Bioaccessibility and health risk assessment of hydrophobic organic pollutants in soils from four typical industrial contaminated sites in China.

There have been reports of potential health risks for people from hydrophobic organic pollutants, such as polycyclic aromatic hydrocarbons (PAHs), polychlorinated hydrocarbons (PCHs), and organophosphate flame retardants (OPFRs). When a contaminated site is used for residential housing or public utility and recreation areas, the soil-bound organic pollutants might pose a threat to human health. In this study, we investigated the contamination profiles and potential risks to human health of 15 PAHs, 6 PCHs, and 12 OPFRs in soils from four contaminated sites in China. We used an in vitro method to determine the oral bioaccessibility of soil pollutants. Total PAHs were found at concentrations ranging from 26.4 ng/g to 987 ng/g. PCHs (0.27‒14.3 ng/g) and OPFRs (6.30‒310 ng/g) were detected, but at low levels compared to earlier reports. The levels of PAHs, PCHs, and OPFRs released from contaminated soils into simulated gastrointestinal fluids ranged from 1.74% to 91.0%, 2.51% to 39.6%, and 1.37% to 96.9%, respectively. Based on both spiked and unspiked samples, we found that the oral bioaccessibility of pollutants was correlated with their logKow and molecular weight, and the total organic carbon content and pH of soils. PAHs in 13 out of 38 contaminated soil samples posed potential high risks to children. When considering oral bioaccessibility, nine soils still posed potential risks, while the risks in the remaining soils became negligible. The contribution of this paper is that it corrects the health risk of soil-bound organic pollutants by detecting bioaccessibility in actual soils from different contaminated sites.

Soil colloids can significantly enhance spreading of polybromodiphenyl ethers in groundwater by serving as an effective carrier.

Polybromodiphenyl ethers (PBDEs), the widely used flame retardants, are common contaminants in surface soils at e-waste recycling sites. The association of PBDEs with soil colloids has been observed, indicating the potential risk to groundwater due to colloid-facilitated transport. However, the extent to which soil colloids may enhance the spreading of PBDEs in groundwater is largely unknown. Herein, we report the co-transport of decabromodiphenyl ester (BDE-209) and soil colloids in saturated porous media. The colloids released from a soil sample collected at an e-waste recycling site in Tianjin, China, contain high concentration of PBDEs, with BDE-209 being the most abundant conger (320 ± 30 mg/kg). The colloids exhibit relatively high mobility in saturated sand columns, under conditions commonly observed in groundwater environments. Notably, under all the tested conditions (i.e., varying flow velocity, pH, ionic species and ionic strength), the mass of eluted BDE-209 correlates linearly with that of eluted soil colloids, even though the mobility of the colloids varies markedly depending on the specific hydrodynamic and solution chemistry conditions involved. Additionally, the mass of BDE-209 retained in the columns also correlates strongly with the mass of retained colloids. Apparently, the PBDEs remain bound to soil colloids during transport in porous media. Findings in this study indicate that soil colloids may significantly promote the transport of PBDEs in groundwater by serving as an effective carrier. This might be the reason why the highly insoluble and adsorptive PBDEs are found in groundwater at some PBDE-contaminated sites.

Association between brominated flame retardants (PBDEs and PBB153) exposure and hypertension in U.S. adults: results from NHANES 2005-2016.

BACKGROUND: Brominated Flame Retardants (BFRs) have attracted widespread concern due to their environmental persistence and potential toxicity. This study aims to examine the association between BFRs exposure and hypertension. METHODS: We used data from the National Health and Nutrition Examination Survey (NHANES) spanning 2005 to 2016 for the cross-sectional analysis. To evaluate the individual and combined impacts of BFRs exposure on hypertension, we utilized multivariate models, including generalized additive models, weighted quantile sum (WQS) regression, and Bayesian kernel machine regression (BKMR) models. RESULTS: 9882 individuals (48% male) aged ≥ 20 were included in the final analysis, of whom 4114 had hypertension. After controlling for potential covariates, higher serum concentrations of PBDE100 (OR: 1.26; 95% CI: 1.01, 1.57) and PBDE153 (OR: 1.50; 95% CI: 1.18, 1.88) were significantly associated with hypertension. A nonlinear relationship between PBDE28 and hypertension was observed (P = 0.03). Moreover, BFRs mixture were positively associated with the prevalence of hypertension in both the WQS (ß:1.09; 95% CI: 1.02, 1.17; P = 0.02) and BKMR models. CONCLUSION: Our study suggested that BFRs exposure is positively associated with hypertension in the general population. To confirm this association and elucidate the mechanisms, further research is required.

