Potentially toxic elements in sediments near mines-a comprehensive approach for the assessment of pollution status and associated risk for the surface water environment.

This research is focused on the assessment of the pollution status of river and lake sediments near Pb, Zn, and Cu mines and tailings in the southeastern part of Serbia-Krajiste area. The study is based on hypothesis that investigated rivers and lakes in the Krajiste area could be polluted by potentially toxic elements (PTEs) and that these elements could pose considerable ecological risk to the studied surface water environment. High PTE contents are detected in studied river sediments (up to 7892 mg kg-1 for Zn, 3224 mg kg-1 for Cu, 36,790 mg kg-1 for Pb, 64.2 mg kg-1 for Cd, and 1444 mg kg-1 for As). Given that the contents of the studied elements in most of the river sediments exceeded the background values, values prescribed by regulations of the Republic of Serbia, as well as probable effect concentration (PEL), it is possible to conclude that sediments were heavily polluted and that detrimental effects can be expected. Contamination indices including the enrichment factor (EF), contamination factor (CF), index of geoaccumulation (Igeo), potential ecological risk index (Eri), ecological risk index (RI), pollution load index (PLI), and aggregative toxicity index (ATI) were used to assess the degree of pollution by PTEs. The ecological risk assessment revealed that there is a significant risk observed for toxic elements (primarily Pb, Cu, Cd, and As) at this moment. The highest contamination indices (EF, Igeo, CF, PLI, and ATI) are mainly associated with historical and current mining activities. The Monte Carlo analysis based on the risk assessment indices was used to evaluate the uncertainty. The most pronounced toxic risk is found for the Pb, Cu, Cd, and As which assessment was in the range of high and extremely high-risk probabilities. The obtained results suggest that levels of toxic elements pose a significant ecological risk to the surface water environment near Pb, Zn, and Cu mines in the Krajiste area. The methodology applied in this paper could be very useful for other researchers dealing with the problem of environmental pollution by toxic elements.

Geochemical Fractionation and Assessment of Probabilistic Ecological Risk of Potential Toxic Elements in Sediments Using Monte Carlo Simulations.

The need for further research into potentially toxic elements in Serbian rivers led to an investigation of distributions, sources, and ecological risks in a sample base of sediments from 15 rivers. The analyses were carried out through both experimental and theoretical methods. Geochemical fractionation of Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, As, V, and Zn in sediments was studied using a sequential extraction procedure. Both a Håkanson risk index (RI) and a Monte Carlo simulation (MCS) were used in order to estimate ecological risk, applying the probability distribution of RI values instead of single-point calculations. In order to both further the development of the used method and include additional processes, software for the simulations was developed instead of using proprietary solutions. Metal fractionation showed high percentage recoveries of Cd, Cr, Co, Cu, Fe, Ni, and V in residual fractions. The high content of Pb, Mn, and Zn in mobile fractions might cause serious environmental concerns. In some localities, Cu and Cd could be problematic elements, since their mobility was high. An environmental assessment based on the described criteria provided risk levels varying from low to median (mainly contributed by Cd and Cu).

Fractionation, Mobility, and Contamination Assessment of Potentially Toxic Metals in Urban Soils in Four Industrial Serbian Cities.

The main soil properties, concentrations of selected elements (As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn), and the chemical speciation of each element were determined in urban soil samples taken from urban parks in four Serbian cities (Belgrade, Pancevo, Obrenovac, and Smederevo) exposed to different sources of pollution. Pollution indices (PI, PIN) and factors (MF, ICF, GCF) also were evaluated. The study revealed As and Cd concentrations below the detection limit, whereas the content of Cr, Cu, Fe, Mn, Ni, Pb, and Zn at some sites exceeded the limits established by local regulations, as well as the background values, which may represent an environmental threat. Sequential extraction results show that Fe, Cr, Cu, and Ni were predominantly in the residual fraction at most sites; however, Ni from Pancevo and Smederevo also was bound to the reducible fraction. The presence of Pb at all sites and Zn in Smederevo and Belgrade was mainly associated with the reducible and residual fractions. The highest Mn content was found in the reducible fraction, followed by the acid soluble/exchangeable and residual fractions. Based on the obtained indices and factors, the overall soil status at the selected sampling sites was found to range from the warning limit to slightly polluted, whereby Smederevo had the highest risk, and Pancevo and the control site the lowest risk of contamination by toxic metals.

Assessment of contamination, environmental risk, and origin of heavy metals in soils surrounding industrial facilities in Vojvodina, Serbia.

Content of potentially toxic elements was examined in soils from Srem (Vojvodina), to evaluate industrial facilities as pollution sources. Based on the distribution of the elements, the results of sequential extraction, enrichment factor (EF), ecological risk factor (Er), ecological risk index (RI), and statistical analysis, the current ecological status of the soils was determined. Elements in soils around the industrial facilities can be grouped into the five significant components derived by the principal component analysis (PCA), which explains 78.435% of the total variance. Al, Fe and Mg, and K and Mn are associated with two lithogenic components, respectively. Anthropogenic origin is identified for Hg and Cd. Mixed sources, geogenic and anthropogenic, are identified within two PCA components; one wich includes As, Pb, B, Zn, and the other: K and Cr, Ni and Cu. Cluster analysis (CA) corroborated the results obtained by PCA. The preliminary results revealed that the soils studied in a vicinity of industrial facilities in Srem have been exposed to different degrees of pollution. Among the characterized studied elements, Pb, Cd, Hg, Cu, Ni, and Cr are the main contaminants. Based on calculated EF, the studied soils show minor to severe enrichment with heavy metals. Ecological risk assessment results indicate that Cd and Hg carry the highest ecological risk level, and Zn and Cr the lowest.

