Use Of Polybrominated Diphenyl Ethers Research Articles

Rising concentrations of polybrominated diphenyl ethers (PBDEs) in Nigerian foodstuffs despite global restrictions

The presence of brominated flame retardants (BFRs) in foodstuffs of African origin is poorly understood. To fill this gap, animal-derived food samples comprising 13 different items originally from Nigeria were obtained in 2021, and concentrations of novel brominated flame retardants (NBFRs), polybrominated diphenyl ethers (PBDEs), and hexabromocyclododecane (HBCDD) were measured. Arithmetic mean concentrations of NBFRs, PBDEs, and HBCDD in Nigerian foodstuffs were 2.1 ng/g (18 ng/g lipid weight (lw)), 1.3 ng/g (9.2 ng/g lw), and 0.42 ng/g (2.8 ng/g lw), with median concentrations of 1.7 ng/g (14 ng/g lw), 1.1 ng/g (8.2 ng/g lw), and <0.34 ng/g (<3.3 ng/g lw), respectively. Higher concentrations of NBFRs than of PBDEs and HBCDDs in Nigerian foodstuffs likely reflect use of NBFRs as substitutes for legacy BFRs in Nigeria. Comparison with previous dietary studies reveals rising concentrations of PBDEs in Nigerian foodstuffs in recent years with associated rises in dietary exposure, possibly due to active domestic use of PBDEs in Nigeria. Reassuringly, comparison of our exposure estimates with health-based limit values suggests adverse health effects of dietary intake of BFRs by Nigerians are unlikely to occur.

Alternative and legacy flame retardants in marine mammals from three northern ocean regions

Flame retardants are globally distributed contaminants that have been linked to negative health effects in humans and wildlife. As top predators, marine mammals bioaccumulate flame retardants and other contaminants in their tissues which is one of many human-imposed factors threatening population health. While some flame retardants, such as the polybrominated diphenyl ethers (PBDE), have been banned because of known toxicity and environmental persistence, limited data exist on the presence and distribution of current-use alternative flame retardants in marine mammals from many industrialized and remote regions of the world. Therefore, this study measured 44 legacy and alternative flame retardants in nine marine mammal species from three ocean regions: the Northwest Atlantic, the Arctic, and the Baltic allowing for regional, species, age, body condition, temporal, and tissue comparisons to help understand global patterns. PBDE concentrations were 100–1000 times higher than the alternative brominated flame retardants (altBFRs) and Dechloranes. 2,2′,4,5,5′-pentabromobiphenyl (BB-101) and hexabromobenzene (HBBZ) were the predominant altBFRs, while Dechlorane-602 was the predominant Dechlorane. This manuscript also reports only the second detection of hexachlorocyclopentadienyl-dibromocyclooctane (HCDBCO) in marine mammals. The NW Atlantic had the highest PBDE concentrations followed by the Baltic and Arctic which reflects greater historical use of PBDEs in North America compared to Europe and greater industrialization of North America and Baltic countries compared to the Arctic. Regional patterns for other compounds were more complicated, and there were significant interactions among species, regions, body condition and age class. Lipid-normalized PBDE concentrations in harbor seal liver and blubber were similar, but HBBZ and many Dechloranes had higher concentrations in liver, indicating factors other than lipid dynamics affect the distribution of these compounds. The health implications of contamination by this mixture of compounds are of concern and require further research.

Temporal trends in concentrations of brominated flame retardants in UK foodstuffs suggest active impacts of global phase-out of PBDEs and HBCDD