A new approach to monitoring typical organophosphorus compounds (OPs) in environmental media: From database building to suspect screening.

Organophosphorus compounds (OPs) are widely used as flame retardants (FRs) and plasticizers, yet strategies for comprehensively screening of suspect OPs in environmental samples are still lacking. In this work, a neoteric, robust, and general suspect screening technique was developed to identify novel chemical exposures by use of ultra-high performance liquid chromatography-Q Exactive hybrid quadrupole-Orbitrap high resolution mass spectrometry (UHPLC-Q-Orbitrap HRMS). We firstly established a suspect chemical database which had 7,922 OPs with 4,686 molecular formulas, and then conducted suspect screening in n = 50 indoor dust samples, n = 76 sediment samples, and n = 111 water samples. By use of scoring criteria such as retention time prediction models, we successfully confirmed five compounds by comparison with their authentic standards, and prioritized three OPs candidates including a nitrogen/fluorine-containing compound, that is dimethyl {1H-indol-3-yl[3-(trifluoromethyl)anilino]methyl} phosphonate (DMITFMAMP). Given that the biodegradation half-life values in water (t1/2,w) of DMITFMAMP calculated by EPI Suite is 180 d, it is considered to be potentially persistent. This strategy shows promising potential in environmental pollution assessment, and can be expected to be widely used in future research.

Environmental exposures to organophosphorus flame retardants in early pregnancy and risks of gestational diabetes mellitus: a nested case-control study.

OPFRs are emerging environmental pollutants with reproductive and endocrine toxicity. This study aimed to examine the association between environmental exposure to OPFRs during early pregnancy and GDM. This nested case-control study was based on a birth cohort that was constructed at a maternal and child health hospital, including 74 cases of GDM among 512 pregnant women. The OPFRs, including TBP, TBEP, TCEP, TDCPP, TMCP, TOCP, and TPHP during 10-14 weeks of pregnancy were determined using GC-MS. The association between the OPFRs and GDM was assessed using WQS and BKMR models. The levels of OPFRs were significantly elevated in GDM patients (60) compared with the controls (90). The WQS analysis showed that mixtures of the OPFRs were significantly associated with GDM (OR 1.370, 95% CI 1.036-1.810, P = 0.027), and TBP, TPHP, and TMCP were the major contributors to the mixed exposure effect. In the BKMR model, individual exposure to TBP, TPHP, and TMCP, and the interaction of TMCP with TBP and TPHP were significantly associated with GDM. Environmental exposure to OPFRs is positively associated with GDM. These findings provide evidence for the adverse effects of OPFR exposure on the health of pregnant women.

Monitoring Ammonium Polyphosphate (APP) Biodegradation by Acinetobacter nosocomialis D-3 Using DAPI.

