Characterization and classification of complex PAH samples using GC-qMS and GC-TOFMS

The aim of this study was to compare the polycyclic aromatic hydrocarbon (PAH) contents in a number of complex samples, including soil samples from industrial sites, anti-skid sand, urban dust and ash samples from municipal solid waste incinerators. The samples were characterized by routine analysis of PAHs (gas chromatography–quadrupole mass spectrometry) and gas chromatography–time of flight mass spectrometry (GC–TOFMS). Classification of the samples by principal component analysis (PCA) according to their composition of PAHs revealed that samples associated with traffic and the municipal incinerator formed homogeneous clusters, while the PAH-contaminated soils clustered in separate groups. Using spectral data to resolve co-eluting chromatographic peaks, 962 peaks could be identified in the GC–TOFMS analysis of a pooled sample and 123–527 peaks in the individual samples. Many of the studied extracts included a unique set of chemicals, indicating that they had a much more diverse contamination profile than their PAH contents suggested. Compared to routine analysis, GC–TOFMS provided more detailed information about each sample and in this study a large number of alkylated PAHs were found to be associated with the corresponding unsubstituted PAHs. The possibility to filter peaks according to different criteria (e.g. to include only peaks that were detected in the analysis of another sample) was explored and used to identify unique as well as common compounds within samples. This procedure could prove to be valuable for obtaining relevant chemical data for use in conjunction with results from various biological test systems.     

Ah Receptor Agonists in UV-exposed Toluene Solutions of Decabromodiphenyl Ether (decaBDE) and in Soils Contaminated with Polybrominated Diphenyl Ethers (PBDEs) (9 pp)

Goal, Scope and Background The use of polybrominated diphenyl ethers (PBDEs) as flame retardants increases the risk for emissions of other brominated compounds, such as polybrominated dibenzodioxins (PBDDs) and dibenzofurans (PBDFs). The large homology in structure of PBDD/Fs and mechanism of toxic action, i.e. the capacity to activate the Ah receptor (AhR) pathway, compared to their well-studied chlorinated analogues, justifies a raised concern to study the environmental levels and fate of these compounds. Decabromodiphenyl ether (decaBDE) is the most widely used PBDE today. Studies on photolytic debromination of decaBDE in organic solvents have shown debromination of decaBDE, as well as formation of PBDFs. However, little is known about the transformation mechanisms and there are only scarce data on photoproducts and PBDE transformation in environmentally relevant matrices. In this study, mechanism-specific dioxin bioassays were used to study photolytic formation of AhR agonists in toluene solutions of decaBDE. In addition, the influence of irradiation time and UV-light wavelength on the formation was studied. PBDE congener patterns and presence of PBDD/Fs were analysed. Further, AhR agonists were analysed in agricultural soils contaminated with PBDEs. Soils were also exposed to UV-light to study changes in AhR agonist levels. Methods Toluene solutions of decaBDE were irradiated using three different spectra of UV-light, simulating UV-A (320-400 nm), UV-AB (280-400 nm), and UV-ABC (250-400 nm). Additionally, decaBDE solutions were exposed to narrow wavelength intervals (10 nm bandwidth) with the central wavelengths 280, 290, 300, 310, 320, 330, 340, 350, 360 nm. AhR agonists in decaBDE solutions were analysed with two different bioassays, the chick embryo liver-cell assay for dioxins (Celcad) and the dioxin responsive, chemically activated luciferase expression assay (DR-Calux). Also, the decaBDE solutions were analysed with LRGC-LRMS to obtain PBDE congener patterns for breakdown of decaBDE, and with HRGC-HRMS, for presence of PBDD/Fs. Four soils were exposed to UV-AB light, under both dry and moist conditions. Levels of AhR agonists in soil extract fractions, before and after UV-exposure, were analysed with the DR-Calux. Results and Discussion Significant levels of photoproducts able to activate the AhR pathway, up to 31 ng bio-TEQ/ml, were formed in UV-exposed decaBDE solutions. The transformation yield of decaBDE into AhR agonists was estimated to be at the 0.1%-level, on a molar basis. The net formation was highly dependent on wavelength, with the sample irradiated at 330 nm showing the highest level of dioxin-like activity. No activity was detected in controls. PBDE analysis confirmed decaBDE degradation and a clear time-dependent pattern for debromination of PBDE congeners. AhR agonist effect in the recalcitrant fractions of the soils corresponded to the levels of chemically derived TEQs, based only on chlorinated dioxin-like compounds in an earlier study. It was concluded that no significant levels of other AhR agonists, e.g. PBDFs, were accumulated in the soil. UV-light caused changes in AhR-mediated activity in the more polar and less persistent fractions of the soils, but it is not known which compounds are responsible for this. Recommendations and Perspective . The laboratory experiments in this study show that high levels of AhR agonists can be formed as photoproducts of decaBDE and it is important to elucidate if and under which conditions this might occur in nature. However, soil analysis indicates that photoproducts of PBDE do not contribute to the accumulated levels of persistent dioxin-like compounds in agricultural soil. Still, more data is needed to fully estimate the environmental importance of PBDE photolysis and occurrence of its photoproducts in other environmental compartments. Analysis with dioxin bioassays enabled us to gather information about photoproducts formed from decaBDE even though the exact identities of these compounds were not known. Conclusion Bioassays are valuable for studying environmental transformation processes like this, where chemical analysis and subsequent toxicological evaluation requires available standard compounds and information on toxicological potency. The use of bioassays allows a rapid evaluation of toxicological relevance.     