Global restrictions on use of legacy brominated flame retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDD) have generated demand for novel BFRs (NBFRs) as substitutes. Our research group has previously reported decreased concentrations of PBDEs and HBCDD and increased concentrations of NBFRs in UK indoor environments, suggesting that restrictions on PBDEs and HBCDD are exerting an impact. In this study, we analysed UK foodstuffs collected in 2020–21 and compared the BFR concentrations found with those found in similar samples collected in 2015 to investigate whether similar trends in BFR concentrations would be observed. Concentrations of PBDEs and HBCDD isomers detected in our samples had declined by 78–92 % and 59–97 % since the 2015 study, respectively. Moreover, concentrations of NBFRs (dominated by 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE or TBE), and bis(2-ethyl hexyl) tetrabromophthalate (BEH-TEBP or TBPH)) in UK foodstuffs increased significantly (28–1400 %) between 2015 and 2020–21. Combined, these findings suggest that restrictions on use of PBDEs and HBCDD have had a discernible impact on concentrations of these legacy BFRs and their NBFR replacements in UK foodstuffs. Interestingly, given recent reports of a significant increase in concentrations of decabromodiphenyl ethane (DBDPE) in UK house dust between 2014 and 2019, a significant decline (70–84 %) in concentrations of DBDPE was observed in UK foodstuffs.

The environmental fate of biomass associated polybrominated diphenyl ethers

The widespread use of polybrominated diphenyl ethers (PBDEs) inevitably leads to their occurrence in the atmosphere, soil, and sediment. Biomass, especially dry branches and fallen leaves, may act a large reservoir for PBDEs through atmospheric deposition or soil bioaccumulation. Thus, clarifying the sunlight-induced transformation behaviors of PBDEs on biomass is highly significant for our understanding on its natural self-purification process. In this work, the degradation kinetics and mechanisms of two common PBDEs congeners, decabromodiphenyl ether (BDE-209) and 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47), on biomass were systematically studied under natural and simulated sunlight irradiation conditions. The highest photodegradation rate constant of BDE-209 and BDE-47 was observed on sour cherry (SC) and zoysia matrella (ZM), respectively, which was related to their larger light receiving area and poor crystallinity. Due to the higher apparent quantum efficiency, BDE-209 degrades faster than BDE-47 (0.063–0.223 vs 0.006–0.026 h−1). The sunlight self-purification cycle of BDE-209 and BDE-47 on biomass were 6 and 14 days, respectively, with the corresponding sunlight contribution in the range of 0.12–0.51 ng mW−1. Products analysis by GC-MS and HPLC-MS/MS revealed that the main reactions involved in the photodegradation of BDE-209 and BDE-47 on biomass were debromination, hydroxylation, cyclization, and C–O bond breaking reaction. Especially, it was firstly proposed that hydroxyl H in lignin from biomass participated in the formation of primary products, which were rationalized by density functional theory (DFT) calculations and control experiments.

Insight into phototransformation mechanism and toxicity evolution of novel and legacy brominated flame retardants in water: A comparative analysis

The novel brominated flame retardants (NBFRs) have become widespread as a consequence of the prohibition on the use of polybrominated diphenyl ethers (PBDEs). However, the transformation mechanism and potential environmental risk are largely unclear. In this study, we have explored the phototransformation behavior of the most abundant NBFRs, 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) in water under ultraviolet (UV) irradiation. Meanwhile, the legacy 2,2′,4,4′,6,6′-hexabromodiphenyl ether (BDE155) with similar structure was investigated contrastively. Results show that novel BTBPE is more persistent than legacy BDE155, with nearly four times slower photodegradation rate constants (0.0120 min−1and 0.0447 min−1, respectively). 18 products are identified in the phototransformation of BTBPE. Different from the only debrominated products formed in legacy BDE155 transformation, the ether bond cleavage photoproducts (e.g. bromophenols) are also identified in novel BTBPE transformation. Compound-specific stable isotope analysis (CSIA) confirms the phototransformation mechanism is mainly via debromination accompanying with the breaking of ether bond. Computational toxicity assessment implies that transformation products of BTBPE still have the high kidney risks. Especially the bromophenols formed via the ether bond cleavage could significantly increase the health effects on skin irritation. This study emphasizes the importance of understanding the photolytic behavior and potential risks of novel NBFRs and other structurally similar analogues.

