Soil Contamination by Pb, Zn and Cn from a Lead Smeltery

In the environment of a lead smeltery contamination with lead, zinc and cadmium was measured over a 15-year period. Efficient bag filters were installed in order to remove dust from the flue gases. This measure of improvement resulted in a drastic reduction of lead, zinc and cadmium content in suspended particles (by 92, 94 and 89%), to a lesser extent in depositions (by 79, 75 and 68%), whereas in household dust the reduction was considerably lower (by 53, 55 and 70%). It can be assumed that household dust contains also redispersed soil particles on which the dust from the smeltery flue gases has deposited over years. To determine to what extent contaminated soil continues to cause increased population exposure directly or through plants or pastures, in the period 1981–1985 the content of metallic ions in the soil was measured at three depths. Selective solubility of soil metallic compounds was analysed in water, in 1 mol ammoniumacetate solution and in 0.05 mol ethylenediaminetetra-acetic acid (EDTA) solution in relation to their solubility in suspended particles, depositions and household dust. A considerably low portion of soluble metallic compounds was found in the soil and physico-chemical characteristics of the soil and portion of metallic ions bound to fulvice and humic acids were determined. The behaviour of metallic ions in contact with soil samples was studied in laboratory and it was found that approximately 50% of lead, 70% of zinc and 7% of cadmium ions change into non-soluble or poorly soluble compounds. By qualitative phase analysis in the non-soluble fraction PbO₂, Pb₃P₄O₁₃, Zn(OH)₂, ZnO, Fe₂O₃ and Cd(OH)₂ were identified.     

Extending the use of air quality indices to reflect effective population exposure

Although there are tendencies to develop a single common index which would describe an overall air quality status within an area, constructed from a choice of measurements of individual pollutants, indices describing individual pollutants themselves have several potentials which can be used in ways which are not possible with pollutant concentrations. On the case of Belgrade, Serbia, we investigated possibilities of using such indices for comparisons between pollutants, characterization of monitoring sites, and extending their use to include elements of population exposure. A methodology of adjusting the results obtained at monitoring stations located in severe pollution conditions, like street canyons, is proposed and used.     

Arsenic distribution in water/sediment system of Sevojno

Arsenic is a toxic and carcinogenic element. Its toxicity depends on its oxidation state and its concentration. The aim of this paper is to determine, for the first time, the concentration levels of arsenic in water and sediment during the spring/summer period of 2009 in Sevojno, a region in West Serbia with a long industrial tradition, as well as to determine the model of arsenic distribution in water/sediment system and the level of its compatibility with the existing theoretical model. Adsorption is a continual process in the environment. It plays a very important role in the transport and fate of pollutants, especially in sediment. The adsorption of arsenic was examined using the Freundlich adsorption isotherm.     

Trace elements as tracers of environmental pollution in the canal sediments (alluvial formation of the Danube River, Serbia)

The purpose of this study was to examine the levels of trace elements and to discuss the origin and mobility of these contaminants in the canal sediments (alluvial formation of the Danube River). The most significant fractions binding all of the studied elements were oxides and silicates. The high proportion of elements in the residual fraction and the generally low contents of extractable elements reflected the background geochemical conditions. The contents of trace elements (except Hg and As) were dominantly controlled by the presence of Fe and Mn oxides as well as by the grain size and the geochemical composition of the sediment. The studied alluvial sediments were not heavily contaminated; there were only few sites where an anthropogenic influence on the concentrations of some metals (Cu, Cd, Zn, and Pb) was noticed. The results from this study show that impact of Pan?evo industrial zone on the quality of the Danube River and its contamination with trace element is minor.     

Depleted uranium mobility and fractionation in contaminated soil (Southern Serbia)

GOAL, SCOPE AND BACKGROUND: During the Balkan conflict in 1999, soil in contaminated areas was enriched in depleted uranium (DU) isotopic signature, relative to the in-situ natural uranium present. After the military activities, most of kinetic DU penetrators or their fragments remained buried in the ground in certain geomorphological and geochemical environments exposed to local weathering conditions. The contamination distribution, mobility and/or fixation of DU in the contaminated soil profile at one hot spot were the subject of our study. The results should disclose what happened with released DU corrosion products in three years elapsed, given the scope of their geochemical fractionation, and mark out the most probable host substrates in investigated soil type. METHODS: Gamma-spectrometric analysis of soil samples taken in the DU penetrator impact-zone was done to obtain present contamination levels. Set of samples is subjected to five-step and three-step sequential extraction procedures, specifically selective to different physical/chemical associations in soil. The stable elements are determined in extracts by the atomic absorption spectroscopy. After the ion-exchange based uranium separation procedure, alpha-spectrometric analysis of obtained fractions was done and DU distribution in five extraction phases found from 235U/238U and 234U/238U isotopic ratios. RESULTS: Depleted uranium concentration falls down to the 1% of the initial value, at approximately 150 mm distance to the source. Carbonates and iron/manganese hydrous oxides are indicated as the most probable substrates for depleted uranium in the characterized soil type. Therefore, in the highly contaminated soil samples, depleted uranium is still weakly bonded and easy exchangeable. The significant levels of organic-bonded depleted uranium are found in surface soil only. DISCUSSION: Dependence of the fractionation on the contamination levels is evident. Samples with higher DU contents have shown a longer maintenance in the exchangeable phases, probably because adsorption/desorption mass transfer through the medium was not very fast. Organic-bonded, depleted uranium is present in surface soil samples due to its higher humus content. Considering geochemical composition of investigated soil, the indicating chemical associations as substrates are in agreement with some considerations based on the results for low-level waste unsaturated zones. CONCLUSIONS: The soil contamination with depleted uranium in investigated area is still 'spot' type and not widespread. Dependence of the fractionation on the contamination levels and presence of weakly bonded, depleted uranium in the hot spots areas is evident. RECOMMENDATIONS AND PERSPECTIVES: A detailed study may be undertaken with suitable extractive reagents to define a bio-available fraction of depleted uranium in soil. The comparison of results for different soil types investigated by the same methodology may be useful. An applied combination of physical/chemical procedures and analysis may help in the decision making on the remediation strategy for sites contaminated with depleted uranium used in military operations.     

