Altered toxicity of organic pollutants in water originated from simultaneous exposure to UV photolysis and CdSe/ZnS quantum dots

The paper reports unforeseen results of increased toxicity of water, subsequent to interactions between CdSe/ZnS quantum dots (QDs), phenol and toluene under UV irradiation. The consistent pattern of changes in measured toxicity (TU) was observed and correlated with degradation of phenol and/or toluene. Spearman rank coefficients (SRCs) for data pairs sum-parameters vs. TU were calculated. The highest correlation between toxicity and degradation by-products was observed for hydroquinone (0.86) and catechol (0.89). The presence of QDs in tested concentration range in the absence of UV has shown low toxicity and no interactions with phenol and/or toluene. The leak of constituent core and shell metal ions was observed. The minor differences in physical characteristics of tested QDs of the same chemical composition led to rather different degradation patterns of phenol and toluene, and the amount of leak of the metal ions as well.     

Toxicity of metalaxyl, azoxystrobin, dimethomorph, cymoxanil, zoxamide and mancozeb to Phytophthora infestans isolates from Serbia

A study of the in vitro sensitivity of 12 isolates of Phytophthora infestans to metalaxyl, azoxystrobin, dimethomorph, cymoxanil, zoxamide and mancozeb, was conducted. The isolates derived from infected potato leaves collected at eight different localities in Serbia during 2005-2007. The widest range of EC(50) values for mycelial growth of the isolates was recorded for metalaxyl. They varied from 0.3 to 3.9 μg mL(-1) and were higher than those expected in a susceptible population of P. infestans. The EC(50) values of the isolates were 0.16-0.30 μg mL(-1) for dimethomorph, 0.27-0.57 μg mL(-1) for cymoxanil, 0.0026-0.0049 μg mL(-1) for zoxamide and 2.9-5.0 μg mL(-1) for mancozeb. The results indicated that according to effective concentration (EC(50)) the 12 isolates of P. infestans were sensitive to azoxystrobin (0.019-0.074 μg mL(-1)), and intermediate resistant to metalaxyl, dimethomorph and cymoxanil. According to resistance factor, all P. infestans isolates were sensitive to dimethomorph, cymoxanil, mancozeb and zoxamide, 58.3% of isolates were sensitive to azoxystrobin and 50% to metalaxyl. Gout's scale indicated that 41.7% isolates were moderately sensitive to azoxystrobin and 50% to metalaxyl.     

Effects of temperature on sorption-desorption processes of imidacloprid in soils of Croatian coastal regions

Sorption-desorption behavior of imidacloprid in six soils collected from five coastal regions in Croatia at 20, 30 and 40°C was investigated using batch equilibrium technique. Isothermal data were applied to Freundlich, Langmuir and Temkin equations, and the thermodynamic parameters ΔH°, ΔG°, ΔS° were calculated. The sorption isotherm curves were non-linear and may be classified as L-type, suggesting a relatively high sorption capacity for imidacloprid. Our results showed that the K( sor ) ( F ) values decreased for all the tested soils as the temperature increased, indicating that the temperature strongly influences the sorption. Values of ΔG° were negative (-4.65 to -2.00 kJ/mol) indicating that at all experimental temperatures the interactions of imidacloprid with soils were spontaneous processes. The negative and small ΔH° values (-19.79 to -8.89 kJ/mol) were in the range of weak forces, such as H-bonds, consistent with interactions and partitioning of the imidacloprid molecules into soil organic matter. The ΔS° values followed the range of -57.12 to -14.51 J/molK, suggesting that imidacloprid molecules lose entropy during transition from the solution phase to soil surface. It was found that imidacloprid desorption from soil was concentration and temperature-dependent, i.e. at lower imidacloprid concentrations and temperature, lower desorption percentage occurred. Desorption studies revealed that hysteretic behavior under different temperature treatments existed, and it was more pronounced at 20°C in the soils with higher OC content. The study results emphasize the importance of thermodynamic parameters in controlling soil pesticide mobility in different geographical locations, seasons and greenhouse conditions.     

