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A polystyrene (PS) certified reference material (CRM) for the analysis of decabromodiphenyl ether (BDE 209) was issued. PS disk was prepared by injection molding of the mixture of versine PS and BDE 209. The certification of the PS CRM was conducted by two analytical methods with different sample preparation methods using isotope dilution mass spectrometry (IDMS). The certified value, wCRM, was 978 mg/kg, and this value coincided with the regulation value of BDE 209 in the Restriction of Hazardous Substances directive (1000 mg/kg). The uncertainties related to certification, uwmean, inhomogeneity, uhom, and long- and short-term instability, usts and ults, respectively, were evaluated based on the mass fraction of BDE 209. The uwmean, uhom, usts, and ults were 0.0265, 0.0046, 0.0061, and 0.0099 (relative), respectively, and the expanded uncertainty for this CRM was determined as 57 mg/kg (coverage factor is 2). Additionally, the quantitative capability of the thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) method was evaluated. In TD-GC/MS, the analytical values of the developed CRM obtained by the external and internal standard methods with matrix-free calibrants were out of the range of the wCRM (almost 10% larger or smaller), whereas those with matrix-matched calibrants agreed with the wCRM. In contrast to these results, the analytical values obtained by TD-GC/MS using IDMS were consistent with the wCRM no matter if matrix-free or matrix-matched calibrants were used. These results indicated that, for quantification of BDE 209 in PS, the trueness and precision of TD-GC/MS can be enhanced by applying IDMS without matrix-matched calibrants.

This study investigated the occurrence, distribution of several additive brominated flame retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs) and some novel brominated flame retardants (NBFRs) in urban indoor dust collected from ten inner districts of Hanoi, Vietnam to assess the contamination status, emission sources, as well as their associated human exposure through indoor dust ingestion and health risks. Total concentrations of PBDEs and NBFRs in indoor dust samples ranged from 43 to 480 ng g −1 (median 170 ng g −1 ) and from 56 to 2200 ng g −1 (median 180 ng g −1 ), respectively. The most abundant PBDE congener in these dust samples was BDE-209 with concentrations ranging from 29 to 360 ng g −1 , accounting for 62.6–86.5% of total PBDE levels. Among the NBFRs analyzed, decabromodiphenyl ethane (DBDPE) was the predominant compound with a mean contribution of 98.6% total NBFR amounts. Significant concentrations of DBDPE were detected in all dust samples (median 180 ng g −1 , range 54–2200 ng g −1 ), due to DBDPE as a substitute for deca-BDE. Other NBFRs such as 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), pentabromoethylbenzene (PBEB) and 2,2’,4,4’,5,5’-hexabromobiphenyl (BB-153) were found at very low levels. Based on the measured BFR concentrations, daily intake doses (IDs) of PBDEs and NBFRs via dust ingestion at exposure scenarios using the median and 95 th percentile levels for both adults and children were calculated for risk assessment. The results showed that the daily exposure doses via dust ingestion of all compounds, even in the high-exposure scenarios were also lower than their reference dose (RfD) values. The lifetime cancer risks (LTCR) were much lower than the threshold level (10 −6 ), which indicated the acceptable health risks resulting from indoor BFRs exposure for urban residents in Hanoi.

Information regarding the contamination of brominated flame retardants (BFRs) in lake sediments from Vietnam and Southeast Asia is still very limited. To fill such knowledge gaps, surface sediment samples from five urban lakes in Hanoi, Vietnam, were analyzed for polybrominated diphenyl ethers (PBDEs) and some other BFRs. Concentrations of total PBDEs ranged from 1.1 to 26 (median 6.6) ng/g dry weight with the most predominant congeners as BDE-209 (62 ± 17%), BDE-99 (10 ± 8%), and BDE-47 (6 ± 5%). Concentrations of other BFRs decreased in the order: decabromodiphenyl ethane (DBDPE) > 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) > hexabromobiphenyl (BB-153) > pentabromoethylbenzene (PBEB), which were about one to two orders of magnitude lower than PBDEs. BDE-209 and DBDPE were highly correlated (Pearson’s r  = 0.879; p  < 0.01), suggesting their similar applications and/or environmental fate. Potential sources of BFRs in lake sediments are estimated to be wastewater discharge, riverine inflow, and atmospheric deposition.

