. The present results indicate limited risk for endocrine or reproductive effects of current environmental PBDE contamination in fish.     

Depleted uranium mobility and fractionation in contaminated soil (Southern Serbia)

GOAL, SCOPE AND BACKGROUND: During the Balkan conflict in 1999, soil in contaminated areas was enriched in depleted uranium (DU) isotopic signature, relative to the in-situ natural uranium present. After the military activities, most of kinetic DU penetrators or their fragments remained buried in the ground in certain geomorphological and geochemical environments exposed to local weathering conditions. The contamination distribution, mobility and/or fixation of DU in the contaminated soil profile at one hot spot were the subject of our study. The results should disclose what happened with released DU corrosion products in three years elapsed, given the scope of their geochemical fractionation, and mark out the most probable host substrates in investigated soil type. METHODS: Gamma-spectrometric analysis of soil samples taken in the DU penetrator impact-zone was done to obtain present contamination levels. Set of samples is subjected to five-step and three-step sequential extraction procedures, specifically selective to different physical/chemical associations in soil. The stable elements are determined in extracts by the atomic absorption spectroscopy. After the ion-exchange based uranium separation procedure, alpha-spectrometric analysis of obtained fractions was done and DU distribution in five extraction phases found from 235U/238U and 234U/238U isotopic ratios. RESULTS: Depleted uranium concentration falls down to the 1% of the initial value, at approximately 150 mm distance to the source. Carbonates and iron/manganese hydrous oxides are indicated as the most probable substrates for depleted uranium in the characterized soil type. Therefore, in the highly contaminated soil samples, depleted uranium is still weakly bonded and easy exchangeable. The significant levels of organic-bonded depleted uranium are found in surface soil only. DISCUSSION: Dependence of the fractionation on the contamination levels is evident. Samples with higher DU contents have shown a longer maintenance in the exchangeable phases, probably because adsorption/desorption mass transfer through the medium was not very fast. Organic-bonded, depleted uranium is present in surface soil samples due to its higher humus content. Considering geochemical composition of investigated soil, the indicating chemical associations as substrates are in agreement with some considerations based on the results for low-level waste unsaturated zones. CONCLUSIONS: The soil contamination with depleted uranium in investigated area is still 'spot' type and not widespread. Dependence of the fractionation on the contamination levels and presence of weakly bonded, depleted uranium in the hot spots areas is evident. RECOMMENDATIONS AND PERSPECTIVES: A detailed study may be undertaken with suitable extractive reagents to define a bio-available fraction of depleted uranium in soil. The comparison of results for different soil types investigated by the same methodology may be useful. An applied combination of physical/chemical procedures and analysis may help in the decision making on the remediation strategy for sites contaminated with depleted uranium used in military operations.     

Comparative toxicity of imidacloprid, of its commercial liquid formulation and of diazinon to a non-target arthropod, the microcrustacean Daphnia magna

Imidacloprid (IMI) is at the moment the insecticide with the world's fastest growing sales and is considered possible replacement for the widely used organophosphorus pesticide, diazinon, which is subject to phased revocation in many countries. In this study, biochemical, reproductive and survival parameters of the water flea (Daphnia magna) after chronic exposure to IMI, its commercial liquid formulation Confidor SL 200 and diazinon are presented and compared. According to the lowest observed effect concentrations, diazinon is more toxic to the reproduction of D. magna than IMI and Confidor SL 200, which exert similar toxicity. The same was observed for the survival, except that Confidor SL 200 is more toxic than IMI. In polluted aquatic environments, the actual levels of diazinon are potentially chronically hazardous to the reproduction of D. magna (risk quotient >1). According to very few measured environmental levels of IMI, the latter is not expected to be chronically hazardous, unless it is accidentally spilled in a small pond. In such case, the predicted concentrations of IMI would present a potential chronic risk to D. magna, and a potential acute risk to other aquatic invertebrates. In the future, higher environmental levels of IMI are expected due to its increasing use and physico-chemical properties. The literature survey summarized in this work suggests that further ecotoxicological studies with a broader spectrum of aquatic organisms are needed before IMI is classified as safer than currently applied pesticides.     

Radiocaesium activity concentrations in potatoes in Croatia after the Chernobyl accident and dose assessment

Systematic investigations of (137)Cs and (134)Cs activity concentrations in potatoes (Solanum tuberosum) for the post-Chernobyl period (1986-2005) in the Republic of Croatia are summarized. The correlation between (137)Cs activity concentrations in fallout and potatoes, has been found to be very good, the correlation coefficient being r = 0.88 with P(t) < 0.001 for 18 degrees of freedom. As the radiocaesium levels in potatoes decreased exponentially, the mean residence time of (137)Cs in potatoes was estimated by fitting the measured activity concentrations to the exponential curve. The mean residence time was found to be 6.8 +/- 1.1 years, the standard deviation being estimated by the Monte Carlo simulations. The initial observed (134)Cs:(137)Cs activity ratio in potatoes has been found to be quite variable, but slightly lesser than the theoretically predicted value of 0.5, calculated by applying the known inventory of these radionuclides in the Chernobyl reactor to the equation for the differential radioactive decay. This can be explained by presence of the pre-Chernobyl (137)Cs in soil that originated from nuclear fallout. The annual effective doses received by (134)Cs and (137)Cs intake due to consumption of potatoes estimated for an adult member of the Croatian population were found to be very small, as the per caput Dose for the entire 1986-2005 period was calculated to be about 2.9 microSv, (134)Cs accounting approximately for 1/3 of the entire dose. Therefore, after the Chernobyl accident consumption of potatoes was not the critical pathway for human intake of radiocaesium from the environment in Croatia.     

