BDE-209 Research Articles

Transcriptomic data from the rat liver after five days of exposure to legacy or emerging brominated flame retardants.

Large-scale gene expression analysis of legacy* and emerging** brominated flame retardants were conducted in the male Harlan Sprague Dawley rat [1]. Each animal was dosed for 5 days with the chemical at concentrations of 0.1 – 1000 μmol/kg body weight per day. Following the last dose, a specimen of the left liver was removed for RNA extraction. The amplified RNA (aRNA) was fragmented and then hybridized to Affymetrix Rat Genome 230 2.0 Arrays. Each GeneChip® array was scanned using an Affymetrix GeneChip® Scanner 3000 7 G to generate raw expression level data (.CEL files). Statistical contrasts were used to find pairwise gene expression differences between the control group and each dose group using the R/maanova package [2]. The transcriptomic data can be used to provide insights into the degree of toxicity, toxic mechanisms, disease pathways activated by exposure, and for benchmark dose analysis. The gene expression data for each of the nine flame retardants discussed here accompanies the research article entitled, “Comparative Toxicity and Liver Transcriptomics of Legacy and Emerging Brominated Flame Retardants following 5-Day Exposure in the Rat” [1].* polybrominated diphenyl ether 47 (PBDE 47), decabromodiphenyl ether (decaBDE), hexabromocyclododecane (HBCD); ** 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB); bis(2-ethylhexyl) tetrabromophthalate (TBPH); tetrabromobisphenol A-bis(2,3-dibromopropyl ether (TBBPA-DBPE); 1,2-bis(tribromophenoxy)ethane (BTBPE); decabromodiphenylethane (DBDPE); hexachlorocyclopentadienyl-dibromocyclooctane (HCDBCO).

Proton-dependent photocatalytic dehalogenation activities caused by oxygen vacancies of In2O3

Increasing number of evidences has proved that the oxygen vacancies played a key role in the photocatalytic reactions. However, traditional theories for oxygen vacancies to participate in the reactions mainly focused on its accompanying enhanced trapping capability of photo-induced electrons. In this work, by turning the amounts of oxygen vacancies in In2O3 photocatalysts, it was found that the photocatalytic dehalogenation of decabromodiphenyl ether and hexabromobenzene by In2O3 was also strongly dependent on the enhanced trapping of protons caused by the oxygen vacancies. Through a series of characterizations and measurements, the photo-induced electrons and protons were proved to be simultaneously trapped and confirmed to be determined by the concentration of oxygen vacancies. Moreover, the kinetic isotope studies investigated the proton coupled electron transfer (PCET) pathway in the photocatalytic dehalogenation reactions of In2O3. Protons transfer was demonstrated to be existed in the rate-determining step of the whole photocatalytic reaction. The enhanced concentration of oxygen vacancies resulted in the superior trapping capability of photo-induced electrons and protons, simultaneously promoted the transfer efficiency of protons and electrons, accelerated the separation of photo-reduced carriers and finally improved the photocatalytic activities of In2O3 in the PCET reactions.

Brominated flame retardants (BFRs) in Western Australian biosolids and implications for land application

This study evaluates the prevalence of eight priority polybrominated diphenyl ethers (PBDEs; −28, −47, −99, −100, −153, −154, −183 and −209) and six novel brominated flame retardants (NBFRs; pentabromotoluene (PBT), pentabromoethylbenzene (PBEB), hexabromobenzene (HBB), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) and decabromodiphenyl ethane (DBDPE)) in biosolids samples from 15 wastewater treatment plants (WWTPs) in Western Australia. Analytes were extracted using selective pressurized liquid extraction (S-PLE) and quantified by gas chromatography coupled to tandem mass spectrometry (GC-MS/MS) operated in electron impact (EI) ionization mode. ∑8PBDE levels in biosolids ranged from 11 to 18,000 μg/kg dw with a median concentration of 1800 μg/kg dw. BDE-209 was the most prevalent congener constituting a median of 98% of ∑8PBDE concentrations in samples with BDE-99, -47 and −100 each typically contributing less than 3% to total levels. NBFRs were detected in 71% of samples with ∑6NBFR levels ranging between ND-1100 μg/kg dw (median; 600 μg/kg dw). Levels of DBDPE greatly exceeded those of all other NBFRs, while the next most prevalent compounds were EH-TBB and HBB. Australia produced approximately 327,000 dry tonnes of biosolids in 2017, of which approximately 75% was beneficially utilized on farmland as a fertilizer. Based on these results, an estimated 440 kg of BDE-209 and 150 kg of DBDPE are applied to agricultural land via biosolids applications annually in Australia. This study provides the first account of NBFR concentrations in Australian biosolids.

