Ivan Gržetić

Synergic adsorption of Pb2+ and reactive dye--RB5 on two series of organomodified bentonites.

Two series of organobentonites (OBs) were synthesized from Na(+)-exchanged bentonite clay from Bogovina, Serbia. In the first series the starting material was modified using hexadecyltrimethylammonium (HDTMA(+)) ion in the amounts corresponding to 0.2, 0.5, 1.0 and 2.0 of the CEC value. The second series was obtained using quaternary alkyl ammonium cations (QAACs) with different alkyl chain lengths: hexadecyltrimethylammonium (HDTMA(+)), dodecyltrimethylammonium (DDTMA(+)) and tetramethylammonium (TMA(+)) ions. The synthesized OBs were characterized. The adsorption of anionic reactive dye Reactive Black 5 (RB5) and Pb(2+) from single component solutions and their bi-component solution was investigated for both series of OBs. The adsorptive properties of the OBs were correlated to the amount and type of incorporated QAACs. The correlation was tested using different mathematical models and best fits were found. Experimental results showed that simultaneous adsorption of RB5 and Pb(2+) exhibited synergic effect. The adsorption capacity for both RB5 and Pb(2+) was higher in their bi-component solution than in single-component solutions. These results indicate the creation of new adsorption sites during the simultaneous adsorption.

Long-term seasonal changes of the Danube River eco-chemical status in the region of Serbia

Seasonal spatial and temporal changes of selected eco-chemical parameters in section of the Danube River flowing through Serbia were analyzed. Data for electrical conductivity (EC), dry and suspended matter, residue on ignition, chemical oxygen demand (COD), biochemical oxygen demand (BOD-5), ultraviolet extinction, dissolved oxygen (DO), oxygen saturation, pH, nitrates, total phosphorus, and nitrogen were collected between 1992 and 2006. The use of monthly medians combined with linear regression and two-sided t test has been proven to be the best approach for resolving trends from natural variability of investigated parameters and for determining trend significance. Patterns of temporal changes between different months were examined. It was also determined that spatial trends of some parameters oscillate in predictable manner, increasing in one part of the year and declining in the other. Regression slope coefficients, an excellent indicator for determining when the water quality is changing the most along the course of the Danube, reach their maximum during summer for temperature (t), electric conductivity, nitrates, and total N, while in the same season suspended matter, COD, BOD-5, DO, and oxygen saturation coefficients reach their minimum. Correlations for used data sets of selected parameters were analyzed for better understanding of their behavior and mutual relations. It was observed that as Danube flows through Serbia, its general eco-chemical status either stagnates or improves, but the rate of river self-purification often depends on the season of the year.

Use of honeybees (Apis mellifera L.) as bioindicators for assessment and source appointment of metal pollution

The ability of honeybees to collect particulate matter (PM) on their bodies makes them outstanding bioindicators. In this study, two cities, Pančevo (PA) and Vršac (VS), South Banat district, Vojvodina, Serbia, were covered with two sampling sites each. The aims of this study were to determine concentrations of Al, Ba, Cd, Co, Cr, Cu, Fe, Mn, Na, Ni, Sr, and Zn in the bodies of honeybees during July and September of 2013, 2014, and 2015 and to analyze their spatial and temporal variations and sources of analyzed elements, as well as to assess pollution levels in the two cities. Significant temporal differences were found for Al, Ba, Cd, Co, Cr, Cu, Fe, Mn, Na, Ni, and Zn. Trend of reduction in metal concentrations in bodies of honeybees during the years was observed. Statistically significant spatial variations were observed for Al, Ba, and Sr, with higher concentrations in VS. PCA and CA analyses were used for the first time to assess sources of metals found in honeybees. These analyses showed two sources of metals. Co, Cd, Na, Fe, Mn, Zn, and partly Cu were contributed to anthropogenic sources, while Ca, Al, Mg, Cr, Ba, Sr, and Ni were contributed to natural sources.

ENVIRONMENTAL EFFECTS ON SUPEROXIDE DISMUTASE AND CATALASE ACTIVITY AND EXPRESSION IN HONEY BEE

Understanding the cellular stress response in honey bees will significantly contribute to their conservation. The aim of this study was to analyze the response of the antioxidative enzymes superoxide dismutase and catalase in honey bees related to the presence of toxic metals in different habitats. Three locations were selected: (i) Tunovo on the mountain Golija, as control area, without industry and large human impact, (ii) Belgrade as urban area, and (iii) Zajača, as mining and industrial zone. Our results showed that the concentrations of lead (Pb) in whole body of bees vary according to habitat, but there was very significant increase of Pb in bees from investigated industrial area. Bees from urban and industrial area had increased expression of both Sod1 and Cat genes, suggesting adaptation to increased oxidative stress. However, in spite increased gene expression, the enzyme activity of catalase was lower in bees from industrial area suggesting inhibitory effect of Pb on catalase.