E-waste, a global environmental concern, particularly affects developing nations due to the rise in informal recycling practices. This leads to contamination of environmental matrices, posing threats to both ecosystems and human health. To assess this issue, we monitored brominated flame retardants (BFRs) in 164 samples (soil) from 32 informal e-waste operational locations and 9 background locations across nine mega cities of Pakistan from September 2020 to December 2021. The mean concentrations (ng/g) of ∑ 27 PBDEs (polybrominated diphenyl ethers), ∑ 2 PBB (polybrominated biphenyls), HBB (hexabromobiphenyl), and ∑HBCDD (hexabromocyclododecane) were 176 ( 0.76–11141), 31.0 (0.65–58.0), 1.39 (0.01–42.8), and 12.0 (0.22–461), respectively. These levels were significantly higher (6 to tenfold) than those at background sites. Karachi, Faisalabad, Gujranwala, and Lahore exhibited high levels of all BFRs. Notably, BDE-209 (mean = 45.5 ng/g) ranged (0.13–1152 ng/g) exhibited higher level in soil samples. Seasonally, total ΣBFR concentrations (ng/g) ranked higher in winter (11,620), followed by spring (3874), autumn (3139), and summer (1207) indicating a seasonal impact of recycling activities. The average daily dose for soil ingestion (ng/kg/day) was estimated for BDE-209 (0.10973) in Faisalabad, followed by BDE-47 (0.08616) and BDE-99 (0.06788) in Karachi. Our findings showed that these values were lower than RfD values, suggesting no ingestion risk from studied BFRs. However, the growing prevalence of such informal e-waste recycling facilities could lead to increased exposure to toxic chemicals in near future.

Settled dust samples from Vietnamese end-of-life vehicle (ELV) processing, urban, and rural areas were analyzed for polybrominated diphenyl ethers (PBDEs) and other current-use brominated flame retardants (BFRs). PBDE levels found in dust samples collected from ELV workshops (median 390; range 120–520 ng/g) and nearby living areas (110; 36–650 ng/g) were generally higher than those in common house dust (25–170 ng/g). BDE-209 was the most predominant congener detected in almost all the samples, indicating extensive application of products containing deca-BDE mixtures. The dust samples from ELV workplaces showed a more abundance of lower brominated congeners (e.g., tetra- to hexa-BDEs) that may originate from car interior materials treated by penta-BDE formulations. Concentrations of other BFRs decreased in the order urban > rural > ELV dust, reflecting the current use of these compounds in new consumer products. Decabromodiphenyl ethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) were the major alternative BFRs. Daily intake doses and hazard indexes of PBDEs and some other BFRs through dust ingestion were estimated and showed acceptable levels of risk. However, more comprehensive risk assessment considering multiple exposure pathways should be performed, especially for ELV workers and children in the ELV processing and urban areas.

Tetrabromobisphenol A-bis(2,3-dibromopropyl ether) (TBBPA-BDBPE), a commonly used brominated flame retardant as a decabromodiphenyl ether substitute, has been detected in various environmental compartments, but its health hazards remain largely unknown. Our recent study showed that low-dose exposure of male mice to TBBPA-BDBPE from postnatal day (PND) 0 to 56 caused remarkable damage to the microtubule skeleton in Sertoli cells and the blood-testis barrier (BTB) but exerted little effect on conventional reproductive endpoints in adulthood. To investigate whether TBBPA-BDBPE may cause severe reproductive impairments at late reproductive age, here, we extended exposure of historically administrated male mice to 8-month age and allowed them to mate with non-treated females for the evaluation of fertility, followed by a general examination for the reproductive system. As expected, we found that 8-month exposure to 50 μg/kg/d as well as 1000 μg/kg/d TBBPA-BDBPE caused severe damage to the reproductive system, including reduced sperm counts, increased sperm abnormality, histological alterations of testes. Moreover, microtubule damage and BTB-related impairment were still observed following 8-month exposure. Noticeably, high-dose TBBPA-BDBPE-treated mice had fewer offspring with a female-biased sex ratio. All results show that long-term exposure to TBBPA-BDBPE caused severe reproductive impairment, including poor fertility at late reproductive age. It is therefore concluded that slight testicular injuries in early life can contribute to reproductive impairment at late reproductive age, highlighting that alterations in certain non-conventional endpoints should be noticed as well as conventional endpoints in future reproductive toxicity studies.

Polybrominated diphenyl ethers (PBDEs) are considered emerging organic contaminants that attract more attention in the environment. Herein, online coupling of solid-phase microextraction and ultrahigh-resolution mass spectrometry was developed for rapid screening of eight PBDEs in water samples. This procedure was completed in 22 min, about 6 times faster than the routine workflow such as solid-phase extraction coupled with gas chromatography-mass spectrometry. Thermal desorption and solvent-assisted atmospheric pressure chemical ionization were developed for the effective coupling of solid-phase microextraction (SPME) with ultrahigh-resolution mass spectrometry (UHRMS), which contributed to the signal enhancement and made the methodology feasible for environmental screening. The limits of detection and quantification were 0.01–0.50 ng/mL and 0.05–4.00 ng/mL, respectively. The recoveries were 57.2–75.2% for quality control samples at spiking levels of 0.8–10 ng/mL (4–50 ng/mL for BDE209), with relative standard deviation less than 19.0%. Twelve water samples from different river sites near industrial areas were screened using the developed method. The results showed that BDE-209 was the dominant PBDE (1.02–1.28 ng/mL in positive samples), but its amount was lower than the human health ambient water quality criteria. Consequently, the developed method provides a rapid and reliable way of evaluating contamination status and risks of PBDEs in aqueous environment.

