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.     

Human maternal and umbilical cord blood concentrations of polybrominated diphenyl ethers

Polybrominated diphenyl ethers (PBDEs), widely used as flame retardants in commercial products, have become ubiquitous environmental contaminants. Although adult human exposure to PBDEs is well documented, developmental exposure is less well characterized. The objectives of this study were to measure maternal and fetal exposure to nine PBDE congeners and to investigate potential associations with birth weight. PBDE congeners were quantified in maternal serum at 24-28 weeks of pregnancy, delivery, and umbilical cord serum (UCS) by gas chromatography-mass spectrometry (GC/MS/MS). Complete blood sample sets were obtained from 97 pregnant women (mean age 33.1 ± 0.5 years). PBDE-28, -47 and -99 were quantified in all samples tested and PBDE-47 was the most abundant congener measured in both maternal (mid-pregnancy and delivery samples geometric mean = 26.9 and 26.9, respectively) and UCS (GM = 56.0 ng g⁻¹ lipid). The UCS concentration for all congeners with the exception of PBDE-153 was higher vs. maternal delivery samples (p < 0.001). Only the UCS concentration of PBDE-17 and -99 were significantly associated (β = −49.860, p = 0.032, and β = −3.645, p = 0.05) with birth weight. However, after adjustment for potential confounders only the association between PBDE-99 and birth weight remained significant (β = −3.951 and p = 0.016). We conclude that: the fetus is exposed to PBDEs from at least the second trimester of pregnancy onward; PBDE congeners are higher in UCS compared to maternal serum samples collected at delivery; and that developmental PBDE exposure is potentially associated with lower birth weight.     

Altitudinal distributions of BDE-209 and other polybromodiphenyl ethers in high mountain lakes

The present study shows the occurrence of 2,2′,3,3′,4,4′,5,5′,6,6′-decabromodiphenyl ether (BDE-209) in microbial biofilms of Pyrenean and Tatra high mountain lakes despite its low vapor pressure and high hydrophobicity. Aerosol air transport is therefore a feasible mechanism for BDE-209 accumulation in sites up to 2688 m above sea level. This compound and other PBDEs exhibit altitudinally-dependent distribution involving higher concentrations with increasing mountain lake elevation. However, the apparently very high enthalpies of the concentration gradients observed, including BDE-209, suggest that bacterial anaerobic debromination also plays a significant role in the resulting altitudinal distributions. This microbial mechanism explains the relative abundances of PBDEs and their within lake differences between rocky and sediment microbial biofilms, thereby showing that the altitudinal pattern observed is not purely due to water temperature control on bacterial activity but also to changes in the availability of anaerobic microenvironments which increase with increasing lake productivity at lower altitudes.     

Polybrominated diphenyl ethers in food and associated human daily intake assessment considering bioaccessibility measured by simulated gastrointestinal digestion

The concentrations of PBDEs in 299 vegetable and animal-based food samples of 31 species, collected in Shanghai, China, and the bioaccessibility of PBDEs in part of the samples were determined. The PBDE concentrations ranged from 0 to 1245.4 pg g⁻¹ with animal-based food containing more PBDEs than vegetables. The bioaccessibility of PBDEs, determined by a method simulating human gastrointestinal digestion process, were from 2.6% to 39.9% in vegetables, and from 5.2% to 105.3% in animal-based food. For animal-based food, good correlations were observed between the bioaccessibility of PBDEs and the fat content, thus the fat content in animal-based food was able to be used to estimate the bioaccessibility of PBDEs. The total daily intake of PBDEs via ingestion of vegetables and animal-based food for an average Shanghai resident was estimated as 13 235.7 and 13 668.0 pg d⁻¹, respectively, but the amounts available for human absorption were reduced to 2674.4 and 4316.6 pg d⁻¹ after the PBDE bioaccessibility was considered. Finally, the contributions of different food groups to the total daily intake of PBDEs were evaluated. The results revealed that, when not considering the bioaccessibility of PBDEs, vegetables were the leading contributor (49.2%), followed by fish (34.0%). However, the sequence was reversed after the PBDE bioaccessibility was taken into account. The results indicated that human exposure to PBDEs via food ingestion might have been significantly overestimated and the exposure assessment could be misleading if the bioaccessibility of PBDEs was not considered.     

Polybrominated diphenyl ethers (PBDEs) in soils along a rural-urban-rural transect: sources, concentration gradients, and profiles

This study reports concentrations of PBDEs in surface soil samples collected along a 140 km transect across Kuwait to assess the role of urban centers as sources of persistent organic pollutants to the surrounding environment. The ΣPBDE concentrations varied by a factor of ∼250 and ranged from 289 to 80,078 pg g⁻¹ d.w. The concentrations of PBDEs in Kuwait City were significantly higher (p < 0.01) than those collected from sites outside the city supporting the hypothesis that urban centers are sources of PBDEs. The congener profiles were dominated by BDE-209, accounting for 93% of the PBDEs in the soil samples. The concentrations of all congeners (except BDE-209) were highly correlated with percent organic carbon (%OC) (p > 0.05) when the data from Kuwait City was omitted from the analysis. These findings suggest that soil concentrations outside the urban centers were close to equilibrium with the atmosphere.     

