Polychlorinated biphenyls in polysulfide sealants--occurrence and emission from a landfill station

Approximately 80,000 kg polysulfide sealant containing 10,000-18,000 kg polychlorinated biphenyls (PCB) was deposited at a Swedish municipal landfill station during 1965-1973. Investigations during 1994 showed that soil layers underneath the landfill had concentration of PCB not alarmingly high. The concentration of PCB congeners in ground water samples was elevated 4-750 times compared to a reference sample. Based on samples of ground water, leachate water, and flux chambers measuring evaporation of PCB from the landfill surface, the emission of PCB was estimated to be 1 g sigmaPCB/yr. This very low rate was attributed to the high sorptive capacity of the sealant. Compared to a reference site, the evaporation flux was elevated for the most volatile congeners, but factors 20-1400 lower than from another landfill which was contaminated with PCB in paper-pulp fibres.     

SALSA: a simulation tool to assess ecological sustainability of agricultural production

In order to assess the ecological sustainability of agricultural production systems, there is a need for effective tools. We describe an environmental systems analysis tool called SALSA (Systems Ana/ysis for Sustainable Agriculture). It consists of substance/material flow models in which the simulation results are interpreted with life-cycle assessment methodology. The application of SALSA is demonstrated in a case study in which three different ways of producing pigs are compared with respect to energy input and the environmental impacts of global warming, eutrophication, and acidification. The scenario that combined a low-protein diet without soy meal with an improved manure-management technique with low nitrogen losses was the best for all impact categories studied. The strength of the SALSA models was their capacity to capture consequences of management options that had an influence on several processes on a farm, which enabled the type of complex studies we describe.     

A chemical and toxicological profile of Dutch North Sea surface sediments

Chemical and toxicological profiles were assessed in surface sediments (fraction <63 μm) from the southern North Sea. In extracts of freeze-dried samples, polybrominated biphenyl (PBB), Irgarol 1051 and phthalate concentrations were below the respective detection limits (except di(2-ethylhexyl)phthalate, which was between 170 and 3300 μg kg⁻¹ dry weight (dw)). Hexabromocyclododecane (HBCD) concentrations were between 0.8 and 6.9 μg kg⁻¹ dw, with highest concentrations at river mouths. Polybrominated diphenylethers (PBDE) concentrations were 0.4–0.6 μg kg⁻¹ dw, decabromodiphenylether (BDE209) 1–32 μg kg⁻¹ dw. The ratio BDE209/PCB153 was used as a tracer for recent emissions, and pointed towards a BDE209 source in the Western Scheldt’s upper estuary. PCBs and PAHs were between 0.19–4.7 and 2.6–200 μg kg⁻¹ dw respectively and generally had highest concentrations at near-shore locations and river mouths.

Responses in the Microtox broad-spectrum and the Mutatox genotoxicity assays were generally low, with near-shore locations giving higher responses. The umu-C genotoxicity and the ER-CALUX assay for estrogenicity showed no response, with the exception of one near-shore location (IJmuiden outer harbour, ER-CALUX).

Highest dioxin-like toxicity (DR-CALUX) was found at near-shore locations, in the outflow of the Rhine/Meuse estuary including a dumping site of harbour sludge. At the Oyster Grounds, DR-CALUX responses appeared to be linked to the occurrence of larger PAHs (4–6 rings). A new, non-destructive clean up procedure resulted in significantly higher DR-CALUX responses than the current protocol. The Dutch legislation on disposal of harbour sludge at sea, dictates the use of the conventional clean up procedure. Our results therefore indicate that probably more dioxin-like toxicity associated with harbour sludge is disposed off at sea than assumed.     

Molecular orbital studies on brominated diphenyl ethers. Part I--conformational properties

Polybrominated diphenyl ethers (PBDEs) are widely used as additive flame retardants and quantities in the environment are on the rise. Because they are structurally related to polychlorinated biphenyls and also to thyroid hormones, there is serious concern that PBDEs may pose a danger to human health. Knowledge of their conformational properties is key to assessing their environmental fate and risk. The conformational properties of PBDEs were investigated by quantum chemical methods including semiempirical self-consistent field molecular orbital (SCF-MO), ab initio SCF-MO and density functional theory (DFT). Conformational analyses of model congeners 2,2',4,6'-tetrabromodiphenyl ether and 2,3,4,4',5,6-hexabromodiphenyl ether, based on energy maps calculated by semiempirical AM1 method, may indicate that all PBDE congeners except those with the tetra-ortho-bromination are conformationally flexible (or soft) due to low energy barriers for interconversion of stable conformers. The results of the conformational analyses are in conformity with recently published X-ray crystallographic data. For comparison with the results of the semiempirical method, higher level ab initio and DFT models were applied as well. The optimized geometries all lie well inside low energy regions on the maps and thus also ascertain the semiempirical calculations. According to computed geometric parameters and net atomic charges, the model B3LYP/3-21G* seemed to give better results than B3LYP/6-31G* and HF/6-31G*.     