Effects of Decabromodiphenyl Ether and Elevated Carbon Dioxide on Rice (Oryza sativa L.).

We assessed the effects of carbon dioxide (CO2) and decabromodiphenyl ether (BDE-209, 0, 3 and 30 mg/kg) on rice (Oryza sativa L. cv. Wuyunjing) in field free-air CO2 enrichment system. Rice at elevated (580 ppm) CO2 had increased net photosynthetic rate, intercellular CO2 concentration, shoot biomass, yield and phosphorus content in grains. However, there were no significant changes in such parameters observed on rice at elevated CO2 combined with BDE-209 (3 and 30 mg/kg). Elevated CO2 alone had no significant effects on sugar or starch content in rice grains, whereas its combination with BDE-209 (3 mg/kg) significantly decreased grain sugar and starch content. In conclusion, rice reared in soil polluted by BDE-209 under elevated CO2 modulates the effects in grain feature.

Oral exposure to BDE-209 modulates metastatic spread of melanoma in C57BL/6 mice inoculated with B16–F10 cells

Polybrominated diphenyl ethers (PBDEs) are brominated, persistent and bioaccumulative flame retardants widely used in the manufacture of plastic products. Decabromodiphenyl ether (BDE-209) is the most prevalent PBDE in the atmosphere and found in human blood, breast milk and umbilical cord. In vitro studies showed that BDE-209 interferes with murine melanoma cells (B16F10), modulating cell death rates, proliferation and migration, important events for cancer progression. In order to evaluate if BDE-209 modulates metastasis formation in murine models, C57BL/6 mice were exposed to BDE-209 (0.08, 0.8 and 8 μg⁄kg) via gavage (5-day intervals for 45 days) (9 doses in total). Then, mice were inoculated with melanoma cells (B16–F10) at caudal vein receiving 4 additional doses of BDE-209. At 20th day post-cell inoculation, blood, lung, liver, kidney and brain were sampled for hematological, biochemical and morphological analyses. The slightly higher levels of alanine aminotransferase (ALT) and aspartate aminotransferase (AST) in the blood and pro-oxidant state in the liver of BDE-exposed mice indicated liver damage. Although the in vivo approach is for metastasis formation in the lung, they were unexpectedly observed in non-target organs (liver, brain, kidney and gonads). The similarity test showed high proximity among individuals from the control and a dissimilarity index between the control and exposed groups. The present data corroborate the known hepatotoxicity of BDE-209 to mice (C57BL/6) and demonstrate for the first time the increase of metastatic dissemination of B16F10 cells in vivo due to previous and continuous BDE-209 exposure, revealing possible implications of this organic compound with melanoma malignancy related traits.

A noninvasive environmental monitoring tool for brominated flame-retardants (BFRs) assisted by conservation detection dogs

Fecal matter is a useful noninvasive/nondestructive media for evaluating contaminants in wildlife, as residues therein have been observed to correlate with body burdens. Conservation detection dog-handler teams can be used to optimize the acquisition of fecal samples. To build on previous work, sentinel-species’ (i.e. mink (Mustela vison) and otter (Lontra canadensis)) fecal matter was opportunistically located by a detection dog team along the tri-river system of Missoula, Montana, USA. Sediments were also collected. Samples were used to develop an analytical method from fecal matter to determine habitat exposure to the brominated flame-retardants (BFRs): polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCDD), 2-ethylhexyl 2, 3, 4, 5-tetrabromobenzoate (EH-TBB), di (2-ethylhexyl)-2, 3, 4, 5-tetrabromophthalate (BEH-TEBP) and decabromodiphenyl ethane (DBDPE). Sediments contained PBDEs (BDE-99 and BDE-209) and EH-TBB at detection rates of 67%, 33% and 67%, respectively. BDE-99, -209 and EH-TBB were also detected in mink and otter feces, at rates of 81%, 25% and 81%, respectively; plus BEH-TEBP at 13%. BFR levels correlated positively with human population density except along the lower Bitterroot River, where BDE-209 sediment and feces levels exceeded other sites by several orders of magnitude. Fecal matter body burden estimates indicated marginal PBDE exposure. However, exposure to their replacements, EH-TBB and BEH-TEBP, were at levels that may adversely affect healthy Mustelidae populations. Proof-of-concept was achieved; validation results were within established standards for the development of analytical methods. The established application of conservation dog-handler teams to facilitate the collection of fecal matter for BFR analysis represents a valuable, but currently underutilized environmental monitoring tool.

