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.

Reduction of CO2 in the presence of light via excited-state hydride transfer reaction in a NADPH-inspired derivative.

The photo-catalytic reduction of CO2 into chemical feedstocks using solar energy has attracted vast interest in environmental science because of global warming. Based on our previous study on the CO2 complex with one of the benzimidazoline (BI) derivatives, we explore the photochemical reduction of CO2 in one of the benzimidazoline derivatives (1,3-dimethyl-5,6-diol-2,3-dihydro-1H-benzimidazole) by quantum-chemical methods. Our results reveal that carbon dioxide can be reduced to formate (HCOO-) by a hydride transfer reaction in the excited state of this complex of benzimidazoline derivative and CO2. While the ground-state hydride transfer reaction in this complex exhibits a substantial barrier, a charge-transfer can occur in the first singlet excited state of the complex in the UV-A region (326 nm), and after overcoming a moderate barrier (∼0.4 eV) the system can have access to the products. The interaction with a polar solvent decreases further the barrier such that the reaction in dimethyl sulfoxide can proceed with a negligibly small barrier (∼0.1 eV) or in a nearly barrierless manner. Our results show that this benzimidazoline derivative may act as a catalyst in the photoreduction of CO2.

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.

Light-driven reduction of CO2: thermodynamics and kinetics of hydride transfer reactions in benzimidazoline derivatives.

CO2 capture, conversion and storage belong to the holy grail of environmental science. We therefore explore an important photochemical hydride transfer reaction of benzimidazoline derivatives with CO2 in a polar solvent (dimethylsulfoxide) by quantum-chemical methods. While the excited electronic state undergoing hydride transfer to formate (HCOO-) shows a higher reaction path barrier compared to the ground state, a charge-transfer can occur in the near-UV region with nearly barrierless access to the products involving a conical intersection between both electronic states. Such radiationless decay through the hydride transfer reaction and formation of HCCO-via excited electronic states in suitable organic compounds opens the way for future photochemical CO2 reduction. We provide a detailed analysis for the chemical CO2 reduction to the formate anion for 15 different benzimidazoline derivatives in terms of thermodynamic hydricities (ΔGH-), activation free energies (ΔG‡HT), and reaction free energies (ΔGrxn) for the chosen solvent dimethylsulfoxide at the level of density functional theory. The calculated hydricities are in the range from 35.0 to 42.0 kcal mol-1i.e. the species possess strong hydride donor abilities required for the CO2 reduction to formate, characterized by relatively low activation free energies between 18.5 and 22.2 kcal mol-1. The regeneration of the benzimidazoline can be achieved electrochemically.

Fractionation of Potentially Toxic Elements (PTEs) in Urban Soils from Salzburg, Thessaloniki and Belgrade: An Insight into Source Identification and Human Health Risk Assessment.

Concentrations of potentially toxic elements (PTEs) (Al, As, Cd, Cr, Cu, Ni, Pb, and Zn) were measured in topsoil samples collected from parks in the cities of Salzburg (Austria), Thessaloniki (Greece), and Belgrade (Serbia) in order to assess the distribution of PTEs in the urban environment, discriminate natural (lithogenic) and anthropogenic contributions, identify possible sources of pollution, and compare levels of pollution between the cities. An assessment of the health risks caused by exposure to PTEs through different pathways was also conducted. The study revealed that, with the exception of Pb in Salzburg, levels of PTEs in the soils in polluted urban parks were higher than in unpolluted ones, but still lower than those recorded in other European soils. Results of sequential analyses showed that Al, Cr, and Ni were found in residual phases, proving their predominantly lithogenic origin and their low mobility. In contrast, the influence of anthropogenic factors on Cu, Pb, and Zn was evident. Site-dependent variations showed that the highest concentrations of As, Cu, Pb, and Zn of anthropogenic origin were recorded in Salzburg, while the highest levels of Al, Cr, and Ni of lithogenic origin were recorded in Belgrade and Thessaloniki, which reflects the specificity of the geological substrates. Results obtained for the health risk assessment showed that no human health risk was found for either children or adults.

Pollution and Health Risk Assessments of Potentially Toxic Elements in Soil and Sediment Samples in a Petrochemical Industry and Surrounding Area.