Mineralogy and characterization of deposited particles of the aero sediments collected in the vicinity of power plants and the open pit coal mine: Kolubara (Serbia)

In this paper, particular attention was paid to the presence of aerosol solid particles, which occurred mainly as a result of exploitation and coal combustion in the thermal power plants of the Kolubara basin. Not all of the particles created by this type of anthropogenic pollution have an equal impact on human health, but it largely depends on their size and shape. The mineralogical composition and particle size distribution in the samples of aero sediments were defined. The samples were collected close to the power plant and open pit coal mine, in the winter and summer period during the year 2007. The sampling was performed by using precipitators placed in eight locations within the territory of the Lazarevac municipality. In order to characterize the sedimentary particles, several methods were applied: microscopy, SEM-EDX and X-ray powder diffraction. The concentration of aero sediments was also determined during the test period. Variety in the mineralogical composition and particle size depends on the position of the measuring sites, geology of the locations, the annual period of collecting as well as possible interactions. By applying the mentioned methods, the presence of inhalational and respiratory particles variously distributed in the winter and in the summer period was established. The most common minerals are quartz and feldspar. The presence of gypsum, clay minerals, calcite and dolomite as secondary minerals was determined, as well as the participation of organic and inorganic amorphic matter. The presence of quartz as a toxic mineral has a particular impact on human health.     

Toxicological characterization of the landfill leachate prior/after chemical and electrochemical treatment: A study on human and plant cells

In this research, toxicological safety of two newly developed methods for the treatment of landfill leachate from the Piškornica (Croatia) sanitary landfill was investigated. Chemical treatment procedure combined chemical precipitation with CaO followed by coagulation with ferric chloride and final adsorption by clinoptilolite. Electrochemical treatment approach included pretreatment with ozone followed by electrooxidation/electrocoagulation and final polishing by microwave irradiation. Cell viability of untreated/treated landfill leachate was examined using fluorescence microscopy. Cytotoxic effect of the original leachate was obtained for both exposure periods (4 and 24 h) while treated samples showed no cytotoxic effect even after prolonged exposure time. The potential DNA damage of the untreated/treated landfill leachate was evaluated by the comet assay and cytokinesis-block micronucleus (CBMN) assay using either human or plant cells. The original leachate exhibited significantly higher comet assay parameters compared to negative control after 24 h exposure. On the contrary, there was no significant difference between negative control and chemically/electrochemically treated leachate for any of the parameters tested. There was also no significant increase in either CBMN assay parameter compared to the negative control following the exposure of the lymphocytes to the chemically or electrochemically treated landfill leachate for both exposure periods while the original sample showed significantly higher number of micronuclei, nucleoplasmic bridges and nuclear buds for both exposure times. Results suggest that both methods are suitable for the treatment of such complex waste effluent due to high removal efficiency of all measured parameters and toxicological safety of the treated effluent.     

U and Th in some brown coals of Serbia and Montenegro and their environmental impact

GOAL, SCOPE AND BACKGROUND: The objective of this paper is to determine and compare the concentrations of U and Th in soft to hard brown (lignite to sub-bituminous) coals of Serbia and Montenegro. It also presents comparison of the obtained data on U and Th concentrations with the published data on coals located in some other countries of the world. Almost the whole coal production of Serbia and Montenegro is used as feed coals for combustion in thermal power plants. METHODS: Channel samples from open pit and underground mines and core samples were collected for hard and soft brown coals. For the analysis the samples were decomposed using microwave technique. Obtained solutions containing U and Th were analyzed by inductively coupled plasma mass spectroscopy (ICP-MS) using NIST standards. RESULTS: Concentration of U from the investigated basins and the corresponding mine fields ranges within 0.60-70.10 mg/kg, 0.65-3.20 mg/kg, 0.95-6.59 mg/kg, 1.20-6.05 mg/kg, 0.80-6.66 mg/kg, 0.18-89.90 mg/kg, 0.19-4.14 mg/kg, and 0.28-3.52 mg/kg for the Kostolac, Kolubara, Krepoljin, Sjenica, Soko Banja, Bogovina East field, Senje-Resavica and Pljevlja basins, respectively. Concentration of Th ranges within 0.20-2.60 mg/kg, 0.84-6.57 mg/kg, 1.48-6.48 mg/kg, 0.12-2.71 mg/kg, 0.13-4.95 mg/kg, 0.14-3.48 mg/kg, 0.29-3.56 mg/kg, and 0.17-1.89 mg/kg for the Kostolac, Kolubara, Krepoljin, Sjenica, Soko Banja, Bogovina East field, Senje-Resavica and Pljevlja basins, respectively. DISCUSSION: Brown coal from Senje-Resavica, Kolubara, Kostolac and Pljevlja is characterized by low U concentration. Coals form the Krepoljin, Soko Banja and Sjenica basins have slightly higher U concentrations than the mentioned group. The highest concentration of U is characteristic for the coal from the Bogovina East field. Concentration of Th in coals from Serbia and Montenegro has proved to be low. Out of all investigated coal basins, only the coal from the Krepoljin and Kolubara basins has high concentration of Th. The hydrothermally altered rocks of the Timok dacite-andesite complex, representing the basement of the Bogovina basin, could be a potential source of U, especially at the bottom part of the Lower seam of the Bogovina East field. CONCLUSIONS: This study shows that brown coals in Serbia and Montenegro (soft to hard brown coals or lignite to sub-bituminous) contain low levels of U (5.30 mg/kg, average value and 2.10 mg/kg geometric mean value) and Th (1.80 mg/kg, average value and 1.12 mg/kg geometric mean value). There are some obvious differences in concentration of U and Th in coals from different basins in Serbia and Montenegro. The approximate value for U and Th release mainly from power plants was 644.33 t and 983.46 t, respectively within the period 1965-2000 for the studied mines in Serbia, and 23.76 t and 15.05 t for the Potrlica mine (Montenegro) within the period 1965-1997. RECOMMENDATIONS: The coals in Serbia and Montenegro show no identifiable unfavourable impact on the surrounding environment, due to low natural radioactive concentration of U and Th, but further investigations concerning human health should be performed. PERSPECTIVES: Preliminary research revealed that in some Serbian coals (and, particularly, parts of the coal seam) U and Th content are rather high. Such coals should be carefully studied, as well as U and Th concentrations in ash, fly ash, waste disposals, nearby soil and ground water. Further studies should include determination of the radioactivity of all these products, and estimation of possible health impact.     