Legacy and novel halogenated flame retardants in seawater and atmosphere of the Bohai Sea: Spatial trends, seasonal variations, and influencing factors

Seventeen halogenated flame retardants (HFRs) were concurrently analyzed in surface seawater and low atmospheric samples from the Bohai Sea during four research cruises. HFRs mainly existed in particulate phases, and in general decabromodiphenyl ethane (DBDPE) was the predominant compound in both air and water samples. Relatively high concentrations were observed in the water of Laizhou Bay (LB), where the largest manufacturing base of brominated flame retardants (BFRs) in China is located and weak water exchange occurs. Transport from LB by coastal currents may be the main source of BFRs in some areas without emission sources. The HFRs in seawater exhibited distinct seasonal variation, with significantly higher concentrations in winter than those in summer. The controlling factors include the resuspension of sediment induced by large wind waves in winter and phytoplankton scavenging in spring and seawater stratification in summer. HFRs composition varied largely in different seasons, due to the different extents of riverine input and atmospheric deposition. Normally, for air masses passing through the nearby industrial regions, high concentrations of DBDPE (up to 1780 pg m−3) co-existed with high total suspended particle (TSP) levels (up to 150 μg m−3). The estimated atmospheric deposition fluxes of HFRs were 19, 51, and 80 kg season−1 in spring, summer, and winter, respectively, indicating that the Bohai Sea is a sink of HFRs via atmospheric deposition. This study has increased our understanding of the behaviors and fates of the legacy and novel HFRs in the shallow coastal sea.

Full-scale evaluation of reversed A2/O process for removal of multiple pollutants in sewage

This study evaluated the removal of multiple pollutants, i.e., polybrominated diphenyl ethers (PBDEs), novel halogenated flame retardants (HFRs), sulfonamide antibiotics (SAs), and heavy metals (HMs), by a full-scale reversed A2/O process in a sewage treatment plant (STP) in Guangzhou, China. The reversed A2/O process demonstrated high removal efficiencies (REs) for total PBDEs (60.5% ± 4.3%), novel HFRs (98.4% ± 2.8%) and HMs (70.1% ± 1.2%), and a relatively low RE for SAs (25.0% ± 2.3%). BDE 209, the dominant PBDE congener, showed a high residual concentration (13.41 ± 5.18 ng/L) in the suspended particulate matter (SPM) of treated effluents. Some novel HFRs, dechlorane plus (DP) and decabromodiphenyl ethane (DBDPE), were detected in the SPM of the raw sewage (7.50 ± 4.14 ng/L and 11.52 ± 11.65 ng/L, respectively). The removal of SAs was mainly through biodegradation in the activated sludge bioreactors (ASBs). Of the HMs, Mn and Ni exhibited the lowest REs (47.5% ± 2.2% and 35.0% ± 2.6%, respectively), while Cr and Cu showed the highest removal (REs > 80%). In terms of treatment units in the reversed A2/O process, ASBs showed the highest RE (27.8%) for the multiple pollutants. The information can aid in our understanding of removal properties of STPs on various pollutants and evaluating the ecological/health risks of STPs as point pollutant sources

Desorbing of decabromodiphenyl ether in low permeability soil and the remediation potential of enhanced electrokinetic