Ammonium polyphosphate (APP), a pivotal constituent within environmentally friendly flame retardants, exhibits notable decomposition susceptibility and potentially engenders ecological peril. Consequently, monitoring the APP concentration to ensure product integrity and facilitate the efficacious management of wastewater from production processes is of great significance. A fluorescent assay was devised to swiftly discern APP utilizing 4',6'-diamino-2-phenylindole (DAPI). With increasing APP concentrations, DAPI undergoes intercalation within its structure, emitting pronounced fluorescence. Notably, the flame retardant JLS-PNA220-A, predominantly comprising APP, was employed as the test substrate. Establishing a linear relationship between fluorescence intensity (F-F0) and JLS-PNA220-A concentration yielded the equation y = 76.08x + 463.2 (R2 = 0.9992), with a LOD determined to be 0.853 mg/L. The method was used to assess the degradation capacity of APP-degrading bacteria. Strain D-3 was isolated, and subsequent analysis of its 16S DNA sequence classified it as belonging to the Acinetobacter genus. Acinetobacter nosocomialis D-3 demonstrated superior APP degradation capabilities under pH 7 at 37 °C, with degradation rates exceeding 85% over a four-day cultivation period. It underscores the sensitivity and efficacy of the proposed method for APP detection. Furthermore, Acinetobacter nosocomialis D-3 exhibits promising potential for remediation of residual APP through environmental biodegradation processes.

Organophosphate esters in human serum: a relatively simple and efficient liquid chromatography-mass spectrometry method.

Organophosphate esters (OPEs) are widely used as flame retardants and plasticizers, which are of growing concern due to their endocrine-disrupting effects, developmental toxicity, and potential carcinogenicity. However, data on human exposure to OPEs is still scarce. In this study, a relatively simple and efficient method with less serum consumption for the detection of OPEs in human serum was developed and validated. Nine OPEs in 200 µL of human serum were extracted by an acetonitrile-formic acid system and analyzed using ultra-high-performance liquid chromatography-quadrupole tandem time-of-flight high-resolution mass spectrometry. Several experiments were conducted to optimize the chromatographic and mass spectrometric conditions as well as sample preparation to obtain a more sensitive and efficient analytical protocol. The proposed method was examined in terms of its linearity, accuracy, precision, detection limit, and matrix effect. The matrix-spiked recoveries of the target OPEs ranged from 83.3% to 111.1%, with relative standard deviations between 2.7% and 16.6%. The detection limits were within (0.002 to 0.029) ng mL-1, while the quantification limits were within (0.007 to 0.098) ng mL-1. The internal standard-corrected matrix effects varied from 82.7% to 113.9%. Finally, the method was applied to detect OPEs in actual human serum samples. All nine OPEs were detected in 269 serum samples to varying degrees, with the average concentrations ranging from (0.08 to 1.77) ng mL-1. After validation, the method was found to be simple in pretreatment, high in sensitivity, good in practicality, and suitable for exposure evaluation of OPEs in populations.

Synthesis of a novel Si-N-S flame retardant and its application on cotton cellulose biomacromolecule.

A novel flame retardant containing Si, N, and S elements, ((2-(triethoxysilyl)ethyl)thio)ethan-1-amine hydrochloride (TETEA), was synthesized via a click reaction and characterized using nuclear magnetic resonance spectroscopy (NMR) and fourier transform infrared spectroscopy (FTIR). Subsequently, the flame-retardant cotton fabric was fabricated by sol-gel method. The results indicated that TETEA was successfully loaded on cotton fabric and formed a uniform protective layer on the surface of cotton fabric, exhibiting excellent flame retardancy. The flame-retardant cotton fabric achieved limiting oxygen index (LOI) of 28.3 % and passed vertical combustion test without after-flame or afterglow time at TETEA concentration of 500 g/L. Thermogravimetric analysis revealed that the residual carbon content of the flame-retardant cotton fabric was much higher than that of the control under air and N2 conditions. Besides, the flame-retardant cotton fabric was not ignited in cone calorimeter test with an external heat flux of 35 kW/m2. The peak heat release rate and the total heat release decreased from 133.4 kW/m2 to 25.8 kW/m2 and from 26.46 MJ/m2 to 17.96 MJ/m2, respectively. This phosphorus-free flame retardant offers a simplified synthesis process without adverse environmental impacts, opening up a new avenue for the development environmentally friendly flame retardants compared to traditional alternatives.

Bio-based melamine formaldehyde resins for flame-retardant polyurethane foams.

