Seasonal and spatial variations of Po and Pb activity concentrations in Mytilus galloprovincialis from Croatian coast of the Adriatic Sea

Results of 2 years monitoring of ²¹⁰Po and ²¹⁰Pb activity concentrations in soft tissue of the species Mytilus galloprovincialis from Croatian part of the Adriatic coast are presented. The samples were collected at thirteen coastal stations (some of which are also a part of the Mediterranean Mussel Watch Project) in spring and autumn of 2010 and 2011. The collected mussels were ranging between 4 cm and 6 cm in shell length. After sample pre-treatment lead and polonium were radiochemically separated on Sr resin. ²¹⁰Po was determined by alpha-particle spectrometry and ²¹⁰Pb was determined, via ²¹⁰Bi, by a low-level gas proportional counter. The results of ²¹⁰Po activity concentrations were found to vary between (104 ± 11) and (1421 ± 81) Bq kg⁻¹ dry weight while ²¹⁰Pb activity concentrations were much lower and in range (8.2 ± 5.3)–(94.1 ± 29.8) Bq kg⁻¹ dry weight. Higher ²¹⁰Po and ²¹⁰Pb activity concentrations were determined in spring period. The inter-site differences seen in their activity concentrations can be due to natural background levels of sites. The ²¹⁰Po/²¹⁰Pb activity concentration ratios in all cases exceeded unity for all mussel samples and ranged between 4.0 and 47.9.     

Malondialdehyde and heavy metal concentrations in tissues of wild boar (Sus scrofa L.) from central Croatia

The aim of this research was to assess the degree of heavy metal (cadmium, lead and mercury) contamination of wild boars from central Croatia and thereby conduct further tests to connect the contamination to oxidative stress occurrence. The highest cadmium concentration was noticed in the kidneys of older boars, the lead concentration was approximately the same in the liver and kidneys, but it was much higher than the concentration in the muscles, while the highest mercury concentration was measured in the kidneys of all wild boars. The correlation between the malondialdehyde (MDA) and the heavy metal concentrations was higher in tissue samples taken from younger animals (1 to 3 years of age) than in the tissue samples taken from older animals (5 to 6 years of age). In the kidneys of all wild boars there was a statistically significant connection between the MDA and cadmium concentration; in the kidneys of younger wild boars there was a statistically significant connection between the MDA and lead concentration. Further research on this topic should focus on MDA potential to find its use, not only as a contamination biomarker in the area of ecotoxicology, but also in the evaluation of the hygienic acceptability of animal products.     

Cadmium effects on the fitness-related traits and antioxidative defense of Lymantria dispar L. larvae

Cadmium, like many other pollutants, is nondegradable and can be accumulated by Lymantria dispar at a level that affects fitness components, physiology, and development, which could indicate presence of environment pollution by heavy metals. The cadmium effect on fitness-related traits in the third, fourth, fifth, and sixth instar of L. dispar L. was determined. Furthermore, activities of the following antioxidative defense components after the larvae had been fed on the artificial cadmium-supplemented diet (50 μg Cd/g dry food) were assessed: superoxide dismutase (SOD), catalase (CAT), ascorbate peroxidase (APOX), total glutathione amount (GSH), glutathione-S-transferase (GST), glutathione reductase (GR), and the amount of free sulfhydryl (SH) groups. Statistically significant delay of development in the fourth, fifth, and sixth instar and decrease of the larval mass in the third and fourth instar were estimated after the exposure to cadmium through food in comparison to the control. There were no changes in SOD activity of cadmium-treated larvae. Significantly lower CAT, APOX, and GR activities were recorded in the third, fifth, and in the third instar, respectively. At the same time, higher activity was recorded in the sixth instar, while GST activity was higher in the third. GSH content was significantly lower during all instars after treatment but the amount of SH groups was higher in older larvae. The strategy of antioxidative defense and the adjustment or modulation of fitness-related traits in presence of cadmium was dependent on the age of larvae in L. dispar, which might be used in early metal risk assessment in Lepidoptera and other insects.     

