Radionuclides and heavy metals in Borovac,Southern Serbia

BACKGROUND, AIM, AND SCOPE: The paper presents the complex approach to the assessment of the state of the environment in Southern Serbia, surroundings of Bujanovac, the region which is of great concern as being exposed to contamination by depleted uranium (DU) ammunition during the North Atlantic Treaty Organization (NATO) attacks in 1999. It includes studies on concentrations of radionuclides and heavy metals in different environmental samples 5 years after the military actions. MATERIALS AND METHODS: In October 2004, samples of soil, grass, lichen, moss, honey, and water were collected at two sites, in the immediate vicinity of the targeted area and 5 km away from it. Radionuclide ((7)Be, (40)K, (137)Cs, (210)Pb, (226)Ra, (232)Th, (235)U, (238)U) activities in solid samples were determined by standard gamma spectrometry and total alpha and beta activity in water was determined by proportional alpha-beta counting. Concentrations of 35 elements were determined in the samples of soil, moss, grass, and lichen by instrumental neutron activation analysis (INAA). RESULTS: The results are discussed in the context of a possible contamination by DU that reached the environment during the attacks as well as in the context of an environmental pollution by radionuclides and heavy metals in Southern Serbia. The results are compared to the state of environment in the region and other parts of the country both prior to and following the attacks. DISCUSSION: This is the first comprehensive study of the contents of radionuclides and heavy metals in Southern Serbia and consequently highly important for the assessment of the state of environment in this part of the country concerning possible effects of DU ammunition on the environment, as well as anthropogenic source of pollution by radionuclides and heavy metals and other elements. Also, the highly sensitive method of INAA was used for the first time to analyze the environmental samples from this area. CONCLUSIONS: The results of the study of radionuclides in the samples of soils, leaves, grass, moss, lichen, honey, and water in Southern Serbia (Bujanovac) gave no evidence of the DU contamination of the environment 5 years after the military actions in 1999. Activities of radionuclides in soils were within the range of the values obtained in the other parts of the country and within the global average. The ratio of uranium isotopes confirmed the natural origin of uranium. In general, concentrations of heavy metals in the samples of soils, plant leaves, mosses, and lichen are found to be less or in the lower range of values found in other parts of the country, in spite of the differences in plant and moss species or soil characteristics. Possible sources of heavy metal contamination were identified as a power coal plant in the vicinity of the sampling sites and wood and waste burning processes. RECOMMENDATIONS AND PERSPECTIVES: The collected data should provide a base for the health risk assessments on animals and humans in the near future. It should be emphasized that the sampling was carried out 5 years after the military action and that the number of samples was limited; therefore, the conclusions should be accepted only as observed tendencies and a detailed study should be recommended in the future.     

Organochlorine pesticides and polychlorinated biphenyls in surface soils of Novi Sad and bank sediment of the Danube River

The contents of 16 organochlorine pesticides (OCPs) and six so-called indicator polychlorinated biphenyls (PCBs) were determined in the surface zone (0–5 cm) of soil and sediment samples, taken from different locations in the city of Novi Sad, capitol of Vojvodina Province (North of the Serbia) covering residential and commercial area, recreational and arable zone. The total organochlorine pesticides concentration in soil varied from 2.63 to 31.78 ng g^?1 dry weight, while the level in sediment was 10.35 ng g^?1 dry weight. Maximum content of identified individual organochlorine pesticide in soil samples was 10.40 ng g^?1 dry weight for p, p-DDE in the market garden and 6.31 ng g^?1 dry weight for p, p'-DDT in sediment of the Danube River, although their application is restricted in Serbia. Some of investigated PCBs were identified only in the soil samples from a park-school backyard in the city downtown (0.32 ng g^?1 dry weight) and market garden (0.22 ng g^?1 dry weight), and also in sediment sample from left bank of the Danube River (0.41 ng g^?1 dry weight). Data of the OCPs and PCBs present in this study were compared with the ones found for soils and river sediments throughout the world, and with limit values set by soil and sediment quality guidelines. Also, correlation between the levels of certain pesticides and soil characteristics (organic matter, pH and clay content) was investigated.     