Feasibility assessment of electrocoagulation towards a new sustainable wastewater treatment

BACKGROUND, AIM AND SCOPE: Electrocoagulation (EC) may be a potential answer to environmental problems dealing with water reuse and rational waste management. The aim of this research was to assess the feasibility of EC-process for industrial contaminated effluents from copper production, taking into consideration technical and economical factors. EC-technology claims to offer efficient removal rates for most types of wastewater impurities at low power consumption and without adding any precipitating agents. MATERIALS AND METHODS: Real wastewater from Saraka stream with high concentrations of heavy metals was provided by RTB-BOR, a Serbian copper mining and smelting complex. Runs were performed on a 10 l EC-reactor using aluminum plates as sacrificial electrodes and powered by a 40 A supply unit. Results concerning key factors like pH, conductivity and power consumption were measured in real time. Analysis of dissolved metal concentrations before and after treatment were carried out via ICP-OES and confirmed by an independent test via AAS. RESULTS: Several aspects were taken into account, including current density, conductivity, interfacial resistivity and reactor settings throughout the runs, in order to analyze all possible factors playing a role in neutralization and metal removal in real industrial wastewater. DISCUSSION: Electrode configurations and their effects on energy demand were discussed and exemplified based on fundamentals of colloidal and physical chemistry. CONCLUSIONS: Based on experimental data and since no precipitating agents were applied, the EC-process proved to be not only feasible and environmentally-friendly, but also a cost-effective technology RECOMMENDATIONS AND PERSPECTIVES: The EC-technology provides strategic guidelines for further research and development of sustainable water management processes. However, additional test series concerning continuous operation must be still performed in order to get this concept ready for future large-scale applications.     

Soil Contamination by Pb, Zn and Cn from a Lead Smeltery

In the environment of a lead smeltery contamination with lead, zinc and cadmium was measured over a 15-year period. Efficient bag filters were installed in order to remove dust from the flue gases. This measure of improvement resulted in a drastic reduction of lead, zinc and cadmium content in suspended particles (by 92, 94 and 89%), to a lesser extent in depositions (by 79, 75 and 68%), whereas in household dust the reduction was considerably lower (by 53, 55 and 70%). It can be assumed that household dust contains also redispersed soil particles on which the dust from the smeltery flue gases has deposited over years. To determine to what extent contaminated soil continues to cause increased population exposure directly or through plants or pastures, in the period 1981–1985 the content of metallic ions in the soil was measured at three depths. Selective solubility of soil metallic compounds was analysed in water, in 1 mol ammoniumacetate solution and in 0.05 mol ethylenediaminetetra-acetic acid (EDTA) solution in relation to their solubility in suspended particles, depositions and household dust. A considerably low portion of soluble metallic compounds was found in the soil and physico-chemical characteristics of the soil and portion of metallic ions bound to fulvice and humic acids were determined. The behaviour of metallic ions in contact with soil samples was studied in laboratory and it was found that approximately 50% of lead, 70% of zinc and 7% of cadmium ions change into non-soluble or poorly soluble compounds. By qualitative phase analysis in the non-soluble fraction PbO₂, Pb₃P₄O₁₃, Zn(OH)₂, ZnO, Fe₂O₃ and Cd(OH)₂ were identified.     

Arsenic distribution in water/sediment system of Sevojno

Arsenic is a toxic and carcinogenic element. Its toxicity depends on its oxidation state and its concentration. The aim of this paper is to determine, for the first time, the concentration levels of arsenic in water and sediment during the spring/summer period of 2009 in Sevojno, a region in West Serbia with a long industrial tradition, as well as to determine the model of arsenic distribution in water/sediment system and the level of its compatibility with the existing theoretical model. Adsorption is a continual process in the environment. It plays a very important role in the transport and fate of pollutants, especially in sediment. The adsorption of arsenic was examined using the Freundlich adsorption isotherm.     

Extending the use of air quality indices to reflect effective population exposure

Although there are tendencies to develop a single common index which would describe an overall air quality status within an area, constructed from a choice of measurements of individual pollutants, indices describing individual pollutants themselves have several potentials which can be used in ways which are not possible with pollutant concentrations. On the case of Belgrade, Serbia, we investigated possibilities of using such indices for comparisons between pollutants, characterization of monitoring sites, and extending their use to include elements of population exposure. A methodology of adjusting the results obtained at monitoring stations located in severe pollution conditions, like street canyons, is proposed and used.