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.     

Phytoplankton abundance and pigment biomarkers in the oligotrophic, eastern Adriatic estuary

Phytoplankton distribution and environmental characteristics were determined in a shallow, highly stratified and oligotrophic estuary (Zrmanja, eastern Adriatic). Samples were collected in two contrasting seasons; winter (February 2000), when river discharge was high, and in summer (July 2003), a period of drought. Phytoplankton distribution was closely related to salinity gradients, nutrient levels, and water residence time. Microscopic analysis revealed that phytoplankton was composed mainly of marine diatoms, dinoflagellates, cryptophytes, green flagellates, and coccolithophorids. The dominant biomarker pigments were fucoxanthin, alloxanthin and 19'-hexanoyloxyfucoxanthin, while lower, but indicative contributions of peridinin and chlorophyll b were also noted. Maximum abundance and biomass were found in the middle estuary in winter and in the upper estuary in summer. The estuary is mostly P-limited. Development of chain-forming marine diatoms was evident in winter. Due to the reduced nutrient input in summer, the biomass accumulated in the upper estuary (1,000 ng chlorophyll a l(-1)) was composed mostly of nanoplanktonic unicellular diatoms, nanoplanktonic marine dinoflagellates, cryptophytes, and chlorophytes. The concentrations of about 200 ng l(-1) hex-fuco, suggested that the contribution of prymnesiophytes to total biomass was comparable to that of diatoms and dinoflagellates. In the middle estuary and coastal sea, PO(4) and TIN were 3.5 times lower, resulting in a fivefold decrease in biomass (<100 ng chlorophyll a l(-1)). The oligotrophic Zrmanja and other karstic rivers discharging in the eastern Adriatic Sea, provide insufficient source of nutrients and low productivity of the eastern Adriatic Sea.     

Analysis of mosses and topsoils for detecting sources of heavy metal pollution: multivariate and enrichment factor analysis

In order to assess the contribution of emission sources to the pollution of areas remote from industrial facilities, a combined approach of enrichment factor analysis and multivariate statistics was used for detecting the origin of heavy metal pollution in the Zlatibor ecosystem, in Serbia. Samples of moss (Pleurozium schreberi, Hylocomium splendens, Scleropodium purum, Hypnum cupressiforme and Thuidum delicatulum) and of topsoil (0-5 cm) were collected in 2005. The concentrations of seven heavy metals (Cd, Cr, Cu, Mn, Ni, Pb and Zn) were determined in moss and soil samples by atomic absorption spectrometry. The results obtained by enrichment factor analysis and two multivariate statistical methods, principal component analysis and cluster analysis, enabled discrimination of the lithologic and anthropogenic sources of heavy metals in the mosses. Enrichment factors, calculated to evaluate the contribution to the metal content in moss from anthropogenic sources, revealed pollution of the investigated area by Cd and Pb, originating from long-range transport and fossil fuel burning.     

Fractionation and potential mobility of trace metals in Danube alluvial aquifer within an industrialized zone

Thirty-five alluvial sediments of the River Danube and 12 groundwater samples were taken within the Pan?evo Oil Refinery (Serbia). The results for groundwater samples exceed European primary drinking water standards for Fe (obtained results, >200 μg/l) and Mn (obtained results, >50 μg/l), while the levels of the trace metals are below the thresholds for drinking water quality. Sediments were treated by sequential extraction procedure with five different solutions, each having a higher extraction capacity than the previous one. We also wanted to determine the possible relationships among trace metals and between sediment properties and elemental concentrations. These solutions partitioned metals into CH₃COONH₄ extractable (F1); HCl carbonate extractable and NH₂OH·HCl easily reducible (F2); (NH₄)₂C₂O₄/H₂C₂O₄ moderately reducible (F3); H₂O₂–HNO₃ organic/sulfide extractable fractions (F4); and HCl acid-soluble residue (F5). The sum of trace metals Ni, Pb, Cu, and Zn associated with the first two fractions (exchangeable, carbonate, and easily reducible) is significant and extremely important because it represents the proportion of heavy metals that can be easily remobilized by changes in environmental conditions such as pH, redox potential, salinity, etc. Sediments located nearer the groundwater flow are exposed to stronger groundwater fluctuation and had a higher quantity of amorphous and less stable substrates of trace metals. Principal component analysis was used to understand and visualize the associations between the trace metals and certain geological forms within analyzed sediments. The observed association between Cr with total sulfur and Mn from the acid-soluble residue could indicate that Cr is in the form of reduced, less toxic Cr(III), which is from the ecochemical point of view very important.     

