Indication of PCDD/F formation through precursor condensation in a full-scale hazardous waste incinerator

This paper gives the PCDD/F fingerprint of boiler and fly ash of a full scale hazardous waste incinerator and demonstrates that, when the waste to be incinerated contains high concentrations of PCBs and chlorinated pesticides, heterogeneous precursor condensation is the dominant PCDD/F formation mechanism rather than de novo synthesis. This is in contrast to full-scale municipal solid waste incinerators, where de novo synthesis has been shown to be the dominant PCDD/F formation mechanism. This paper agrees with earlier predictions based on numerous lab scale experiments.     

Effects of air pollution on lung function and symptoms of asthma, rhinitis and eczema in primary school children

Health effects of ambient air pollution were studied in three groups of schoolchildren living in areas (suburban, urban and urban-traffic) with different air pollution levels in Eski?ehir, Turkey. This study involved 1,880 students aged between 9 and 13 years from 16 public primary schools. This two-season study was conducted from January 2008 through March 2009. Symptoms of asthma, rhinitis and eczema were determined by the International Study of Asthma and Allergies in Childhood questionnaire in 2008. Two lung function tests were performed by each child for summer and winter seasons with simultaneous ambient air measurements of ozone (O₃), nitrogen dioxide (NO₂) and sulfur dioxide (SO₂) by passive sampling. Effects of air pollution on impaired lung function and symptoms in schoolchildren were estimated by multivariate logistic regression analyses. Girls with impaired lung function (only for the summer season evaluation) were more observed in suburban and urban areas when compared to urban-traffic area ([odds ratio (OR)?=?1.49; 95 % confidence interval (CI) 1.04–2.14] and [OR?=?1.69 (95 % CI 1.06–2.71)] for suburban vs. urban-traffic and urban vs. urban-traffic, respectively). Significant association between ambient ozone concentrations and impaired lung function (for an increase of 10 μg m^?3) was found only for girls for the summer season evaluation [OR?=?1.11 (95 % CI 1.03–1.19)]. No association was found for boys and for the winter season evaluation. No association was found between any of the measured air pollutants and symptoms of current wheeze, current rhinoconjunctivitis and current itchy rash. The results of this study showed that increasing ozone concentrations may cause a sub-acute impairment in lung function of school aged children.     

Factors controlling phosphate interaction with iron oxides

Factors such as pH, solution ion composition, and the presence of natural organic matter (NOM) play a crucial role in the effectiveness of phosphorous adsorption by iron oxides. The interplay between these factors shows a complicated pattern and can sometimes lead to controversial results. With the help of mechanistic modeling and adsorption experiments, the net macroscopic effect of single and combined factors can be better understood and predicted. In the present work, the relative importance of the above-mentioned factors in the adsorption of phosphate was analyzed using modeling and comparison between the model prediction and experimental data. The results show that, under normal soil conditions, pH, concentration of Ca, and the presence of NOM are the most important factors that control adsorption of phosphate to iron oxides. The presence of Ca not only enhances the amount of phosphate adsorbed but also changes the pH dependency of the adsorption. An increase of dissolved organic carbon from 0.5 to 50 mg L can lead to a >50% decrease in the amount of phosphate adsorbed. Silicic acid may decrease phosphate adsorption, but this effect is only important at a very low phosphate concentration, in particular at high pH.     

Estimation of uncertainty arising from different soil sampling devices: the use of variogram parameters

In the frame of the international SOILSAMP project, funded and coordinated by the National Environmental Protection Agency of Italy (APAT), uncertainties due to field soil sampling were assessed. Three different sampling devices were applied in an agricultural area using the same sampling protocol. Cr, Sc and Zn mass fractions in the collected soil samples were measured by k(0)-instrumental neutron activation analysis (k(0)-INAA). For each element-device combination the experimental variograms were calculated using geostatistical tools. The variogram parameters were used to estimate the standard uncertainty arising from sampling. The sampling component represents the dominant contribution of the measurement uncertainty with a sampling uncertainty to measurement uncertainty ratio ranging between 0.6 and 0.9. The approach based on the use of variogram parameters leads to uncertainty values of the sampling component in agreement with those estimated by replicate sampling approach.     

