Biomarkers of Organophosphate and Polybrominated Diphenyl Ether (PBDE) Flame Retardants of American Workers and Associations with Inhalation and Dermal Exposures.

This study evaluated workers' exposures to flame retardants, including polybrominated diphenyl ethers (PBDEs), organophosphate esters (OPEs), and other brominated flame retardants (BFRs), in various industries. The study aimed to characterize OPE metabolite urinary concentrations and PBDE serum concentrations among workers from different industries, compare these concentrations between industries and the general population, and evaluate the likely route of exposure (dermal or inhalation). The results showed that workers from chemical manufacturing had significantly higher (p <0.05) urinary concentrations of OPE metabolites compared to other industries. Spray polyurethane foam workers had significantly higher (p <0.05) urinary concentrations of bis(1-chloro-2-propyl) phosphate (BCPP) compared to other industries. Electronic scrap workers had higher serum concentrations of certain PBDE congeners compared to the general population. Correlations were observed between hand wipe samples and air samples containing specific flame-retardant parent chemicals and urinary metabolite concentrations for some industries, suggesting both dermal absorption and inhalation as primary routes of exposure for OPEs. Overall, this study provides insights into occupational exposure to flame retardants in different industries and highlights the need for further research on emerging flame retardants and exposure reduction interventions.

Amino Acid Transporter as a Potential Carrier Protein for the Root-to-Shoot Translocation of Polybrominated Diphenyl Ethers in Rice.

As typical persistent organic pollutants, polybrominated diphenyl ethers (PBDEs) tend to accumulate in edible parts of rice, posing great ecological and health risks. The translocation of PBDEs from underground to aboveground parts of rice is a crucial procedure to determine the final bioaccumulation level. Herein, this study aimed to identify the transporter proteins for PBDEs in rice plants in order to strengthen our understanding of the bioaccumulation mechanism and the potential prevention strategy of the PBDE risk. Similar time-dependent patterns were observed among the root-to-shoot translocation factors (TFs) of PBDEs, the expression of lysine histidine transporter (LHT) protein, and the relative levels of LHT substrates (phenylalanine or tyrosine), implying the potential co-transport of PBDEs, phenylalanine, and tyrosine by the carrier LHT. Fluorescence spectra and circular dichroism showed that PBDE congeners interfered with LHT via static fluorescence quenching and changes in the protein's secondary structure. The in vitro sorption fraction of LHT to PBDEs, as revealed by sorption equilibrium analysis, was comparable to the in vivo TF values. Knockout of OsLHT1 in rice using CRISPR/Cas9 technology caused a 48.2-78.4% decrease in PBDE translocation. Molecular docking simulation suggested that PBDEs, phenylalanine, and tyrosine were inserted into the same ligand-binding cavity of LHT, substantiating the potential carrier role of LHT for PBDEs from a conformational perspective. Quantitative structure activity relationship analysis demonstrated that the ether-bond oxygen and the carbons at the site 4 and 4' of PBDE molecules are significant determinants of the binding affinity with the LHT protein and in vivo translocation of PBDEs. In summary, this study discovered that LHT acts as the cellular carrier for PBDEs and offered a comprehensive molecular explanation for the bioaccumulation and translocation of PBDEs in rice plants, covering both biological and chemical perspectives. These findings fill in a knowledge gap on the endogenous transporter proteins for exogenous organic pollutants.

Adipose tissue levels of polybrominated diphenyl ethers in relation to prognostic biomarkers and progression-free survival time of breast cancer patients in eastern area of southern China: A hospital-based study.

