Enantiomeric fractions and congener specific determination of polychlorinated biphenyls in eggs of predatory birds from Doñana National Park (Spain)

The content of 30 polychlorinated biphenyls (PCBs) and the enantiomeric fractions of 10 chiral PCBs were determined in 17 infertile eggs from three different predatory bird species collected in Do?ana National Park (DNP, Spain) in the period 1999-2000. The highest PCB concentration was found in eggs from red kites (0.52-110 microg/g on a fresh weight basis, f.w.) followed by buzzard (0.08-13 microg/g f.w.) and booted eagle (0.10-1.5 microg/g f.w.). Seventy-five percent of the red kite eggs had PCB levels above 4.7 microg/g f.w., which is associated in the literature with reproductive failure. This could be related to the fact that red kite populations have decreased by more than 50% in the last five years in DNP. PCBs # 138, 153, and 180 were the most abundant in all cases. This is the first time that atropisomers of 10 chiral PCBs (PCBs # 45, 84, 91, 95, 132, 135, 136, 149, 174, and 176) in predatory bird eggs have been performed. The enantiomeric fractions (EFs) for most PCBs investigated were non-racemic (EF not = 0.5), ranging from 0.05 to 0.95. The results suggested that predatory birds, mainly red kite species, are highly polluted by PCBs, and PCBs # 95, 132, 135, 136, and 174 strongly deviate from the racemic-mixture values.     

Measuring bioavailability of polychlorinated biphenyls in soil to earthworms using selective supercritical fluid extraction

If the release mechanisms during selective chemical extraction of persistent organic pollutants (POP) mimic release mechanisms in natural systems during biological uptake, then a selective non-exhaustive extraction could give a quantitative measure of the bioavailable POP fraction. Supercritical fluid extraction (SFE) is suggested as a possible technique to estimate the amount of bioavailable polychlorinated biphenyls (PCBs) at contaminated sites and hence serve as a new tool in risk assessment. The uptake of PCBs by earthworm (Eisenia foetida) was investigated. PCB contaminated soil was pre-extracted with selective non-exhaustive SFE (50 degrees C, 350 bar, 1h), which removed on average 70% of the individual PCBs. Earthworms were placed in this pre-extracted soil, as well as in untreated soil. After 10 days, the PCB uptake by earthworms in the two systems was compared. The bioaccumulation factor (BAF) was 83% lower in the pre-extracted system than in the untreated system, demonstrating that SFE extracts primarily bioavailable contaminants. From the data, the bioavailable fraction could also be calculated to be 75%, which is very close to the 70% removed by SFE under the applied conditions. This suggests that the chemical methodology is capable of measuring the bioavailable fraction very accurately in this system.     

Coupling of 2,4,6-trinitrotoluene (TNT) metabolites onto humic monomers by a new laccase from Trametes modesta

During degradation of trinitrotoluene (TNT) by Trametes modesta, addition of humic monomers prevented the accumulation of all major stable TNT metabolites (aminodinitrotoluenes [AMDNT]) by at least 92% in the presence of 200 mM ferulic acid and guaiacol. Acute toxicity tests with individual TNT metabolites and in T. modesta cultures supplemented with 200 microM TNT demonstrated that the TNT biodegradation process lead to less toxic metabolites. Toxicity decreased in the order TNT>4-HADNT (4-hydroxylaminodinitrotoluene)>2-HADNT>2,6-DNT (2,6-dinitrotoluene)>2',2',6,6-azoxytetranitrotoluene>4-AMDNT>2-AMDNT>2,4-diamninonitrotoluene (2,4-DAMNT) while 2,4-DNT and 2,6-DAMNT were the least toxic. Ferulic acid is the best candidate for immobilization TNT biodegradation metabolites since it prevented the accumulation of AMDNTs in cultures during TNT biodegradation and its products were less toxic. All humic monomers were very effective in immobilizing 2-HADNT [100%], 4-HADNT [100%] and 2,2,6,6-azoxytetranitrotoluene [100%]. Two distinct laccase isoenzymes (LTM1 and LTM2) potentially involved in immobilization of TNT degradation products were purified to electrophoretic homogeneity. LTM1 and LTM2 have molecular weights of 77.6 and 52.5 kDa, are 18% and 24% glycosylated, have pI values of 3.6 and 4.2, respectively. Both enzymes oxidized all the typical laccase substrates tested. LTM1 showed highest kinetic constants (K(m)=0.03 microM; K(cat)=8.8 4x 10(7)s(-1)) with syringaldazine as substrate.     

Reductive dehalogenation of tetrabromobisphenol-A by sediment from a contaminated ephemeral streambed and an enrichment culture

This study was aimed at improving our understanding of the physiology of the microorganisms that reductively dehalogenate tetrabromobisphenol-A (TBBPA). Activity was followed in contaminated sediments from a polluted streambed as well as from fracture filling material underlying the stream. Reductive dehalogenation was observed in surface sediments but not in fracture filling samples from a depth of 3m. Likewise, anaerobic microbial activity, represented by sulphate reduction, was much higher in the surface sediment. In the culture enriched from the surface sediment, optimal microbial debromination of TBBPA took place at a salinity of 2% and 3% NaCl, temperature of 30 degrees Celsius, and pH of 7-8. Ethanol, pyruvate and the combination of hydrogen with acetate were the most suitable electron donors and carbon sources for this culture. Alternative electron acceptors like Fe(3+), SO(4)(2-), SO(3)(2-), NO(3)(-) and 2,4,6-tribromophenol inhibited TBBPA debromination. The debrominating bacteria were heat sensitive (80 degrees Celsius, for 10min) but were not inhibited by bromoethanesulphonate or molybdate. This study allowed optimisation of our culturing conditions, but was also important for understanding the factors which influence TBBPA debromination in situ.     