Crystal structure of (Bi 0.94 Sb 1.06 )S 3 and reconsideration of cation distribution over mixed sites in the bismuthinite- stibnite solid-solution series

The intermediate member of the (Bi,Sb)2S3 solid-solution series was prepared by dry synthesis at low temperature (200 °C) with a long annealing period in sealed silica tube. The EDS analysis yielded an empirical formula (Bi0.96Sb1.04)S3, which is very close to the formula (Bi0.94Sb1.06)S3 obtained by crystal structure analysis. The crystal structure was refined to the R-factors: R1 = 0.0288 for I > 2 s (I) and wR2 = 0.0542 for all data. (Bi0.94Sb1.06)S3 has orthorhombic symmetry with space group Pnma (No. 62). The asymmetric unit contains two independent mixed cation sites, both coordinated to seven S atoms in a form of mono- capped trigonal prism. They combine into infinite (M 4S6)n rods parallel to the (010) direction with only weak interactions between rods where the lone electron pairs are directed. Our data and the revaluation of previous data resolve a controversy about the distribution of Sb and Bi over the two structural sites which exists in previously published works. It is shown that the structural constraints favour a slight preference of the larger cation for the marginal M1 site over the whole span of the solid-solution series. The unit cell parameters show a deviation form the Vegards law connected with different rates of the parallel increase of lengths of the strong bonds and the decreasing influence of the lone electron pair with the replacement of Sb by Bi. The changes in the char - acter of the two independent cation sites introduced by this replacement are similar to those produced during compression of Sb2S3.

Honeybees as sentinels of lead pollution: Spatio-temporal variations and source appointment using stable isotopes and Kohonen self-organizing maps

In this study, honeybees were used to determine spatio-temporal variations and origin sources of Pb. Lead concentrations and isotopic composition were used in combination with selected statistical methods. The sampling was carried out at five different locations in Serbia: urban region (BG), petrochemical industry (PA), suburban region (PV), rural region (MS) and thermal power plant region (TPP) during 2014. At PA and PV locations, samples were taken during multiple years. This is the first use of Kohonen self-organizing map (SOM) in combination with honeybees as bioindicators to determine spatio-temporal variations and origin of Pb pollution. It was observed that during the years Pb concentrations were in decline. Anthropogenic sources are most dominant in BG and TPP, in PA there are mixed sources of natural and anthropogenic origin and in PV Pb is of natural origin. It can be concluded that honeybees in combination with SOM can be used to differentiate between slight changes in spatio-temporal variations of Pb, as well as for source appointment.

Assessment of spatial and temporal variations in trace element concentrations using honeybees (Apis mellifera) as bioindicators

With the increase in anthropogenic activities metal pollution is also increased and needs to be closely monitored. In this study honeybees were used as bioindicators to monitor metal pollution. Metal pollution in honeybees represents pollution present in air, water and soil. Concentrations of As, Cs, Hg, Mo, Sb, Se, U and V were measured. The aim of this study was to assess spatial and temporal variations of metal concentrations in honeybees. Samples of honeybees were taken at five different regions in Serbia (Belgrade - BG, Pančevo - PA, Pavliš - PV, Mesić - MS, and Kostolac - TPP) during 2014. Spatial variations were observed for Sb, which had higher concentrations in BG compared to all other regions, and for U, with higher concentrations in the TPP region. High concentrations of Sb in BG were attributed to intense traffic, while higher U concentrations in the TPP region are due to the vicinity of coal fired power plants. In order to assess temporal variations at two locations (PA and PV) samples were taken during July and September of 2014 and June, July, August and September of 2015. During 2014 observing months of sampling higher concentrations in July were detected for Sb and U in BG, which is attributed to lifecycle of plants and honeybees. During the same year higher concentrations in September were observed for As, Sb in PA and Hg in PV. This is due to high precipitation during the peak of bee activity in spring/summer of 2014. No differences between months of sampling were detected during 2015. Between 2014 and 2015 statistically significant differences were observed for Hg, Mo and V; all elements had higher concentrations in 2014. This is in accordance with the trend of reduction of metal concentrations in the bodies of honeybees throughout the years in this region.

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, Pančevo, 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 Pančevo 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 Pančevo and the control site the lowest risk of contamination by toxic metals.