Evidence indicates that individual or groups of polybrominated diphenyl ethers (PBDEs) are associated with risk of breast cancer (BC). Epidemiological studies of PBDEs and BC progression are scarce. This study aimed to investigate the relationships between PBDE burdens in adipose tissues and prognostic biomarkers of BC as well as progression-free survival (PFS) of patients for the first time. The concentrations of 14 PBDE congeners in breast adipose tissues of 183 cases from the eastern area of southern China were analyzed by gas chromatography-mass spectrometry (GC-MS). Odds ratios (ORs) and 95% confidence intervals (CIs) were estimated by logistic regression models for the associations between PBDE levels and prognostic biomarkers. Kaplan-Meier and Cox regression analyses were conducted to identify the correlations between PBDEs and PFS. The results showed that BDE-99 and 190 levels were positively associated with clinical stage and N stage respectively (OR = 2.61 [1.26-5.40], OR = 2.78 [1.04-7.46]). Concentrations of BDE-28 and BDE-183 were negatively associated with the expression of estrogen receptor (ER) (OR = 0.30 [0.11-0.81]; 0.39 [0.15-0.99]) and progesterone receptor (PR) (OR = 0.36 [0.14-0.92]; 0.37 [0.15-0.91]), and increased BDE-47 was associated with lower human epidermal growth factor receptor 2 (HER2) expression (OR = 0.44 [0.23-0.86]). Adipose levels of BDE-71, 99, 138, 153, 154 and total PBDEs were positively associated with p53 expression (all P < 0.05). Finally, BDE-47, 99 and 183 were considered as independent prognostic factors for shorter PFS in the Cox models (adjusted hazard ratios = 3.14 [1.26-7.82]; 2.25 [1.03-4.94]; 2.60 [1.08-6.25], respectively). The recurrence risk and prognosis of BC may be closely bound to the body burdens of certain PBDE congeners. Further epidemiological and experimental studies are needed for confirmation.

Chemical reductive technologies for the debromination of polybrominated diphenyl ethers: A review.

Polybrominated diphenyl ethers (PBDEs) are widely used as brominated flame retardants, which had attracted amounts of attention due to their harmful characteristics of high toxicity, environmental persistence and potential bioaccumulation. Many chemical reductive debromination technologies have been developed for the debromination of PBDEs, including photolysis, photocatalysis, electrocatalysis, zero-valent metal reduction, chemically catalytic reduction and mechanochemical method. This review aims to provide information about the degradation thermodynamics and kinetics of PBDEs and summarize the degradation mechanisms in various systems. According to the comparative analysis, the rapid debromination to generate bromine-free products in an electron-transfer process, of which photocatalysis is a representative one, is found to be relatively difficult, because the degradation rate of PBDEs depended on the Br-rich phenyl ring with the lowest unoccupied molecular orbital (LUMO) localization. On the contrary, the complete debromination occurs easily in other systems with active hydrogen atoms as the main reactive species, such as chemically catalytic reduction systems. The review provides the knowledge on the chemical reductive technique of PBDEs, which would greatly help not only clarify the degradation mechanism but also design the more efficient system for the rapid and deep debromination of PBDEs in the future.

The interaction mechanisms of co-existing polybrominated diphenyl ethers and engineered nanoparticles in environmental waters: A critical review.

This review focuses on the occurrence and interactions of engineered nanoparticles (ENPs) and brominated flame retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs) in water systems and the generation of highly complex compounds in the environment. The release of ENPs and BFRs (e.g. PBDEs) to aquatic environments during their usage and disposal are summarised together with their key interaction mechanisms. The major interaction mechanisms including electrostatic, van der Waals, hydrophobic, molecular bridging and steric, hydrogen and π-bonding, cation bridging and ligand exchange were identified. The presence of ENPs could influence the fate and behaviour of PBDEs through the interactions as well as induced reactions under certain conditions which increases the formation of complex compounds. The interaction leads to alteration of behaviour for PBDEs and their toxic effects to ecological receptors. The intermingled compound (ENPs-BFRs) would show different behaviour from the parental ENPs or BFRs, which are currently lack of investigation. This review provided insights on the interactions of ENPs and BFRs in artificial, environmental water systems and wastewater treatment plants (WWTPs), which are important for a comprehensive risk assessment.