In this study, desorption kinetic was determined for decabromodiphenyl ether (BDE209) in a low permeability soil, and the remediation potential of hydroxypropyl-β-cyclodextrin (HPCD) enhanced electrokinetic (EK) technique was investigated. The results indicated that the release rate of BDE209 in slowly and very slowly desorbing process was accounted for 31% and 68% in the whole desorption process, respectively. The final desorption rate of BDE209 was 20.7% after 70 h treatment with 5% HPCD in an ideal solution reaction system (without electric field). However, the removal efficiency of BDE209 in section S5 (near anode) of EK1 and EK2 had reached 22% and 20% after 14 days treatment, respectively. Thus it can be assumed that the interaction between BDE209 (on soil particles) and HPCD had been promoted under the electric field. A higher cumulative EOF did not remove more BDE209 with HPCD as facilitating agent, which might due to the low viscosity of HPCD and it did not react completely with BDE209 in soils. In addition, the removal efficiency of BDE209 in section S5 of CK1 and CK2 (without HPCD) had reached 6% and 10%, respectively, which might attribute to the desorption promoting effect of the uniform electric field on hydrophobic organic contaminants. In summary, it is feasible to use the EK to remove BDE209 in low permeability soils using HPCD as solubilizing agent, and the technique key is maintaining sufficient EOF and ensuring the contact reaction efficiency between HPCD and BDE209 synchronously.

Occurrence of Halogenated and Organophosphate Flame Retardants in Sediments and Eels (Anguilla anguilla) From Bizerte Lagoon, Tunisia

Contamination by classic (polybromodiphenyl ethers, PBDEs) and emerging halogenated flame retardants (HFRs) like pentabromobenzene (PBEB), hexabromobenzene (HBB), decabromodiphenyl ethane (DBDPE ) and halogenated norbornenes (HNs), as well as organophosphate flame retardants (OPFRs) were investigated in sediment and eel (Anguilla Anguilla) samples from Bizerte Lagoon, northern Tunisia. This is the first time that OPFR levels have been reported in this area, showing higher concentrations than HFRs: from 9.77 to 164 ng/g dry weight (dw) and from 19.7 to 2154 ng/g lipid weight (lw) for sediment and eel samples, respectively. As regards HFRs, concentrations ranged from 3.30 to 28.5 ng/g dw in sediments and from 4.72 to 151 ng/g lw in eels. The relationship between OPFR and HFR concentrations in sediment and total organic content (TOC) was examined. Results suggested that OPFR levels were significantly correlated with TOC, whereas no correlation was found for HFRs and TOC. The study of potential health risks by eel consumption suggested that there is no significant human health risk associated with the dietary intakes for PBDEs.

Exploring the environmental fate of novel brominated flame retardants in a sediment-water-mudsnail system: Enrichment, removal, metabolism and structural damage

Novel brominated flame retardants (NBFRs) are now ubiquitous in the environment with the extensive production and application. In the present study, pentabromotoluene (PBT), hexabromobenzene (HBB) and decabromodiphenyl ethane (DBDPE) were spiked into the sediments where mudsnails (Bellamya aeruginosa) were cultivated. In the 35-day enrichment process, the highest concentration of the three NBFRs measured in mudsnail is 2.0 mg/kg, 22 mg/kg and 5.2 mg/kg dry weight (dw), respectively. The average enrichment of NBFRs in viscera was about 3 times of pleopod with the same mass. Meanwhile, the parent mudsnails can transfer NBFRs to their offspring. The removal half-life of the three NBFRs was in the range of 2.6 and 5.7 days according to the first-order kinetic equation. Several degradation products of the NBFRs were detected in mudsnail samples, which were exposed to single substance. 2,4,6-tribromotoluene was identified as degradation product of PBT; 1,2,4,5-tetrabromobenzene and 1,2,4-tribromobenzene were identified as debromination products of HBB. Possible degradation pathways were further proposed. Additionally, mudsnails after exposed to 50 mg/kg of NBFRs were observed under a scanning electron microscope, indicating that shrinkage, tissue hyperplasia and perforation occurred on the visceral surface. Such damage might be related to the accumulation of more pollutants in mudsnails viscera. As one of the few studies to explore the biological process of NBFRs, our observation could provide a scientific basis for evaluating the environmental risks of NBFRs to benthic organisms.

