Brominated flame retardant (BFRs) and Dechlorane Plus (DP) in paired human serum and segmented hair.

Brominated flame retardants (BFRs) and Dechlorane Plus (DP) were measured in both human hair and paired serum samples from a cohort of university students in South China. Segmental analysis was conducted to explore gender difference and the relationships between the hair and serum. The concentrations of total PBDEs in the hair and serum samples were in a range of 0.28-34.1ng/g dry weight (dw) and 0.16-156ng/g lipid weight (lw), respectively. Concentrations of ∑DPs (sum of the syn-DP and anti-DP isomers) in all hair samples ranged from nd-5.45ng/g dry weight. Concentrations of most PBDEs and decabromodiphenylethane (DBDPE) in distal segments (5-10cm from the scalp) were higher than those in the proximal segments (0-5cm from the scalp) (t-test, p < 0.05), which could be due to the longer exposure time of distal segments. The proximal segments exhibited a unique congener profile, more close to that in the serum rather than the distal segments of hair. An obvious gender difference was found in the levels of ∑PBDEs using integrated hair samples, while the difference disappeared when considering alone the proximal segments of hair (0-5cm from scalp) for both genders. This paper provides supplement to the current knowledge on sources of BFRs and DPs in hair and declares the importance of segmental analysis.

Insights into the photocatalytic degradation of hydrophobic organic contaminants on the surface of nitrogen doped silica: New findings of the formation of silicon-based substitution products.

In this work, nitrogen-doped SiO2 (N-SiO2) was successfully synthesized to develop an "adsorption-photocatalytic degradation" water purification technology to remove hydrophobic organic contaminants (HOCs). As a representative of HOCs, decabromodiphenylethane (DBDPE) could be efficiently degraded under simulated sunlight after adsorption on the surface of N-SiO2. Due to the generation of reactive oxygen species (ROS) and silicon-based radicals, the photodegradation rate of DBDPE on water-SiO2 interface was 1.5-fold higher than that in water. Furthermore, the transformation pathways of DBDPE on N-SiO2 surface were compared with that in water. Bond breaking and debromination reactions were the common pathways, while hydroxylation and silicon-based substitution reactions were the specific transformation pathways for DBDPE on the surface of N-SiO2. Density functional theory (DFT) calculation was used to reveal the generation mechanism of silicon-based radicals and determine the rationality of the involvement of silicon-based radicals in DBDPE transformation. The energy barriers of silicon-based substitution reaction were comparable to that of hydroxylation and debromination reactions, which confirmed the plausibility of the generation of silicon-based substitution products. This study provides an efficient method for the disposal of HOCs, which also gives some new insights into the conversion mechanism of organic pollutants mediated by silicon-based radicals.

Legacy and alternative flame retardants in typical freshwater cultured fish ponds of South China: Implications for evolving industry and pollution control.

The production and usage of polybrominated diphenyl ethers (PBDEs) has been gradually phased out and the application of alternative halogenated flame retardants (AHFRs) has been continuously increased. It is essential to understand how the evolving flame retardants industry has affected the occurrence and flux of legacy and alternative flame retardants so that better pollution control measures can be made accordingly. Air, rainwater, inflowing river water, pond water, pond sediment, fish feed, and fish collected from freshwater cultured fish ponds (FWCFPs) within the Pearl River Delta, South China were analyzed for PBDEs and AHFRs. Concentrations of AHFRs in air (range; median: 7.8-870; 210 pg m-3), rainwater (0.88-65; 4.8 ng L-1), and sediment (19-120; 54 ng g-1 dry weight (d.w.)) were one order of magnitude higher than those of PBDEs in air (12-98; 21 pg m-3), rainwater (0.18-15; 0.70 ng L-1), and sediment (1.5-9.6, 2.9 ng g-1 d.w.) (t-test; p < 0.05). Decabromodiphenyl ether and decabromodiphenylethane were the predominant BDE and AHFR components, respectively, agreeing well with the production and usage patterns of flame retardants in China. The average input fluxes of AHFRs to the FWCFPs via dry deposition, wet deposition, net air-water exchange, and feeding (38.6, 20.6, and 2.14, µg m-2 yr-1) were one order of magnitude higher than those of PBDEs (3.44, 5.17, and -10.1, µg m-2 yr-1). Elevated occurrence and input fluxes of AHFRs suggested that aquaculture production is potentially facing a new challenge from alternative flame retardants. Atmospheric dry and wet deposition are important input sources of AHFRs to the FWCFPs. Feeding is an important input pathway for both PBDEs and AHFRs. Pollution control measures should be modified to accommodate the evolving flame retardants industry.

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.

Neurological responses of embryo-larval zebrafish to short-term sediment exposure to decabromodiphenylethane.

Decabromodiphenylethane (DBDPE) has been widely used as an alternative flame retardant due to the restriction or phase-out of traditional polybrominated diphenyl ethers (PBDEs), and is of increasing concern regarding its ubiquity, persistence, and potential adverse effects. In the present study, the toxicological effects of DBDPE were evaluated using zebrafish as an in vivo model. Upon being exposed to DBDPE-polluted sediments for a short term, it was found that the mortality and malformation of zebrafish (including edema, bent notochord, and bent tail) were not affected even at the highest concentration tested (1000.0 µg/kg dry sediment). Regarding behavioral responses, it was found that zebrafish larvae of 48 hours post fertilization (hpf) in all groups escaped successfully with a touch to the dorsal fin. However, when exposed to the highest DBDPE concentration, the larvae of 120 hpf exhibited significantly smaller distances as compared to the control. Moreover, the results of the acetylcholinesterase (AChE) activity, the expression levels of two important nerve-related genes, and the cell apoptosis all indicated that DBDPE posed low neurotoxicity in embryo-larval zebrafish. The results in this study shed some light on the potential risks of DBDPE in the real environment and highlight the application of the sediment exposure route in the future.

Neurological responses of embryo-larval zebrafish to short-term sediment exposure to decabromodiphenylethane / 浙江大学学报（英文版）（B辑：生物医学和生物技术）

Decabromodiphenylethane (DBDPE) has been widely used as an alternative flame retardant due to the restriction or phase-out of traditional polybrominated diphenyl ethers (PBDEs), and is of increasing concern regarding its ubiquity, persistence, and potential adverse effects. In the present study, the toxicological effects of DBDPE were evaluated using zebrafish as an in vivo model. Upon being exposed to DBDPE-polluted sediments for a short term, it was found that the mortality and malformation of zebrafish (including edema, bent notochord, and bent tail) were not affected even at the highest concentration tested (1000.0 µg/kg dry sediment). Regarding behavioral responses, it was found that zebrafish larvae of 48 hours post fertilization (hpf) in all groups escaped successfully with a touch to the dorsal fin. However, when exposed to the highest DBDPE concentration, the larvae of 120 hpf exhibited significantly smaller distances as compared to the control. Moreover, the results of the acetylcholinesterase (AChE) activity, the expression levels of two important nerve-related genes, and the cell apoptosis all indicated that DBDPE posed low neurotoxicity in embryo-larval zebrafish. The results in this study shed some light on the potential risks of DBDPE in the real environment and highlight the application of the sediment exposure route in the future.