Levels and distribution of polybrominated diphenyl ethers (PBDEs) in the freshwater environment surrounding a PBDE manufacturing plant in China

Polybrominated diphenyl ethers (PBDEs) were determined in muscle, liver and eggs of freshwater fishes and surface sediments from the Nongkang River in Jinhu, Jiangsu Province, China. The present study is the first to report PBDE concentrations in the freshwater environment surrounding a PBDE manufacturing plant in China. The concentrations of 13 PBDE congeners in muscle, liver and eggs of freshwater fishes ranged from <LOD to 130, <LOD to 252 and <LOD to 33.3 ng/g lipid wt, respectively, while the concentrations of 13 PBDE congeners in surface sediments from sewage outfall, upstream and downstream of the river were 52, 9.2, 7.1 ng/g organic carbon wt, respectively. Contamination by PBDEs in this area was not serious when compared with other regions of the world. A relatively high proportion of BDE-183 was found, consistent with the octa-BDE technical mixtures from the manufacturing plant by the side of the river.     

Tri-decabrominated diphenyl ethers and hexabromocyclododecane in indoor air and dust from Stockholm microenvironments 2: indoor sources and human exposure

Data on polybrominated diphenyl ether (PBDE) and hexabromocyclododecane (HBCD) concentrations from Stockholm, Sweden, indoor microenvironments were combined with information from detailed questionnaires regarding the sampling location characteristics, including furnishing and equipment present. These were used to elucidate relationships between possible flame-retarded sources and the contaminant concentrations found in air and dust. Median concentration ranges of ΣPenta-, ΣOcta-, ΣDecaBDE and HBCD from all microenvironments were 19-570, 1.7-280, 29-3200 and < 1.6-2 pg/m³ in air and 22-240, 6.1-80, 330-1400 and 45-340 ng/g in dust, respectively. Significant correlations were found between concentrations of some PBDEs and HBCD in air and/or dust and the presence of electronic/electrical devices, foam furniture, PUF mattresses and synthetic bed pillows in, as well as floor area and construction year of the microenvironment. Car interiors were a source to indoor air in dealership halls. Using median and maximum concentrations of ΣPenta-, ΣOcta-, ΣDecaBDE and HBCD in air and dust, adult and toddler (12-24 months) intakes from inhalation and dust ingestion were estimated. Toddlers had higher estimated intakes of ΣPenta-, ΣDecaBDE and HBCD (7.8, 43, 7.6 ng/d, respectively) from dust ingestion than adults (5.8, 38, 6.0 ng/d, respectively). Air inhalation in offices was also an important exposure pathway for ΣPenta-, ΣOcta- and ΣDecaBDE in adults. For ΣPentaBDE and HBCD, air inhalation and dust ingestion play minor roles when compared to previously published Swedish dietary intakes (median exposures). However, in worst case scenarios using maximum concentrations, dust ingestion may represent 77 and 95% of toddler intake for ΣPentaBDE and HBCD, respectively.     

Fate of PBDEs during food processing: Assessment of formation of mixed chlorinated/brominated diphenyl ethers and brominated dioxins/furans

The aim of this study was to evaluate effects of food processing on PBDE levels, in particular influence of heat treatment on degradation of PBDEs, including possible formation of chlorinated diphenyl ethers or brominated dioxins/furans as degradation products. It was shown that PBDEs heated in the presence of chlorine (from either organic or inorganic sources) formed mixed chlorinated/brominated diphenyl ethers. However, no PCDEs were formed in the presence of lipids. Lipid medium increased stability of PBDEs exposed to UV irradiation. Profile of congeners formed in result of the debromination reaction was significantly different than profiles observed by some other authors in aliphatic organic solvents. Grilling processes increased concentrations (calculated on the fresh product basis) of the studied compounds by 4–8/22–34% for electric/coal grill, respectively. Depending on the congener and on the applied heat treatment, PBDE mass in pork meat after grilling dropped by 26–53%. No detectable quantities of either brominated dioxins or furans were formed during thermal processing of food containing typical levels of PBDEs.     

Teratogenicity of bifenox and nitrofen in rodents

Abstract

The teratogenicity of the diphenyl ether herbicide bifenox [2,4‐dichlorophenyl 3'‐carboxymethyl‐4'‐nitrophenyl ether] was compared to that of nitrofen [2,4‐dichlorophenyl 4'‐nitrophenyl ether] in rats and in mice. Neither compound increased prenatal mortality in mice. Because nitrofen causes both malformations that are compatible with survival to weaning and a high incidence of perinatal (but not of fetal) mortality, emphasis was placed on postnatal parameters of bifenox toxicity. In rats, bifenox caused a low incidence of “bloody tears”;, but it did not decrease survival to term or to weaning in rats or mice, and did not reduce Harderian gland weight in mice. Because the weight of the Harderian glands is a more objective measure of their status than is the presence of an eye discharge, it is concluded that bifenox is not teratogenic at the levels administered. Nitrofen decreased litter size, pup weight, and Harderian gland weight in mice.     

Stable carbon isotope analysis (δ13C values) of polybrominated diphenyl ethers and their UV-transformation products

Polybrominated diphenyl ethers (PBDEs) are frequently detected in food and environmental samples. We used compound specific isotope analysis to determine the δ¹³C values of individual PBDEs in two technical mixtures. Within the same technical product (DE-71 or DE-79), BDE congeners were the more depleted in ¹³C the higher brominated they were. In contrast, the products of light-induced hydrodebromination of BDE 47 and technical DE-79 were more enriched in ¹³C because of more stable bonds between ¹³C and bromine. As a result, the δ¹³C values of the irradiated solution progressed diametrically compared to those of the technical synthesis. The ratio of the δ¹³C values of BDE 47 to BDE 99 and of BDE 99 to BDE 153 are thus suggested as indicators to distinguish native technical products from transformation products. Ratios <1 are typical for native congeners (e.g. in DE-71) while the reversed ratio (>1) is typical of transformation products.