Sediment texture and cannibalism affect survival during moult in Saduria entomon (Isopoda)

Laboratory experiments were performed to investigate the effects of sediment texture and presence of non-moulting conspecifics on size-specific moulting survival of the omnivorous benthic isopod Saduria entomon (L.). The moult survival of S. entomon was significantly higher in coarse sand than in very soft muddy clay sediment. However, there was no size-related difference in moult survival between the substrates. Due to cannibalism, moult survival of S. entomon was substantially reduced in the presence of non-moulting conspecifics. Moult survival was higher when the moulter was larger than the non-moulters compared to when the moulter was smaller. In contrast, the absolute size of the moulter or the non-moulters did not affect moult survival. The sex of the moulting or non-moulting isopods had no effect on the survival of the moulters. Based on the results from laboratory experiments, sediment texture and cannibalism are suggested to affect survival during moult of S. entomon in the field. Received: 12 February 1998 / Accepted: 14 November 1998     

Great cormorants (<Emphasis Type="Italic">Phalacrocorax carbo</Emphasis>) can detect auditory cues while diving

In-air hearing in birds has been thoroughly investigated. Sound provides birds with auditory information for species and individual recognition from their complex vocalizations, as well as cues while foraging and for avoiding predators. Some 10% of existing species of birds obtain their food under the water surface. Whether some of these birds make use of acoustic cues while underwater is unknown. An interesting species in this respect is the great cormorant (Phalacrocorax carbo), being one of the most effective marine predators and relying on the aquatic environment for food year round. Here, its underwater hearing abilities were investigated using psychophysics, where the bird learned to detect the presence or absence of a tone while submerged. The greatest sensitivity was found at 2 kHz, with an underwater hearing threshold of 71 dB re 1 μPa rms. The great cormorant is better at hearing underwater than expected, and the hearing thresholds are comparable to seals and toothed whales in the frequency band 1–4 kHz. This opens up the possibility of cormorants and other aquatic birds having special adaptations for underwater hearing and making use of underwater acoustic cues from, e.g., conspecifics, their surroundings, as well as prey and predators.     

Differences in stress tolerance and brood size between a non-indigenous and an indigenous gammarid in the northern Baltic Sea

Differences in stress tolerance and reproductive traits may drive the competitive hierarchy between non-indigenous and indigenous species and turn the former ones into successful invaders. In the northern Baltic Sea, the non-indigenous Gammarus tigrinus is a recent invader of littoral ecosystems and now occupies comparable ecological niches as the indigenous G. zaddachi. In laboratory experiments on specimens collected between June and August 2009 around Tvärminne in southern Finland (59°50′N/23°15′E), the tolerances towards heat stress and hypoxia were determined for the two species using lethal time, LT₅₀, as response variable. The brood size of the two species was also studied and some observations were made on maturation of juveniles. Gammarus tigrinus was more resistant to hypoxia and survived at higher temperatures than G. zaddachi. Brood size was also greater in G. tigrinus than in G. zaddachi and G. tigrinus matured at a smaller size and earlier than G. zaddachi. Hence, there are clear competitive advantages for the non-indigenous G. tigrinus compared to the indigenous G. zaddachi, and these may be further strengthened through ongoing environmental changes related to increased eutrophication and a warming climate in the Baltic Sea region.     