Enzymatic biomarkers as indicators of dietary cadmium in gypsy moth caterpillars

Heavy metals damage the structure, chemistry, and function of cells, including enzyme systems inside them. Variation in the profile of biochemical biomarkers in prevalent species should be used for assessing environmental contamination. The present study pays attention to the phosphatases present in the midgut of gypsy moth fourth instar caterpillars, which had been exposed to short- and long-term cadmium intake at 10 and 30 μg Cd/g dry food. Chronic cadmium ingestion significantly inhibited the activity of all examined phosphatases, while only the activity of lysosomal phosphatase was acutely decreased. Total acid phosphatase activity recovered from both long-term cadmium treatments within 3 days. The low index of phenotypic plasticity was connected to high variability of plasticity. Dependence of phosphatase isoforms on genotype and duration of cadmium treatment was determined. We concluded that, with further investigations, profiling of total acid phosphatase activity, as well as the lysosomal fraction can be used as a biomarker for acute sublethal metal toxicity.     

Active moss biomonitoring of small-scale spatial distribution of airborne major and trace elements in the Belgrade urban area

In urban environments, human exposure to air pollutants is expected to be significantly increased, especially near busy traffic streets, street canyons, tunnels, etc. where urban topography and microclimate may additionally cause poor air conditions giving rise to pollution hotspots. As a practical and cost-effective approach, active moss biomonitoring survey of some major and trace element air pollution was performed in the Belgrade street canyons and city tunnel in 2011 with the aim to evaluate possibility of using Sphagnum girgensohnii moss bags for investigation of the small-scale vertical and horizontal distribution patterns of the elements. In five street canyons, the moss bags were hung at heights of about 4, 8 and 16 m, during 10 weeks, and also, for the same time, the moss bags were exposed in the tunnel, in front of and out of it. After the exposure period, the concentrations of Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Sr, V and Zn in the moss were determined by inductively coupled plasma optical emission spectrometry. According to the results, in all street canyons, the vertical distribution patterns of the moss elements concentration (Al, Ba, Co, Cr, Cu, Ni, Pb, Sr, V and Zn) showed statistically significant decrease from the first to the third heights of bags exposure. In the tunnel experiment, from inner to out of the tunnel, for Al, Ba, Cd, Co, Cr, Cu, Fe, K and Zn, decreasing trend of concentrations was obtained. Significantly higher concentration of the elements was pronounced for the tunnel in comparison with the street canyons. The results indicate that the use of S. girgensohnii moss bags is a simple, sensitive and inexpensive way to monitor the small-scale inner city spatial distribution of airborne major and trace element content.     

The electronic properties of trimethylnaphthalenes as properties for the prediction of biodegradation rates: ab initio and DFT study

There is little information on trimethylnaphthalenes (TMNs) which are constituents of diesel fuel and bitumen emissions. In this study, a theoretical investigation of the electronic properties of all trimethylnaphthalene (TMN) isomers and their relation to biodegradation are presented. Equilibrium geometries, ionization potentials (IPs), electron affinities (EAs), dipole moments and electronic dipole polarizabilities of TMN isomers calculated by ab initio and Density Functional Theory (DFT) methods are reported. Polarizability and dipole moment computations have been performed in gas and in water solution using the polarizable continuum model (PCM). The results obtained show that the IP value varies little along the series of isomers while averaged static dipole polarizabilities (〈α〉) increase on passing from α,α,α-TMN to β,β,β-TMN isomers. This indicates that the binding affinity between TMNs and active site of bacterial enzymes is mainly determined by dispersive and inductive effects. Therefore, the computed polarizability values of TMNs can be used as predictors of the rates of biodegradation of TMNs.     