Associations between polybrominated diphenyl ethers (PBDEs) levels in adipose tissues and blood lipids in women of Shantou, China.

Animal studies have indicated that exposure to polybrominated diphenyl ethers (PBDEs) during development can permanently affect blood/liver lipid balance. However, no epidemiological study has assessed the relationship between PBDEs in adipose tissues and blood lipid metabolism. In this study, we explored the associations between PBDEs levels in female adipose tissues and lipid profiles. We recruited 150 female patients undergoing plastic surgery from hospital in Shantou, China, collected their characteristics, clinical information, and adipose tissue samples. Fourteen PBDE congeners in adipose tissues were analyzed by gas chromatography-mass spectrometry (GC-MS). Multiple linear and logistic regression models were used to explore the relationships between PBDEs and lipid profiles, while restricted cubic spline (RCS) regression and Bayesian kernel machine regression (BKMR) models were used to evaluate the nonlinearity of mixtures. Median levels of ΣPBDEs and dominant congeners BDE-153, -209, and -183 in adipose tissues were 73.91, 26.12, 14.10 and 9.01 ng/g lipid, respectively. In the multiple linear model, BDE-153 and BDE-209 were negatively associated with triglycerides (TG), similarly for BDE-190 and total cholesterol (TC). While in the adjusted logistic models, BDE-138 was negatively associated with TC (OR = 0.76, 95%CI: 0.58, 0.99) and total lipids (TL) (OR = 0.76, 95%CI: 0.58, 0.99). Diastolic blood pressure was positively correlated with BDE-28 and BDE-71 (P < 0.05). Furthermore, a non-linear relationship was observed in BDE-138 and blood lipid levels using a RCS model (Pnonlinearity<0.05). BKMR analysis indicated that with the cumulative levels across PBDEs increased, the health risks of hypertriglyceridemia gradually rebounded, and the health risks of hypercholesterolemia and high total lipid gradually rebounded and then declined, but without statistical significance. PBDEs pollution was still prevalent in Shantou city, and several PBDE congeners were significant risk factors for dyslipidemia and blood pressure alteration. There exist deleterious effects of PBDEs and blood lipids.

The relationship between persistent organic pollutants and Attention Deficit Hyperactivity Disorder phenotypes: Evidence from task-based neural activity in an observational study of a community sample of Canadian mother-child dyads.

BACKGROUND: Prenatal exposure to persistent organic pollutants (POPs), widespread in North America, is associated with increased Attention Deficit/Hyperactivity Disorder (ADHD) symptoms and may be a modifiable risk for ADHD phenotypes. However, the effects of moderate exposure to POPs on task-based inhibitory control performance, related brain function, and ADHD-related symptoms remain unknown, limiting our ability to develop interventions targeting the neural impact of common levels of exposure. OBJECTIVES: The goal of this study was to examine the association between prenatal POP exposure and inhibitory control performance, neural correlates of inhibitory control and ADHD-related symptoms. METHODS: Prospective data was gathered in an observational study of Canadian mother-child dyads, with moderate exposure to POPs, including polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs), as part of the GESTation and the Environment (GESTE) cohort in Sherbrooke, Quebec, Canada. The sample included 87 eligible children, 46 with maternal plasma samples, functional magnetic resonance imaging (fMRI) data of Simon task performance at 9-11 years, and parental report of clinical symptoms via the Behavioral Assessment System for Children 3 (BASC-3). Simon task performance was probed via drift diffusion modeling, and parameter estimates were related to POP exposure. Simon task-based fMRI data was modeled to examine the difference in incongruent vs congruent trials in regions of interest (ROIs) identified by meta analysis. RESULTS: Of the 46 participants with complete data, 29 were male, and mean age was 10.42 ± 0.55 years. Increased POP exposure was associated with reduced accuracy (e.g. PCB molar sum rate ratio = 0.95; 95% CI [0.90, 0.99]), drift rate (e.g. for PCB molar sum ß = -0.42; 95% CI [-0.77, -0.07]), and task-related brain activity (e.g. in inferior frontal cortex for PCB molar sum ß = -0.35; 95% CI [-0.69, -0.02]), and increased ADHD symptoms (e.g. hyperactivity PCB molar sum ß = 2.35; 95%CI [0.17, 4.53]), supporting the possibility that prenatal exposure to POPs is a modifiable risk for ADHD phenotypes. DISCUSSION: We showed that exposure to POPs is related to task-based changes in neural activity in brain regions important for inhibitory control, suggesting a biological mechanism underlying previously documented associations between POPs and neurobehavioral deficits found in ADHD phenotypes.

