Identification and quantification of products formed via photolysis of decabromodiphenyl ether

Background, aim, and scope  Decabromodiphenyl ether (DecaBDE) is used as an additive flame retardant in polymers. It has become a ubiquitous environmental contaminant, particularly abundant in abiotic media, such as sediments, air, and dust, and also present in wildlife and in humans. The main DecaBDE constituent, perbrominated diphenyl ether (BDE-209), is susceptible to transformations as observed in experimental work. This work is aimed at identifying and assessing the relative amounts of products formed after UV irradiation of BDE-209. Materials and methods  BDE-209, dissolved in tetrahydrofuran (THF), methanol, or combinations of methanol/water, was exposed to UV light for 100 or 200 min. Samples were analyzed by gas chromatography/mass spectrometry (electron ionization) for polybrominated diphenyl ethers (PBDEs), dibenzofurans (PBDFs), methoxylated PBDEs, and phenolic PBDE products. Results  The products formed were hexaBDEs to nonaBDEs, monoBDFs to pentaBDFs, and methoxylated tetraBDFs to pentaBDFs. The products found in the fraction containing halogenated phenols were assigned to be pentabromophenol, dihydroxytetrabromobenzene, dihydroxydibromodibenzofuran, dihydroxytribromodibenzofuran, and dihydroxytetrabromodibenzofuran. The PBDEs accounted for approximately 90% of the total amount of substances in each sample and the PBDFs for about 10%. Discussion  BDE-209 is a source of PBDEs primarily present in OctaBDEs but also to some extent in PentaBDEs, both being commercial products now banned within the EU and in several states within the USA. It is notable that OH-PBDFs have not been identified or indicated in any of the photolysis studies performed to date. Formation of OH-PBDFs, however, may occur as pure radical reactions in the atmosphere. Conclusions  Photolysis of decaBDE yields a wide span of products, from nonaBDEs to hydroxylated bromobenzenes. It is evident that irradiation of decaBDE in water and methanol yields OH-PBDFs and MeO-PBDFs, respectively. BDE-202 (2,2′,3,3′,5,5′,6,6′-octabromodiphenyl ether) is identified as a marker of BDE-209 photolysis. Recommendations and perspectives  BDE-209, the main constituent of DecaBDE, is primarily forming debrominated diphenyl ethers with higher persistence which are more bioaccumulative than the starting material when subjected to UV light. Hence, DecaBDE should be considered as a source of these PBDE congeners in the environment. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Model selection and evaluation for risk assessment of dioxin-contaminated sites

The general European population has a total intake of dioxins and dioxin-like chemicals near the limit recommended by the European Union, making additional exposure above background levels undesirable. For populations living near dioxin-contaminated sites, additional exposure may occur by intake of locally produced food, inhalation of particles, dermal contact with soils, or other exposure pathways. Risk assessment tools are required to estimate risks associated with contaminated sites and to set priorities for site remediation. Here, we review several multimedia models that can be applied as tools to support risk assessment. We then present a strategy to select, apply, evaluate, and adapt a model to address a specific situation. The case study we consider is a risk assessment of generic background dioxin exposure in Sweden, and we compare the predictions with environmental observations and exposure data from Sweden. Arguments are presented for selecting the CalTOX model for this case study. We demonstrate the application, evaluation, and adaptation of the model and discuss the requirements for extending the analysis to conduct risk assessment for subpopulations living near dioxin-contaminated sites.     

Using Vessel Monitoring System Data to Improve Systematic Conservation Planning of a Multiple-Use Marine Protected Area,the Kosterhavet National Park (Sweden)

When spatial fishing data is fed into systematic conservation planning processes the cost to a fishery could be ensured to be minimal in the zoning of marine protected areas. We used vessel monitoring system (VMS) data to map the distribution of prawn trawling and calculate fishing intensity for 1-ha grid cells, in the Kosterhavet National Park (Sweden). We then used the software Marxan to generate cost-efficient reserve networks that represented every biotope in the Park. We asked what were the potential gains and losses in terms of fishing effort and species conservation of different planning scenarios. Given a conservation target of 10 % representation of each biotope, the fishery need not lose more than 20 % of its fishing grounds to give way to cost-efficient conservation of benthic diversity. No additional reserved area was needed to achieve conservation targets while minimizing fishing costs. We discuss the benefits of using VMS data for conservation planning.     

Porosity investigation of compacted bentonite using XRD profile modeling

Many countries intend to use compacted bentonite as a barrier in their deep geological repositories for nuclear waste. In order to describe and predict hydraulic conductivity or radionuclide transport through the bentonite barrier, fundamental understanding of the microstructure of compacted bentonite is needed. This study examined the interlayer swelling and overall microstructure of Wyoming Bentonite MX-80 and the corresponding homo-ionic Na(+) and Ca(2+) forms, using XRD with samples saturated under confined swelling conditions and free swelling conditions. For the samples saturated under confined conditions, the interparticle, or so-called free or external porosity was estimated by comparing the experimental interlayer distances obtained from one-dimensional XRD profile fitting against the maximum interlayer distances possible for the corresponding water content. The results showed that interlayer porosity dominated total porosity, irrespective of water content, and that the interparticle porosity was lower than previously reported in the literature. At compactions relevant for the saturated bentonite barrier (1.4-1.8 g/cm(3)), the interparticle porosity was estimated to ≤3%.     