Risk assessment of added chemicals in plastics in the Danish marine environment

A risk assessment framework for direct exposure of residual additives and monomers present in ingested plastic particles, including microplastics, in the Danish marine environment, was presented. Eight cases of different polymer types and product groups were defined that represent the most significant exposures, and thus potential high-risk cases, towards marine organisms. Risk Quotients (RQ) were calculated for three trophic levels, i.e. pelagic/planktonic zooplankton: copepod, benthopelagic fish: Atlantic cod and seabird: northern fulmar. European and Danish Environmental Quality Standard (EQS) values were used as Predicted No-Effect Concentrations (PNEC). RQ larger than unity, indicating potential risks, were found for copepod and cod (pelagic community) and the flame-retardant pentabromodiphenyl ether (PeBDE) used in polyurethane (PUR), the biocide tributyltin (TBT) present as impurity in polyvinylchloride (PVC) and PUR, and the flame-retardant hexabromocyclododecane (HBCDD) used in expanded polystyrene (EPS). A potential risk was found for fulmar (secondary poisoning) and PeBDE used in PUR.

Enhanced oxidative degradation of decabromodiphenyl ether in soil by coupling Fenton-persulfate processes: Insights into degradation products and reaction mechanisms

Decabromodiphenyl ether (BDE-209) has extreme hydrophobicity, which results in its significant accumulation in soil, sediments and other solid materials. In this work, an oxidation method coupling Fenton with persulfate (PS) was proposed for the effective degradation of BDE-209 adsorbed on solid surfaces. After adding 0.1 M PS to the Fenton system at 1.0 h, the removal rate of BDE-209 was significantly increased from 62.2% to 94.0%. The degradation of BDE-209 in various soil samples was also investigated by the coupling Fenton-PS method. Removal efficiency of 73.4–95.8% was obtained, suggesting that this coupling method was feasible in real application. According to the radical scavenging experiments, •OH dominated the overall reaction of BDE-209 in the coupling system. Meanwhile, the enhanced removal was attributed to the generation of SO4•- from the catalytic decomposition of PS. The calculated energy barriers for SO4•- attacking on the carbons were smaller than •OH initiated reactions, which further confirmed that SO4•- plays a role in the accelerated removal of BDE-209. The initial attack of BDE-209 by SO4•- generated the SO4•- adducts, which may undergo debromination or CO bond cleavage reaction together with subsequent hydroxyl substitution to form the primary product OH-Nona-BDEs and pentabromophenol. Under the successive attack of radicals, these primary products were further transformed into lower-brominated hydroxylation products and bromophenols via direct debromination and hydroxyl substitution reaction. This work provides an economical and effective method for treating BDE-209 contaminated soils and samples.

Preliminary Screening of Polybrominated Diphenyl Ethers (PBDEs); Decabromodiphenyl Ether (BDE-209) and Tetrabromobisphenol-A (TBBPA) Flame Retardants in Municipal Dumpsite in Delta State, Nigeria

Aims: This study is aimed at determining the concentration of two widely used BFRs; Decabromodiphenyl Ether (BDE-209) and Tetrabromo Bisphenol-A (TBBPA) in sediment and leachate samples.
 Place and Duration of Study: Field sampling were carried out from five major dumpsites around Warri Municipality, Delta State, Nigeria. Analyte extraction was done in 2017 at the Science laboratory, Federal University of Petroleum Resources, Effurun Delta State, Nigeria and quantification done in Switzerland by Bachema Analytical Laboratories in 2017.
 Methods: Three soil samples were collected from each site 15cm from the soil surface. Also, three leachate samples from three different trial pits done for each site. Collected soil samples were stored in glass bottles and labelled. While the leachate samples are stored using glass containers and labelled. The BFRs were extracted using Aceton and cyclohexane for each soil matrix and cyclohexane for the leachate samples, then the extract was analysed using GC coupled with an ECD supplied by Thermo Trace GC Ultra, Italy.
 Results: The results showed the average concentration for TBBPA in the sediments was 0.0234 g/kg and that of the BDE-209 was recorded as 0.1828 g/kg. Results from the leachate sample were below the detectable range of the analytical equipment, TBBPA (0.02 g/kg) and BDE (0.1 g/kg). There is no statistical difference between the mean concentration of TBBPA for the sediment in each of the locations (P>.05) and no difference (P>.05) for BDE-209 for the sediment in each of the locations (P>.05).
 Conclusion: Findings from this study holds that the concentration of TBBPA and BDE-209 in sediment is higher when compared with concentrations presented in other literatures studied in this report and this calls for immediate action due to the health risk associated with exposure in these municipalities.