Structural binding perspectives of common plasticizers and a flame retardant, BDE-153, against thyroxine-binding globulin: potential for endocrine disruption.

The human exposure to diverse endocrine-disrupting chemicals (EDCs) has increased dramatically over several decades with very adverse health effects. Plasticizers and flame retardants constitute important classes of EDCs interfering in endocrine physiology including the thyroid function. Thyroxine (T4) is an important hormone regulating metabolism and playing key roles in developmental processes. In this study, six phthalate and nonphthalate plasticizers and one flame retardant (BDE-153) were subjected to structural binding against thyroxine-binding globulin (TBG). The aim was to understand their potential role in thyroid dysfunction using structural binding approach. The structural study was performed using Schrodinger's induced fit docking, followed by binding energy estimations of ligands and the molecular interaction analysis between the ligands and the amino acid residues in the TBG ligand-binding pocket. The results indicated that all the compounds packed tightly into the TBG ligand-binding pocket with similar binding pattern to that of TBG native ligand, T4. A high majority of TBG interacting amino acid residues for ligands showed commonality with native ligand, T4. The estimated binding energy values were highest for BDE-153 followed by nonphthalate plasticizer, DINCH, with values comparable with native ligand, T4. The estimated binding energy values of other plasticizers DEHP, DEHT, DEHA, ATBC, and TOTM were less than DINCH. In conclusion, the tight docking conformations, amino acid interactions, and binding energy values of the most of the indicated ligands were comparable with TBG native ligand, T4, suggesting their potential for thyroid dysfunction. The results revealed highest potential thyroid disruptive action for BDE-153 and DINCH.

Selected Persistent Organic Pollutants in Ambient Air in Turkey: Regional Sources and Controlling Factors.

As a result of its unique location, Turkey receives air masses from Europe, Russia, Middle East, and Africa, making it an important place in terms of long-range atmospheric transport (LRT) of contaminants. Atmospheric levels of 22 organochlorine pesticides (OCPs), 45 polychlorinated biphenyls (PCBs), and 14 polybrominated diphenyl ethers (PBDEs) were measured in two metropolitan cities, Istanbul and Izmir, on a weekly basis from May 2014 to May 2015. Dichlorodiphenyltrichloroethane (DDT) and its derivatives were dominant OCP species, followed by isomers of hexachlorocyclohexane (HCH) at both sites. The annual mean concentration of ∑DDX (sum of o,p'-DDT, p,p'-DDT, o,p'-DDD, p,p'-DDD, o,p'-DDE, and p,p'-DDE) was 82 pg/m3 for Istanbul and 89 pg/m3 for Izmir, while these levels were about 46 pg/m3 for ∑HCHs (sum of α-, ß-, γ-, and δ-HCH) at both of the sites. At both stations, tri- and tetra-PCBs and tetra- and penta-PBDEs were dominant congeners. The temperature dependence indicates that both LRT and local contaminated areas contribute to the elevated levels. A Lagrangian particle dispersion model (FLEXPART) showed a few potential source regions in northern Africa and Middle East, southern-southwestern and eastern Europe including Russia, as well as from local domestic metropolitan areas.

Novel Bayesian Method to Derive Final Adjusted Values of Physicochemical Properties: Application to 74 Compounds.

