Natural radionuclides in waste water discharged from coal-fired power plants in Serbia.

Investigation of the natural radioactivity levels in water around power plants, as well as in plants, coal, ash, slag and soil, and to assess the associated radiation hazard is becoming an emerging and interesting topic. This paper is focused on the results of the radioactivity analysis in waste water samples from five coal-fired power plants in Serbia (Nikola Tesla A, Nikola Tesla B, Kolubara, Morava and Kostolac), which were analyzed in the period 2003-2015. River water samples taken upstream and downstream from the power plants, drain water and overflow water were analyzed. In the water samples gamma spectrometry analysis was performed as well as determination of gross alpha and beta activity. Natural radionuclide 40K was detected by gamma spectrometry, while the concentrations of other radionuclides, 226Ra, 235U and 238U, usually were below the minimum detection activity (MDA). 232Th and artificial radionuclide 137Cs were not detected in these samples. Gross alpha and beta activities were determined by the α/ß low level proportional counter Thermo Eberline FHT 770 T. In the analyzed samples, gross alpha activity ranged from MDA to 0.47 Bq L-1, while the gross beta activity ranged from MDA to 1.55 Bq L-1.

Verification of the sampling procedure for radioactivity analysis of waste and industrial material.

In accordance with ISO/IEC 17025:2017, the testing laboratory needs to verify its ability to properly perform methods. For radiological testing, the sampling does not affect the results directly, but it has to ensure that sample adequately represents the tested material. To verify the procedure, a sampling of red mud and bauxite ore was conducted. All samples were measured in identical geometry by HPGe spectrometer. The counting rates per unit mass in the recorded spectra were compared. For each measurement series, the mean and standard deviations of respected peaks were calculated, as well as average and standard deviation of all series. The obtained results of each individual series were considered satisfactory, i.e. sampling procedure ensures the representativeness of the bulk material, if it is within ± two standard deviations of the average of the mean values.

Radioactivity of mining sites of lead, zinc and phosphate ores in Serbia.

Natural resources such as ores contain radioactive nuclides at various concentrations. Therefore it is important to investigate the radioactivity in these resources as well as in the soil at the locations of ore deposits. For that reason we conducted preliminary measurements in the soil samples taken from the locations of lead and zinc ore deposits in Bosilegrad and Raska and from the locations of phosphate ore deposits in Bosilegrad to estimate the environmental conditions prior to the ore excavation. The activity concentrations of radionuclides in soil, water and plant samples were determined by gamma spectrometry (HPGe detector, relative efficiency 23%). Results showed the presence of natural radionuclides (226)Ra, (232)Th, (40)K, (235)U, (238)U as well as the produced radionuclide (137)Cs (from the Chernobyl accident). Ambient gamma radiation dose rate in ground level air was also measured. In order to estimate the influence of subsequent mining on the working and living environment, radium equivalent (Ra(eq)), external hazard index (H(ex)), external gamma absorbed dose rate ([Formula: see text]) and annual effective dose (D(E)) were determined.

Tritium concentration analysis in atmospheric precipitation in Serbia.

Tritium activity concentration were monitored in monthly precipitation at five locations in Serbia (Meteorological Station of Belgrade at Zeleno Brdo, Vinca Institute of Nuclear Sciences, Smederevska Palanka, Kraljevo and Nis) over 2005, using electrolytic enrichment and liquid scintillation counting. The obtained concentrations ranged from 3.36 to 127.02 TU. The activity values obtained in samples collected at Zeleno Brdo were lower or close to the minimum detectable activity (MDA), which has a value of 3.36 TU. Significantly higher tritium levels were obtained in samples collected in Vinca Institute of Nuclear Sciences compared with samples from the other investigated locations. Amount of precipitation were also recorded. A good linear correlation (r = 0.75) for Zeleno Brdo and VINS between their tritium activity was obtained. It was found that the value of the symmetrical index n (which indicates the magnitude of tritium content changes with time (months) through its second derivative) is the highest for Vinca Institute of Nuclear Sciences compared to other locations, which is in accordance with the fact that the highest concentrations of tritium were obtained in the samples from the cited place.

