Polybrominated diphenyl ethers in aircraft cabins--a source of human exposure?

Commercial aircrafts need a high degree of fire protection for passenger safety. Brominated flame retardants (BFRs), including polybrominated diphenyl ethers (PBDEs), may be used for this purpose. Because PBDEs readily absorb to dust particles, aircraft crew and passengers may receive significant PBDEs exposure via inhalation. The aims of this work were to assess whether PBDEs could be found in aircraft cabin dust and whether serum levels of PBDEs increased in passengers after long-distance flights. Hence nine subjects on intercontinental flights collected cabin dust samples, as well as donated blood samples before departure and after return to Sweden. Two subjects who were domestic frequent flyers were also investigated. The levels of PBDEs in dust and serum were determined by GC/MS in electron capture negative ionization (ECNI) mode. Authentic reference substances were used for identification and quantitation. PBDEs were found in all aircraft dust samples at high concentrations, higher than in common household dust. Congener patterns indicated that the technical products PentaBDE, OctaBDE and DecaBDE were used in the aircrafts. Serum concentrations in the travellers were similar to those observed in Swedish residents in general. Post-travel serum levels of BDE-28, BDE-99, BDE-100, BDE-153, and BDE-154 were significantly higher (p<0.05) than concentrations prior to travel. The findings from this pilot study call for investigations of occupational exposures to PBDEs in cabin and cockpit crews.     

Minderung von Lärmimmissionen des Kfz-Verkehrs

Although the permissible emission limits for new motor vehicles are continuously being reduced year after year, the proportion of citizens in the Federal Republic of Germany who are affected by such traffic noise continues to remain practically constant. Thus, aside from the innovations in motor-vehicle technology, the question must be raised concerning what other possibilities are actually available for achieving a reduction in the emission of traffic noises. In the following, planning possibilities are presented for the traffic routes themselves and for their direct vicinities. An evaluation is also made concerning their efficiency. In addition to the prognostic tools of the guidelines which have been introduced in Germany and Austria, the application of modern research must also be taken into consideration.     

Irrigation of treated wastewater in Braunschweig, Germany: an option to remove pharmaceuticals and musk fragrances

In this study the fate of pharmaceuticals and personal care products which are irrigated on arable land with treated municipal wastewater was investigated. In Braunschweig, Germany, wastewater has been irrigated continuously for more than 45 years. In the winter time only the effluent of the sewage treatment plant (STP) of Braunschweig is used for irrigation, while during summer digested sludge is mixed with the effluent. In the present case study six wells and four lysimeters located in one of the irrigated agricultural fields were monitored with regard to the occurrence of 52 pharmaceuticals and two personal care products (PPCPs; e.g. betablockers, antibiotics, antiphlogistics, carbamazepine, musk fragrances, iodinated contrast media (ICM) and estrogens). No differences in PPCP pollution of the groundwater were found due to irrigation of STP effluents with and without addition of digested sludge, because many polar compounds do not sorb to sludge and lipophilic compounds are not mobile in the soil-aquifer. Most of the selected PPCPs were never detected in any of the lysimeter or groundwater samples, although they were present in the treated wastewater irrigated onto the fields. In the groundwater and lysimeter samples primarily the ICM diatrizoate and iopamidol, the antiepileptic carbamazepine and the antibiotic sulfamethoxazole were detected up to several mugl(-1), while the acidic pharmaceuticals, musk fragrances, estrogens and betablockers were likely sorbed or transformed while passing the top soil layer. Potential estrogenic effects are likely to disappear after irrigation, since the most potent steroid estrogens were not measurable.     

Possible effects of persistent organochlorinated pollutants cocktail on thyroid hormone levels and pituitary-thyroid interrelations

In polluted district of Michalovce in East Slovakia (POLL) and two districts with background pollution (BCGR) 2046 adults (834 males and 1212 females aged 20-75 years) were examined. Serum levels of thyrotropin (TSH), free thyroxine (FT4), total triiodothyronine (TT3) and antithyroperoxidase antibodies (TPOab) were estimated by electrochemiluminiscent assay and also these of 15 polychlorinated biphenyl congeners (PCBs), p,p'-DDE, p,p'-DDT, hexachlorobenzene (HCB) and hexachlorocyclohexane were measured by high resolution gas chromatography/mass spectrometry. In addition, also dioxins, furans, coplanar- and mono-ortho-PCBs as well as selected hydroxylated and methylsulphonated PCBs and DDE metabolites were measured by appropriate methods based on gas chromatography/mass spectrometry principle. In POLL significantly higher levels of all organochlorines were found than these in BCGR. When pooled values from both areas were stratified in terms of PCBs level and treated as continuous variables, positive association of PCBs with FT4 and TT3 was found, the latter two being also mutually associated. However, within the category of PCBs level <530 ng/glipid (n=232) the association between PCBs and both the FT4 (p<0.09) and TT3 (p<0.03) was negative and any association of these was not found within the category of PCBs level of 531-1000 ng/g (n=691). In contrast, in the category of 531-2000 ng/g (n=1307) positive association appeared between PCBs and FT4 (p<0.001) as well as TT3 (p<0.05). Highly significant association of PCBs with FT4 (p<0.001) was further found in the categories with PCBs level of 1001-101414 ng/g (n=1307) and 2001-101414 (n=1123), while significant association with TT3 was observed only in the category of 531-2000 ng/g. Such findings suggest possible threshold level in positive effect of PCBs on FT4 and TT3 level which seems to be individual and located somewhere around the PCBs level of 1000 ng/g. However, highly significant negative association of both FT4 and TT3 with TSH was found in each of above indicated PCBs categories. Considerable difference in FT4 and TT3 level between large groups of subjects with the same range of PCBs level was also found suggesting different individual susceptibility to the effects of organochlorines. Among a total of 26 cases from POLL with very low TSH level (<0.5 mU l(-1)) 13 cases showed very high level of PCBs, FT4 and TT3, thus supporting a hypothesis on a novel sporadic form of high PCBs related peripheral subclinical hyperthyroidism possibly resulting from the long-term disruption of equilibrium between bound and free thyroxine in plasma by high PCBs level followed by a striking inhibition of TSH release from the pituitary.     