The polyurethane (PU) foams can be functionally tailored by modifying the formulation with different additives. One such additive is melamine (MA) formaldehyde resin for improving their flame-retardant properties. In this work, the glycerol-modified (GMF), sodium alginate (SGMF)- and lignosulfonate-modified melamine formaldehyde (LGMF) were prepared and used as flame retardants reacting with isocyanate to prepare the corresponding rigid polyurethane foams (GMF-PU, SGMF-PU and LGMF-PU). The thermomechanical properties and flame-retardant properties of the foams were characterized. The results showed that the specific compression strength of GMF-PU, SGMF-PU and LGMF-PU increased substantially compared to the foams from physical addition of MA, sodium alginate and lignosulfonate, all of which were greater than that of the foam without any flame retardant (PPU). Meanwhile, the cell wall of the foam pores became thicker and the closed pore ratio increased. The sodium alginate and lignosulfonate played a key role in enhancing foam thermal stability. The limiting oxygen index values and cone calorimetry results indicated the flame-retardant efficiency of GMF-PU, SGMF-PU and LGMF-PU was significantly enhanced relative to PPU. Meanwhile, the heat and smoke release results indicated sodium alginate and lignosulfonate could reduce the amount of smoke generation to different degrees during the combustion of the foam.

Empowering the flame retardancy and adhesion for various substrates using renewable feedstock.

Developing biobased flame retardant adhesives using a green and simple strategy has recently gained significant attention. Therefore, in this study, we have orange peel waste (OPW) and Acacia gum (AG) phosphorylated at 140 °C to synthesize biomass-derived flame retardant adhesive. OPW is a biomass material readily available in large quantities, which. Has been utilized to produce an eco-friendly, efficient adhesive. Functionalized polysaccharides were used as a binder rather than volatile, poisonous, and unsustainable petroleum-based aldehydes. The P@OPW/AG green adhesive exhibited a higher tensile strength of 11.25 MPa when applied to cotton cloth and demonstrated versatility across various substrates such as glass, cardboard, plastic, wood, and textiles. Additionally, this bio-based robust adhesive displayed remarkable flame-retardant properties. To optimize its flame retardancy, three tests were employed: the spirit lamp flame test, the vertical flammability test (VFT), and the limiting oxygen index (LOI) test. The P@OPW/AG-coated cotton fabric achieved an impressive LOI result of 42 %, while the VFT yielded a char length of only 4 cm. Additionally, during the flame test, P@OPW/AG coated cloth endured more than 845 s of continuous flame illumination. This work offers a sustainable and fire-safe method for creating environmentally friendly high-performance composites using a recyclable bio-based flame-retardant OPW/AG glue.

Contamination characteristics and dietary intake risk of brominated flame retardants in fishes around a typical e-waste dismantling site in Southern China.

Polybrominated diphenyl ethers (PBDEs) and their substitutes, novel brominated flame retardants (NBFRs), are ubiquitously present in the aquatic environment of electronic waste (e-waste) dismantling region, leading to their inevitable absorption and accumulation by aquatic organisms, which can be transferred to human via directly aquatic product consumption or through food chain, thereby posing potential health risks. This study focused on fish samples from Guiyu and its surrounding areas, and found the total PBDEs concentrations were 24-7400 ng/g lw (mean: 1800 ng/g lw) and the total NBFRs concentrations were 14 to 2300 ng/g lw (mean: 310 ng/g lw). Significant positive correlations were found among PBDE congeners, among different NBFRs, and between NBFRs and commercial PBDEs that they replace. ΣPBDEs and ΣNBFRs in the intestine were 620-350,000 and 91-81,000 ng/g lw (mean: 83000 and 12,000 ng/g lw, respectively), significantly exceeding those in the gills, where ΣPBDEs and ΣNBFRs were 14-37,000 and 39-45,000 ng/g lw (mean: 9200 and 2400 ng/g lw, respectively). The ΣPBDEs and ΣNBFRs showed no non-carcinogenic risks to the target population through dietary intake. Despite the significantly higher daily intake of decabromodiphenyl ethane (DBDPE) compared to decabromodiphenyl ether (BDE209), the non-carcinogenic risk associated with BDE209 remained higher than that of DBDPE. Our findings can assist researchers in understanding the presence of BFRs in aquatic organisms, inhabiting e-waste dismantling areas, and in evaluating the associated health risks posed to humans through dietary exposure.