Comparison of single extraction procedures and the application of an index for the assessment of heavy metal bioavailability in river sediments.

Metals in sediments are present in different chemical forms which affect their ability to transfer. The objective of this body of work was to compare different extraction methods for the bioavailability evaluation of some elements, such as Ba, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Ni, Pb, V and Zn from Serbian river sediments. A bioavailability risk assessment index (BRAI) was used for the quantification of heavy metal bioavailability in the sediments. Actual and potential element availability was assessed by single extractions with mild (CaCl2 and CH3COONH4) and acidic (CH3COOH) extractants and complexing agents (EDTA). Aqua regia extraction was used for the determination of the pseudo-total element content in river sediments. In different single extraction tests, higher extraction of Cd, Cu, Zn and Pb was observed than for the other elements. The results of the single extraction tests revealed that there is a considerable chance of metal leaching from the sediments assessed in this study. When the BRAI was applied, the results showed a high risk of heavy metal bioavailability in Serbian river sediments.

Assessment of the environmental significance of nutrients and heavy metal pollution in the river network of Serbia.

In this paper, the data for ten water quality variables collected during 2009 at 75 monitoring sites along the river network of Serbia are considered. The results are alarming because 48% of the studied sites were contaminated by Ni, Mn, Pb, As, and nutrients, which are key factors impairing the water quality of the rivers in Serbia. Special attention should be paid to Zn and Cu, listed in the priority toxic pollutants of US EPA for aquatic life protection. The employed Q-model cluster analysis grouped the data into three major pollution zones (low, moderate, and high). Most sites classified as "low pollution zones" (LP) were in the main rivers, whereas those classified as "moderate and high pollution zones" (MP and HP, respectively) were in the large and small tributaries/hydro-system. Principal component analysis/factor analysis (PCA/FA) showed that the dissolved metals and nutrients in the Serbian rivers varied depending on the river, the heterogeneity of the anthropogenic activities in the basins (influenced primarily by industrial wastewater, agricultural activities, and urban runoff pollution), and natural environmental variability, such as geological characteristics. In LP dominated non-point source pollution, such as agricultural and urban runoff, whereas mixed source pollution dominated in the MP and HP zones. These results provide information to be used for developing better pollution control strategies for the river network of Serbia.

Assessment of arsenic and mercury contamination in the Tisa River sediments and industrial canal sediments (Danube alluvial formation), Serbia.

The purpose of this study was to examine the levels of As and Hg and mobility of these contaminants in the sediments of the River Tisa and canal sediments (alluvial formation of the Danube River, Serbia), in order to determine the degree to which the ecosystem is harmed by these pollutants. The sequential extraction procedure (modified Tessier method) was used to extract the metals from the sediments. Arsenic is extracted in the second, third and fifth fraction, with dominant extraction in the second fraction. This distribution indicates that As is significantly present in the form of carbonates, whereas the part of As is present in the form of oxides. The most important extraction of Hg is in the fifth stage (extraction with 6M HCl), with over 80 % of extracted element in both types of sediment, indicating a strong association between Hg and Fe crystalline oxides as well as presence of Hg in the form of sulfides. Based on arsenic and mercury content in sediments and results of sequential extraction it can be concluded that on the studied localities there is no significant As and Hg contamination.

Assessment of heavy metal pollutants accumulation in the Tisza river sediments.

In this study we have worked on the evaluation of heavy metal contamination in the sediments taken from the Tisza River and its tributaries, and thereby used the sequential extraction method, geochemical normalization, the calculation of the enrichment factor (EF), and the methods of statistical analysis. The chemical fractionation of Ni, Cu, Zn, Cr, Pb, Fe, and Mn, carried out by using the modified Tessier method, points to different substrates and binding mechanisms of Cu, Zn and Pb in sediments of the tributaries and sediments of the Tisza River. The similarities in the distributions of Fe and Ni in all types of sediments are the result of geochemical similarity as well as of the fact that natural sources mainly affect the concentration levels of these elements. The calculated enrichment factors (EF, measured metal vs. background concentrations) indicated that metal contamination (Cu, Pb, Zn and Cr) was recorded in the sediments of the Tisza River, while no indications of pollution were detected in the tributaries of the Tisza River and the surrounding pools. The maximum values of the EF were close to 6 for Cu and Pb (moderately severe enrichment) and close to 4.5 for Zn (indicating moderate enrichment). It can be said that the Tisza River is slightly to moderately severely polluted with Cu, Zn, and Pb, and minorly polluted with Cr. It is concluded that sediments of the Tisza serve as a repository for heavy metal accumulation from adjacent urban and industrial areas.