PCDD/Fs, dioxin-like PCBs and marker PCBs in eggs of peregrine falcons from Germany

Thirty one egg samples of peregrine falcons were collected in different regions of Germany (South-West, North and East) and analysed for PCDD/Fs, PCBs and marker PCBs. Altogether, 37 PCB congeners were determined, allowing a more detailed discussion of different aspects of the relative importance of these individual congeners. For comparison with dioxin data from other studies, differences between toxic equivalency factors (TEF) have to be taken into consideration. The results of this study are discussed on the basis of WHO-TEFs for birds published in 1998. All samples showed high levels of PCDD/Fs (median of all samples: 368 pg WHO-PCDD/F-TEQ/g fat; range 137-1453) and even higher levels of PCBs (median 967 pg WHO-PCB-TEQ/g fat; range 243-7482). The upper range of these levels reach concentrations found at the beginning of the Belgian dioxin crisis when a significant reduction in hens' egg hatchability was observed. The relative contribution of PCBs to the total TEQ is on average 71% (range 55-92%) with a tendency to higher values in South-West Germany compared to different sites in East Germany or one site in northern Germany. Within a region, a wide range of contamination can be found. Even in the same cities (Stuttgart and Ludwigshafen), results derived from eggs collected in the same year (2003) varied by factors 5-10. These findings show the high degree of variation occurring even within the same kind of biological matrix. Therefore, to allow for comparison of regions or time trends, a considerable number of samples has to be analysed.     

Sorption of organic contaminants by biopolymers: role of polarity, structure and domain spatial arrangement

Sorption behavior of hydrophobic organic contaminants (HOCs) (i.e., pyrene, phenanthrene and naphthalene) by native and chemically modified biopolymers (lignin, chitin and cellulose) was examined. Lignins (native and treated) showed nonlinear sorption for all compounds studied, emphasizing their glassy character. Chitins and celluloses had linear isotherms for phenanthrene and naphthalene, illustrating the dominance of partitioning, while pyrene yielded nonlinear isotherms. Sorption capacity (K(oc)) of HOCs was negatively correlated with the polarity [(O+N)/C] of the biopolymers. Aromatic and alkyl+aromatic C percentages, rather than alkyl C content, demonstrated a better correlation with K(oc) values, indicating the importance of aromatic structures for HOC affinity. Hydrophobicity (K(ow))-normalized K(oc) values decreased sharply with increasing percentage of O-alkyl C versus total aliphatic C (O-alkyl C/total aliphatic C) or with polar C/(alkyl+aromatic C) ratio of the biopolymers until their values reached 80% and 4, respectively, illustrating the effect of surrounding polar groups on reducing affinity for HOCs. Overall, the results of this study highlight the role of spatial arrangement of domains within biopolymers in sorption of HOCs, and point to sorbent properties, such as functionality, polarity and structure, jointly regulating the sorption of HOCs in biopolymers.     

Application of microbial hot spots enhances pesticide degradation in soils

Through transfer of an active, isoproturon degrading microbial community, pesticide mineralization could be successfully enhanced in various soils under laboratory and outdoor conditions. The microbes, extracted from a soil having high native ability to mineralize this chemical, were established on expanded clay particles and distributed to various soils in the form of microbial "hot spots". Both, diffusion controlled isoproturon mass flow towards these "hot spots" (6microg d(-1)) as well as microbial ability to mineralize the herbicide (approximately 5microg d(-1)) were identified as the main processes enabling a multiple augmentation of the native isoproturon mineralization even in soils with heavy metal contamination. Soil pH-value appears to exert an important effect on the sustainability of this process.     

Advanced oxidation processes for the treatment of olive-oil mills wastewater

In this work, the treatment of an actual industrial waste with three advanced oxidation processes (AOP) has been studied: conductive-diamond electrooxidation (CDEO), ozonation and Fenton oxidation. The wastewater comes from olive-oil mills (OMW) and contains a COD of nearly 3000 mg dm(-3). CDEO allowed achieving the complete mineralization of the waste with high current efficiencies. Likewise, both ozonation and Fenton oxidation were able to treat the wastes, but they obtained very different results in terms of efficiency and mineralization. The accumulation of oxidation-refractory compounds as final products excludes the use of ozonation and Fenton oxidation as a sole treatment technology. This confirms that besides the hydroxyl-radical mediated oxidation, CDEO combines other important oxidation processes such as the direct electro-oxidation on the diamond surface and the oxidation mediated by other electrochemically formed compounds generated on this electrode.     

