Presence of DDT metabolites in water,sediment and fish muscle tissue from Lake Prespa,Republic of Macedonia

Organochlorine pesticides were determined in water and sediment samples collected from the littoral zone of Lake Prespa, as well as from its three main tributaries (the rivers Golema, Brajcinska and Kranska), during the period 2004 to 2006. In addition, muscle tissue samples of barbus fish (Barbus prespensis Karaman, 1928) collected from the littoral zone of Lake Prespa were also analysed. The obtained results give an overview of the contamination levels of these problematic compounds at their potential sources in the river mouths, in the potentially affected, species-rich littoral section of the lake and in the muscle tissue of one selected fish species, collected near the rivers’ deltas. Special attention was paid to the presence of some DDT metabolites (1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene (p,p′–DDE); (1,1-dichloro-2,2-bis(p-chlorophenyl)ethane (p,p′–DDD) and 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (p,p′–DDT). The extraction of pesticides from water samples was done by liquid-liquid partition in dichloromethane. For the sediment and fish tissue we used solid-liquid extraction. The extracted residues were analyzed on a gas chromatograph equipped with an electron capture detector (GC-ECD). The results of the respective studies indicated the presence of DDT metabolic forms in the samples of the three analysed matrixes. The highest levels of presence for these pollutants were found in the muscle tissue of the fish samples. The total DDTs content in the analysed muscle tissue samples range from 11.67 to 13.58 μg kg^?1of fresh tissue. The average total DDTs content for the sediment samples were within the range of 2.32 to 4.17 μg kg^?1 of dry sediment. Higher DDT metabolites content were found in the sediments collected from the rivers than in the samples from the littoral zone. The lowest average total concentrations of DDTs, on the other hand, were recorded in the water samples and ranged between 0.036 and 0.057 μg L^?1. The obtained results indicated that the dominant metabolic form in the samples of the three investigated matrixes (water, sediment and fish tissue) from Lake Prespa was p,p′-DDE. There was a very good linear correlation in this study between the content of DDT's (total DDT metabolites) detected and the percentage of total organic material in the sediment. The detected concentrations are clearly below the toxicity thresholds; consequently, severe effects on the endemic species of Lake Prespa are not very likely.     

Assessment of ozone variations and meteorological influences in a tourist and health resort area on the island of Mali Lošinj (Croatia)

The purpose of this study was to investigate ozone, variations, and its correlation with meteorological parameters at a remote location on the Mali Lo?inj Island, which has been a tourist and health resort area in the northern Adriatic. The measured data are discussed in relation to the EU guidelines (Directive 2002/3/EC; Directive 2008/50/EC). In order to characterize ambient air with respect to ozone vegetation injury and photochemical pollution, we calculated accumulated dose over a threshold of 40 parts per billion index and two photochemical pollution indicators. The influence of local meteorological parameters on the measured ozone volume fractions was also investigated. We used the multivariate technique principal component analysis to trace correlations between measured ozone concentration and meteorological parameters.     

Applicability of MIEX®DOC process for organics removal from NOM laden water

The aim of this study was to evaluate applicability of ion exchange process for organics removal from Douro River surface water at the intake of Lever water treatment plant using magnetized ion exchange resin MIEX®. Qualitative analysis of the natural organic matter present in the surface water and prediction of its amenability to removal in conventional coagulation process were assessed. Results obtained in MIEX®DOC process kinetic batch experiments allowed determination of ion exchange efficiency in dissolved organic carbon (DOC), UV absorbing organics, and true color removal. The data were compared with the efficiencies of the conventional unit processes for organics removal at Lever WTP. MIEX®DOC process revealed to be more efficient in DOC removal than conventional treatment achieving the efficiencies in the range of 61–91 %, lowering disinfection by-products formation potential of the water. DOC removal efficiency at Lever WTP depends largely on the raw water quality and ranges from 28 % for water of moderated quality to 89 % of significantly deteriorated quality. In this work, MIEX®DOC process was also used as a reference method for the determination of contribution of anionic fraction to dissolved organic matter and selectivity of the unit processes at Lever WTP for its removal.     