The pollution state and health risk assessment of potentially toxic elements (PTE) in soil and sediment samples of the petrochemical industry and its surrounding area are evaluated in this study. The pseudo-total contents of Ba, Cd, Co, Cu, Cr, Mn, Ni, Pb, V, Zn, As, Hg, and Se were measured by inductively coupled plasma-optical emission spectrometry (ICP/OES) in analyzed samples. Instead of determining total content, we performed aqua regia of the samples. The silicate matrix remained, and the quantities of elements that are within the silicate matrix do not represent an environmental danger. The soils from the chlor-alkali plant are highly polluted by Hg (the enrichment factor values were above 6000), and by Cu, Cd, Pb, and Zn, while the sediment samples from the wastewater channel are polluted with Cr, Cd, and Hg. The measured element contents are used for calculating health risk criteria for a composite worker (a worker who is exposed, long-term, during the work day) and for residential people. Hg is the element that mainly contributes to non-carcinogenic risks within the petrochemical area. The highest value of total carcinogenic risk obtained in the sediment sample from the wastewater channel, and the metal that mostly contributes is Cr. The areas closest to the petrochemical industry have higher values of health risk criteria parameters and pollution indices. The areas that are located further to the north and south from the petrochemical industry are less burdened with the analyzed elements, which is significant because the closest city and village are situated in those directions.

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).

Size-segregated trace elements in continental suburban aerosols: seasonal variation and estimation of local, regional, and remote emission sources.

We have measured trace element contents in suburban aerosols from six size fractions in the range of PM0.27-16 from a background station in Belgrade (Serbia). The distribution and concentration of elements were determined within each of the investigated Dp fractions with emphasis on the fine and coarse modes. Fine/coarse mode ratios of element can provide information regarding their anthropogenic or natural origin. Analysis of seasonal variations of element contents in fine and coarse mode show that Cd, Co, K, and V have higher concentrations in the fine mode during heating season, while Fe contents are lower. In the coarse mode, Cu and V have higher concentrations during the heating season, while Al, Fe, Mg, Mn, and Sb contents are lower. We also apply a distribution probability model (normal, log-normal, and three-parameter Weibull) as new approach to estimate the distances of emission sources that can contribute to pollutant contents in particulate matter of the investigated location.

Clinical and analytical experience of the National Poison Control Centre with synthetic cannabinoids.

A rising number of patients are being treated for overdosing with new psychoactive substances (NPS) available at the illegal drug market in Serbia. The aim of this study was to report clinical and analytical experience of the National Poison Control Centre of Serbia (NPCC) with synthetic cannabinoids (SCs) and point to the NPS available at the illegal drug market in our country. From January 2013 to December 2016, 58 patients (aged between 14 and 25) were treated for the effects of synthetic cannabinoids at the NPCC. Tachycardia was established in 53, mydriasis in 31, somnolence, nausea, vomiting, and agitation in 16, dizziness in 10, disorientation in 9, dyspnoea and chest pain in 4, and loss of consciousness, pallor, paraesthesia, muscle twitches, and short-term memory impairment in 2 patients. After receiving symptomatic and supportive treatment in the emergency ward, all patients had fully recovered within 8 h and were discharged shortly afterwards. Another part of the study was focused on the analysis of the products known under their local street names as "Biljni tamjan" (herbal incense), "Beli slez", and "Rainbow Special" and the analysis of urine sampled from the patients with gas chromatography - mass spectrometry and high performance liquid chromatography. The detected synthetic cannabinoids were AB-PINACA, JWH-018, JWH-122, JWH-210, 5F-AKB48, and MDMB-CHMICA in herbal products and AB-FUBINACA, AB-CHMINACA, and MDMB-CHMICA in the urine samples. Our findings have shown the great capacity of NPCC to I) monitor NPS abuse in Serbia, II) reliably detect SCs in illicit products and biological samples, and III) clinically manage the adverse effects in their users. Future commitments of the NPCC will include systematic collection of relevant data on SCs and their adverse effects, detection of changes in purity and composition of the controlled NPS-based products, and raising the public awareness of NPS to improve the effectiveness of the national Early Warning System.

Partitioning of particulate matter and elements of suburban continental aerosols between fine and coarse modes.