Vehicles are unique indoor environments, with interiors dominated by plastic/synthetic materials and exposure to extremes of temperature and radiation, leading to substantial potential for emissions of plastic additives from vehicle materials and subsequent exposure to drivers and passengers. Flame retardants (FRs) and per- and polyfluoroalkyl substances (PFAS) were measured in 30 dust samples collected from dashboards, seats, and trunks of cars of the same make and model (year of manufacture 1996–2021) to evaluate levels in dust and time patterns in additive use across cars of different ages. PFAS were detected in all dust samples at low levels, while FRs were detected in all samples, with some compounds consistently exceeding µg/g levels, especially tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) and decabromodiphenyl ether (BDE-209), substantially higher than in other indoor environments. Although cars were of the same model, large variations were observed in FR concentrations in dust between cars, emphasizing the challenge in generalizing FR exposures from vehicle dust. Concentrations of BDE-209 in vehicle dust did not decrease over the 1996–2021 period, suggesting that restrictions on DecaBDE have had limited impact, likely due to exemptions in regulations for the automotive industry. The high FR levels indicate ongoing use of both organophosphate and brominated FRs in vehicles on the European market, although flammability standards for interior car materials are not mandated by European regulations, and the continued presence of long-restricted FRs suggests the presence of recycled plastics in vehicles; this potential exposure source may be increasing as vehicle producers aim to improve material circularity.

Many materials use polybrominated diphenyl ethers (PBDEs) as flame retardants. As one of the most common congeners of PBDEs, decabromodiphenyl ether (PBDE-209) is reported to harm reproductive health. However, little is known research on attenuating the reproductive toxicity induced by PBDE-209. The present study aimed to investigate the effects of hesperidin against PBDE-209-induced reproductive toxicity in male mice. Pubertal male C57BL/6 J mice were exposed to PBDE-209 groups (20, 100, 500 mg/kg·bw) and hesperidin groups (100 mg/kg·bw PBDE-209 + 100 mg/kg·bw hesperidin) for 8 weeks. The results showed that PBDE-209 increased the amount of abnormal morphological sperms and decreased the sex hormone levels. PBDE-209 induced the histopathological lesions of seminiferous tubules and blood-testis barrier in mice testis. Expressions of apoptosis-associated proteins and mRNA (Bax, Bcl-2, etc.) were altered by the PBDE-209 treatment. PBDE-209 prominently increased the malondialdehyde (MDA) levels, the biomarker of oxidative stress. Hesperidin treatment partly alleviated PBDE-209-induced histopathological lesions and apoptosis in mice testis. These findings suggested that hesperidin partly protects against PBDE-induced reproductive toxicity in pubertal mice. We conclude that more work needs to be done to explore the appropriate dosage of hesperidin or find other drugs to protect against the reproductive toxicity of PBDEs. Graphical abstract

Polybrominated diphenyl ethers (PBDEs) have widely been used for decades as flame retardants in a variety of products like plastics for building insulation, upholstered furniture, electrical appliances, vehicles, aircrafts, polyurethane foams, textiles, cable insulation, appliance plugs and various technical plastics in concentrations of 5–30%. However, PBDEs also act as endocrine disrupters, neurotoxins, and negatively affect fertility. In 2001, worldwide consumption of technically relevant penta-BDEs was still estimated at 7500 tons, octa-BDEs at 3790 tons, and deca-BDE at 56,100 tons, but 50–60% of this total volume are discharged into the environment via sewage sludge and its agricultural use alone. In addition, soils are ubiquitously contaminated by the gaseous or particle-bound transport of PBDEs, which today has its main source in highly contaminated electronic waste recycling sites. The emitted PBDEs enter the food chain via uptake by the plants’ roots and shoots. However, uptake and intrinsic transport behaviour strongly depend on crop specifics and various soil parameters. The relevant exposure and transformation pathways, transport-relevant soil and plant characteristics and both root concentration factors (RCF) and transfer factors (TF) as derivable parameters are addressed and quantified in this review. Finally, a simple predictive model for quantification of RCF and TF based on log KOW values and the organic content of the soil/lipid content of the plants is also presented.