Accurate values of physicochemical properties are essential for screening semivolatile organic compounds for human and environmental hazard and risk. In silico approaches for estimation are widely used, but the accuracy of these and measured values can be difficult to ascertain. Final adjusted values (FAVs) harmonize literature-reported measurements to ensure consistency and minimize uncertainty. We propose a workflow, including a novel Bayesian approach, for estimating FAVs that combines measurements using direct and indirect methods and in silico values. The workflow was applied to 74 compounds across nine classes to generate recommended FAVs (FAVRs). Estimates generated by in silico methods (OPERA, COSMOtherm, EPI Suite, SPARC, and polyparameter linear free energy relationships (pp-LFER) models) differed by orders of magnitude for some properties and compounds and performed systematically worse for larger, more polar compounds. COSMOtherm and OPERA generally performed well with low bias although no single in silico method performed best across all compound classes and properties. Indirect measurement methods produced highly accurate and precise estimates compared with direct measurement methods. Our Bayesian method harmonized measured and in silico estimated physicochemical properties without introducing observable biases. We thus recommend use of the FAVRs presented here and that the proposed Bayesian workflow be used to generate FAVRs for SVOCs beyond those in this study.

Assessing decontamination and laundering processes for the removal of polycyclic aromatic hydrocarbons and flame retardants from firefighting uniforms.

Firefighter uniforms protect firefighters from exposure to potentially harmful chemicals including a range of semi-volatile organic compounds (SVOCs). Contaminated uniforms can become a secondary source of firefighters' exposure to these chemicals. There is inconsistency on the removal efficiency of SVOCs during the cleaning, laundering and field decontamination of firefighting uniforms. Therefore, this study aims to assess how effective decontamination and laundering processes are in reducing firefighter uniforms as a vector for transport and exposure to SVOCs. Firefighters who had attended a controlled house fire and simulated container burns had their uniforms sampled pre- and post-laundering. Clean station wear was laundered with contaminated uniforms and after a load of contaminated uniforms to assess inter and intra load contamination. Surface wipes were collected from uniforms across 12 fire stations, after they had returned from a laundering provider. Concentrations of 13 polycyclic aromatic hydrocarbons (PAHs), six organophosphate flame retardants (OPFRs) and seven polybrominated diphenyl ethers (PBDEs) were measured in the collected samples. The concentrations of ∑13 PAHs in firefighters uniforms ranged between 0.063 and 43 µg g-1, while concentration of ∑6 OPFRs were between 0.061 and 90 µg g-1 with ∑7 PBDEs concentrations being measured between 0.00054 and 0.97 µg g-1.The highest concentrations of ∑13 PAHs were measured on the outer layers of gloves at an average of 19 µg g-1, with the highest ∑6 OPFRs concentrations being measured in the middle layers of gloves at an average of 31 µg g-1. The highest ∑7 PBDEs concentrations were measured on the shell layers of turnout jackets at 0.42 µg g-1. The significant reduction in ∑13 PAHs after laundering or decontamination was only found in 3 of the 16 sampled areas from firefighting uniforms. No significant differences were found in the between pre- and post-laundering concentrations of ∑6 OPFRs or ∑7 PBDEs in firefighting uniforms. The current laundering techniques do not appear to effectively remove PAHs, OPFRs and PBDEs at the measured concentrations from firefighters' uniforms. Further research is required to assess if chemical exposure though firefighting uniforms poses a health risk to firefighters and to develop methods for the removal of SVOCs from firefighting uniforms.

Absorption, distribution, metabolism, and excretion of three [14C]PBDE congeners in laying hens and transfer to eggs.