Measuring and modelling experimental densities and ultrasonic velocities of aromatic and halogenated environmental pollutants

The potential environmental impact of aromatic and halogenated chemicals from the petrochemical and steel industry is of growning concern. The present paper deals with the modelling and experimental determination of density and speed of sound at the range 278.15-323.15 of six aromatic and halogenated compounds (Benzene, Toluene, Ethylbenzene, Fluorobenzene, 2-Fluorotoluene and Chlorobenzene). Fitting equations were applied to the data in order to correlate for later computer based design. The estimation of the studied properties was made by the application of different theoretical procedures. The Mchaweh-Nasrifar-Moshfeghian model (MNM), an equation of state based on the generalized van der Waals theory which combines the Staverman-Guggenheim combinatorial term of lattice statistics with an attractive lattice gas expression and the Free Length Theory showed a good response at the studied conditions.     

Daytime resolved analysis of polycyclic aromatic hydrocarbons in urban aerosol samples - impact of sources and meteorological conditions

Urban aerosol was collected in a summer and a winter campaign for 7 and 3 days, respectively. Low volume samples were taken with a time resolution of 160 min using a filter/sorption cartridge system extended by an ozone scrubber. Concentrations of mainly particle associated polycyclic aromatic hydrocarbons (PAH) and oxidised PAH (O-PAH) were determined by gas chromatography/high resolution mass spectrometry. The sampling site was located in the city centre of Augsburg, Germany, near major roads with high traffic volume. The daily concentrations and profiles were mainly governed by local emissions from traffic and domestic heating, as well as by the meteorological conditions. During the winter campaign, concentrations were more than 10 fold higher than during the summer campaign. Highest concentrations were found concurrent with low boundary layer heights and low wind speeds. Significant diurnal variation of the PAH profiles was observed. Enhanced influences of traffic related PAH on the PAH profiles were evident during daytime in summer, whereas emissions from hot water generation and domestic heating were obvious during the night time of both seasons. A general idea about the global meteorological situation was acquired using back trajectory calculations (NOAA ARL HYSPLIT4). Due to high local emissions in combination with low air exchange during the two sampling campaigns, effects of mesoscale transport were not clearly observable.     

Uptake and loss of dissolved 109Cd and 75Se in estuarine macroinvertebrates

Semaphore crabs (Heloecius cordiformis), soldier crabs (Mictyris platycheles), ghost shrimps (Trypaea australiensis), pygmy mussels (Xenostrobus securis), and polychaetes (Eunice sp.), key benthic prey items of predatory fish commonly found in estuaries throughout southeastern Australia, were exposed to dissolved (109)Cd and (75)Se for 385 h at 30 k Bq/l (uptake phase), followed by exposure to radionuclide-free water for 189 h (loss phase). The whole body uptake rates of (75)Se by pygmy mussels, semaphore crabs and soldier crabs were 1.9, 2.4 and 4.1 times higher than (109)Cd, respectively. There were no significant (P>0.05) differences between the uptake rates of (75)Se and (109)Cd for ghost shrimps and polychaetes. The uptake rates of (109)Cd and (75)Se were highest in pygmy mussels; about six times higher than in soldier crabs for (109)Cd and in polychaetes for (75)Se - the organisms with the lowest uptake rates. The loss rates of (109)Cd and (75)Se were highest in semaphore crabs; about four times higher than in polychaetes for (109)Cd and nine times higher than in ghost shrimps for (75)Se - the organisms with the lowest loss rates. The loss of (109)Cd and (75)Se in all organisms was best described by a two (i.e. short and a longer-lived) compartment model. In the short-lived, or rapidly exchanging, compartment, the biological half-lives of (75)Se (16-39 h) were about three times greater than those of (109)Cd (5-12h). In contrast, the biological half-lives of (109)Cd in the longer-lived, or slowly exchanging compartment(s), were typically greater (1370-5950 h) than those of (75)Se (161-1500 h). Semaphore crabs had the shortest biological half-lives of both radionuclides in the long-lived compartment, whereas polychaetes had the greatest biological half-life for (109)Cd (5950 h), and ghost shrimps had the greatest biological half-life for (75)Se (1500 h). This study provides the first reported data for the biological half-lives of Se in estuarine decapod crustaceans. Moreover, it emphasises the importance of determining metal(loid) accumulation and loss kinetics in keystone prey items, which consequently influences their trophic transfer potential to higher-order predators.     