Bone developmental toxicity of organophosphorus flame retardants TDCIPP and TPhP in marine medaka Oryzias melastigma

The global phase-out has decreased the use of polybrominated diphenyl ethers (PBDEs), thereby, rapidly increasing the production and use of their important surrogates, organophosphorus flame retardants (OPFRs). Currently, OPFRs are often found at higher levels in the environments compared to PBDEs. Although the two typical OPFRs, tris (1,3-dichloroisopropyl) phosphate (TDCIPP) and triphenyl phosphate (TPhP), have been frequently detected in marine environments with significant concentrations, their toxicity to marine organisms remains unknown. We used Oryzias melastigma to investigate and compare their developmental toxicity in marine organisms through two-generational chronic exposure. The results showed that TDCIPP and TPhP exposure shortened the body length and length of the pectoral fin of O. melastigma. Both TDCIPP and TPhP deformed the pectoral fins in the 1st fry and caused spinal curvature in adult fish. Therefore, these two chemicals may pose potential risks to marine fish and marine ecosystems. Further studies suggested that although these two chemicals caused similar developmental bone toxicity, they had different modes of modulating the expression of bone developmental genes such as, bmp4, bmp2 and runx2.

Long-term effects of decabromodiphenyl ether on denitrification in eutrophic lake sediments: Different sensitivity of six-type denitrifying bacteria

The widespread use of polybrominated diphenyl ethers inevitably results in their increased release into natural waters and subsequent deposition in sediments. However, their long-term effects on the bacteria participating in each step of denitrification in eutrophic lake sediments are still unknown. Here, we conducted a one-year microcosm experiment to determine the long-term effects of decabromodiphenyl ether (BDE-209), at low (2 mg kg−1 dry weight) and high (20 mg kg−1 dry weight) contamination levels, on six-type denitrifying bacteria and their activities in sediments collected from Taihu Lake, a typical eutrophic lake in China. At the end of the experiment, sediment denitrifying reductase activities were inhibited by BDE-209 at both levels, with the greatest inhibition seen for nitric oxide reductase activity. The higher nitrate concentration in the contaminated sediments was attributed to the inhibition of nitrate reductase activities. The abundances of six-type denitrifying genes (narG, napA, nirK, nirS, norB, and nosZ) significantly decreased under high BDE-209 treatment, and narG and napA genes were more sensitive to the toxicity of BDE-209. The results from pyrosequencing showed that BDE-209, at either treatment concentration, decreased the six-type denitrifying bacterial diversities and altered their community composition. This shift of six-type denitrifying bacterial communities might also be driven by the debrominated products concentrations of BDE-209 and variations in sediment inorganic nitrogen concentrations. In particular, some genera from phylum Proteobacteria such as Pseudomonas, Cupriavidus, and Azoarcus were decreased significantly because of BDE-209 and its debrominated products.

Temporal trends in radiometrically dated sediment cores from English lakes show polybrominated diphenyl ethers correlate with brominated but not mixed bromo/chloro dioxins and furans

This paper reports concentrations between ~1950 and present, of polybrominated diphenyl ethers (PBDEs) and polybrominated dibenzo-p-dioxins and furans (PBDD/Fs), in radiometrically-dated sediment cores from three English lakes. Mixed bromo/chloro dibenzo-p-dioxins and furans (PXDD/Fs) were measured in two of the same lakes. Concentrations of PXDD/Fs decreased over time to the present. To our knowledge, this is the first report of temporal trends of PXDD/Fs in the environment. In contrast, concentrations of PBDEs increased towards the present and were significantly correlated (R = 0.88–0.98; p < 0.05) with concentrations of PBDFs in all three lakes. These observations suggest that the sources of PXDD/Fs are not related to PBDEs and differ from those of PBDFs. We also report for the first time the presence of octabromodibenzofuran (OBDF) in the two most recent core slices at one lake. The source of OBDF in these samples is unclear. While OBDF has been reported previously as a significant contaminant of some commercial formulations of Deca-BDE, it is also present in Octa-BDE products and in emissions from a variety of combustion activities. Overall, while the positive correlation between PBDEs and PBDFs suggests increased use of PBDEs has contributed substantially to environmental contamination with PBDFs; examination of PBDF homologue patterns implies emissions from combustion activities are likely also important.