Residual ratio analysis and pyrolysis kinetic study of deca-BDE in PE plastic

The fate of added decabromodiphenyl ether (deca-BDE), a flame retardant, has attracted the attention of environmental researchers because of its biological and chemical characteristics. We performed a residual ratio analysis and pyrolysis kinetic study of deca-BDE in polyethylene (PE) plastic. Our investigations explored the effects of atmosphere type, heating rate, and PE matrix presence on deca-BDE loss, which left in the thermal stress remnants. With respect to environmental impacts, detailed brominated flame retardant (BFR) release information is missing. In this work, we studied the pyrolysis kinetics of deca-BDE in a PE matrix. We used a detector to acquire data regarding deca-BDE residual content, and calculated the residual equation using software. The obtained equation can be used to estimate remainder BFRs in electrical and electronic equipment on the basis of working conditions.

Plasma concentration of brominated flame retardants and postmenopausal breast cancer risk: a nested case-control study in the French E3N cohort

BackgroundBrominated flame retardants (BFRs) are lipophilic substances with endocrine-disrupting properties. To date, only few investigations, mainly retrospective case-control studies, have explored the link between internal levels of BFRs and the risk of breast cancer, leading to conflicting results. We investigated the associations between plasma concentrations of two main groups of BFRs, PBDEs (pentabromodiphenyl ethers) and PBBs (polybrominated biphenyls), and the risk of breast cancer in a nested case-control study.MethodsA total of 197 incident breast cancer cases and 197 controls with a blood sample collected in 1994–1999 were included. Plasma levels of PBDE congeners (BDE-28, BDE-47, BDE-99, BDE-100, BDE153, BDE-154) and of PBB-153 were measured by gas chromatography coupled to high-resolution mass spectrometry. Conditional logistic regression models, adjusted for potential confounders, were used to estimate odds ratios (ORs) and 95% confidence intervals (CIs).ResultsWomen were aged 56 years on average at blood draw. All cases, except for one, were diagnosed after menopause, with an average age at diagnosis of 68 years. Overall, we found no evidence of an association between plasma levels of PBDEs and PBB-153 and postmenopausal breast cancer risk (log-concentrations of BFRs yielding non-statistically significant ORs of 0.87 to 1.07). The analysis showed a non-linear inverse association for BDE-100 and BDE-153 and postmenopausal breast cancer risk; nevertheless, these findings were statistically significant only when the exposure was modeled as ng/L plasma (third vs. first quintile: OR = 0.42, 95%CI = 0.19–0.93 and OR = 0.42, 95%CI = 0.18–0.98, respectively) and not when modeled as ng/gr of lipids (OR = 0.58, 95%CI = 0.27–1.25 and OR = 0.53, 95%CI = 0.25–1.17). These results were unchanged in stratified analyses by tumor hormone receptor expression or body mass index.ConclusionsOur results suggest no clear association between internal levels of PBDEs and PBB-153 and the risk of breast cancer in postmenopausal women. However, these findings need to be carefully interpreted, taking into account limitations due to the limited number of women included in the study, the lack of information concerning genetic susceptibility of cases, and the unavailability of exposure assessment during critical windows of susceptibility for breast cancer. More studies are warranted to further investigate the relationships between PBDE and PBB exposure and breast cancer risk.

Photodegradation of 1,3,5-Tris-(2,3-dibromopropyl)-1,3,5-triazine-2,4,6-trione and decabromodiphenyl ethane flame retardants: Kinetics, Main products, and environmental implications

Photodegradation has been demonstrated as one of the important environmental factors affecting the fate of contaminants such as brominated flame retardants (BFRs). However, a number of emerging BFRs, particularly those with high bromine substitution, have rarely been investigated for their photodegradation kinetics. Our study evaluated photodegradation of two highly brominated FRs, 1,3,5-tris-(2,3-dibromopropyl)-1,3,5-triazine-2,4,6-trione (TDBP-TAZTO) and decabromodiphenyl ethane (DBDPE), under various conditions. The results indicated that the degradation kinetics was affected by UV irradiation wavelength, intensity, solvent type, as well as the structural characteristics. TDBP-TAZTO exhibited degradation half-lives (t1/2) of 23.5–6931 min under various UV irradiation conditions and 91.2 days under natural sunlight. Its degradation was much slower than that of DBDPE which exhibited t1/2 of 0.8–101.9 min under UV and 41.3 min under natural sunlight. A variety of degradation products were detected as a result of different breakdown pathways. This indicated that photodegradation could substantially influence the fate of these highly brominated FRs, resulting in a cocktail of degradation products as environmentally occurring contaminants. This could also complicate the evaluation of the ecological risks of these target flame retardants, given that degradation products generally possess physicochemical properties and biological effects different from their parent chemicals.