Organochlorine pesticides and polychlorinated biphenyls in surface soils of Novi Sad and bank sediment of the Danube River

The contents of 16 organochlorine pesticides (OCPs) and six so-called indicator polychlorinated biphenyls (PCBs) were determined in the surface zone (0-5 cm) of soil and sediment samples, taken from different locations in the city of Novi Sad, capitol of Vojvodina Province (North of the Serbia) covering residential and commercial area, recreational and arable zone. The total organochlorine pesticides concentration in soil varied from 2.63 to 31.78 ng g(-1) dry weight, while the level in sediment was 10.35 ng g(-1) dry weight. Maximum content of identified individual organochlorine pesticide in soil samples was 10.40 ng g(-1) dry weight for p, p-DDE in the market garden and 6.31 ng g(-1) dry weight for p, p'-DDT in sediment of the Danube River, although their application is restricted in Serbia. Some of investigated PCBs were identified only in the soil samples from a park-school backyard in the city downtown (0.32 ng g(-1) dry weight) and market garden (0.22 ng g(-1) dry weight), and also in sediment sample from left bank of the Danube River (0.41 ng g(-1) dry weight). Data of the OCPs and PCBs present in this study were compared with the ones found for soils and river sediments throughout the world, and with limit values set by soil and sediment quality guidelines. Also, correlation between the levels of certain pesticides and soil characteristics (organic matter, pH and clay content) was investigated.     

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.     

Antifungal activity of the pygidial gland secretion of <Emphasis Type="Italic">Laemostenus punctatus</Emphasis> (Coleoptera: Carabidae) against cave-dwelling micromycetes

The antifungal potential of the pygidial gland secretion of the troglophilic ground beetle Laemostenus punctatus from a cave in Southeastern Serbia against cave-dwelling micromycetes, isolated from the same habitat, has been investigated. Eleven collected samples were analyzed and 32 isolates of cave-dwelling fungi were documented. A total of 14 fungal species were identified as members of the genera Aspergillus, Penicillium, Alternaria, Cladosporium, Rhizopus, Trichoderma, Arthrinium, Aureobasidium, Epicoccum, Talaromyces, and Fusarium. Five isolates were selected for testing the antifungal activity of the pygidial gland secretion: Talaromyces duclauxi, Aspergillus brunneouniseriatus, Penicillium sp., Rhizopus stolonifer, and Trichoderma viride. The microdilution method has been applied to detect minimal inhibitory concentrations (MICs) and minimal fungicidal concentrations (MFCs). The most sensitive isolate was Penicillium sp., while the other isolates demonstrated a high level of resistance to the tested agent. L. punctatus has developed a special mechanism of producing specific compounds that act synergistically within the secretion mixture, which are responsible for the antifungal action against pathogens from the cave. The results open opportunities for further research in the field of ground beetle defense against pathogens, which could have an important application in human medicine, in addition to the environmental impact, primarily.     

Potential genotoxic effects of melted snow from an urban area revealed by the Allium cepa test

The presence of well-known atmospheric pollutants is regularly screened for in large towns but knowledge about the effects of mixtures of different pollutants and especially their genotoxic potential is largely missing. Since falling snow collects pollutants from the air, melted snow samples could be suitable for evaluating potential genotoxicity. For this purpose the Allium cepa anaphase–telophase test was used to analyse melted snow samples from Belgrade, the capital city of Serbia. Samples of snow were taken at two sites, characterized by differences in pollution intensity, in three successive years. At the more polluted site the analyses showed a very high degree of both toxicity and genotoxicity in the first year of the study corresponding to the effects of the known mutagen used as the positive control. At the other site the situation was much better but not without warning signals. The results showed that standard analyses for the presence of certain contaminants in the air do not give an accurate picture of the possible consequences of urban air pollution because the genotoxic potential remains hidden. The A. cepa test has been demonstrated to be very convenient for evaluation of air pollution through analyses of melted snow samples.     