Temporal trends in concentrations of legacy and novel brominated flame retardants in house dust from Birmingham in the United Kingdom

Concentrations of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCDD), tetrabromobisphenol-A (TBBPA) and two potential replacements decabromodiphenylethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) were measured in dust samples collected from 14 homes across Birmingham (UK). Concentrations were compared with those from the same city in previous studies to ascertain any temporal changes and to assess the effects of legislative restrictions. The average ∑HBCDDs concentration (46,000 ng/g; median = 280 ng/g) included the highest dust concentration recorded globally (570,000 ng/g). This is despite the listing of HBCDD under the Stockholm Convention in 2013, demonstrating that decreases in indoor contamination will likely be slow as existing sources are gradually discarded. In contrast, concentrations of BDE-47 (mean = 5.7 ng/g; median = 0.93 ng/g) and BDE-99 (mean = 11 ng/g; median = 2.9 ng/g) were significantly lower than in all previous (p < 0.01) studies in the same city since 2006, suggesting restrictions on the Penta-BDE formulation have been effective. The average BDE-209 concentration (4800 ng/g; median = 1600 ng/g) is lower than the peak average concentration, which was observed in 2007 (280,000 ng/g), however this is not a significant decline, probably due to the later imposition of Deca-BDE restrictions compared to those on Penta-BDE. Decreases in PBDE concentrations have coincided with a significant (p < 0.01) increase in DBDPE concentrations (average = 1500 ng/g; median = 660 ng/g) since 2014, suggesting its use as a replacement flame retardant for Deca-BDE. While no significant change was detected for BTBPE (average 11 ng/g; median = 0.84 ng/g in this study); concentrations of TBBPA (average = 34 ng/g; median = 35 ng/g) were significantly lower (p < 0.05) than in 2007 (average 62 ng/g). The decreases observed in PBDE concentrations, demonstrates that legislation has been effective in reducing the commercial use of PBDEs, however this has coincided with increases of alternative flame retardants such as DBDPE.

Clarifying Temporal Trend Variability in Human Biomonitoring of Polybrominated Diphenyl Ethers through Mechanistic Modeling.

Human biomonitoring data collected from individuals of the same age sampled in different years provide within-age temporal trends, which are often employed to evaluate the effectiveness of chemical regulatory policies. For polybrominated diphenyl ethers (PBDEs), this within-age temporal trend has been observed to vary between congeners and age groups. We systematically explore the mechanisms responsible for such variability through simulating human exposure via multiple exposure pathways to PBDEs released from multiple lifecycle stages. Our simulation indicates that, after new use of PBDEs is banned, emissions to the outdoor environment from use and waste disposal outlast those to the indoor environment from the indoor use phase, leading to slower decline rates in the contamination of food items sourced from the outdoor environment than that from indoors. Compared with indoor exposure pathways, the consumption of contaminated food contributes more to the exposure (i) to more hydrophobic, recalcitrant congeners, and (ii) of adults than children, which results in slower rates of decline in the within-age temporal trend of those congeners and in adults. The within-age temporal trend is influenced to a lesser extent by the elimination of PBDEs from the human body, e.g., differences in biotransformation potential of congeners, growth dilution, and pre- and postnatal exposures by children.

Organophosphate Ester Flame Retardants: Are They a Regrettable Substitution for Polybrominated Diphenyl Ethers?

As the use of polybrominated diphenyl ethers (PBDEs), and the entire class of organohalogen flame retardants, is declining, the use of organophosphate esters flame retardants (OPFRs) is increasing. In this paper, we ask whether OPFRs are a better choice than PBDEs. To address this question, we compared OPFRs with PBDEs for a wide range of properties. OPFRs exposure is ubiquitous in people and in outdoor and indoor environments, and are now often found at higher levels compared to PBDE peak exposure levels. Furthermore, data from toxicity testing, epidemiological studies, and risk assessments all suggest that there are health concerns at current exposure levels for both halogenated and non-halogenated OPFRs. Obtaining the scientific evidence needed for regulation of OPFRs can take many years. Given the large number of OPFRs in use, manufacturers can move towards healthier and safer products by developing innovative ways to reduce fire hazard for electronics enclosures, upholstered furniture, building materials and other consumer products without adding flame retardant chemicals.