The results presented in this work demonstrate for the first time a distribution of elements in the spectral analysis of aerosols in the suburban continental Balkan Peninsula. Samples were collected in the suburban area of Belgrade (Serbia) in the period from March 2012 till December 2013. Results presented here are from long-term measurements of masses of size-segregated aerosols and macro- and microelements in the range of PM0.27-16. The following elements were analyzed: Al, Ag, As, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Mo, Na, Ni, Pb, Sb, Ti, Tl, V, and Zn; levels of Be, Hg, and Se were under the detection limits in all samples. Average concentrations and time and seasonal variations of particulate matter (PM) as well as element contents and their percentage shares are given. The results showed the domination of particle content around the accumulation mode in the range of 0.53 < Dp < 1.06 µm, but the fractional distribution of elements showed maximal average concentrations in different fractions depending on the origin of each element. Crustal elements (Al, Ca, Fe, Mg, Mn, Ti, etc.) dominated in coarse mode, while anthropogenic elements (As, Cd, Cu, Pb, Sb, etc.) were mainly distributed in fine mode fractions. Some elements, such are As and Ni, were detected in investigated aerosols only occasionally, while others, such as Ca, Fe, and Mg, were detected in all analyzed samples. The application of multivariate analysis (PCA) demonstrated the connection between the elements of similar origin, in fine fractions mainly of anthropogenic origin, while in coarse mode of crustal origin, indicating the resuspension with contribution of about 40%. The contents of some measured elements were compared with their contents in aerosols in some European suburban areas.

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.

Ranking and similarity of conventional, microwave and ultrasound element sequential extraction methods.

This study aims to compare three extraction techniques of four sequential element extraction steps from soil and sediment samples that were taken from the location of the Pancevo petrochemical industry (Serbia). Elements were extracted using three different techniques: conventional, microwave and ultrasound extraction. A novel procedure - sum of the ranking differences (SRD) - was able to rank the techniques and elements, to see whether this method is a suitable tool to reveal the similarities and dissimilarities in element extraction techniques, provided that a proper ranking reference is available. The concentrations of the following elements Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Si, Sn, Sr, V and Zn were determined through ICP OES. The different efficiencies and recovery values of element concentrations using each of the three extraction techniques were examined by the CRM BCR-701. By using SRD, we obtained a better separation between the different extraction techniques and steps when we rank their differences among the samples while lower separation was obtained according to analysed elements. Appling this method for ordering the elements could be useful for three purposes: (i) to find possible associations among the elements; (ii) to find possible elements that have outlier concentrations or (iii) detect differences in geochemical origin or behaviour of elements. Cross-validation of the SRD values in combination with cluster and principal component analysis revealed the same groups of extraction steps and techniques.

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.

Five primary sources of organic aerosols in the urban atmosphere of Belgrade (Serbia).

Biomass burning and primary biological aerosol particles (PBAPs) represent important primary sources of organic compounds in the atmosphere. These particles and compounds are able to affect climate and human health. In the present work, using HPLC-orbitrapMS, we determined the atmospheric concentrations of molecular markers such as anhydrosugars and phenolic compounds that are specific for biomass burning, as well as the concentrations of sugars, alcohol sugars and d- and l-amino acids (D-AAs and L-AAs) for studying PBAPs in Belgrade (Serbia) aerosols collected in September-December 2008. In these samples, high levels of all these biomarkers were observed in October. Relative percentages of vanillic (V), syringic compounds (S) and p-coumaric acid (PA), as well as levoglucosan/mannosan (L/M) ratios, helped us discriminate between open fire events and wood combustion for domestic heating during the winter. L-AAs and D-AAs (1% of the total) were observed in Belgrade aerosols mainly in September-October. During open fire events, mean D-AA/L-AA (D/L) ratio values of aspartic acid, threonine, phenylalanine, alanine were significantly higher than mean D/L values of samples unaffected by open fire. High levels of AAs were observed for open biomass burning events. Thanks to four different statistical approaches, we demonstrated that Belgrade aerosols are affected by five sources: a natural source, a source related to fungi spores and degraded material and three other sources linked to biomass burning: biomass combustion in open fields, the combustion of grass and agricultural waste and the combustion of biomass in stoves and industrial plants. The approach employed in this work, involving the determination of specific organic tracers and statistical analysis, proved useful to discriminate among different types of biomass burning events.

Pollution by Urticaceae pollen-influence of selected air pollutants and meteorological parameters.

The goal of this study was to analyze the influence of pollutants (concentrations of NO2, SO2, and soot in the air) and meteorological parameters (air temperature, humidity, wind speed, air pressure, cloud index) on Urticaceae pollen type emission measured in the region of Subotica, Serbia. The concentrations of the air pollutants, Urticaceae pollen, and meteorological parameters were measured over a 5-year period (2009-2013), followed by a statistical analysis of the values obtained. For most of the years examined, the concentration of NO2 correlates significantly with the concentration of Urticaceae pollen type. It was also established that air temperature, humidity, wind speed, atmospheric pressure, and cloud index have an influence on Urticaceae pollen type emission, while SO2 and soot do not contribute.