Molecular orbital studies on brominated diphenyl ethers. Part II--reactivity and quantitative structure-activity (property) relationships

Polybrominated diphenyl ethers (PBDEs) are widely used as flame retardants and are increasingly turning up in the environment. Their structural similarities to polychlorinated biphenyls and thyroid hormones suggest they may be a risk to human health. The present study examines the reactivity of brominated diphenyl ethers (BDEs) on the basis of the electronic structures as calculated by semiempirical AM1 self-consistent field molecular orbital (SCF-MO) method. Frontier orbital energies were used to elucidate the reactivity of BDEs in electrophilic, nucleophilic and photolytic reactions. From an examination of the frontier electron densities, the regioselectivity, or orientation, of metabolic reactions of BDEs was predicted. Furthermore, satisfactory quantitative structure-activity (property) relationship (QSAR and QSPR) models were derived to calculate gas chromatographic and ultraviolet spectral properties and luciferase induction activities from the AM1-computed electronic parameters.     

Mitigation of a radon-rich Belgian dwelling using active subslab depressurization

In a radon prone area in Belgium, a dwelling with high indoor radon concentrations was identified through a passive measurement. Next, a continuous, active radon monitoring device was installed for one month. A 20-a retrospective radon assessment was also performed. The house was subsequently mitigated through active subslab depressurization with a radial fan. Afterwards the dwelling was actively monitored for several more months to observe the effects of the mitigation and to study the effect of reducing the fan power. Dose evaluations were made to evaluate the health benefit of the mitigation. It was seen that the results of the three measuring techniques before mitigation all yielded between 1700 and 2000 Bq/m3. Clear diurnal radon variations showed up only after mitigation. After mitigation, the average radon concentration fell to less than 200 Bq/m3. The yearly average dose was reduced from potentially 45 mSv/y to less than 4.5 mSv/y through mitigation. Reducing fan power to 50% did not clearly influence the amount of radon entering into the dwelling.     

Pre-dispersal seed predation: the role of fruit abortion and selective oviposition

Oviposition sites of phytophagous insects should correlate with plant traits that maximize survival of the progeny. Plants, on the other hand, should benefit from traits and developmental patterns that complicate oviposition decisions. In the antagonistic interaction between plant and pre-dispersal seed predator the time lag between egg laying and seed development may allow for abortion of fruits in plants, potentially reducing fitness loss through predation. We studied the perennial herb Lathvrus vernus and the beetle pre-dispersal seed predator Bruchus atomarius in Sweden to determine the fitness consequences of nonrandom fruit abortion in the plant and oviposition patterns of the beetle. The beetle had a sophisticated ability to locate fruits with high probability of retention, partly by fruit position and phenology but also by some additional unidentified cue. Mortality of eggs was density dependent, but still the egg-laying pattern was clumped. We found no defensive strategy in the plant; instead the predictable fruit abortion pattern was associated with decreased plant fitness. We discuss how interactions may pose simultaneous selection pressures on plant and insect traits and how life history traits and other selective forces may shape the adaptive outcome of the interaction in plant and insect, respectively.     

Change in spring arrival of migratory birds under an era of climate change,Swedish data from the last 140 years

Many migratory bird species have advanced their spring arrival during the latest decades, most probably due to climate change. However, studies on migratory phenology in the period before recent global warming are scarce. We have analyzed a historical dataset (1873–1917) of spring arrival to southern and central Sweden of 14 migratory bird species. In addition, we have used relative differences between historical and present-day observations (1984–2013) to evaluate the effect of latitude and migratory strategy on day of arrival over time. There was a larger change in spring phenology in short-distance migrants than in long-distance migrants. Interestingly, the results further suggest that climate change has affected the phenology of short-distance migrants more in southern than in central Sweden. The results suggest that the much earlier calculated arrival to southern Sweden among short-distance migrants mirrors a change in location of wintering areas, hence, connecting migration phenology and wintering range shifts.