Pollutant dispersion in idealized city models with different urban morphologies

The mechanism of pollutant dispersion in idealized city models is investigated numerically by the introduction of a uniformly distributed pollutant source at street pedestrian level. We first study three short city forms with a single main street or two crossing streets, characterized by street length/street height ratios of L/H = 6 or 7 and a street height/street width ratio of H/W = 1, including a sharp-edged round city model, a smooth-edged round city model, and a sharp-edged square city model. For short city models with a single street and a parallel approaching wind, pollutant dilution mainly depends on the horizontal flow rate which decreases along the street. This decreasing rate is smallest for the smooth-edged round city model, which results in the lowest street concentrations. For city models with two crossing streets and the approaching wind parallel to the main street, the differences in overall city form result in different dispersion processes. For a sharp-edged round city model with two crossing streets, an approaching wind slightly non-parallel to the main street generates a lower pollutant concentration in the entire street volume. We also studied a sharp-edged round city model with one narrow street (L/H = 6; H/W = 6.7), finding that the uniformly distributed pollutants are transported from two street entries to the city centre, and are then removed out across the street roof. In contrast to the short city models we studied a single-street sharp-edged long rectangular city model (L/H = 21.7; H/W = 1) in which the horizontal flow rate remained nearly constant in a region far from the two entries. Within this region the turbulence across the street roof contributed more to the pollutant removal than vertical mean flows.     

Aniline and 2,4,6-trinitrotoluene associate preferentially to low molecular weight fractions of dissolved soil organic matter

Aniline and 2,4,6-trinitrotoluene (TNT) were equilibrated with particulate (POM) and dissolved organic matter (DOM) from an organic soil at different compositions of adsorbed major cations (Na, Al) and pH (aniline: 3.7–5.1, TNT: 4.8–5.0). After separation of POM, concentrations of ¹⁴C-labelled aniline and TNT* (including TNT degradation products) were determined in DOM size fractions using size-exclusion chromatography (SEC) and UV-detection. Concentrations in the <3.5 kDa size fraction were 2.8–6.0 and 8.5–9.5 times higher for aniline and TNT*, respectively, as compared to the >40 kDa fraction. Thus, both aniline and TNT* were preferentially associated to the smallest DOM size fraction. The significant binding to DOM (similar extent as to POM) and the fact that the <3.5 kDa DOM fraction was less susceptible to flocculation by major metals suggests that the mobility of aniline and TNT is highly affected by the solubility of soil organic matter.     

Effects of whole spine alignment patterns on neck responses in rear end impact

Objective: The aim of this study was to investigate the whole spine alignment in automotive seated postures for both genders and the effects of the spinal alignment patterns on cervical vertebral motion in rear impact using a human finite element (FE) model.

Methods: Image data for 8 female and 7 male subjects in a seated posture acquired by an upright open magnetic resonance imaging (MRI) system were utilized. Spinal alignment was determined from the centers of the vertebrae and average spinal alignment patterns for both genders were estimated by multidimensional scaling (MDS). An occupant FE model of female average size (162 cm, 62 kg; the AF 50 size model) was developed by scaling THUMS AF 05. The average spinal alignment pattern for females was implemented in the model, and model validation was made with respect to female volunteer sled test data from rear end impacts. Thereafter, the average spinal alignment pattern for males and representative spinal alignments for all subjects were implemented in the validated female model, and additional FE simulations of the sled test were conducted to investigate effects of spinal alignment patterns on cervical vertebral motion.

Results: The estimated average spinal alignment pattern was slight kyphotic, or almost straight cervical and less-kyphotic thoracic spine for the females and lordotic cervical and more pronounced kyphotic thoracic spine for the males. The AF 50 size model with the female average spinal alignment exhibited spine straightening from upper thoracic vertebra level and showed larger intervertebral angular displacements in the cervical spine than the one with the male average spinal alignment.

Conclusions: The cervical spine alignment is continuous with the thoracic spine, and a trend of the relationship between cervical spine and thoracic spinal alignment was shown in this study. Simulation results suggested that variations in thoracic spinal alignment had a potential impact on cervical spine motion as well as cervical spinal alignment in rear end impact condition.     

Simulating transport of 129I and idealized tracers in the northern North Atlantic Ocean

Transport of the radioactive tracer Iodine-129 (¹²⁹I, T _1/2 = 15.7 Myr) in the northern North Atlantic Ocean has been investigated using a global isopycnic Ocean General Circulation Model (OGCM) and observed data. ¹²⁹I originates mainly from the nuclear fuel reprocessing plants in Sellafield (UK) and La Hague (France), and is transported northwards along the Norwegian coast, and then into surface and intermediate layers in the Arctic Ocean through the Barents Sea and the Fram Strait, but also partly recirculating south along the eastern coast of Greenland. In the North Atlantic Subpolar Seas, ¹²⁹I is mainly found in dense overflow waters from the Nordic Seas being exported southwards in the Deep Western Boundary Current, and to a lesser extent in surface and intermediate layers circulating cyclonically within the Subpolar Gyre. Observed concentration of ¹²⁹I along a surface transect in the eastern Nordic Seas in 2001 is captured by the OGCM, while in the Nansen Basin of the Arctic Ocean the OGCM overestimates the observed values by a factor of two. The vertical profile of ¹²⁹I in the Labrador Sea, repeatedly observed since 1997 to present, is fairly realistically reproduced by the OGCM. This indicates that the applied model system has potential for predicting the magnitude and depth of overflow waters from the Nordic Seas into the North Atlantic Subpolar Seas. To supplement the information obtained from the ¹²⁹I distribution, we have conducted a number of idealized tracer experiments with the OGCM, including tracers mimicking pure water masses, and instantaneous pulse releases. New insight into time-scales of tracer transport in this region is obtained by utilizing a few recently developed methods based on the theory of Transit Time Distribution (TTD) and age of tracers. Implications for other types of “anomalies” in the northern North Atlantic Ocean, being anomalous hydrography or chemical tracers, and how they are interpreted, are discussed.