Principal component analysis for soil contamination with organochlorine compounds

In order to investigate the distribution pattern of individual organochlorine compounds in soil samples collected from the sites (Canary Island – Spain, China, Germany, India, Romania, Russia, Serbia, Swiss, UK) affected by industrial activities to the more remote areas, principal component analysis was performed on the data taken from literature. Loading plots pointed out the strong correlation among the variables. Score plots revealed similar PCB- and OCP-soil patterns for majority of the investigated sites. Nevertheless, the temporal differences of PCB-soil loads have been identified: the late 1990s and early 2000s concentrations are similar to those of the early 1940s, and they are below the levels existed in 1980. The most pronounced PCB concentrations characterized the soil from 1966. For OCPs the influence of sites location on the detected concentration has been revealed: China and India were characterized by comparably higher loads of DDX (DDT and its metabolites) and of HCH-isomers, respectively.     

Water reclamation during drinking water treatments using polyamide nanofiltration membranes on a pilot scale

The aim of this study was to investigate the performances of polyamide nanofiltration membranes during water reclamation. The study was conducted using nanofiltration concentrates obtained from two different nanofiltration drinking water treatment plants placed in the northern part of Serbia (Kikinda and Zrenjanin). Used nanofiltration concentrates contained high concentrations of arsenic (45 and 451 μg/L) and natural organic matter (43.1 and 224.40 mgKMnO₄/L). Performances of polyamide nanofiltration membranes during water reclamation were investigated under various fluxes and transmembrane pressures in order to obtain drinking water from nanofiltration concentrates and, therefore, reduce the amount of produced concentrates and minimize the waste that has to be discharged in the environment. Applied polyamide nanofiltration membranes showed better removal efficiency during water reclamation when the concentrate with higher content of arsenic and natural organic matter was used while the obtained permeates were in accordance with European regulations. This study showed that total concentrate yield can be reduced to ~5 % of the optimum flux value, in both experiments. The obtained result for concentrate yield under the optimum flux presents considerable amount of reclaimed drinking water and valuable reduced quantity of produced wastewater.     

Heavy metals in soils: distribution, relationship with soil characteristics and radionuclides and multivariate assessment of contamination sources

The study is dealing with the distribution and the origin of heavy metals (Cd, Cr, Cu, Mn, Ni, Pb and Zn) in soils from a priori non-polluted areas. Positive correlations with organic matter and clay content but not with pH have been observed for most of elements analyzed in this study. Correlations of some metals (Cr, Pb and Zn) and radionuclides (238U and 137Cs) observed for analyzed soils could be explained by their common affinity for clay minerals. Enrichment factor (EF) analysis and cluster analysis (CA) highlighted the lithogenic origin of Cr, Cu, Mn, Ni, Pb and Zn and pointed out the primary input of Cd from anthropogenic sources. It also revealed the need for detailed geochemical surveys in the future in order to decrease the uncertainty of discrimination between lithogenic and anthropogenic origin of metals of interest.