Do hazardous substances in demolition waste hinder circular economy?

Hazardous substances in demolition waste are often deemed a barrier to a circular economy owing to concerns about their fate in recycled materials. However, with the growing demand for recycling materials, it is essential to find circular solutions for construction materials but still protect health and the environment by managing hazardous substances. In this study, selected hazardous substance groups were analysed from demolition waste samples. Most of the concentrations did not raise any concerns when the safety of recycling materials was considered. However, the detection limits of laboratory chemical analysis can be discussed, as bromine was found in samples by an X-ray fluorescence (XRF)-analyser, but only one laboratory detected brominated flame retardants (BRFs). New technologies and practices are needed to follow the chemical content of materials used in the construction phase. Detecting hazardous substances in recyclable materials is the only way to achieve harmless material cycles.

Community-level risk assessments on organophosphate esters in the sediments from the Bohai Sea of China based on multimodal species sensitivity distributions coupled with the equilibrium partitioning method.

Organophosphate esters (OPEs), increasingly used as alternatives to brominated flame retardants, are ubiquitous in the global aquatic environment. Despite their potential toxicological impact on ecosystems, community-level risk assessments for OPEs in sediments remain scarce. This study investigated OPE occurrences and composition characteristics in the Bohai Sea's sediments and appraised both individual and joint ecological risks posed by characteristic OPE homologs using ten commonly used species sensitivity distribution (SSD) models, integrating acute-to-chronic conversion and phase equilibrium partitioning. OPEs were detected across all sediment samples, with total concentrations ranging from 0.213 ng/g dry weight (dw) to 91.1 ng/g dw. The predominant congeners included tri-n-butyl phosphate (TnBP), triisobutyl phosphate (TiBP), tri(2-ethylhexyl) phosphate, tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCPP), tris(1, 3-dichloro-2-propyl) phosphate (TDCIPP), and triphenylphosphine oxide. Best-fit SSD models varied among TnBP, TiBP, TCEP, TCPP, and TDCIPP, demonstrating Sigmoid, Burr III, Sigmoid, Burr III, and Burr III, respectively. The same parametric model demonstrated variability in the fitting process for different OPE congeners, which also happened to the fitting results of ten parametric models for the same specific characteristic congener, underscoring the necessity of employing multiple models for precise community-level risk assessments. Hazard concentrations for a 5% cumulative probability were 0.116 mg/L, 2.88 mg/L, 1.30 mg/L, 1.44 mg/L, and 1.85 mg/L for each respective congener. The resulting risk quotients (RQ) and overall hazard index (HI) were selected as criteria to assess the individual and joint ecological risks of OPEs in sediments from the Bohai Sea, respectively. RQ and HI were both below 0.1, indicating a low risk to the local ecosystems. Multi-model SSD analysis could provide refined data for community-level risk evaluation, offering valuable insights for the development of evidence-based environmental standards and pollution control strategies.

Brominated flame retardants in surface sediment from Western Guangdong, South China: Occurrence, distribution and toxicity in Caenorhabditis elegans.

