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In the present study, statistical correlation analysis and multivariate statistical techniques (PCA/FA) were employed to investigate polycyclic aromatic hydrocarbons (PAHs) in sediments, such as illite-montmorillonite (IM) and calcite (Ct), from two sedimentary environments of the Tertiary Krepoljin brown coal basin in Serbia. The coal and sediment layers were formed in fresh-water bogs during the Lower Miocene period. The total amount of extractable PAHs was determined by gas chromatography with a triple quad mass detector (GC-MS-MS), and it ranged from 449 to 10585 μg l-1 in all sediments. Eight of the total 16 PAHs, which ranged from 175.17 to 658.42 μg l-1, include benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenzo[a,h]anthracene, benzo[ g,h,i]perylene, and indeno[1,2,3-cd]pyrene, which are regarded as potentially carcinogenic, indicating a higher possibility of adverse ecological effects. Medium molecular-weight (MMW) PAHs were found to be predominant in all sediments. PAH concentrations are affected by several factors, such as carbon content, H/C mole ratio, and (less significant) O/C mole ratio. The non-existence of a correlation between the N/C ratio and other parameters indicates unspecific changes which accompany the original organic matter. The lower-sulfur Ct sediment samples were found to have a higher PAH content than higher sulfur IM samples, leading to the conclusion that the PAH content of sediments may be related to the depositional environment. [ABSTRACT FROM AUTHOR]

Concentrations of 10 potentially toxic trace elements were measured in soil samples collected from 18 sites in urban areas of Belgrade, the capital and the largest city in Serbia. Samples were analysed in order to assess the extent of soil contamination and to distinguish natural and anthropogenic input. The results demonstrated a general Zn, Pb, and Cd enrichment in surface samples, hence, after comparison with guidelines, it has been determined that there is a potential risk for human health. In the surface and buried samples, traces of cooper were detected. The highest concentrations of Cr (121 ± 12.3 mg/kg) and Ni (94.9 ± 12.6 mg/kg) were found at a sediment depth of 2 m and should be ascribed to geogenic sources. The results of HCA and PCA analysis supported a natural origin of Co, Cu, Mn, Cr, and Ni, while Cd, Zn, and Pb originated from anthropogenic inputs. Based on the pollution indices, Cd made the most dominant contribution, posing a high contamination risk in the studied area. Results of Nemerow pollution index (PIN) and potential ecological risk index (PER) demonstrated that pollution by heavy metals in sediments on several sites is moderately intense. [ABSTRACT FROM AUTHOR]

The purpose of this study was to evaluate sediment heavy metals (Cd, Cu, Co, Mn, Cr, Ni, Pb, and Zn) related to pollution in freshwater sediments in Serbia. The heavy metal enrichment determination in studied sediments was conducted by using total metal content with strong acidic digestion (HCl + HNO3 + HF), a calculated enrichment factor (EF), and application of correlation analysis and the box plot method. For identification of appropriate elemental normalisers for enrichment factor calculations, Fe, Al, Ti, and Si were used. The significant variation in heavy metal distribution among samples collected in this large region, encompassing all Serbian watersheds, suggests the selective contamination of sediments by heavy metals. Values for EF indicate nil to moderate enrichment for most studied elements, except for Cd, Cu, and Zn at some sampling points, where the enrichment was, in some cases, even severe. The high content of heavy metals and EFs in Serbia is related to the human activities around the sampling sites. The results indicate that all elements used for normalisation in this paper can also be used to estimate the anthropogenic influence, with an exception of Co, which should be considered as an element for normalisation in future studies. [ABSTRACT FROM AUTHOR]

To effectively manage potential environmental and human health impacts of contaminated river sediments, it is important that information about the source (anthropogenic vs geogenic), variability and environmental risks associated with the contamination are well understood. The present study was carried out to assess the source and severity of contamination and to undertake a risk assessment for selected elements (As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, V and Zn) in river sediments in Serbia. The estimate of the anthropogenic component of contamination was derived by determining the total element content and the background values for elements in sediments, and the severity of pollution was assessed by calculating a number of pollution indices including the contamination factor, the enrichment factor, the index of geoaccumulation, the ecological risk factor, the potential ecological risk index, the pollution load index, the combined pollution index, the modified degree of contamination and the toxic unit factor. This analysis indicates that river sediments in Serbia are primarily polluted with Zn, Cu and Cd. The most contaminated river systems are the Ibar, Pek, West Morava and Great Morava rivers. Mining activities were found to have a significant influence on sediment. Multivariate analyses suggested anthropogenic origins for Pb, Zn, Cd, As, Ni and Cu, whilst Fe, V, Mn, Co and Cr appear to have a mixed origin (both lithogenic and anthropogenic sources). A geochemical approach, with a calculation of pollution indices and statistical methods, is recognised as useful for the risk management of trace elements in sediments around the world. [ABSTRACT FROM AUTHOR]

