Dietary exposure to dioxin-like compounds in three age groups: results from the Flemish environment and health study

Lipophilic contaminants are present in the environment and bioaccumulate in the food chain. Therefore, their intake via animal fat of various sources was assessed for three age groups of the Flemish population, participating in a large biomonitoring program of the Flemish government. In total, 1636 adolescents (14-15 years), 1186 mothers (18-44 years), and 1586 adults (50-65 years) participated in the study and completed a semi quantitative food frequency questionnaire. Individual consumption data were combined, via a so-called simple distribution approach, with recent data on polychlorinated dibenzo-p-dioxins/furans and dioxin-like polychlorinated biphenyls, measured via the chemical-activated luciferase gene expression (CALUX) bio-assay in food items available on the Flemish market. The median (95th percentile) estimated intakes of dioxin-like contaminants were 2.24 (4.61), 2.09 (4.26), and 1.74 (3.53) pg CALUX-TEQ kg(-1) bw d(-1) for, respectively adolescents, mothers and adults. These data are in the same range as those found in other European studies. The CALUX-TEQ results of respectively 59.8%, 53.7% and 36.2% of the adolescent, mother and adult population exceed the tolerable weekly intake (TWI) of 14 pg WHO-TEQ kg(-1) bw w(-1), as derived by the Scientific Committee on Food [Scientific Committee on Food, 2001. Opinion of the Scientific Committee on Food on the Risk Assessment of Dioxins and Dioxin-like PCBs in Food, CS/CNTM/DIOXIN/20 final Brussels, Belgium]. The main contributors of dioxin-like substances are fish and seafood (25-43% of the total intake), added fats (22-25% of the total intake) and dairy products (17-20% of the total intake).     

Hydrogeological study of an anti-tank range

The Arnhem Anti-Tank Range (Canadian Forces Base [CFB] Valcartier, Canada, in operation since the 1970s) has been characterized, including the drilling, installation, and characterization of 25 wells and a ground-penetrating radar survey. The observed particular features of this site include highly variable flow velocities (from < 3 to 1200 m/yr) and transient flow regime in the regional aquifer below the contaminant source zone of the impact area, sharp flow direction shifts, discontinuous stratigraphy and a local perched aquifer. A transient ground water flow model permitted us to understand how the complex hydrogeological setting shapes contaminant transport in the regional aquifer. The model explains the highly variable energetic material (EM) concentrations measured in the plume with peaks associated to spring and to a lesser extent to fall recharge events. As a conclusion from this work, the authors suggest that the characterization of contaminant sources on slopes should extend over all seasons to be sure to detect potential transient flow conditions and variable contaminant concentrations.     

Photolytic dehalogenation of the marine halogenated natural product Q1

The marine halogenated natural product 2,3,3',4,4',5,5'-heptachloro-1'-methyl-1,2'-bipyrrole (Q1) has been detected in high-trophic level biota throughout the world. In this study we UV-irradiated Q1 in order to produce hexahalogenated 1'-methylbipyrroles (Cl(6)-MBPs). Q1 was transformed with half-lives of <5 min. Already after 5 min, all of the five existing Cl(6)-MBPs (H1-H5) were detected in the irradiated sample. Only one Cl(6)-MBP (2,3,3',4',5,5'-hexachloro-1'-methyl-1,2'-bipyrrole (MBP-77, H2) has been previously described in the literature. H5 was identified as 2,3,3',4,4',5'-hexachloro-1'-methyl-1,2'-bipyrrole (MBP-75) by a specific fragment ion detected by GC/ECNI-MS. Fractionations of the irradiation mixture by reversed-phase HPLC followed by (1)H NMR analysis led to the structure of H4, i.e. 2,3,3',4,4',5-hexachloro-1'-methyl-1,2'-bipyrrole (MBP-74). H1 and H3 showed virtually identical (1)H NMR data. Therefore, it could not determined which of either isomers is 2,3,3',4,5,5'-hexachloro-1'-methyl-1,2'-bipyrrole (MBP-76) and which is 2,3,4,4',5,5'-hexachloro-1'-methyl-1,2'-bipyrrole (MBP-78). In addition, two pentachloro-MBPs (P1 and P3) could be traced back to MBP-62 and MBP-69. Cl(6)-MBPs were analyzed in whale blubber from Australia and skua adipose tissue from Antarctica. The marine mammals contained all Cl(6)-MBPs except for the most abundant in the irradiation experiment. The concentrations of the Cl(6)-MBPs amounted to 0.04-1.76% of the concentration of Q1. The highest concentrations of Cl(6)-MBP isomers in the biota samples were found for MBP-76, MBP-77, and MBP-78. These congeners appeared to be the most lipophilic ones owing to the highest retention time in RP-HPLC. Nevertheless, it remained unclear whether the Cl(6)-MBPs were actual halogenated natural products or environmental metabolites of Q1.     