Sediment is the ultimate sink of environmental pollutants. A total of 128 surface sediment samples were collected from 8 rivers and 3 reservoirs in Maoming City, Guangdong Province. This study assessed the content and distribution of brominated flame retardants in sediments. The acute toxicity effects of tetrabromobisphenol A (TBBPA) and hexabromocyclododecane (HBCDs) in sediments were evaluated using Caenorhabditis elegans as model organisms. The concentration of TBBPA in sediments ranged from not detected (ND) to 12.59 µg/kg and was mainly distributed in the central area, which was affected by the emission of TBBPA from residential and factory. The concentration of HBCDs ranged from ND to 6.31 µg/kg, and the diastereoisomer distribution was consistent, showing a trend close to the South China Sea. The composition pattern of HBCDs in the surface sediments from rivers were 41.73%-62.33%, 7.89%-25.54%, and 18.76%-40.65% for α-, ß-, and γ-HBCD, respectively, and in the sediments from reservoirs were 26.15%-45.52%, 7.44%-19.23%, and 47.04%-61.89% for α-, ß-, and γ-HBCD, respectively. When the sum of concentrations of TBBPA and HBCD in sediments were above high levels, reactive oxygen species in nematodes significantly increased, resulting in an oxidative stress response. Intestinal permeability was also enhanced, causing intestinal damage. In addition, in terms of this study, TBBPA had a greater impact on biotoxicity compared to HBCDs, and more attention should be paid to the toxic effects of the river ecosystem organisms in Maoming City, Guangdong Province. This study can complement the pollution database in the study area and provide basic data for pollution control.

Reviewing the current state of legacy POP-brominated flame retardants in plastic childcare products and toys: a scoping review protocol.

BACKGROUND: Due to their adverse environmental and health impacts, brominated flame retardants (BFRs) are listed in Annex A of the Stockholm Convention for global elimination of production and use. Their health impacts include endocrine disruption, cancer, reproductive effects, and neurobehavioral and developmental disorders in children. Emerging literature suggests that legacy POP-BFRs are increasingly found in consumer products, including those used for and by children. The presence of legacy POP-BFRs in children's products is a big concern. Children are more vulnerable to chemical exposure risks than adults because their bodies are still developing and fragile. The rising problem is contributed to by the global push towards a circular economy that encourages responsible production and consumption by practising the recycling of waste materials. Waste materials such as electronic and electrical equipment plastics often contain POP-BFRs. POP-BFRs in waste materials are transferred into new products through recycling. The recycled products have become a potential source of exposure to legacy POP-BFRs for vulnerable populations, particularly children. Our scoping review aims to map and summarise the emerging literature. This information is needed to inform evidence-based policies to protect children from toxic exposures. METHODS: Our scoping review will follow a methodological framework proposed by Arksey and O'Malley. Peer-reviewed and grey literature on the topic will be retrieved from electronic databases and other relevant sites. Two reviewers will screen titles and abstracts, followed by a full-text review of studies for eligibility based on the established inclusion and exclusion criteria. Data will be extracted, and findings will be mapped in a table according to study settings, types of children's products tested, and concentration of legacy POP-BFRs in contaminated products. A map chart will be created to display how contaminated products are spread globally. DISCUSSION: Because of their unique vulnerabilities, children continue to suffer disproportionate exposures to toxic chemicals compared to adults. Information on potential exposures, particularly for children, is crucial to make evidence-based policies. We intend to map and summarise the emerging literature on legacy POP-BFRs in children's products. Findings will be disseminated to relevant stakeholders through publishing in a peer-reviewed scientific journal and policy briefs. SYSTEMATIC REVIEW REGISTRATION: The protocol is registered with the Open Science Framework ( https://doi.org/10.17605/OSF.IO/7KDE5 ).

Distribution, traceability, and risk assessment of organophosphate flame retardants in agricultural soils along the Yangtze River Delta in China.

Severe pollution threatens the ecosystem and human health in the Yangtze River Delta (YRD) in China because of the rapid development of industry in this area. This study examines the types, distribution, concentration, and origin of fourteen typical organophosphate flame retardants (OPFRs) in agricultural soils within the YRD region to offer insights for pollutant control and policy-making. The total concentration of OPFRs (ΣOPFRs) varied between 79.19 and 699.58 µg/kg dry weight (dw), averaging at 209.61 µg/kg dw. Among the OPFRs detected, tributoxyethyl phosphate (TBEP) was identified as the main congener, followed by tri-n-butyl phosphate (TnBP), tris(2-chloroisopropyl) phosphate (TCPP), and trimethyl phosphate (TMP). Source analysis, conducted through correlation coefficients and PCA, indicated that OPFRs in agricultural soils within the YRD region mainly originate from emissions related to plastic products and transportation. The health risk exposure to ΣOPFRs in agricultural soil was considered negligible for farmers, with values below 1.24 × 10-2 and 1.76 × 10-9 for noncarcinogenic and carcinogenic risks, respectively. However, the ecological risk of ΣOPFRs in all the samples ranged from 0.08-1.08, indicating a medium to high risk level. The results offer a comprehensive understanding of OPFR pollution in agricultural soils in the YRD region and can be useful for pollution control that mitigates ecological and health risks in this region.