Prioritization of Flame Retardants for Human Risk Evaluation Based on Population Levels and Toxicity

Due to flammability standards, flame retardants (FRs) are widely used in consumer products and building materials. International restrictions on the use of polybrominated diphenyl ethers (PBDEs) ha...

Effects of tris(1-chloro-2-propyl)phosphate and tris(2-chloroethyl)phosphate on cell viability and morphological changes in peripheral blood mononuclear cells (in vitro study).

Organophosphorus flame retardants (OPFRs) are a group of chemicals widely used in various everyday use products. Tris(2-chloroethyl)phosphate (TCEP) and tris(1-chloro-2-propyl)phosphate (TCPP) are one of the commonly used chemicals belonging to this group. Due to the need of limitation of the use of polybrominated diphenyl ethers (PBDEs) as retardants, the share of the compounds tested in our experiments in chemicals production systematically increases. There is limited information about the influence of halogenated OPFRs on living cells, especially on the immune system cells. That is why the aim of this study was to assess the impact of TCEP and TCPP on viability and morphological alterations of human peripheral blood mononuclear cells (PBMCs). The cells were incubated with selected flame retardants in the concentrations ranging from 0.001 to 1 mM for 24 h. It was found that TCEP at 1 mM and TCPP at 0.5 mM decreased viability of PBMCs, while only TCPP induced morphological alterations in the incubated cells. The results of our experiments suggest that TCPP is more cytotoxic than TCEP, which can be explained by the presence of methyl groups in the molecule of this compound. Similar to other studies, our data also suggest that OPFRs are suitable replacements for PBDEs.

Harmful flame retardant found in electronic cigarette aerosol

Studies on the health impact of vaping so far have largely ignored the fact that electronic cigarette (e-cigarette) is essentially an electronic product which is likely to contain a group of endocrine disrupting flame retardants, namely, polybrominated diphenyl ethers (PBDEs) as additives in the combustible components of the product. Thus, the conclusion that e-cigarette is less harmful to health than tobacco smoking may be based on incomplete information. This study reports moderate to elevated levels of PBDEs in 5 out of the 13 samples of e-cigarettes. This finding is suggestive of the continued use of PBDEs in the manufacturing of e-cigarette atomizers and the associated protective casing. This study is unique as it confirms the existence of this developmental neurotoxicant in e-cigarette aerosols. In view of the significant levels of PBDEs and other known carcinogens (polycyclic aromatic hydrocarbons and formaldehydes) in e-cigarette aerosol, there is an urgent need for conducting a thorough review of the health risks of vaping by relevant professionals. A further lesson learnt from this study is that policy makers and relevant product manufacturers should be aware of the possible presence of PBDEs in the aerosol of body care and medical electrical devices such as face steamers, inhalators and nebulizers, especially when PBDEs are utilized in the combustible components of these devices.

Oxidation reactivity of 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) by Compound I model of cytochrome P450s

Alternative brominated flame retardants (BFRs) have become prevalent as a consequence of restrictions on the use of polybrominated diphenyl ethers (PBDEs). For risk assessment of these alternatives, knowledge of their metabolism via cytochrome P450 enzymes is needed. We have previously proved that density functional theory (DFT) is able to predict the metabolism of PBDEs by revealing the molecular mechanisms. In the current study, the reactivity of 1,2-bis(2,4,6-tribromophenoxy)ethane and structurally similar chemicals with the Compound I model representing the active site of P450 enzymes was investigated. The DFT calculations delineated reaction pathways which lead to reasonable explanations for products that were detected by wet experiments, meanwhile intermediates which cannot be determined were also proposed. Results showed that alkyl hydrogen abstraction will lead to bis(2,4,6-tribromophenoxy)ethanol, which may undergo hydrolysis yielding 2,4,6-tribromophenol, a neurotoxic compound. In addition, a general pattern of oxidation reactivity regarding the 2,4,6-tribromophenyl moiety was observed among several model compounds. Our study has provided insights for convenient evaluation of the metabolism of other structurally similar BFRs.