Thermogravimetric desorption and de novo tests I: method development and validation

Thermogravimetric analysis (TGA) has been combined with evolved gas analysis (EGA) with the purpose of simulating the thermal behaviour of filter dust samples under inert (desorption) and de novo test oxidising conditions. Emphasis is on studying de novo formation of dioxins, surrogates and precursors arising from filter dust derived from thermal processes, such as municipal solid waste incineration and metallurgy. A new method is tested for sampling and analysing dioxin surrogates and precursors in the TGA effluent, which are collected on sampling tubes; the adsorbed compounds are eventually desorbed and quantified by TD-GC-MS. The major sources of error and losses are considered, including potential sorbent artefacts, possible breakthrough of volatiles through sampling tubes, or eventual losses of semi-volatiles due to their incomplete desorption or re-condensation inside the TG Analyser. The method is optimised and validated for di- to hexa-chlorinated benzenes in a range of 10-1000ppb with average recovery exceeding 85%. The results are compared with data obtained in similar studies, performed by other research groups. As a result, the method provides the means for simulating de novo synthesis of dioxins in fly-ash and facilitates reliable and easy estimation of de novo activity, comparable with results of other studies, in combination with wide flexibility of testing conditions.     

Fugacity modelling to predict the distribution of organic contaminants in the soil:oil matrix of constructed biopiles

Level I and II fugacity approaches were used to model the environmental distribution of benzene, anthracene, phenanthrene, 1-methylphenanthrene and benzo[a]pyrene in a four phase biopile system, accounting for air, water, mineral soil and non-aqueous phase liquid (oil) phase. The non-aqueous phase liquid (NAPL) and soil phases were the dominant partition media for the contaminants in each biopile and the contaminants differed markedly in their individual fugacities. Comparison of three soils with different percentage of organic carbon (% org C) showed that the % org C influenced contaminant partitioning behaviour. While benzene showed an aqueous concentration worthy of note for leachate control during biopiling, other organic chemicals showed that insignificant amount of chemicals leached into the water, greatly reducing the potential extent of groundwater contamination. Level II fugacity model showed that degradation was the dominant removal process except for benzene. In all three biopile systems, the rate of degradation of benzo(a)pyrene was low, requiring more than 12 years for soil concentrations from a spill of about 25 kg (100 mol) to be reduced to a concentration of 0.001 microgg(-1). The removal time of 1-methylphenanthrene and either anthracene or phenanthrene was about 1 and 3 years, respectively. In contrast, benzene showed the highest degradation rate and was removed after 136 days in all biopile systems. Overall, this study confirms the association of risk critical contaminants with the residual saturation in treated soils and reinforces the importance of accounting for the partitioning behaviour of both NAPL and soil phases during the risk assessment of oil-contaminated sites.     

Microcosm investigations of stormwater pond sediment toxicity to embryonic and larval amphibians: variation in sensitivity among species

Stormwater ponds have become common features of modern development and often represent significant amounts of open space in urbanized areas. Although stormwater ponds may provide habitat for wildlife, factors responsible for producing variation in wildlife use of ponds have received limited attention. To investigate the role of variation in species tolerances of pollutants in structuring pond-breeding amphibian assemblages, we exposed species tolerant (Bufo americanus) and not tolerant (Rana sylvatica) of urbanization to pond sediments in laboratory microcosms. Pond microcosms had elevated sediment metal levels and chloride water concentrations. Among R. sylvatica embryos, exposure to pond sediments resulted in 100% mortality. In contrast, B. americanus embryos and larvae experienced only sublethal effects (i.e., reduced size at metamorphosis) due to pond sediment exposure. Our results suggest variation in pollutant tolerance among early developmental stages of amphibians may act in concert with terrestrial habitat availability to structure amphibian assemblages associated with stormwater ponds.     

Associations between sleep,risk and safety climate: A study of offshore personnel on the Norwegian continental shelf

The demands and constraints of the offshore working environment can have adverse effects on health, particularly the quality of sleep. Perceived risk and safety are significant psychological stress factors which may interfere with and deteriorate the sleep quality of offshore personnel. The present study explores the relationship between risk perception, safety climate and sleep quality. Data were collected under the auspices of the Petroleum Safety Authorities in Norway using a cross-sectional design. A total of 9601 offshore workers from 52 offshore installations on the Norwegian continental shelf participated in the study. Our findings indicate that both risk perception and safety climate are significantly related to sleep quality. The results of the present study suggest that risk perception and safety climate not only are important aspects of safety performance in the offshore industry, but also have an impact on sleep quality.