Polybrominated diphenyl ethers (PBDEs) levels in environmental matrices have generally declined following their phaseout as flame retardants. The objective of this study was to determine the absorption, distribution, metabolism, and excretion of three persistent PBDEs in laying hens and their transfer into eggs. Laying hens (n = 4 per congener) received a single oral dose of BDE-99, -153, or -209 and eggs and excreta were collected daily for 7 days, then tissues were collected and analysed. Cumulative BDE-209 excretion was 93% of dose, and bioavailability was approximately 17%. Lesser amounts of BDE-99 (41%) and -153 (26%) were excreted with bioavailabilities of 87% and 79%, respectively. Phenolic metabolites were observed in excreta extracts from BDE-99 dosed birds. Cumulative transfers based on bioavailability of BDE-99, -153, and -209 to eggs were 17%, 34%, and 15%, respectively. Egg residues were primarily present in yolk (12.3%, 23.5%, and 2.1% of the total dose for BDE-99, -153, and -209, respectively). Adipose, skin, ova, intestine, and thigh muscle contained the highest levels of radioactive tissue residues. These studies demonstrate movement of PBDE residues into edible tissues and eggs of laying hens.

Molecular Modifications and Control of Processes to Facilitate the Synergistic Degradation of Polybrominated Diphenyl Ethers in Soil by Plants and Microorganisms Based on Queuing Scoring Method.

In this paper, a combination of modification of the source and regulation of the process was used to control the degradation of PBDEs by plants and microorganisms. First, the key proteins that can degrade PBDEs in plants and microorganisms were searched in the PDB (Protein Data Bank), and a molecular docking method was used to characterize the binding ability of PBDEs to two key proteins. Next, the synergistic binding ability of PBDEs to the two key proteins was evaluated based on the queuing integral method. Based on this, three groups of three-dimensional quantitative structure-activity relationship (3D-QSAR) models of plant-microbial synergistic degradation were constructed. A total of 30 PBDE derivatives were designed using BDE-3 as the template molecule. Among them, the effect on the synergistic degradation of six PBDE derivatives, including BDE-3-4, was significantly improved (increased by more than 20%) and the environment-friendly and functional evaluation parameters were improved. Subsequently, studies on the synergistic degradation of PBDEs and their derivatives by plants and microorganisms, based on the molecular docking method, found that the addition of lipophilic groups by modification is beneficial to enhance the efficiency of synergistic degradation of PBDEs by plants and microorganisms. Further, while docking PBDEs, the number of amino acids was increased and the binding bond length was decreased compared to the template molecules, i.e., PBDE derivatives could be naturally degraded more efficiently. Finally, molecular dynamics simulation by the Taguchi orthogonal experiment and a full factorial experimental design were used to simulate the effects of various regulatory schemes on the synergistic degradation of PBDEs by plants and microorganisms. It was found that optimal regulation occurred when the appropriate amount of carbon dioxide was supplied to the plant and microbial systems. This paper aims to provide theoretical support for enhancing the synergistic degradation of PBDEs by plants and microorganisms in e-waste dismantling sites and their surrounding polluted areas, as well as, realize the research and development of green alternatives to PBDE flame retardants.

Polybrominated Diphenyl Ethers and Heavy Metals in a Regulated E-Waste Recycling Site, Eastern China: Implications for Risk Management.

Serious pollution of multiple chemicals in irregulated e-waste recycling sites (IR-sites) were extensively investigated. However, little is known about the pollution in regulated sites. This study investigated the occurrence of 21 polybrominated diphenyl ethers (PBDEs) and 10 metals in a regulated site, in Eastern China. The concentrations of PBDEs and Cd, Cu, Pb, Sb, and Zn in soils and sediments were 1-4 and 1-3 orders of magnitude lower than those reported in the IR-sites, respectively. However, these were generally comparable to those in the urban and industrial areas. In general, a moderate pollution of PBDEs and metals was present in the vegetables in this area. A health risk assessment model was used to calculate human exposure to metals in soils. The summed non-carcinogenic risks of metals and PBDEs in the investigated soils were 1.59-3.27 and 0.25-0.51 for children and adults, respectively. Arsenic contributed to 47% of the total risks and As risks in 71.4% of the total soil samples exceeded the acceptable level. These results suggested that the pollution from e-waste recycling could be substantially decreased by the regulated activities, relative to poorly controlled operations, but arsenic pollution from the regulated cycling should be further controlled.