Aquatic sediments pollution estimate using the metal fractionation, secondary phase enrichment factor calculation, and used statistical methods.

The sequential extraction procedure of the European Community Bureau of Reference (BCR) was applied for the fractionation of Cd, Cr, Cu, Ni, Pb, Zn, Fe, Mn, and V in the Serbian river sediments. The aim of this paper was to describe a new approach in detection of anthropogenic elements in sediments, related to the Serbian river courses in order to assess their metal contamination. For sediment pollution evaluation, the risk assessment code (RAC) and the secondary phase enrichment factor (KSPEF) were used. Metal fractionation showed more easily mobilized forms predominant for copper, zinc, cadmium, manganese, and lead, which can be one of the indicators for anthropogenic source input. Chromium, nickel, iron, and vanadium found in the residual fraction indicate these metals may be an indicator for natural sources input. Based on RAC classification, results of sediments show no risk (Cr and V), low risk (Ni, Pb, and Fe), medium risk (Cu), high risk (Cd and Zn), and very high risk (Mn). The mean values of KSPEF were Cd > Cu > Zn > Ni > Mn > Pb > Fe > Cr > V, decreasing scale of no to moderately severe enrichment. The sediments were found to be contaminated by heavy metals to various extents, mostly Cd, Cu, and Zn. Research has shown the importance of KSPEF in quantifying degree of metal enrichment in sediments using results of sequential extraction. With the application of this factor, which is not frequently used in the scientific literature, the results obtained with sequential extraction can be used not only for assessment of mobility but also to quantify the metal pollution.

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.

Electronic properties of environmental pollutants and their mutagenic activity: Nitro derivatives of azaphenanthrenes.

The physico-chemical properties of nitroazaphenanthrene isomers: 4-nitro-9-azaphenanthrene (4-N-9-Aph), 5-nitro-9-azaphenanthrene (5-N-9-Aph), 6-nitro-4-azaphenanthrene (6-N-4-Aph), 8-nitro-1-azaphenanthrene (8-N-1-Aph), and 8-nitro-4-azaphenanthrene (8-N-4-Aph) have been investigated theoretically using Density Functional Theory (DFT) calculations. Equilibrium geometries, relative stability, ionization potentials, electron affinities, molecular electrostatic potentials, dipole moments, electric polarizabilities, and vibrational properties of these isomers are presented. Averaged O-N-C-C dihedral angle, dipole moment, polarizability, the summation of IR intensities (∑IIR) and the summation of Raman activities (∑ARaman) over all 3N-6 vibrational degrees of freedom are sensitive to the structure of isomers. A very good linear relationship between ∑ARaman values (R=1.00) and the Salmonella typhimurium strain TA98(-S9) mutagenic activity of the investigated nitroazaphenanthrene isomers (Tokiwa et al., 2003) reveals a very important role of inductive and dispersive forces on the mutagenic pathways of the investigated isomers.

Two nitro derivatives of azabenzo[a]pyrene N-oxide: electronic properties and their relation to mutagenic activity.

The equilibrium geometries, relative energies, IR and Raman spectra, vertical ionization potentials (IP), vertical electron affinities (EA), dipole moments (µ), electronic dipole polarizabilities (α), and molecular electrostatic potentials (MEP) of two species that show very high mutagenicity, 1-nitro-6-azabenzo[a]pyrene N-oxide (1-N-6-ABPO) and 3-nitro-6-azabenzo[a]pyrene N-oxide (3-N-6-ABPO), are investigated by means of Density Functional Theory (DFT) using B3LYP functional with different basis sets. The 3-N-6-ABPO isomer was estimated to be much more mutagenic in Salmonella typhimurium tester strain TA98 (396,000 revertants/nmol) than 1-N-6-ABPO (36100 revertants/nmol) (Fukuhara et al., 1992). The results show that for both isomers the structural, energetic, and vibrational properties are similar. The orientation of the nitro group with respect to the plane of the aromatic system as well as the nitroreduction and oxidation reaction and polarizability seem not be important for the determination of different mutagenic behavior of these isomers. However, the dipole moment of 3-N-6-ABPO is about 3 times that of 1-N-6-ABPO. The larger dipole moment and the different electronic charge distribution of 3-N-6-ABPO compared to 1-N-6-ABPO imply stronger electrostatic and inductive molecular interactions so that the active site of the enzyme involved in the mutagenic activation can more effectively bind 3-N-6-ABPO compared to 1-N-6-ABPO.

Evaluation of sediment contamination with heavy metals: the importance of determining appropriate background content and suitable element for normalization.

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.