Natural radioactivity of materials used in industry and construction in Serbia.

Four different kinds of materials (feldspar, gypsum, clay and kaolin) commonly used in building construction and industry in Serbia were analyzed for their natural radioactivity, using gamma spectrometry. The radium equivalent activity, Ra(eq), the absorbed dose rate, D, the annual effective dose, D(E), and the external hazard index, H(ex), were evaluated to assess the radiation hazard for people living in dwellings made of the materials studied. The radium equivalent activities calculated in all samples are lower than the maximum admissible value 370 Bq kg(-1) set in the UNSCEAR report. The absorbed dose rate in air was found to vary from 0.02 to 0.19 µGy h(-1). Considering the fact that the average gamma dose rate indoors in Europe is 0.07 µGy h(-1), gamma dose rate calculated for feldspar, clay and kaolin samples exceed this limit. The obtained results for annual effective dose exceed limits of 0.41 mSv for feldspar, clay and kaolin samples. If the H(ex) exceeds unity, we might conclude that the potential external dose(s) to exposed individual(s) will exceed the acceptable level, and some action may be required. The obtained values of H(ex) are lower than unity for all investigated samples. All samples were measured immediately after preparation, except 10 samples of feldspar, because a comparative analysis were made between 215 samples which were measured immediately after preparation and 10 samples which were measured after radioactive equilibrium was reached in order to detect differences in the obtained concentrations.

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.

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.

Radon concentrations in a spa in Serbia.

The paper presents the results of indoor radon concentration survey in 201 homes and offices in Niska Banja (the Spa of Nis), a well-known health resort and a spa in the South-East of Serbia. Radon indoor concentrations were determined by active charcoal method, according to standard EPA procedure. The indoor radon concentrations were in the range of up to 200 Bq/m(3) (47%), from 200-600 Bq/m(3) (26%) and over 600 Bq/m(3) (27%). Three areas of extremely high average radon concentrations were found (1,340-4,340 Bq/m(3)), with a maximum above 13,000 Bq/m(3). The content of natural radionuclides ((226)Ra, (214)Pb, (214)Bi, (235)U, (228)Ac, (212)Pb, (212)Bi, (208)Tl, (40)K) and (137)Cs, as well as the content of total uranium, thorium and potassium in mud used in peloidotherapy in the Health Institute "Niska Banja" was determined, too. The activities of the radionuclides were determined on an HPGe detector, by standard gamma spectroscopy. The results indicated considerably high amounts of total uranium and thorium (0.021 g/kg mud and 0.003 g/kg mud, respectively), due to the karsts origin of the soil.

The first experimental test of the MEFFTRAN software on HPGe detector calibration for environmental samples.

The gamma spectrometry of environmental samples poses a series of specific problems for the practitioner. The determination of full energy peak efficiencies is, in the case of environmental samples, one of the greatest challenges. In this paper, the calibration of two HPGe detectors for environmental samples in Marinelli beakers was performed using the newly developed MEFFTRAN software. The results obtained with MEFFTRAN were compared to the experimental efficiencies measured using the calibration sample produced at the Laboratory for Radiation and Environment Protection, Institute for Nuclear Sciences Vinca, Belgrade, in order to confirm the validity of the calculation. It is shown that calculated and experimental efficiencies are in good agreement with the discrepancies from -3.9% to +1.5%. The results were also validated by measuring secondary reference materials provided by the IAEA within several interlaboratory proficiency tests. The activity concentration of the radionuclides in the secondary reference materials was determined using the efficiency obtained by MEFFTRAN and compared with the target value given by the IAEA. All the results in materials provided by the IAEA were acceptable except one, proving that MEFFTRAN produces satisfactory results.

Natural radionuclides in cigarette tobacco from Serbian market and effective dose estimate from smoke inhalation.