An enzyme-linked immunosorbent assay for the determination of dioxins in contaminated sediment and soil samples

A 96-microwell enzyme-linked immunosorbent assay (ELISA) method was evaluated to determine PCDDs/PCDFs in sediment and soil samples from an EPA Superfund site. Samples were prepared and analyzed by both the ELISA and a gas chromatography/high resolution mass spectrometry (GC/HRMS) method. Comparable method precision, accuracy, and detection level (8 ng kg(-1)) were achieved by the ELISA method with respect to GC/HRMS. However, the extraction and cleanup method developed for the ELISA requires refinement for the soil type that yielded a waxy residue after sample processing. Four types of statistical analyses (Pearson correlation coefficient, paired t-test, nonparametric tests, and McNemar's test of association) were performed to determine whether the two methods produced statistically different results. The log-transformed ELISA-derived 2,3,7,8-tetrachlorodibenzo-p-dioxin values and log-transformed GC/HRMS-derived TEQ values were significantly correlated (r=0.79) at the 0.05 level. The median difference in values between ELISA and GC/HRMS was not significant at the 0.05 level. Low false negative and false positive rates (<10%) were observed for the ELISA when compared to the GC/HRMS at 1,000 ng TEQ kg(-1). The findings suggest that immunochemical technology could be a complementary monitoring tool for determining concentrations at the 1,000 ng TEQ kg(-1) action level for contaminated sediment and soil. The ELISA could also be used in an analytical triage approach to screen and rank samples prior to instrumental analysis.     

Modelling of stable isotope fractionation by methane oxidation and diffusion in landfill cover soils

A technique to measure biological methane oxidation in landfill cover soils that is gaining increased interest is the measurement of stable isotope fractionation in the methane. Usually to quantify methane oxidation, only fractionation by oxidation is taken into account. Recently it was shown that neglecting the isotope fractionation by diffusion results in underestimation of the methane oxidation. In this study a simulation model was developed that describes gas transport and methane oxidation in landfill cover soils. The model distinguishes between (12)CH(4), (13)CH(4), and (12)CH(3)D explicitly, and includes isotope fractionation by diffusion and oxidation. To evaluate the model, the simulations were compared with column experiments from previous studies. The predicted concentration profiles and isotopic profiles match the measured ones very well, with a root mean square deviation (RMSD) of 1.7vol% in the concentration and a RMSD of 0.8 per thousand in the delta(13)C value, with delta(13)C the relative (13)C abundance as compared to an international standard. Overall, the comparison shows that a model-based isotope approach for the determination of methane oxidation efficiencies is feasible and superior to existing isotope methods.     

Lipid metabolism of the Antarctic krill Euphausia superba and its ecological implications

 Various developmental stages (early larvae to adults) of Euphausia superba have been collected in different seasons in the Weddell Sea, the Lazarev Sea and off the Antarctic Peninsula to investigate the role of lipids and fatty acids in the life cycle of the Antarctic krill. The total-lipid data for E. superba exhibited seasonal variations, with low lipid levels in late winter/early spring and the highest levels in autumn. Seasonal changes were most pronounced in the immature and adult specimens, increasing from about 10% lipid of dry mass to more than 40%. The fatty-acid compositions of the younger stages were dominated by 20:5(n-3), 22:6(n-3) and 16:0. These are typical phospholipid fatty acids, which are major biomembrane constituents. The phospholipid composition was similar in the older stages. With increasing storage of triacylglycerols in the lipid-rich immature and adult stages, the fatty acids 14:0, 16:0 and 18:1(n-9) prevailed, comprising about 70% of total triacylglycerol fatty acids. The trophic-marker fatty acids 16:1(n-7) and 18:4(n-3), indicating phytoplankton ingestion, were less abundant. They reflected, however, the dependence of the larvae on phytoplankton as well as the seasonal changes in algal composition. The generally close linear relationships between fatty acids and lipid suggest that the fatty-acid compositions of the collected specimens were largely independent of the respective developmental stage, season and region. The linear fit indicates that triacylglycerol accumulation started at a level of about 5% of total lipid. Considering the various overwintering scenarios under discussion, the life cycle and reproductive strategies of krill are discussed in the context of the lipid metabolism and fatty-acid composition of E. superba. Lipid production is effective enough to accumulate large energy reserves for the dark season, but E. superba does not exhibit the sophisticated biosynthetic pathways known from other Antarctic euphausiids and copepods. Although important, lipid utilisation appears to be just one of several strategies of E. superba to thrive under the extreme Antarctic conditions, and this pronounced versatility may explain the success of this species in the Southern Ocean. Received: 16 June 2000 / Accepted: 18 December 2000     