Polybrominated diphenyl ethers in soils from Tianjin, North China: distribution, health risk, and temporal trends.

Available information is still insufficient for a comprehensive understanding of the global distribution of polybrominated diphenyl ethers (PBDEs) in the environment. In particular, little is known about the changing trend of their distribution in urban soils. We conducted a survey of 21 PBDEs in urban soils from Tianjin, China. The chemicals were widely present in the area and summed concentrations ranged from 0.65 to 108 ng/g in soil, indicating low to moderate levels of pollution relative to other areas. BDE-209 was the predominant congener, contributing 88.9% of the concentrations of total soil PBDEs. Source assessment indicated that soil PBDEs in the area were mainly derived from the release of commercial deca-BDE from local industrial production processes and consumer products. We found that the soil concentrations of PBDEs appear to have declined in recent years, compared with other previous reports in this region. However, more studies are needed on this possible change trend of PBDE pollution, especially its impact on human health, although their calculated non-carcinogenic health risks in this study were low.

Concentration profile, spatial distributions and temporal trends of polybrominated diphenyl ethers in sediments across China: Implications for risk assessment.

Polybrominated diphenyl ethers (PBDEs) in sediments of China have been extensively investigated; however, most studies conducted to date have focused on specific locations, and the pollution and risk posed by these chemicals in sediments at the national scale remain unknown. Therefore, we analyzed the concentrations and risks of PBDEs in sediments in China and their spatiotemporal variations based on available literature. Overall, the sediments across China contain moderate to high levels of PBDEs, with BDE-209 being the dominant congener, followed by BDE-47 and BDE-99. The sediment concentrations of PBDEs were highest in southern China and lowest in northeastern China. Additionally, based on their PBDE concentrations, 18.4%, 30.0%, and 11.9% of sediment samples from rivers, lakes, and coastal waters, respectively, posed low to moderate eco-toxicological risks, but 6.90% of river sediments posed high risks. Between 2001 and 2017, the concentrations and risks of PBDEs in the sediments from rivers and coastal waters tended to decrease gradually. Additionally, there were low to moderate risks from PBDEs in lake sediments, and the risks in 2012-2017 were 3.30 times higher than those in 2006-2011. However, more studies about the spatial and temporal trends in PBDEs in sediment across China and their impacts on aquatic organisms are needed because there is still a general lack of relevant information.

A Halogen Bonding Perspective on Iodothyronine Deiodinase Activity.

Iodothyronine deiodinases (Dios) are involved in the regioselective removal of iodine from thyroid hormones (THs). Deiodination is essential to maintain TH homeostasis, and disruption can have detrimental effects. Halogen bonding (XB) to the selenium of the selenocysteine (Sec) residue in the Dio active site has been proposed to contribute to the mechanism for iodine removal. Polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) are known disruptors of various pathways of the endocrine system. Experimental evidence shows PBDEs and their hydroxylated metabolites (OH-BDEs) can inhibit Dio, while data regarding PCB inhibition are limited. These xenobiotics could inhibit Dio activity by competitively binding to the active site Sec through XB to prevent deiodination. XB interactions calculated using density functional theory (DFT) of THs, PBDEs, and PCBs to a methyl selenolate (MeSe-) arrange XB strengths in the order THs > PBDEs > PCBs in agreement with known XB trends. THs have the lowest energy C-X*-type unoccupied orbitals and overlap with the Se lp donor leads to high donor-acceptor energies and the greatest activation of the C-X bond. The higher energy C-Br* and C-Cl* orbitals similarly result in weaker donor-acceptor complexes and less activation of the C-X bond. Comparison of the I···Se interactions for the TH group suggest that a threshold XB strength may be required for dehalogenation. Only highly brominated PBDEs have binding energies in the same range as THs, suggesting that these compounds may inhibit Dio and undergo debromination. While these small models provide insight on the I···Se XB interaction itself, interactions with other active site residues are governed by regioselective preferences observed in Dios.