The activity concentrations of natural radionuclides ((40)K, (210)Pb, (210)Po, (226)Ra and (228)Ra) in 17 most frequently used cigarette brands in Serbia and corresponding effective doses due to smoke inhalation are presented. The mean annual effective doses for (210)Pb and (210)Po were estimated to be 47.3 and 724 µSv y(-1) for (210)Pb and (210)Po, respectively. Serbia currently has the highest smoking rate in the world. The results of this study indicate the high contribution of the annual effective dose due to smoke inhalation to the total inhalation dose from natural radionuclides. The more effective implementation of actions for reducing smoking prevalence in Serbia is highly needed.

Dynamics of FitzHugh-Nagumo excitable systems with delayed coupling.

Small lattices of N nearest-neighbor coupled excitable FitzHugh-Nagumo systems, with time-delayed coupling are studied and compared with systems of FitzHugh-Nagumo oscillators with the same delayed coupling. Bifurcations of equilibria in an N=2 case are studied analytically, and it is then numerically confirmed that the same bifurcations are relevant for the dynamics in the case N>2. Bifurcations found include inverse and direct Hopf and fold limit cycle bifurcations. Typical dynamics for different small time lags and coupling intensities could be excitable with a single globally stable equilibrium, asymptotic oscillatory with symmetric limit cycle, bistable with stable equilibrium and a symmetric limit cycle, and again coherent oscillatory but nonsymmetric and phase shifted. For an intermediate range of time lags, inverse sub-critical Hopf and fold limit cycle bifurcations lead to the phenomenon of oscillator death. The phenomenon does not occur in the case of FitzHugh-Nagumo oscillators with the same type of coupling.

Synchronization of hyperchaotic systems with delayed bidirectional coupling.

Synchronization of three bidirectionally coupled hyperchaotic systems is studied, using the Ikeda model as the hyperchaotic unit. The whole system is given by three delay-differential equations with two distinct time lags. Sufficient condition for the global stability of the manifold of exact synchronization is found analytically. Local stability of the synchronization manifold is studied by numerical computation of the transverse Lyapunov exponent and statistical properties of the orbits.

Priming effects on PAH degradation and ecotoxicity during a phytoremediation experiment.

An experiment was conducted to distinguish priming effects from the effects of phytoremediation of a creosote-polluted soil. The concentration of 13 polycyclic aromatic hydrocarbons (PAHs), and their combined soil toxicity (using four bioassays), was determined on recently excavated, homogenized soil and on such soil subjected to a time-course phytoremediation experiment with lucerne. The results showed a high priming effect, with minor positive and synergistic effects of planting and fertilization on PAH degradation rates. At the end of the experiment, PAH degradation reached 86% of the initial 519 mg PAHs kg(-1). Two of the four toxicity tests (bioluminescence inhibition and ostracod growth inhibition) corroborated the chemical data for residual PAHs, and indicated a significant reduction in soil toxicity. We conclude that priming effects can easily surpass treatment effects, and that an unintentional pre-incubation that ignores these effects can jeopardize the full quantitative assessment of in situ bioremediation of contaminated soil.

Environmental radioactivity in southern Serbia at locations where depleted uranium was used.

In the 1999 bombing of the Federal Republic of Yugoslavia, NATO forces used ammunition containing depleted uranium. The cleaning of depleted uranium that followed was performed in southern Serbia by the Vinca Institute of Nuclear Sciences between 2002 and 2007 at the locations of Pljackovica, Borovac, Bratoselce, and Reljan. This paper presents detailed results of radioactivity monitoring four years after cleaning (2011), which included the determination of gamma emitters in soil, water, and plant samples, as well as gross alpha and beta activities in water samples. The gamma spectrometry results showed the presence of natural radionuclides 226Ra, 232Th, 40K, 235U, 238U, and the produced radionuclide 137Cs (from the Chernobyl accident). In order to evaluate the radiological hazard from soil, the radium equivalent activity, the gamma dose rate, the external hazard index, and the annual effective dose were calculated. Considering that a significant number of people inhabit the studied locations, the periodical monitoring of radionuclide content is vital.

Leaves of higher plants as biomonitors of radionuclides (137Cs, 40K, 210Pb and 7Be) in urban air.