Differences in herbivore preferences, phlorotannin production, and nutritional quality between juvenile and adult tissues from marine brown algae

 Juvenile and adult marine organisms differ in their morphology, chemistry, physiology, behavior, and ecology. Because juvenile algae are thinner, smaller, and have more delicate tissues than adults, they are often assumed to be more susceptible to grazers. We examined within-species food preferences of four common generalist herbivores for juvenile and adult tissues of eight common brown algae in two-choice laboratory food-preference experiments. Our results showed that juvenile algae did not tend to be a preferred food of herbivores. Juvenile tissues were significantly preferred over adult tissues in only four of the 32 combinations of algae and herbivores tested. In 12 experiments, adult tissues were preferred over juvenile tissues, and no choice occurred in the remaining 16 experiments. When sea urchins exhibited a preference, it was always for adult tissues. The other three herbivores, an isopod and two snails, were more variable in their choices, sometimes preferring juveniles, sometimes adults, and sometimes having no preference. We measured nitrogen and phlorotannin concentrations in adult and juvenile seaweeds to see whether these parameters were correlated with herbivore food preferences. Nitrogen levels were similar in juveniles and adults of three algal species and were higher in juveniles of two. Phlorotannin levels were higher in juveniles of four species and lower in juveniles of one. The other three species showed no differences in phlorotannin levels. Phlorotannin concentrations decreased with increasing juvenile size in three species and increased with increasing size in one species. Neither nitrogen nor phlorotannin concentrations explained overall herbivore food preferences for algae of different stages. Our results suggest that preferences of certain grazers for juvenile algae are not as strong as previously assumed and are dependent on herbivore species. Preferences between juveniles and adults are likely to be determined by a combination of morphological and chemical features of the tissues and the unique responses of herbivore species to those features. Received: 10 April 2000 / Accepted: 19 November 2000     

Dimethylsulfoniopropionate and dimethylsulfide in the marine flatworm Convoluta roscoffensis and its algal symbiont

 A distinct smell of dimethylsulfide (DMS) was noted at the edge of the intertidal mudflat of Marennes-Oléron Bay, at the French Atlantic coast, where dense populations of the marine flatworm Convoluta roscoffensis Graff (Platyhelminthes: Turbellaria) were present. DMS is the cleavage product of dimethylsulfoniopropionate (DMSP). DMSP was shown to be present in high amounts in sediment containing the flatworm as well as in axenic cultures of the symbiotic alga Tetraselmis sp. that was isolated from the flatworm. In untreated sediment samples containing C. roscoffensis the concentration of DMS was as high as ∼55 μmol l⁻¹ sediment, and in samples that were fixed with glutaraldehyde the concentration of DMS was even three orders of magnitude higher (∼66 mmol l⁻¹ sediment). This rapid cleavage of DMSP to DMS in fixed samples was unexpected. Pure DMSP was stable in glutaraldehyde, and it was therefore concluded that a DMSP-lyase was responsible for cleavage in the field samples. The isolated symbiotic alga, Tetraselmis sp., did not show DMSP-lyase activity, indicating that DMSP-lyase may have been present in the flatworm, although the role of bacteria could not be excluded. The Chl a-specific DMSP content of C. roscoffensis (∼200 mmol g⁻¹) was much higher than that of Tetraselmis sp. (∼30 mmol g⁻¹). Possibly, DMSP was not only present in the symbiotic alga, but was also incorporated in the body tissue of the flatworm. It remains unclear what the function of DMSP is in C. roscoffensis. In Tetraselmis sp., but not in C. roscoffensis, DMSP increased with increasing salinity. It was concluded that salinity probably does not play an important role in the dynamics of DMSP and DMS in sediment containing C. roscoffensis. Received: 21 January 2000 / Accepted: 29 August 2000