Exposure to organophosphate esters among Inuit adults of Nunavik, Canada.

Halogenated organophosphate esters (OPEs) are increasingly used as flame retardants to replace polybrominated diphenyl ethers (PBDEs), which have been phased out due to their confirmed persistence, toxicity, and ability to undergo long range atmospheric transport. Non-halogenated OPEs are primarily used as plasticizers. While human exposure to PBDEs in the Canadian Arctic is well documented, it is not the case for OPEs. To assess the exposure to OPEs in Inuit living in Nunavik (northern Québec, Canada), we measured 16 metabolites of halogenated and non-halogenated OPEs in pooled urine samples from the last population health survey conducted in Nunavik, the Qanuilirpitaa? 2017 Inuit Health Survey (Q2017). Urine samples (n = 1266) were pooled into 30 pools by sex (female; male), age groups (16-19; 20-29; 30-39; 40-59; 60+ years old) and regions (Hudson Bay; Hudson Strait; Ungava Bay). Q2017 geometric means and 95 % confidence intervals were compared with data from the Canadian Health Measures Survey Cycle 6 (2018-2019) (CHMS). Halogenated OPEs were systematically detected and generally found at higher concentrations than non-halogenated OPEs in both Q2017 and CHMS. Furthermore, urinary levels of BCIPP and BDCIPP (halogenated) were lower in Q2017 compared to CHMS while concentrations of DPhP, DpCP and DoCP (non-halogenated) were similar between Q2017 and CHMS. Across the 16 metabolites measured in Q2017, BCIPHIPP (halogenated) had the highest levels (geometric mean: 1.40 µg/g creatinine). This metabolite was not measured in CHMS and should be included in future surveys. Overall, our results show that Inuit in Nunavik are exposed to lower or similar OPEs levels than the rest of the general Canadian population suggesting that the main current exposure to OPEs may be from consumer goods containing flame retardants and imported from the south rather than long-range atmospheric transport to the Arctic.

Children's exposure to brominated flame retardants in the home: The TESIE study.

Due to differences in chemical properties and half-lives, best practices for exposure assessment may differ for legacy versus novel brominated flame retardants (BFRs). Our objective was to identify the environment matrix that best predicted biomarkers of children's BFR exposures. Paired samples were collected from children aged 3-6 years and their homes, including dust, a small piece of polyurethane foam from the furniture, and a handwipe and wristband from each child. Biological samples collected included serum, which was analyzed for 11 polybrominated diphenyl ethers (PBDEs), and urine, which was analyzed for tetrabromobenzoic acid (TBBA), a metabolite of 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB). Significant positive correlations were typically observed between BFRs measured in dust, handwipes and wristbands, though wristbands and handwipes tended to be more strongly correlated with one another than with dust. PBDEs, EH-TBB and BEH-TEBP were detected in 30% of the sofa foam samples, suggesting that the foam was treated with PentaBDE or Firemaster® 550/600 (FM 550/600). PBDEs were detected in all serum samples and TBBA was detected in 43% of urine samples. Statistically significant positive correlations were observed between the environmental samples and serum for PBDEs. Urinary TBBA was 6.86 and 6.58 times more likely to be detected among children in the highest tertile of EH-TBB exposure for handwipes and wristbands, respectively (95 % CI: 2.61, 18.06 and 1.43, 30.05 with p < 0.001 and 0.02, respectively). The presence of either PentaBDE or FM 550/600 in furniture was also associated with significantly higher levels of these chemicals in dust, handwipes and serum (for PBDEs) and more frequent detection of TBBA in urine (p = 0.13). Our results suggest that children are exposed to a range of BFRs in the home, some of which likely originate from residential furniture, and that silicone wristbands are a practical tool for evaluating external exposure to both legacy and novel BFRs.