Leaves of linden (Tilia tomentosa L. and Tilia cordata Mill.) and horse chestnut (Aesculus hippocastanum L.) were analysed as biomonitors of radionuclides in urban air. Samples of soils, leaves and aerosols were collected in Belgrade, Serbia. Activities of (137)Cs, (40)K, (210)Pb and (7)Be in the samples were measured on an HPGe detector by standard gamma spectrometry. "Soil-to-leaves" transfer factors were calculated. Student's t test and linear Pearson correlation coefficients were used for statistical analysis. Differences in local conditions at the sampling sites were not significant, and the mechanisms of the radionuclides' accumulation in both plant species are similar. Ceasium-137 was detected in some of the leaf samples only. Transfer factors for (137)Cs and (40)K were (0.03-0.08) and 1.3, respectively. The concentrations of (210)Pb and (7)Be in leaves were higher in autumn than in spring, and there were some similarities in their seasonal patterns in leaves and in air. Weak to medium correlation was obtained for the (210)Pb and (7)Be activities in leaves and aerosols. Large positive correlation was obtained for the (210)Pb activities in linden leaves and the mean activity in aerosols for the preceding months. Different primary modes of radionuclides accumulation in leaves were observed. Since large positive correlation was obtained for the (210)Pb activity in linden leaves and the mean in aerosols for the preceding months, mature linden leaves could be used as biomonitors of recent (210)Pb activity in air.

Depth distribution of (137)Cs in anthrosol from the experimental field "Radmilovac" near Belgrade, Serbia.

This is a preliminary study of the depth distribution of (137)Cs radionuclides in cultivated anthrosol soil of a 15-year old peach tree plantation at the experimental field "Radmilovac" near Belgrade. Before planting, the soil was ploughed at the depth of 1 m. The soil had not been annually ploughed, irrigated and treated with mineral fertilizers for three years before sampling. Activity concentration for (137)Cs ranged from 1.8 Bq kg(-1) to 35 Bq kg(-1). Along the soil depth it varied highly, reaching as high a total variation coefficient as 83 %. Radiocaesium distribution patterns depended on the extent of soil mixing in the plough layer, as it was mechanically transferred from the surface to the lower soil layers during cultivation. (137)Cs was associated with humus content and fixation to clay fractions in the soil. Our results single out soil's hygroscopic water as a valuable parameter for (137)Cs behaviour that could be used commonly if the measurement is standardised.

Natural radionuclides in drinking waters in Serbia.

Gross alpha and beta activities, (3)H, (226)Ra, (232)Th and (40)K activities were measured in bottled mineral water produced in Serbia in order to assess its radiological quality. In 11 samples of tap water and in 1 sample of spring waters gross alpha and beta activity were determined. The natural activity concentration of alpha and beta emitting radionuclides are within the range recommended by World Health Organization. The tritium concentration in bottled mineral waters ranged from 0.023 ± 0.012 to 0.046 ± 0.006 Bq l(-1). The activity of (226)Ra, (232)Th and (40)K were below the minimum detectable activity. In order to evaluate the annual effective dose for different classes of age, a conservative dosimetric calculation was carried out.

Radioactivity monitoring in ground level air in Belgrade urban area.

Concentrations of beryllium-7 ((7)Be), lead-210 ((210)Pb) and caesium-137 ((137)Cs) were measured at two sites in the city of Belgrade (Serbia). One monitoring site was located in the central city area with heavy traffic and the other within the Institute of Nuclear Sciences Vinca, in the suburbs. Presented data cover the period 2004-9. Activity of the radionuclides was determined on an HPGe detector (Canberra, relative efficiency 23 %) by standard gamma spectrometry. Activities of (7)Be and (210)Pb exhibit a similar seasonal pattern. The mean monthly concentrations of (7)Be did not exceed 7 mBq m(-3). The maxima are correlated with the seasonal increase in temperature, whereas the minima are linearly correlated with the amount of precipitation. The activity of (210)Pb was below 0.9 mBq m(-3). The activities of both radionuclides were very low in winters and were largely affected by precipitation and snow coverage. Concentrations of (137)Cs were mainly below the limit of detection.