Maternal and cord serum exposure to PCB and DDE methyl sulfone metabolites in eastern Slovakia

Polychlorinated biphenyls (PCBs) were commercially produced between 1959 and 1984 in eastern Slovakia. Improper handling led to a highly contaminated local environment and high levels of PCBs in humans and wildlife in the Michalovce area. The aim of this study was to analyse serum for methylsulfonyl metabolites of PCB (MeSO(2)-PCBs) and DDE (3-MeSO(2)-DDE) in serum samples from pregnant women and in a selected number of paired cord blood samples to assess maternal sulfone levels and patterns, and transplacental transfer of these metabolites. The donating women were from two districts in eastern Slovakia. A liquid-liquid extraction method together with separation of substance groups and further clean-up on silica gel columns were applied prior to analysis by gas chromatography/mass spectrometry. 3-MeSO(2)-DDE was the major methyl sulfone in most of the samples followed by a yet not identified MeSO(2)-hexaCB, 4'-MeSO(2)-CB101, 4'-MeSO(2)-CB87 and 4-MeSO(2)-CB149. The women from the contaminated area had three times higher concentrations of the MeSO(2)-PCBs than women from the reference area. This is the first report on methyl sulfone metabolites of PCB and DDE in human cord serum. It is shown that these metabolites are transported through the placenta. The levels of MeSO(2)-PCBs in the maternal serum were about 1.5 times higher than in the corresponding cord serum on a lipid weight basis. For 3-MeSO(2)-DDE, the levels were about the same in maternal and cord serum. The difference in the maternal:cord ratio, comparing MeSO(2)-PCBs with 3-MeSO(2)-DDE might be due to differences in transport through the placenta caused by their different affinities for lipoproteins and plasma proteins.     

Conceptual development of a harmonised method for tracking change and evaluating policy in the agri-environment: The Agri-environmental Footprint Index

An aggregated farm-level index, the Agri-environmental Footprint Index (AFI), based on multiple criteria methods and representing a harmonised approach to evaluation of EU agri-environmental schemes is described. The Index uses a common framework for the design and evaluation of policy that can be customised to locally relevant agri-environmental issues and circumstances. Evaluation can be strictly policy-focused, or broader and more holistic in that context-relevant assessment criteria that are not necessarily considered in the evaluated policy can nevertheless be incorporated. The Index structure is flexible, and can respond to diverse local needs. The process of Index construction is interactive, engaging farmers and other relevant stakeholders in a transparent decision-making process that can ensure acceptance of the outcome, help to forge an improved understanding of local agri-environmental priorities and potentially increase awareness of the critical role of farmers in environmental management. The structure of the AFI facilitates post-evaluation analysis of relative performance in different dimensions of the agri-environment, permitting identification of current strengths and weaknesses, and enabling future improvement in policy design. Quantification of the environmental impact of agriculture beyond the stated aims of policy using an ‘unweighted’ form of the AFI has potential as the basis of an ongoing system of environmental audit within a specified agricultural context.     

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.     

Radionuclide migration in forest ecosystems--results of a model validation study

The primary objective of the IAEA's BIOMASS Forest Working Group (FWG) was to bring together experimental radioecologists and modellers to facilitate the exchange of information which could be used to improve our ability to understand and forecast radionuclide transfers within forests. This paper describes a blind model validation exercise which was conducted by the FWG to test nine models which members of the group had developed in response to the need to predict the fate of radiocaesium in forests in Europe after the Chernobyl accident. The outcomes and conclusions of this exercise are summarised. It was concluded that, as a group, the models are capable of providing an envelope of predictions which can be expected to enclose experimental data for radiocaesium contamination in forests over the time scale tested. However, the models are subject to varying degrees of conceptual uncertainty which gives rise to a very high degree of divergence between individual model predictions, particularly when forecasting edible mushroom contamination. Furthermore, the forecasting capability of the models over future decades currently remains untested.