Toxicity of leachate from bottom ash in a road construction

A test road constructed with municipal solid waste incineration (MSWI) bottom ash was monitored over a period of 36 months. Using chemical and toxicological characterisation, the environmental impact of leachates from bottom ash was evaluated and compared with leachates from gravel used as reference. Initial leaching of Cl, Cu, K, Na, NH4-N and TOC from bottom ash was of major concern. However, the quality of the bottom ash leachate approached that of the gravel leachate with time. Leachates from the two materials were compared regarding the concentration of pollutants using multivariate data analyses (MVDA). A standardized luminescent bacteria assay using Vibrio fischeri did not show any toxicity, most likely because saline contamination can mask the toxic response and stimulate luminescence in these marine bacteria. A mung bean assay using Phaseolus aureus revealed that the toxicity of bottom ash leachate collected at the very beginning of the experimental period (October 2001 and May 2002) might be attributed to the following components and their respective concentrations in mg l(-1): Al (34.2-39.2), Cl (2914-16,446), Cu (0.48-1.92), K (197-847), Na (766-4180), NH4-N (1.80-8.47), total-N (12.0-18.5), and TOC (34.0-99.0). The P. aureus assay was judged as a promising environmental tool in assessing the toxicity of bottom ash leachate.     

Selective removal of heavy metals from metal-bearing wastewater in a cascade line reactor

Goal, Scope and Background This paper is a part of the research work on ‘Integrated treatment of industrial wastes towards prevention of regional water resources contamination — INTREAT’ the project. It addresses the environmental pollution problems associated with solid and liquid waste/effluents produced by sulfide ore mining and metallurgical activities in the Copper Mining and Smelting Complex Bor (RTB-BOR), Serbia. However, since the minimum solubility for the different metals usually found in the polluted water occurs at different pH values and the hydroxide precipitates are amphoteric in nature, selective removal of mixed metals could be achieved as the multiple stage precipitation. For this reason, acid mine water had to be treated in multiple stages in a continuous precipitation system-cascade line reactor. Materials and Methods All experiments were performed using synthetic metal-bearing effluent with chemical a composition similar to the effluent from open pit, Copper Mining and Smelting Complex Bor (RTB-BOR). That effluent is characterized by low pH (1.78) due to the content of sulfuric acid and heavy metals, such as Cu, Fe, Ni, Mn, Zn with concentrations of 76.680, 26.130, 0.113, 11.490, 1.020 mg/dm³, respectively. The cascade line reactor is equipped with the following components: for feeding of effluents, for injection of the precipitation agent, for pH measurements and control, and for removal of the process gases. The precipitation agent was 1M NaOH. In each of the three reactors, a changing of pH and temperature was observed. In order to verify efficiency of heavy metals removal, chemical analyses of samples taken at different pH was done using AES-ICP. Results Consumption of NaOH in reactors was 370 cm³, 40 cm³ and 80 cm³, respectively. Total time of the experiment was 4 h including feeding of the first reactor. The time necessary to achieve the defined pH value was 25 min for the first reactor and 13 min for both second and third reactors. Taking into account the complete process in the cascade line reactor, the difference between maximum and minimum temperature was as low as 6°C. The quantity of solid residue in reactors respectively was 0.62 g, 2.05 g and 3.91 g. In the case of copper, minimum achieved concentration was 0.62 mg/dm³ at pH = 10.4. At pH = 4.50 content of iron has rapidly decreased to < 0.1 mg/dm³ and maintained constant at all higher pH values. That means that precipitation has already ended at pH=4.5 and maximum efficiency of iron removal was 99.53%. The concentration of manganese was minimum at pH value of 11.0. Minimum obtained concentration of Zn was 2.18 mg/dm³ at a pH value of 11. If pH value is higher than 11, Zn can be re-dissolved. The maximum efficiency of Ni removal reached 76.30% at a pH value of 10.4. Discussion Obtained results show that efficiency of copper, iron and manganese removal is very satisfactory (higher than 90%). The obtained efficiency of Zn and Ni removal is lower (72.30% and 76.31%, respectively). The treated effluent met discharge water standard according to The Council Directive 76/464/EEC on pollution caused by certain dangerous substances into the aquatic environment of the Community. Maximum changing of temperature during the whole process was 6°C. Conclusion This technology, which was based on inducing chemical precipitation of heavy metals is viable for selective removal of heavy metals from metal-bearing effluents in three reactor systems in a cascade line. Recommendations and Perspectives The worldwide increasing concern for the environment and guidelines regarding effluent discharge make their treatment necessary for safe discharge in water receivers. In the case where the effluents contain valuable metals, there is also an additional economic interest to recover these metals and to recycle them as secondary raw materials in different production routes. ESS-Submission Editor: PhD Hailong Wang, hailong.wang@ensisjv.com     