Concentration of trace elements in blood and feed of homebred animals in Southern Serbia.

BACKGROUND, AIM AND SCOPE: The paper presents concentrations of trace elements in blood of homebred animals (cows and sheep) from Southern Serbia (Bujanovac) and the contents of natural and anthropogenic radionuclides and some heavy metals in feed. The region of Southern Serbia was exposed to contamination by depleted uranium ammunition during NATO attacks in 1999 and therefore, is of great concern to environmental pollution and human and animal health. MATERIALS AND METHODS: Conventional instrumental and epithermal neutron activation analyses are used to measure trace elements in cow and sheep blood samples collected randomly at six locations in the region of Bujanovac (village of Borovac) in the spring of 2005. Samples of feed (grass and crops: corn, wheat and oats), collected on the same locations (households), are analysed for the contents of radionuclides on an HPGe detector (Ortec, relative efficiency 23%) by standard gamma spectrometry. The content of Hg, Pb and Cd in feed is determined by standard atomic absorption spectrometry on the VarianSpectra220/ThermoSolar GFS97 spectrometer. RESULTS: Concentrations of 29 elements (Na, Al (P), Cl, K, Sc, Cr, Mn, Ni, Fe, Co, Zn, Se, As, Br, Sr, Rb, Sb, In, I, Ba, Cs, La, Nd, Eu, Sm, Tb, Hf, Ta and Th) are determined in blood of the examined animals. In feeds, natural (40)K is found in all of the samples, cosmogenic (7)Be and fission product (137)Cs are detected only in the grass samples, while heavy metals Hg, Cd and Pb are found in the range of 0.01-0.02, 0.84-1.15 and 0.74-7.34 mg/kg, respectively. Calculated soil-to-blood transfer factors are in a wide range of 8 x 10(-6) to 64, as a result of varying significance of the elements in animal metabolism and feeding habits. DISCUSSION: The results of trace elements' concentrations in animal blood are in good agreement with available data for K, Ni, Zn, Se and Rb. Higher Br concentrations in animal blood are most probably caused by large biomass burning events during blood sampling. Very low concentration of Fe in cows and sheep confirms the results of previous biochemical studies on animal anaemia in the region. High concentration of As correlates with geochemical peculiarities of the Balkans and is also likely influenced by the use of pesticides in the agricultural production. For some of the elements (La, Nd, Eu, Sm, Tb, Sb, Hf, Ta, Th, In, Ba, Sr, Sc and Cs), there are few or no literature data. Therefore, some of the presented data are significant not only for the country and the region, but on a wider scale. Activities of natural radionuclides in feeds are within the average values reported for the region, while the activities of (210)Pb and (235/238)U are below the limit of detection. This is in accordance with previous investigations showing no widespread contamination by depleted uranium in the area. Contents of Hg and Pb in feeds are below the nationally permissible levels, unlike the content of Cd which exceeds it, probably caused by the use of phosphate fertilisers and fossil fuel combustion in the area. CONCLUSIONS: In general, the concentrations of trace elements in blood of homebred cows and sheep are in good agreement with reference materials, available literature data and the results of previous studies in the area. The exceptions are Fe, As and Br. The contents of natural and anthropogenic radionuclides in feeds are within the expected levels, and there are no signs of contamination by depleted uranium or other fission products. Apart from Cd, there are no signs of pollution by heavy metals in feeds. The highly sensitive method of instrumental neutron activation analysis provides data on the concentration of some elements in animal blood not previously reported for the region and elsewhere. RECOMMENDATIONS AND PERSPECTIVES: The presented study is a part of the long term ongoing project on the health risk assessment on animals and humans in the region. The collected data is intended to provide a base for the animal and human risk assessment as well as an estimate of the general pollution status of the environment in the region. Since some of the investigated elements are classified as important trace elements for livestock, the results could also be used to balance and improve the animal diet and thus, improve the growth and reproduction rate.