Influence of a nickel smelter plant on the mineralogical composition of attic dust in the Tikveš Valley, Republic of Macedonia

Mineral phases and their content were determined in attic dust samples collected from 27 houses in the Tikve? Valley, Republic of Macedonia. By using quantitative X-ray diffraction, the principal mineral phases were determined to be the serpentinite group (chrysotile, lizardite) and amphibole group of minerals (ribecite, tremolite, actinolite) present in the attic dust samples from this region which are not common constituents of urban dust. Strong correlations existed between these mineral phases in the dust and those in ores processed at a ferronickel smelter plant situated in this region. Spatial distributions of specific mineral phases were made and were consistent with wind directions and predicted deposition (60–70 %) of dust emitted from the metallurgical plant.     

Anthropometric, socioeconomic, and maternal health determinants of placental transfer of organochlorine compounds

The aim of this study was to relate placental transfer, quantified by the cord to maternal serum concentration ratio (C/M), of five organochlorine pesticides (OCP) hexachlorobenzene (HCB), β-hexachlorocyclohexane (β-HCH), γ-hexachlorocyclohexane (γ-HCH) , p,p'-DDT, p,p'-DDE and 15 polychlorinated biphenyl (PCB) congeners (28, 52, 101, 105, 114, 118, 123⁺¹⁴⁹, 138⁺¹⁶³, 153, 156⁺¹⁷¹, 157, 167, 170, 180, and 189) to anthropometric, socioeconomic, and maternal health characteristics. We included into the study 1,134 births during the period 2002–2004 from two districts in eastern Slovakia with high organochlorine concentrations relative to other areas of the world. Only concentrations >LOD were taken into account. Variables as age, weight and height of mothers, parity, ethnicity, alcohol consumption, illness during pregnancy, smoking during pregnancy, hypertension, respiratory diseases, rheumatoid arthritis and diabetes mellitus, and birth weight were related to C/M. Results of regression analyses showed that C/M was predicted by several factors studied. Positive associations were observed for gestational alcohol consumption, fewer illnesses during pregnancy, maternal age, and maternal weight. Caucasians had a greater C/M compared to Romani for wet weight data of congeners 170 and 180 and in contrast C/M for HCB was greater in Romani. Our results show that drinking mothers compared to abstaining expose their fetuses not only to alcohol but to an increased level of several PCB congeners. A straightforward explanation of associations between C/M shifts and factors studied is very difficult, however, with regard to the high lipophilicity of OCPs and PCBs, changes in their kinetics probably reflect lipid kinetics.     

Air dispersion of heavy metals in the vicinity of the As-Sb-Tl abounded mine and responsiveness of moss as a biomonitoring media in small-scale investigations

A systematic study was carried out to investigate air deposition and to explore the natural distribution and enrichment (contamination) with trace elements in the small area (cca. 13 km²) of an antimony-arsenic-thallium mineralization outcrop at an abandoned mine “Allchar.” The mine is located on the northwestern part of Ko?uf Mount, Republic of Macedonia. The locality of Allchar is unique in its mineral composition; besides a very intriguing mineral, lorandite, there are 45 other minerals, some of which are rare. The distribution of 53 elements (with special attention to As, Sb, and Tl) were detected in 69 moss samples from eight various species collected from this area. Moss samples were analyzed following microwave digestion by inductively coupled plasma–mass spectrometry and inductively coupled plasma–atomic emission spectrometry. It was found that the atmospheric deposition for As in the moss samples on or around the Allchar mine is >6.5 times higher and for Tl is 19 times higher compared to values for the samples from the rest of the Allchar area. By the application of multivariate cluster and R-mode factor analyses (FA), five geochemical associations were determined. Cluster and R-mode FA were used to identify and characterize element associations, and five associations of elements were determined by the method of multivariate statistics. F1 (Co, Cr, Fe, Sc, Li, V, Ga, Y, Ni, Mn, Al, La-Lu, Cu, Ge, Be, Bi, and Hf); F2 (As, Tl, Sb, and Mg); F3 (Rb, Cs, and Mo); F4 (Sr, Ba, Hf, Zr, La-Lu, and Bi), and F5 (Cd, Zn, Ag, and Cu).     