A review of occurrence, bioaccumulation, and fate of novel brominated flame retardants in aquatic environments: A comparison with legacy brominated flame retardants.

Novel brominated flame retardants (NBFRs) have been developed as replacements for legacy brominated flame retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs). The prevalence of NBFRs in aquatic environments has initiated intense concerns that they resemble to BFRs. To comprehensively elucidate the fate of NBFRs in aquatic environments, this review summarizes the physico-chemical properties, distribution, bioaccumulation, and fates in aquatic environments. 1,2-bis(2,3,4,5,6-pentabromophenyl) ethane (DBDPE) as the major substitute for PBDEs is the primary NBFR. The release from industrial point sources such as e-waste recycling stations is the dominant way for NBFRs to enter the environment, which results in significant differences in the regional distribution of NBFRs. Sediment is the major sink of NBFRs attributed to the high hydrophobicity. Significantly, there is no decreasing trend of NBFRs concentrations, while PBDEs achieved the peak value in 1970-2000 and decreased gradually. The bioaccumulation of NBFRs is reported in both field studies and laboratory studies, which is regulated by the active area, lipid contents, trophic level of aquatic organisms, and the log KOW of NBFRs. The biotransformation of NBFRs showed similar metabolism patterns to that of BFRs, including debromination, hydroxylation, methoxylation, hydrolysis, and glycosylation. In addition, NBFRs show great potential in trophic magnification along the aquatic food chain, which could pose a higher risk to high trophic-level species. The passive uptake by roots dominates the plant uptake of NBFRs, followed by acropetal and basipetal bidirectional transportation between roots and leaves in plants. This review will provide the support to understand the current pollution characteristics of NBFRs and highlight perspectives for future research.

Children's exposure to halogenated flame retardants and organophosphate esters through dermal absorption and hand-to-mouth ingestion in Swedish preschools.

Children are exposed to endocrine disrupting chemicals (EDCs) through inhalation and ingestion, as well as through dermal contact in their everyday indoor environments. The dermal loadings of EDCs may contribute significantly to children's total EDC exposure due to dermal absorption as well as hand-to-mouth behaviors. The aim of this study was to measure potential EDCs, specifically halogenated flame retardants (HFRs) and organophosphate esters (OPEs), on children's hands during preschool attendance and to assess possible determinants of exposure in preschool indoor environments in Sweden. For this, 115 handwipe samples were collected in winter and spring from 60 participating children (arithmetic mean age 4.5 years, standard deviation 1.0) and analyzed for 50 compounds. Out of these, 31 compounds were identified in the majority of samples. Levels were generally several orders of magnitude higher for OPEs than HFRs, and 2-ethylhexyl diphenyl phosphate (EHDPP) and tris(2-butoxyethyl) phosphate (TBOEP) were detected in the highest median masses, 61 and 56 ng/wipe, respectively. Of the HFRs, bis(2-ethyl-1-hexyl)-2,3,4,5-tetrabromobenzoate (BEH-TEBP) and 2,2',3,3',4,4',5,5',6,6'-decabromodiphenyl ether (BDE-209) were detected in the highest median masses, 2.8 and 1.8 ng/wipe, respectively. HFR and/or OPE levels were found to be affected by the number of plastic toys, and electrical and electronic devices, season, municipality, as well as building and/or renovation before/after 2004. Yet, the calculated health risks for single compounds were below available reference dose values for exposure through dermal uptake as well as for ingestion using mean hand-to-mouth contact rate. However, assuming a high hand-to-mouth contact rate, at the 95th percentile, the calculated hazard quotient was above 1 for the maximum handwipe mass of TBOEP found in this study, suggesting a risk of negative health effects. Furthermore, considering additive effects from similar compounds, the results of this study indicate potential concern if additional exposure from other routes is as high.