Accumulation and Transformation of 2,2',4,4'-Tetrabrominated Diphenyl Ether (BDE47) by the Earthworm Metaphire vulgaris in Soil.

The accumulation and transformation of 2,2',4,4'-tetrabrominated diphenyl ether (BDE47), one congener of the flame retardants polybrominated diphenyl ethers (PBDEs), in soil-feeding fauna are still unknown. Using radioactivity tracer, we incubated 14C-labelled BDE47 in soil for 21 days in the presence and absence of the geophagous earthworm Metaphire vulgaris. BDE47 accumulated in the earthworm predominantly via oral ingestion of soil, giving a biota-soil accumulation factor (BSAF) value of 1.3 for radioactivity at the end of incubation, and was mostly located in intestine, followed by clitellum (organs region) and skin of earthworms. Accumulation was accompanied by significant decrease of BDE47 concentration in soil porewater and BDE47 mineralization in soil. BDE47 was transformed in the earthworm gut into two metabolites with higher polarities than BDE47. The results provide for the first time insights into accumulation and transformation of lower-brominated congeners of PBDEs in geophagous earthworms, being helpful for environmental risk assessment of PBDEs.

Alteration of Placental Deiodinase 3 Expression by BDE 209 and Possible Protection by Taurine in Human Placenta-Derived JEG Cells Under Hypoxia.

Thyroid hormones are key hormones involved in growth and development. Changes in their levels can cause embryonic brain developmental damage in the first trimester. Studies have shown that polybrominated diphenyl ethers (PBDEs) have developmental neurotoxicity as environmental pollutants, and exposure during pregnancy can cause irreversible brain damage in offspring, similar to the interference effects of thyroid hormones, but its mechanism has not yet been understood. Since the physiological environment for placental cells is highly hypoxic, in the current study, the human placenta-derived JEG cells were cultured at 1% oxygen, 4% carbon dioxide and 94% nitrogen, to reflect in vivo scenario, and the possible protection of taurine on BDE 209-mediated toxicity in JEG cells was studied. Our data showed that different concentrations of BDE 209 can have profound effects on cell viability and placental deiodinase 3 expression under hypoxic culture condition. Taurine was found to improve BDE 209-induced reductions in cell viability and altered gene and protein expressions of placental deiodinases. The results provide a reference for the establishment of early biomarkers and effective preventive measures.

Effect of Taurine on Alterations in Deiodinase 3 Expression Induced by BDE 209 in Human Neuroblasoma-Derived SK-N-AS Cells.

PBDEs (stands for polybrominated diphenyl ethers) are extensively utilized flame retardants, and BDE 209 is one of the most widely used congeners. Studies have suggested the general toxic effects of PBDEs on the endocrine system and neural development. Our previous studies found that BDE 209 changed Type 3 iodothyronine deiodinase (Dio 3) expression in human SK-N-AS neuroblastoma cells. The current study was designed to examine the potential protection of taurine on alterations of Dio 3 expression induced by BDE 209 in SK-N-AS cells. Briefly, SK-N-AS cells were pretreated with taurine prior to the BDE 209 treatment, and the cell viability was evaluated by the MTT (methyl-thiazolyl-tetrazolium) assay. The disturbance or restoration in the levels of Dio 3 proteins and mRNA were observed separately by the western blot and qRT-PCR. Our data showed that taurine moderately attenuated BDE 209-mediated the loss of cell viability. Also, taurine moderately prevented the reduction in the Dio 3 protein expression and mRNA expression induced by BDE 209 in the SK-N-AS cells. Our findings indicated that taurine potentially provide the protection on PBDEs-induced toxicity on endocrine and neuro-development.