The sensitivity of soil enzymes,microorganisms and spring wheat to soil contamination with carfentrazone-ethyl

Herbicides pose a significant threat to the natural environment, in particular in soils that are most exposed to plant protection agents. Prolonged herbicide use leads to changes in soil metabolism and decreases soil productive potential. In this study, the influence of carfentrazone-ethyl (CE) on the microbiological and biochemical properties of soil and the yield of Triticum aestivum L. was evaluated. Carfentrazone-ethyl was applied to sandy loam (pH_KCl – 7.0) in doses of 0.000, 0.264, 5.280, 10.56, 21.18, 42.24, 84.48 and 168.96 µg kg^?1 DM soil. Soil samples were subjected to microbiological and biochemical analyses on experimental days 30 and 60. Carfentrazone-ethyl disrupted the biological equilibrium in soil by decreasing the abundance and biodiversity of soil-dwelling microorganisms, the activity of soil enzymes, the values of the biochemical activity indicator and spring wheat yields. Carfentrazone-ethyl had the most adverse effects when applied in doses many fold higher than those recommended by the manufacturer. The toxic effects of CE were also determined by its soil retention time. Soil treated with CE was characterized by higher counts of oligotrophic bacteria, organotrophic bacteria, bacteria of the genus Azotobacter, actinomycetes and fungi on day 60, and spore-forming oligotrophic bacteria on day 30. The activity of dehydrogenases, urease, alkaline phosphatase and β-glucosidase was higher on day 30 than on day 60.     

Spatio-temporal analysis of land use/land cover change and its effects on soil erosion (Case study in the Oplenac wine-producing area,Serbia)

In this paper, various spatial modelling techniques were applied to analyse changes in soil cover and their impact on soil erosion in the Oplenac wine-producing area in Serbia in the past (1985 and 2013) and in the future (with predictions for 2041). The Integrated Valuation of Ecosystem Services and Trade-offs Sediment Delivery Ratio (InVEST SDR) model and the Modules for Land Use Change Evaluation (MOLUSCE) model, integrated with methods of remote sensing, were successfully applied and were shown to be valid tools for predicting the impact of Land Use Land Cover (LULC) changes when estimating soil loss. The results revealed that the greatest impact of land use changes between 1985 and 2013 was on a reduction in areas under vineyards and an extension of meadow and pasturelands as an individual and social response to economic conditions during the research period. The forecast for 2041 reflected the trends observed in the previous period, with the greatest changes witnessing an increase in urban areas and a decrease in areas of arable land. It was also found that the effect of LULC changes on spatio-temporal patterns in the Oplenac wine-producing area did not have a major impact on soil loss, meaning this area, with its good agro-climatic characteristics, is suitable for the intensification of agricultural production.     

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 PM_0.27–16 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.     

Characteristics and origin of the hydrogen sulphide spring water from the Split spa (Southern Croatia)

The objective of this paper is to study the hydrological characteristics and origin of the hydrogen sulphide spring water from the Split spa in Southern Croatia in 1987, 1988 and 2003. This paper presents the results of monitoring the content of chlorides and hydrogen sulphide as well as the temperature of the hydrogen sulphide spring water. Since the hydrogen sulphide content during the dry periods significantly differs from the hydrogen sulphide content during rainy periods, this paper also compares the results obtained for those two periods. Under the influence of great quantities of rainfall during cold periods (winter and the beginning of spring) the ratio between seawater and surface water changes and thus the reduction of chlorides and other minerals occurs. The lowered temperature also reduces hydrogen sulphide which can disappear completely. The concentration of 12‰ chlorides (76–94.4% days/year) and 12 mg/L hydrogen sulphide (66.7–88.9% days/year) has been taken as a limit value between water with a normal typical content and water in cold rainy periods. According to the monitoring results it can be concluded that hydrogen sulphide spring water consists of seawater and hydrogencarbonate surface water with a fairly constant content during dry periods while the hydrogencarbonate content increases during rainy periods.