Abstract: We investigated early diagenetic processes of the extractable organic matter from the Miocene freshwater sequence, which consists of coal fragments in clays, sandstones and shales alternating with continuous brown coal layers. We examined eight coals, thirteen sediments and three non-coaly underground layers. The molecular assemblages of the identified aliphatic hydrocarbons in the Krepoljin Basin reflect the abundance of plant taxa as precursors or participants in the early diagenetic stage. The data provide insight into the conditions prevailing in the lakes and bogs during early diagenesis. The dominance of diterpanes indicates that the prevalent of the organic matter was of gymnosperous origin. The hopanoid contents are considered to reflect microbial activity. That the organic matter in the Miocene Krepoljin Coal Basin is immature was confirmed by the presence of biolipids such as ββ-hopanes, C27 17 β (H)-trisnorhopanе. Saturated and aromatized abietanes, pimaranes and phyllocladanes, the most abundant compounds in all samples, indicate a predominantly higher plant input related to the Coniferous group, but identification of the individual plant families was not possible. β-Amyrin and other triterpenoid-derived triaromatic and triaromatic C-ring cleaved hydrocarbons with triterpenoid structures are thought to be characteristic for angiosperms. Unsaturated compounds, Δ2-triterpanes, early intermediaries in the diagenetic transformation of angiosperms also indicate a low degree of sediment maturity. [Copyright &y& Elsevier]

The sediments of the coal-bearing series of the Tertiary Krepoljin Brown Coal Basin have been investigated and presented in this manuscript. The samples of the intercalated mixed sediments (pieces of coal in clays, sandstones and shales) originate from two hydrogeochemically differing sedimentary environments: the illite-montmorillonitic (IM), and the calcitic (Ct) environment. The characteristics of the early diagenetic processes which influenced the composition of the organic matter of this sediment were assessed by the statistical correlation analysis and multivariate principal component analysis. The precursor material of higher plants gymnosperms had a significant influence on the overall organic matter of mixed sediments in both hydrochemical environments. A weak effect of N/C ratios on the specific diagenetic transformations of hopanoid molecules is noticed in the samples of the calcite environment. Sterane maturation transformations are not marked as significant for the samples of mixed sediments by the component analysis. The samples of I-M environments show a strong inhibitory effect on the processes of diastereoisomerization. [ABSTRACT FROM AUTHOR]

Abstract: The aim of this study was the evaluation of the trace element contamination level in sediments of the most important rivers in Serbia and their tributaries. The determination of the aqua regia soluble contents of 12 micro- and macro-elements (Ca, Cd, Co, Cr, Cu, Fe, Mn, Pb, Ni, Zn, Be and V) in sediments was developed by the microwave digestion technique combined with inductively coupled plasma atomic emission spectrometry. Correlation analysis and principal component analysis distinguishes factors of lithogenic and anthropogenic origins. The Fe, Mn, Be and V contents are controlled by a regional lithogenic high background factor, while Cd, Cr, Pb, Ni, Zn and Cu are recognized as tracer of pollution. For Co, mixed sources from both lithogenic and anthropogenic inputs were evidenced. The investigated sediment of the major rivers and their tributaries in Serbia showed high concentrations of metals, especially of Cd, Pb, Cu and Zn, which may cause serious environmental impacts. Rivers which flow into the Danube from its entrance into Serbia significantly influence the chemical load of the water and sediments. The experimental study was conducted using two BCR standard reference materials. The calculated accuracy and precision confirmed the good performance of the adopted procedures. [Copyright &y& Elsevier]

In the present study, concentrations of heavy metals (Cd, Cu, Co, Mn, Cr, Ni, Pb, and Zn) were determined at 35 river sediments in Serbia. The anthropogenic heavy metals input and quantification of the metal enrichment degree in sediments were estimated by calculating geo-accumulation indices (I(geo)) and enrichment factors (EF). These pollution indices have been calculated using different background values (continental crust and local background values) and different element used for normalization (Al and Fe), followed by result comparison. The EF values calculated with continental crust as background (minor to extremely severe enrichment) were higher than when regional background values were used (minor to moderate enrichment). Significant influence of background values on the I(geo) values is observed. Values of geo-accumulation index (<2) revealed that studied river sediments are remaining unpolluted to moderately polluted with Co, Mn, Cr, and Ni. Significant pollution in the sediments was observed for Cd, Cu, Pb, and Zn elements. The results of this study confirm the relevance of precise and accurate determining of local background concentrations while assessing sediment pollution. The values of EFs for studied elements were more influenced by the choice of background values than selection of element used for normalization. Our recommendation would be to use the local and regional background content in quantification of metal contamination in sediments, since these values differ and are site and region dependent.