Bactericidal activity of Cu-, Zn-, and Ag-containing zeolites toward <Emphasis Type="Italic">Escherichia coli</Emphasis> isolates

Two types of zeolites—natural clinoptilolite (NZ) and synthetic zeolite A (A)—were enriched with approx. 0.25 mmol of Cu(II), Zn(II), or Ag(I) ions, and the obtained materials (M-Z) were tested against three different isolates of Escherichia coli. Two isolates were environmental isolates from waters in Serbia whereas the third one was DSM 498. Antibacterial activity was studied in different water media—nutrient-rich media (peptone water), water from Sava Lake, and commercially available spring water. The Ag-containing zeolites showed bactericidal activity in the nutrient-rich peptone water after 1 h of contact. Cu- and Zn-containing zeolites showed bactericidal activity in real water samples. Antibacterial activity of the M-Z decreases in all three examined water media in the following order: Ag-NZ ≈ Ag-A > Cu-NZ ≈ Cu-A > Zn-NZ >>> Zn-A, suggesting that mainly the metal type and not the zeolite type have a role in the antibacterial activity. Leaching experiments showed small amounts of the leached Cu(II) and Zn(II) ions, indicating that the antibacterial activity is not due to the metal ions but should be attributed to the M-Z itself. However, leached amounts of Ag(I) from Ag-NZ and Ag-A in peptone water indicate that the released Ag(I) could be mainly responsible for the bactericidal effect of the Ag(I)-containing zeolites. Since no loss of cellular material was found, the antibacterial activity is not attributed to cytoplasmic membrane damage.     

Malondialdehyde and heavy metal concentrations in tissues of wild boar (Sus scrofa L.) from central Croatia

The aim of this research was to assess the degree of heavy metal (cadmium, lead and mercury) contamination of wild boars from central Croatia and thereby conduct further tests to connect the contamination to oxidative stress occurrence. The highest cadmium concentration was noticed in the kidneys of older boars, the lead concentration was approximately the same in the liver and kidneys, but it was much higher than the concentration in the muscles, while the highest mercury concentration was measured in the kidneys of all wild boars. The correlation between the malondialdehyde (MDA) and the heavy metal concentrations was higher in tissue samples taken from younger animals (1 to 3 years of age) than in the tissue samples taken from older animals (5 to 6 years of age). In the kidneys of all wild boars there was a statistically significant connection between the MDA and cadmium concentration; in the kidneys of younger wild boars there was a statistically significant connection between the MDA and lead concentration. Further research on this topic should focus on MDA potential to find its use, not only as a contamination biomarker in the area of ecotoxicology, but also in the evaluation of the hygienic acceptability of animal products.