Toxicity of analytically cleaned pentabromodiphenylether after prolonged exposure in estuarine European flounder (Platichthys flesus), and partial life-cycle exposure in fresh water zebrafish (Danio rerio)

Residues of polybrominated diphenylethers (PBDEs), extensively applied as flame retardants, are widely spread in the aquatic environment and biota. The present study investigates effects of the environmentally relevant lower brominated diphenylethers in two fish species in vivo under controlled laboratory conditions. Euryhaline flounder (Platichthys flesus) and freshwater zebrafish (Danio rerio) were exposed to a range of concentrations of a commercial pentabromodiphenylether mixture, DE-71. Chemical analysis of exposed fish showed a pattern of PBDE congeners that was very similar to that in wild fish. The resulting range included environmentally relevant, as well as higher levels. Animals were investigated histopathologically with emphasis on endocrine and reproductive organs. In zebrafish, hatching of embryos and larval development were assessed. Biochemical parameters were investigated in flounder as markers for suggested dioxin-like activity (ethoxyresorufin-O-deethylase=EROD), and activation of endogenous estrogen synthesis (gonad aromatase activity). Thyroid hormones were analyzed in plasma in both species. Benchmark analysis using internal PBDE concentrations showed a mild dose-dependent decrease of hepatic EROD and ovarian aromatase activities, and plasma thyroxin levels in flounder, and an increase of plasma thyroid hormone levels in zebrafish. These trends did not result in statistically significant differences from control fish, and major histopathological changes were not observed. Reproduction in zebrafish appeared to be the most sensitive parameter with statistically significantly reduced larval survival and non-significant indications for decreased egg production at internal levels that were more than 55 times the highest environmental recordings. The present results indicate limited risk for endocrine or reproductive effects of current environmental PBDE contamination in fish.     

Polyacetal Polyols for Polyurethanes

The synthesis of telechelic polyacetals with terminal hydroxyl groups (polyacetal polyols), by the reaction of triethylene glycol divinyl ether with dipropylene glycol in the presence of trimethylolpropane or other triols or diols as starters, in acidic catalysis, has been studied. The synthesized liquid polyacetal triols and polyacetal diols were characterized by hydroxyl number, viscosity, acidity, number average molecular weight (M_n), weight average molecular weight (M_w), molecular weight distribution (M_w/M_n), FT-IR spectra. The obtained polyacetals were transformed in cast elastomers by the reaction with the isocyanate Mondur CD (modified diphenyl methane diisocyanate) with properties very close to the elastic polyurethanes obtained by using conventional polyether triols, copolymers propylene oxide–ethylene oxide. The polyacetal polyols are suitable for the synthesis of elastic polyurethanes (polyurethane elastomers, flexible polyurethane foams). Polyacetals are well known biodegradable polymers. Therefore, the polyurethanes based on polyacetal polyols are expected to be biodegradable.     

Aporrectodea caliginosa, a suitable earthworm species for field based genotoxicity assessment?

There is a growing interest for the application of biomakers to field-collected earthworms. Therefore we have evaluated the usability of native populations of endogeic, widely distributed earthworm Aporrectodea caliginosa in the assessment of soil genotoxicity using the Comet assay. Validation of the Comet assay on earthworm coelomocytes has been established using commercially available Eisenia fetida exposed to copper, cadmium, and pentachlorophenol, along with A. caliginosa exposed to copper in a filter paper contact test. Neutral red retention time (NRRT) assay was conducted on copper exposed and field-collected earthworms. Significant DNA and lysosomal damage was measured using Comet and NRRT assays in native populations of A. caliginosa sampled from the polluted soils in the urban area in comparison to the earthworms from the reference site. The results of this study confirm the employment of A. caliginosa as a suitable species for the in situ soil toxicity and genotoxicity field surveys.     

Wastewater reuse in Mediterranean semi-arid areas: The impact of discharges of tertiary treated sewage on the load of polar micro pollutants in the Llobregat river (NE Spain)

The presence of sewage-borne micro contaminants in environmental waters is directly related to the discharge of treated effluents from wastewater treatment plants (WWTP) and the flow rate of the receiving river waters. Mediterranean rivers, in particular, are characterized by important fluctuations in the flow rates and heavy pollution pressures resulting from extensive urban, industrial and agricultural activities. This translates into contamination levels in these rivers often higher than those in other larger European basins. The present work provides an overview of the occurrence of five groups of organic contaminants (131 compounds) namely pharmaceuticals, illicit drugs, polar pesticides, estrogens, alkylphenols and related ethoxylates in WWTP tertiary treatment effluents. Data gathered during a period of water reuse carried out in the lower stretch of the Llobregat river (NE Spain), in the surroundings of the town of Barcelona as a consequence of the severe drought that took place along the years 2007-2008 are presented as illustrative example. In general, measured concentrations of the target compounds were in the low to mid ng L⁻¹ range. The total concentration of each compound class downstream to the discharge point was similar or slightly higher than that found upstream. Regarding the loads calculated for each compound, the relative contribution from the river upstream and the tertiary effluent were highly compound depending with no apparent trend. However, estimation of the overall bulk loads for each compound class determined in the Llobregat river showed the following rank order: pharmaceuticals > alkylphenols > pesticides > illicit drugs ? estrogens.