Emerging and legacy flame retardants in UK human milk and food suggest slow response to restrictions on use of PBDEs and HBCDD

The legacy flame retardants (LFRs) polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDD), together with six emerging flame retardants (EFRs) were measured in United Kingdom (UK) human milk collected in 2010 (n=25) and 2014–15 (n=10). These data are the first report of the presence of EFRs in UK human milk. The most abundant EFR was β-tetrabromoethylcyclohexane (DBE-DBCH) (average=2.5ng/g lw; geometric mean=1.5ng/g lw), which is comparable to the concentrations of the most abundant LFRs i.e. BDE 47 and α-HBCDD at 2.8 and 2.1ng/g lw, respectively (geometric mean=2.1 and 1.7). The estimated median dietary intake of ΣEFRs by UK nursing infants was 18ng/kg bw/day. EFRs were also measured in UK foodstuffs with β-DBE-DBCH again the predominant compound detected, accounting – on average – for 64.5±23.4% of ΣEFRs. Average estimated dietary intakes of ∑EFRs in the UK were 89 and 26ng/day (1.3 and 2.6ng/body weight/day) for adults and toddlers, respectively. Concentrations of Σtri-hexa BDEs in our UK food samples exceeded those reported in UK samples from the same food categories collected in 2003–04 and 2006. Despite this and our recent report elsewhere of significant temporal declines in concentrations of BDE 209 in UK indoor dust (p<0.05) and HBCDDs in UK indoor dust and air (p<0.001), no significant temporal differences (p>0.05) were observed between concentrations of Σtri-hexa BDEs, BDE 209 and HBCDDs in human milk sampled in 2010 and those obtained in 2014–15. UK adult body burdens for EFRs were predicted via inhalation, diet and dust ingestion using a simple pharmacokinetic model. The predicted EFR body burdens compared well with observed concentrations in human milk.

Impairment in the mesohippocampal dopamine circuit following exposure to the brominated flame retardant, HBCDD.

Many chemicals have been used to increase the safety of consumer products by reducing their flammability and risk for ignition. Recent focus on brominated flame retardants, such as polybrominated diphenyl ethers (PBDEs) has shown them to contribute to neurobehavioral deficits in children, including learning and memory. As the manufacture and use of PBDEs have been reduced, replacement chemicals, such as hexabromocyclododecane (HBCDD) have been substituted. Our current study evaluated the neurotoxicity of HBCDD, concentrating on dopaminergic innervation to the hippocampus. Using an in vivo model, we exposed male mice to HBCDD and then assessed alterations to the dopamine synapse 6 weeks later. These exposures elicited significant reductions in presynaptic dopaminergic proteins, including TH, COMT, MAO-B, DAT, VMAT2, and alpha-synuclein. In contrast, postsynaptic dopamine receptors were not impaired. These findings suggest that the mesohippocampal dopamine circuit is vulnerable to HBCDD and the dopamine terminal may be a selective target for alteration.

A Biotin-streptavidin-enhanced Carbon Nanotube Amplification Strategy for an Ultrasensitive Immunodetection of Polybrominated Diphenyl Ethers.