Avoidance bio-assays may help to test the ecological significance of soil pollution

We measured the short-term (100 min) avoidance of a soil heavily polluted by hydrocarbons by the soil springtail Folsomia candida, at six rates of dilution in a control, unpolluted soil. We compared the results with those of long-term (40-day) population tests. Five strains were compared, of varying geographical and ecological origin. When pure, the polluted soil was lethal in the long-term and avoided in the short-term by all strains. Avoidance tests, but not population tests, were able to discriminate between strains. Avoidance thresholds differed among strains. Two ecological consequences of the results were discussed: (i) toxic compounds may kill soil animals or deprive them from food, resulting in death of populations, (ii) pollution spots can be locally deprived of fauna because of escape movements of soil animals. Advantages and limitations of the method have been listed, together with proposals for their wider use in soil ecology and ecotoxicology.     

Soil amendments reduce trace element solubility in a contaminated soil and allow regrowth of natural vegetation

We tested the effects of three amendments (a biosolid compost, a sugar beet lime, and a combination of leonardite plus sugar beet lime) on trace element stabilisation and spontaneous revegetation of a trace element contaminated soil. Soil properties were analysed before and after amendment application. Spontaneous vegetation growing on the experimental plot was studied by three surveys in terms of number of taxa colonising, percentage vegetation cover and plant biomass. Macronutrients and trace element concentrations of the five most frequent species were analysed. The results showed a positive effect of the amendments both on soil chemical properties and vegetation. All amendments increased soil pH and TOC content and reduced CaCl(2)-soluble-trace element concentrations. Colonisation by wild plants was enhanced in all amended treatments. The nutritional status of the five species studied was improved in some cases, while a general reduction in trace element concentrations of the aboveground parts was observed in all treated plots. The results obtained show that natural assisted remediation has potential for success on a field scale reducing trace element entry in the food chain.     

Treatment of log yard run-off by irrigation of grass and willows

Log yard run-off is a potential environmental risk, among other things because it creates an oxygen deficiency in receiving watercourses. This study was conducted to investigate the purification efficiency of soil-plant systems with couchgrass (Elymus repens) and willows (Salix sp.) when intensively irrigated with run-off from an open sprinkling system at a Norway spruce (Picea abies) log yard. The purification efficiency was determined both at the field scale (couchgrass) and in 68-L lysimeters (couchgrass and willows). Groundwater in the field and drainage water from the lysimeters were analysed for Total Organic Carbon (TOC), distillable phenols, total P, and total N. Retention of TOC, phenols and P occurred but no difference between couchgrass and willows was observed. The system had better purification capacity at the field scale than in the lysimeters.     

Pilot survey of a broad range of priority pollutants in sediment and fish from the Ebro river basin (NE Spain)

Priority organic pollutants were investigated in sediments and fish collected along the Ebro river basin (NE Spain) to evaluate their occurrence, transport and bioavailability. Sediments were collected in 18 sites and two species of fish were captured in nine sites according to the availability in each area. The sampling sites covered industrial, urban and agricultural areas. Four methods were used to detect 20 organochlorine compounds (OCs), 8 polycyclic aromatic hydrocarbons, 3 organotin compounds, 2 alkylphenols and 40 polybrominated diphenyl ethers (PBDEs) from purified extracts. The contamination pattern was site specific and no downstream increase in concentration of pollutants was observed but rather a generalized low level diffuse pollution. Target compounds were detected in sediments at 0.01 to 2331 microg/kg dry weight, and only OCs and PBDEs were accumulated in benthopelagic fish. Toxicological assessment was performed according to predicted environmental levels and revealed sites where adverse effects could occur.     

Passive air sampler as a tool for long-term air pollution monitoring: Part 1. Performance assessment for seasonal and spatial variations

The potential of passive air sampling devices (polyurethane foam disks) to assess the influence of local sources on the quality of the surrounding environment was investigated. DEZA Valasske Mezirici, a coal tar and mixed tar oils processing plant, and Spolana Neratovice, a chemical factory with the history of high production of organochlorinated pesticides (OCPs), were selected as the point sources of PAHs, and OCPs, respectively. Levels of PCBs, OCPs and PAHs were determined for all sampling sites and sampling periods. The study brought useful data about the air concentrations of POPs in the investigated regions. More important, it provided information on the transport and fate of POPs in the vicinity of local sources of contamination useful for the estimation of their influence. Very good capability of passive samplers to reflect temporal and spatial fluctuation in concentrations of persistent organic pollutants in the ambient air was confirmed which makes them applicable for monitoring on the local scale.     

Passive air sampler as a tool for long-term air pollution monitoring: Part 2. Air genotoxic potency screening assessment

The capability of passive air sampling to be employed in the evaluation of direct genotoxicity of ambient air samples was assessed. Genotoxic effects of the total extracts from the polyurethane foam filters exposed for 28 days during a regional passive air sampling campaign were investigated. Twenty sampling sites were selected in Brno city on the area of approximately 20x20 km in October and November 2004. Brno is the second largest city of the Czech Republic, highly industrialized with approximately 370,000 of permanent inhabitants. The levels of PAHs, PCBs, and chlorinated pesticides were determined in all samples. Fraction of each extract was also assayed in the bacterial genotoxicity test using Escherichia coli sulA::lacZ. Complete dose-response relationships of the air extracts were determined. The statistical analysis showed significant correlation between observed biological effects and PAHs concentrations in samples.