Tolerance of Hyas araneus zoea I larvae to elevated seawater PCO2 despite elevated metabolic costs

Early life stages of marine crustaceans respond sensitively to elevated seawater PCO₂. However, the underlying physiological mechanisms have not been studied well. We therefore investigated the effects of elevated seawater PCO₂ on oxygen consumption, dry weight, elemental composition, median developmental time (MDT) and mortality in zoea I larvae of the spider crab Hyas araneus (Svalbard 79°N/11°E; collection, May 2009; hatch, December 2009). At the time of moulting, oxygen consumption rate had reached a steady state level under control conditions. In contrast, elevated seawater PCO₂ caused the metabolic rate to rise continuously leading to a maximum 1.5-fold increase beyond control level a few days before moulting into the second stage (zoea II), followed by a pronounced decrease. Dry weight of larvae reared under high CO₂ conditions was lower than in control larvae at the beginning of the moult cycle, yet this difference had disappeared at the time of moulting. MDT of zoea I varied between 45 ± 1 days under control conditions and 42 ± 2 days under the highest seawater CO₂ concentration. The present study indicates that larval development under elevated seawater PCO₂ levels results in higher metabolic costs during premoulting events in zoea I. However, H. araneus zoea I larvae seem to be able to compensate for higher metabolic costs as larval MDT and survival was not affected by elevated PCO₂ levels.     

Does job insecurity lead to impaired well‐being or vice versa? Estimation of cross‐lagged effects using latent variable modelling

Although research suggests that job insecurity is associated with impaired employee well‐being, there is insufficient empirical evidence to draw any causal inferences since most studies are cross‐sectional and thus do not control for previous levels of health symptoms. We used longitudinal questionnaire data to investigate the direction of the relationship between job insecurity and health complaints. After controlling for prior levels of mental and physical health complaints and five other variables that could potentially confound the results (gender, age, organizational tenure, family status, and education), the results of latent variable modelling showed that the cross‐lagged effect of job insecurity on mental health complaints, one year later, was significant whereas the reversed effects of mental and physical health complaints on subsequent insecurity were non‐significant. However, there was no significant cross‐lagged effect of job insecurity on physical health complaints. The results provide empirical support for the theoretical notion that job insecurity leads to health complaints, and imply that prior levels of health should be taken into consideration in order to explain the relative effect of perceived job insecurity on the physical and mental health of the workforce. Copyright © 2003 John Wiley & Sons, Ltd.     

Seasonal and Regional Patterns in Performance for a Baltic Sea Drainage Basin Hydrologic Model

This study evaluates the ability of the Catchment SIMulation (CSIM) hydrologic model to describe seasonal and regional variations in river discharge over the entire Baltic Sea drainage basin (BSDB) based on 31 years of monthly simulation from 1970 through 2000. To date, the model has been successfully applied to simulate annual fluxes of water from the catchments draining into the Baltic Sea. Here, we consider spatiotemporal bias in the distribution of monthly modeling errors across the BSDB since it could potentially reduce the fidelity of predictions and negatively affect the design and implementation of land‐management strategies. Within the period considered, the CSIM model accurately reproduced the annual flows across the BSDB; however, it tended to underpredict the proportion of discharge during high‐flow periods (i.e., spring months) and overpredict during the summer low flow periods. While the general overpredictions during summer periods are spread across all the subbasins of the BSDB, the underprediction during spring periods is seen largely in the northern regions. By implementing a genetic algorithm calibration procedure and/or seasonal parameterization of subsurface water flows for a subset of the catchments modeled, we demonstrate that it is possible to improve the model performance albeit at the cost of increased parameterization and potential loss of parsimony.     

On the road to ‘research municipalities’: analysing transdisciplinarity in municipal ecosystem services and adaptation planning

Transdisciplinary research and collaboration is widely acknowledged as a critical success factor for solution-oriented approaches that can tackle complex sustainability challenges, such as biodiversity loss, pollution, and climate-related hazards. In this context, city governments’ engagement in transdisciplinarity is generally seen as a key condition for societal transformation towards sustainability. However, empirical evidence is rare. This paper presents a self-assessment of a joint research project on ecosystem services and climate adaptation planning (ECOSIMP) undertaken by four universities and seven Swedish municipalities. We apply a set of design principles and guiding questions for transdisciplinary sustainability projects and, on this basis, identify key aspects for supporting university–municipality collaboration. We show that: (1) selecting the number and type of project stakeholders requires more explicit consideration of the purpose of societal actors’ participation; (2) concrete, interim benefits for participating practitioners and organisations need to be continuously discussed; (3) promoting the ‘inter’, i.e., interdisciplinary and inter-city learning, can support transdisciplinarity and, ultimately, urban sustainability and long-term change. In this context, we found that design principles for transdisciplinarity have the potential to (4) mitigate project shortcomings, even when transdisciplinarity is not an explicit aim, and (5) address differences and allow new voices to be heard. We propose additional guiding questions to address shortcomings and inspire reflexivity in transdisciplinary projects.