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.

The significance of applying different factors for the evaluation of sediment contamination by toxic elements and estimation of the ecological risk.

The optimized three-step sequential extraction procedure for the fractionation of micro- and macroelements, was conducted to determine fractional characteristics of PTEs (potentially toxic elements) in surface sediments of rivers in the Vlasina watershed. The sequential extraction results, which enable the evaluation of mobility of the studied elements, have indicated that Zn, Ni, Cu, Cr, and As can be considered slightly mobile, whereas Pb, Mn, Cd, and Co were regarded as possibly mobile elements. Lead was dominantly bounded (specifically adsorbed or co-precipitated) to iron and manganese oxides (up to 80%) and may be released by reduction. Since the content of the exchangeable fraction (F1) is an indicator for anthropogenic impact on the aquatic environment, a low percentage (0-8%) of studied toxic elements in this fraction indicated that these elements have lithogenic origin in most sampling locations in the area of study. Except for Pb, the substantial positive correlations between Al and other elements showed that studied elements came primarily from terrigenous sources. Although the values obtained for the risk assessment code (RAC) indicated a slightly increased mobility of some elements (up to 22.44%), the values of the modified risk assessment code (mRAC), which include toxic effects on the environment, showed there is no danger of pollution by studied elements (all values were < 1%). Our recommendation is to use mRAC instead of RAC in ecochemical studies and assessment of the degree of sediment and soil pollution, because mRAC includes toxic effects of elements. Based on ATI values, river sediments show no toxic to a low toxic degree. Even though obtained results indicate that there was no considerable risk for river water contamination, the ecological risk for Fe and Pb should be monitored in the future.

Trace elements in size-segregated urban aerosol in relation to the anthropogenic emission sources and the resuspension.

Size segregated particulate samples of atmospheric aerosols in urban site of continental part of Balkans were collected during 6 months in 2008. Six stages impactor in the size ranges: Dp ≤ 0.49 µm, 0.49 < Dp ≤ 0.95 µm, 0.95 < Dp ≤ 1.5 µm, 1.5 < Dp ≤ 3.0 µm, 3.0 < Dp ≤ 7.2 µm, and 7.2 < Dp ≤ 10.0 µm was applied for sampling. ICP-MS was used to quantify elements: Al, As, Bi, Ca, Cd, Co, Cr, Cu, Fe, Ga, K, Li, Na, Ni, Mg, Mn, Pb, Sb, V, and Zn. Two main groups of elements were investigated: (1) K, V, Ni, Zn, Pb, As, and Cd with high domination in nuclei mode indicating the combustion processes as a dominant sources and (2) Al, Fe, Ca, Mg, Na, Cr, Ga, Co, and Li in coarse mode indicating mechanical processes as their main origin. The strictly crustal origin is for Mg, Fe, Ca, and Co while for As, Cd, K, V, Ni, Cu, Pb, and Zn dominates the anthropogenic influence. The PCA analysis has shown that main contribution is of resuspension (PC1, σ(2) ≈ 30 %) followed by traffic (PC2, σ(2) ≈ 20 %) that are together contributing around 50 % of elements in the investigated urban aerosol. The EF model shows that major origin of Cd, K, V, Ni, Cu, Pb, Zn, and As in the fine mode is from the anthropogenic sources while increase of their contents in the coarse particles indicates their deposition from the atmosphere and soil contamination. This approach is useful for the assessment of the local resuspension influence on element's contents in the aerosol and also for the evaluation of the historical pollution of soil caused by deposition of metals from the atmosphere.

Contribution of marine and continental aerosols to the content of major ions in the precipitation of the central Mediterranean.

The region of the investigated receptor is situated in the southern part of the Adriatic Sea in the Mediterranean. The measuring station is located on the seashore, which, being considered as a border area, is representative for the qualitative and quantitative estimation of the influence of marine and continental aerosols on the content of major ions in precipitation. In the sampling period, precipitation in the region of the investigated receptor was more abundant during the summer and autumn than during the winter and spring. The most frequent precipitation heights were up to 20 mm, while high precipitation came exclusively from the continental region. The results of the measurements of ions readily soluble in water were used for the differentiation of marine from continental contributions of primary and secondary aerosols to their content in the precipitation. Using PCA, it was shown that main contribution of Cl(-), Na(+) and Mg(2+) came from primary marine aerosols, while the contribution from continental sources was dominant for the content of SO(4)(2-), NO(3)(-), NH(4)(+) and Ca(2+) in the precipitation. The continental origin of Ca(2+) was from a primary source, while SO(4)(2-), NO(3)(-) and NH(4)(+) were representatives of secondary aerosols produced by reactions between acid oxides and alkaline species in the atmosphere, but SO(4)(2-) and NO(3)(-) also exist in the precipitation as free acids. The origin of the trace elements Cd, Cu, Pb and Zn in the precipitation came from anthropogenic emission sources. The results obtained in this work are based on experimental data from 609 samples collected during the period 1995-2000.