In vitro activity of antimicrobial agents against Pseudomonas tolaasii,pathogen of cultivated button mushroom

In vitro antibacterial activity tests of seven biofungicides (Ekstrasol, Bisolbisan, Bisolbifit, Serenade, Sonata, Timorex, F-Stop) and two disinfectants (colloidal silver alone and in combination with hydrogen peroxide) against the Pseudomonas tolaasii strain (NS3B6) were carried out by the disc-diffusion, broth microdilution and broth macrodilution method. Biofungicides tested in this study did not exhibit any antimicrobial activity in neither one of the methods used. Disc diffusion method revealed high sensitivity of the tested P. tolaasii strain to Ecocute based on colloidal silver and hydrogen peroxide. Both microdilution and macrodilution methods identified the same MICs and MBCs of Ecocute (0.19 mg/L) for P. tolaasii strain. MICs and MBCs values of silver alone were much higher (10 mg/L) compared to silver in combination with hydrogen peroxide.     

Geochemical and mineralogical characterization of a neutral, low-sulfide/high-carbonate tailings impoundment, Markušovce, eastern Slovakia

Tailings deposits generated from mining activities represent a potential risk for the aquatic environment through the release of potentially toxic metals and metalloids occurring in a variety of minerals present in the tailings. Physicochemical and mineralogical characteristics of tailings such as total concentrations of chemical elements, pH, ratio of acid-producing to acid-neutralizing minerals, and primary and secondary mineral phases are very important factors that control the actual release of potentially toxic metals and metalloids from the tailings to the environment. The aims of this study are the determination of geochemical and mineralogical characteristics of tailings deposited in voluminous impoundment situated near the village of Marku?ovce (eastern Slovakia) and identification of the processes controlling the mobility of selected toxic metals (Cu, Hg) and metalloids (As, Sb). The studied tailings have unique features in comparison with the other tailings investigated previously because of the specific mineral assemblage primarily consisting of barite, siderite, quartz, and minor sulfides. To meet the aims, samples of the tailings were collected from 3 boreholes and 15 excavated pits and subjected to bulk geochemical analyses (i.e., determination of chemical composition, pH, Eh, acid generation, and neutralization potentials) combined with detailed mineralogical characterization using optical microscopy, X-ray diffraction (XRD), electron microprobe analysis (EMPA), and micro-X-ray diffraction (μ-XRD). Additionally, the geochemical and mineralogical factors controlling the transfer of potentially toxic elements from tailings to waters were also determined using short-term batch test (European norm EN 12457), sampling of drainage waters and speciation–equilibrium calculations performed with PHREEQC. The tailings mineral assemblage consists of siderite, barite, quartz, and dolomite. Sulfide minerals constitute only a minor proportion of the tailings mineral assemblage and their occurrence follows the order: chalcopyrite?>?pyrite?>?tetrahedrite?>?arsenopyrite. The mineralogical composition of the tailings corresponds well to the primary mineralization mined. The neutralization capacity of the tailings is high, as confirmed by the values of neutralization potential to acid generation potential ratio, ranging from 6.7 to 63.9, and neutral to slightly alkaline pH of the tailings (paste pH 7.16–8.12) and the waters (pH 7.00–8.52). This is explained by abundant occurrence of carbonate minerals in the tailings, which readily neutralize the acidity generated by sulfide oxidation. The total solid-phase concentrations of metal(loid)s decrease as Cu?>?Sb?>?Hg?>?As and reflect the proportions of sulfides present in the tailings. Sulfide oxidation generally extends to a depth of 2 m. μ-XRD and EMPA were used to study secondary products developed on the surface of sulfide minerals and within the tailings. The main secondary minerals identified are goethite and X-ray amorphous Fe oxyhydroxides and their occurrence decreases with increasing tailings depth. Secondary Fe phases are found as mineral coatings or individual grains and retain relatively high amounts of metal(loid)s (up to 57.6 wt% Cu, 1.60 wt% Hg, 23.8 wt% As, and 2.37 wt% Sb). Based on batch leaching tests and lysimeter results, the mobility of potentially toxic elements in the tailings is low. The limited mobility of metals and metalloids is due to their retention by Fe oxyhydroxides and low solubilities of metal(loid)-bearing sulfides. The observations are consistent with PHREEQC calculations, which predict the precipitation of Fe oxyhydroxides as the main solubility-controlling mineral phases for As, Cu, Hg, and Sb. Waters discharging from tailings impoundment are characterized by a neutral to slightly alkaline pH (7.52–7.96) and low concentrations of dissolved metal(loid)s (<5–7.0 μg/L Cu, <0.1–0.3 μg/L Hg, 5.0–16 μg/L As, and 5.0–43 μg/L Sb). Primary factors influencing aqueous chemistry at the site are mutual processes of sulfide oxidation and carbonate dissolution as well as precipitation reactions and sorption onto hydrous ferric oxides abundantly present at the discharge of the impoundment waters. The results of the study show that, presently, there are no threats of acid mine drainage formation at the site and significant contamination of natural aquatic ecosystem in the close vicinity of the tailings impoundment.     