Isolation and characterization of 1,2,4-trichlorobenzene mineralizing Bordetella sp. and its bioremediation potential in soil

A soil which has been polluted with chlorinated benzenes for more than 25 years was used for isolation of adapted microorganisms able to mineralize 1,2,4-trichlorobenzene (1,2,4-TCB). A microbial community was enriched from this soil and acclimated in liquid culture under aerobic conditions using 1,2,4-TCB as a sole available carbon source. From this community, two strains were isolated and identified by comparative sequence analysis of their 16S-rRNA coding genes as members of the genus Bordetella with Bordetella sp. QJ2-5 as the highest homological strain and with Bordetella petrii as the closest related described species. The 16S-rDNA of the two isolated strains showed a similarity of 100%. These strains were able to mineralize 1,2,4-TCB within two weeks to approximately 50% in liquid culture experiments. One of these strains was reinoculated to an agricultural soil with low native 1,2,4-TCB degradation capacity to investigate its bioremediation potential. The reinoculated strain kept its biodegradation capability: (14)C-labeled 1,2,4-TCB applied to this inoculated soil was mineralized to about 40% within one month of incubation. This indicates a possible application of the isolated Bordetella sp. for bioremediation of 1,2,4-TCB contaminated sites.     

Percentile estimation using variable censored data

Much progress has been made in recent years to address the estimation of summary statistics, using data that are subject to censoring of results that fall below the limit of detection (LOD) for the measuring instrument. Truncated data methods (e.g., Tobit regression) and multiple-imputation are two approaches for analyzing data results that are below the LOD. To apply these methods requires an assumption about the underlying distribution of the data. Because the log-normal distribution has been shown to fit many data sets obtained from environmental measurements, the common practice is to assume that measurements of environmental factors can be described by log-normal distributions. This article describes methods for obtaining estimates of percentiles and their associated confidence intervals when the results are log-normal and a fraction of the results are below the LOD. We present limited simulations to demonstrate the bias of the proposed estimates and the coverage probability of their associated confidence intervals. Estimation methods are used to generate summary statistics for 2,3,7,8-tetrachloro dibenzo-p-dioxin (2,3,7,8-TCDD) using data from a 2001 background exposure study in which PCDDs/PCDFs/cPCBs in human blood serum were measured in a Louisiana population. Because the congener measurements used in this study were subject to variable LODs, we also present simulation results to demonstrate the effect of variable LODs on the multiple-imputation process.     

Uptake and accumulation of cadmium, lead and zinc by Siam weed [Chromolaena odorata (L.) King & Robinson

The Siam weed, Chromolaena odorata (L.) King & Robinson, Family Asteraceae, was found to be a new Pb hyperaccumulator by means of field surveys on Pb soil and hydroponic studies. Plants from field collection accumulated 1377 and 4236mgkg(-1) Pb in their shoots and roots, respectively, and could tolerate soil Pb concentrations up to 100000 mgkg(-1) with a translocation factor of 7.62. Very low concentrations of Cd and Zn were found in plants collected from the field. Under nutrient solution culture condition, C. odorata from the contaminated site (CS) and from non-contaminated site (NCS) grew normally with all three metals (Pb, Cd, Zn) supplied. However, the relative growth rates of all treated plants decreased with increased metal concentrations. The percentage uptakes of Pb, Cd, and Zn by C. odorata increased with increasing metal concentrations. Pb concentration in shoots and roots reached its highest values (1772.3 and 60655.7mgkg(-1), respectively) at a Pb supply level of 10mgl(-1). While the maximum concentrations of Cd (0.5mgl(-1)) in shoots and roots of C. odorata were 102.3 and 1440.9mgkg(-1), and the highest concentrations of Zn (20mgl(-1)) were 1876.0 and 7011.8mgkg(-1), respectively. The bioaccumulation coefficients of Pb and Cd were greater than 1000. These results confirm that C. odorata is a hyperaccumulator which grows rapidly, has substantial biomass, wide distribution and has a potential for the phytoremediation of metal contaminated soils.