Management of hazardous medical waste in Croatia

This article provides a review of hazardous medical waste production and its management in Croatia. Even though Croatian regulations define all steps in the waste management chain, implementation of those steps is one of the country's greatest issues. Improper practice is evident from the point of waste production to final disposal. The biggest producers of hazardous medical waste are hospitals that do not implement existing legislation, due to the lack of education and funds. Information on quantities, type and flow of medical waste are inadequate, as is sanitary control. We propose an integrated approach to medical waste management based on a hierarchical structure from the point of generation to its disposal. Priority is given to the reduction of the amounts and potential for harm. Where this is not possible, management includes reduction by sorting and separating, pretreatment on site, safe transportation, final treatment and sanitary disposal. Preferred methods should be the least harmful for human health and the environment. Integrated medical waste management could greatly reduce quantities and consequently financial strains. Landfilling is the predominant route of disposal in Croatia, although the authors believe that incineration is the most appropriate method. In a country such as Croatia, a number of small incinerators would be the most economical solution.     

Distribution of heavy elements in urban and rural surface soils: the Novi Sad city and the surrounding settlements, Serbia

Concentrations of ten heavy elements (Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, and Zn), as well as the pH values, organic matter contents, and electrical conductivities were measured in the surface soil samples collected from 21 sites of urban areas in the city of Novi Sad, the second largest city in Serbia, its suburban settlement and the nearby villages. Range of the heavy element concentrations was from 0.16 mg/kg (for Hg) to 18,994 mg/kg (for Fe). Significantly higher Hg and Mn concentrations were observed in subgroups with rural and market garden samples in comparison to the subgroups with urban and grassland samples, respectively, while the contents of Pb found in the grasslands subgroup were significantly higher than in the subgroup with market garden soils. Only one sample of urban soil exceeded the maximum permissible value for Zn set by the relevant Serbian legislation. According to the Dutch soil quality standard, the Cd and Co concentrations in majority of the examined soils were higher than the target values for unpolluted soil. The content of Hg was above the target value in 52% of the samples, most of them belonging to the subgroup of market garden soils. The results for the Novi Sad city area were compared to the relevant data available for other cities in the Western Balkan Countries. Principal component analysis of data revealed seven outlying samples, while the rest of the analyzed samples were grouped together indicating similar heavy element patterns most probably due to mixed emission sources.     

Assessment of GC–MS response of selected pesticides in apple matrices related to matrix concentration

A uniform analyte response is required for GC–MS analysis in order to obtain acceptable quantitative results. The response of pesticides in complex matrices is susceptible to variation due to the interactions of co-extractives, both with pesticides or with GC–MS system. This study was conducted to determine the magnitude of the interactions, called matrix effect, and their behavior with the matrix dilution. The response of pyrimethanil (4,6-dimethyl-N-phenylpyrimidin-2-amine), cyprodinil (4-cyclopropyl-6-methyl-N-phenylpyrimidin-2-amine), trifloxystrobin (methyl-(2Z)-2-methoxyimino-2-[2-[[(E)-1-[3(trifluoromethyl)phenyl]ethylidene amino]oxymethyl]phenyl]acetate) and bifenthrin(2-methyl-3-phenylphenyl)methyl-3-[(Z)-2-chloro-3,3,3-trifluoroprop-1-enyl]-2,2-dimethylcyclopropane-1-carboxylate), used in apple crops protection, was evaluated in different concentrations of peel and flesh extracts of Granny Smith, Golden Delicious and Demi Rouge, selected as representatives of different matrix types. The matrix effect ranged from ?0.05 to 146.14%, depending on matrix type and pesticide. The highest response variation was observed in extracts of Granny Smith—an enhancement in flesh and suppression in peel extract. With the dilution, the matrix effect decreased with different magnitudes, but for Granny Smith peel extract an inverted effect was observed. The presence of the matrix effect in GC–MS pesticides analysis was obvious, requiring the application of matrix-matched calibration in quantification procedures for each variety, with calibration standards matched by the matrix concentration.