Optimized yeast-based in vitro bioassay for determination of estrogenic and androgenic activity of hydroxylated / methoxylated metabolites of BDEs / CBs and related lipophilic organic pollutants

ABSTRACT

Persistent organic pollutants (POPs) are known to show endocrine disrupting (ED) activity, including interactions with hormone receptors. The aim of this work was to develop a bioassay applicable for evaluation of ED potency of highly lipophilic metabolites of POPs. To that end, a yeast-based bio-assay protocol was used. Estrogenic / androgenic activity of some native brominated biphenyl ethers (BDEs) / chlorinated biphenyls (CBs), and their hydroxylated / methoxylated metabolites was assessed. Since data (including potency compared to reference native hormones) obtained using different protocols vary, the possibility that yeast transforms POPs into some more potent compounds was first checked; it seems that no such transformation is important from the test applicability standpoint. The developed method was sensitive with EC50 values 6.5*10^?11 M and 4.5*10^?9 M calculated for E2 and DHT, respectively. Both CBs and BDEs show weak estrogenic activity negatively correlated with the degree of their halogenation, but their metabolites are significantly more potent xenohormones. 4-OH-2,2′,4′,6′-TeCB was the most potent estrogen receptor (ER) agonist among all tested compounds; its activity was only 1,000 times lower than that of native E2.     

Effect of Dursban 480 EC (chlorpyrifos) and Talstar 10 EC (bifenthrin) on the physiological and genetic diversity of microorganisms in soil

This investigation was undertaken to determine the impact of the insecticides Dursban 480 EC (with organophosphate compound chlorpyrifos as the active ingredient) and Talstar 10 EC (with pyrethroid bifenthrin as the active ingredient) on the respiration activity and microbial diversity in a sandy loam luvisol soil. The insecticides were applied in two doses: the maximum recommended dose for field application (15 mg kg^?1 for Dursban 480 EC and 6 mg kg^?1 for Talstar 10 EC) and a 100-fold higher dose for extrapolation of their effect. Bacterial and fungal genetic diversity was analysed in soil samples using PCR DGGE and the functional diversity (catabolic potential) was studied using BIOLOG EcoPlates at 1, 3, 7, 14, 28, 56 and 112 days after insecticide application. Five bacterial groups (α, β, γ proteobacteria, firmibacteria and actinomycetes) and five groups of fungi or fungus-like microorganisms (Ascomycota, Basidiomycota, Chytridiomycota, Oomycota and Zygomycota) were analysed using specific primer sets. This approach provides high resolution of the analysis covering majority of microorganisms in the soil. Only the high-dose Dursban 480 EC significantly changed the community of microorganisms. We observed its negative effect on α- and γ-proteobacteria, as the number of OTUs (operational taxonomic units) decreased until the end of incubation. In the β-proteobacteria group, initial increase of OTUs was followed by strong decrease. Diversity in the firmibacteria, actinomycetes and Zygomycota groups was minimally disturbed by the insecticide application. Dursban 480 EC, however, both positively and negatively affected certain species. Among negatively affected species Sphingomonas, Flavobacterium or Penicillium were detected, but Achromobacter, Luteibacter or Aspergillus were supported by applied insecticide. The analysis of BIOLOG plates using AWCD values indicated a significant increase in metabolic potential of microorganisms in the soil after the high-dose Dursban application. Analysis of respiration demonstrated high microbial activity after insecticide treatments; thus, microbial degradation was relatively fast. The half-life of the active insecticide compounds were estimated within the range of 25 to 27 days for Talstar and 6 to 11 days for Dursban and higher doses stimulated degradation. The recommended dose levels of both insecticides can be considered as safe for microbial community in the soil.