Flame retardants, dioxins, and furans in air and on firefighters’ protective ensembles during controlled residential firefighting

IntroductionStructure fires that involve modern furnishings may emit brominated flame retardants (BFRs) and organophosphate flame retardants (OPFRs), as well as brominated and chlorinated dioxins and furans, into the environment. ObjectivesThe goal of this study was to quantify the airborne and personal protective equipment (PPE) contamination levels of these compounds during controlled residential fires in the U.S., and to evaluate gross-decontamination measures. MethodsBulk-sampling was done to confirm the presence of flame retardants (FRs) in the furnishings used in 12 controlled residential structure fires. Area air samples were collected during the fires and PPE wipe samples were collected from the firefighters’ turnout jackets and gloves after firefighting. For each fire, half of the jackets were decontaminated and the other half were not. ResultsOf the BFRs and OPFRs measured in air during the fire period, decabromodiphenyl ether (BDE-209) and triphenyl phosphate (TPP) were the most abundant, with medians of 15.6 and 408 µg/m3, respectively, and were also detected during overhaul. These and several other BFRs and OPFRs were measured on PPE. Some gloves had contaminant levels exceeding 100 ng/cm2 and were generally more contaminated than jackets. Air and surface levels of the brominated furans appeared to be higher than the chlorinated dioxins and furans. Routine gross decontamination appeared to reduce many of the BFR contaminants, but results for the OPFRs were mixed. ConclusionsStructure fires are likely to result in a variety of FRs, dioxins, and furans into the environment, leading to PPE contamination for those working on the fireground. Firefighters should wear self-contained breathing apparatus during all phases of the response and launder or decontaminate their PPE (including gloves) after fire events.

Use of integrated biomarker response for evaluating antioxidant stress and DNA damage of earthworms (Eisenia fetida) in decabromodiphenyl ethane-contaminated soil

Decabromodiphenyl ethane (DBDPE) is a new and popular type of brominated flame retardant (BFR) with high bromine content, strong thermal stability, and ultraviolet resistance. To evaluated the potential toxicity of this new BFR to soil ecosystem, different concentrations of DBDPE were used to observe effects on earthworms (Eisenia fetida) in artificial soil. The reactive oxygen species (ROS) contents, activities of antioxidase system and detoxify enzyme, levels of malondialdehyde (MDA), as well as DNA damage in earthworms were measured after exposure to 0, 2.5, 5, 10, and 20 mg/kg DBDPE in artificial soil for 7, 14, 21, and 28 days. The results showed that ROS and MDA content significantly increased for all treatments from days 7–21, followed by a decrease. Throughout the experimental period, SOD, POD, and CAT activities increased. The GST activity was stimulated significantly from days 14–28. Besides, the olive tail moment (OTM) value in all treated groups was significantly higher than that in the control and exhibited a concentration-related and exposure time-related response. This is the first study evaluating the biological toxicity of BFR at different concentrations using an integrated biomarker response index. Our results show that DBDPE has biochemical toxicity on earthworms, which sheds some light on the potential risks of DBDPE in the soil environment and provides a basis for the monitoring and diagnosis of soils contaminated with DBDPE.

Reducing the Combustibility of Polycaproamide Using a Mixture of Polyelemental Flame Retardants

A study was carried out on the effect of 1,1,9-trihydroperfluoro-1-nonanol immobilized on montmorillonite nanoclay in combination with decabromodiphenyl oxide, perfluorinated antimony alcoholate, and diantimony trioxide on the combustibility of polycaproamide. X-ray structural analysis and differential scanning calorimetry were used to establish a relationship between the combustion resistance of the heterochain polymer and its morphology attributed to reorganization of the amorphouscrystalline structure due to the effect of the introduced combustion retarder, which causes redistribution of the fractions of the α- and γ-crystalline forms in the polymorphous composition of the polycaproamide, leading to a fluorine-containing material with reduced combustibility.