The extensive use of polybrominated diphenyl ethers (PBDEs) has resulted in its increasingly widespread presence. Especially the lower halogenated PBDEs accumulate to a greater degree than the higher halogenated PBDEs in house dust, sewage sludge, pets, or even humans. In the present work, we developed an ultrasensitive biotin-streptavidin-enhanced carbon nanotube amplification strategy for the immunodetection of PBDEs, in which single-walled carbon nanotubes were used to immobilize numerous streptavidin. Meanwhile, we used biotin conjugated horseradish peroxidase (B-HRP) and biotin conjugated Goat anti-rabbit (B-IgG) to link the HRP and IgG to CNTs by using a biotin-streptavidin system. The sensitivity of the streptavidin-biotin-IgG-CNTs-HRP bioconjugate was compared with a commercial HRP-labelled IgG by using indirect competitive ELISA. The limit of this proposed ELISA detection (IC10) was 0.0059 ng/mL, showing a 20-time lower detection limit over the commercial one (IC10 = 0.1193 ng/mL). Finally, we applied the assay to the detection of PBDEs in dust samples. The results were consistent with those using GC-ECD, which confirmed that the proposed amplification strategy was accurate and receptive. This proposed biotin-streptavidin-enhanced carbon nanotube amplification strategy would be useful for ultrasensitive immunodetection in environmental studies.

Long-term exposure to triphenylphosphate alters hormone balance and HPG, HPI, and HPT gene expression in zebrafish (Danio rerio).

With the global decline in the use of polybrominated diphenyl ethers, the demand for alternative flame retardants, such as triphenylphosphate (TPP), has increased substantially. Triphenylphosphate is now detected in various environments including aquatic ecosystems worldwide. However, studies on the toxicological consequences of chronic TPP exposure on aquatic organisms are scarce. The zebrafish model was used to investigate the effects of long-term TPP exposure on the endocrine system. Zebrafish embryos were exposed to 5 µg/L, 50 µg/L, or 500 µg/L TPP for 120 d, and hormonal and transcriptional responses were measured along the hypothalamic-pituitary-gonad (HPG) axis, the hypothalamic-pituitary-interrenal (HPI) axis, and the hypothalamic-pituitary-thyroid (HPT) axis. Exposure to TPP significantly increased plasma 17β-estradiol, but decreased 11-ketotestosterone in both sexes. Gene expression data support these changes. In the HPI axis, plasma cortisol and proopiomelanocortin (pomc) and mineralocorticoid receptor transcripts increased in females, but in males cortisol decreased whereas pomc increased (p < 0.05). Thyroxine and triiodothyronine increased, and thyrotrophin-releasing hormone receptor 2 (trhr2) and trh expression were affected only in females (p < 0.05). In summary, long-term exposure to TPP enhanced estrogenicity in both males and females, potentially through influencing the HPG axis, but modulated the HPI, and HPT axes differently by sex, suggesting that both genomic and nongenomic responses might be involved. Environ Toxicol Chem 2016;35:2288-2296. © 2016 SETAC.

Probing the debromination of the flame retardant decabromodiphenyl ether in sediments of a boreal lake.

After decades of use of polybrominated diphenyl ethers (PBDEs) as flame retardants, a large reservoir of these toxins has accumulated in ecosystems worldwide. The present study used an innovative approach to examine whether the fully brominated PBDE decabromodiphenyl ether (decaBDE) degrades to more toxic congeners in aquatic environments. The authors incubated intact sediment microcosms with high-purity [(13)C]decaBDE in a remote boreal lake to assess its debromination under ambient conditions. Although the addition of [(13)C]decaBDE increased total PBDE concentrations in sediment more than 10-fold, the relative amount of [(13)C]decaBDE in sediment did not change significantly over a 1-mo incubation. However, observation of small quantities of lower-brominated [(13)C]BDEs lent support to the hypothesis that decaBDE is slowly debrominated. The authors observed a significant increase in octaBDEs and nonaBDEs in profundal, but not littoral, sediment over 30 d. A second experiment in which sediment was incubated under different light and oxygen regimes yielded a surprising result-oxygen significantly stimulated the formation of octaBDEs and nonaBDEs. The authors also conducted a large-scale in situ enclosure experiment in which they followed the fate of experimentally added decaBDE in sediment over 26 mo, but that study yielded little evidence of decaBDE debromination. Overall, the authors suggest that the debromination of decaBDE occurs very slowly, if at all, in natural sediment of boreal lakes, in contrast to the rapid degradation kinetics reported by most laboratory-based studies, which are usually conducted by dissolving decaBDE in organic solvents. The findings reinforce the need for field studies on contaminant fate to inform environmental policy decisions.