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Polybrominated diphenyl ethers (PBDEs) and their alternatives (e.g., dechlorane plus (DPs) and decabromodiphenyl ethane (DBDPE)) are ubiquitous in various environmental media. However, limited data is available on these chemicals in edible fish species from the wide-open South China Sea (SCS). In the present study, ten legacy PBDEs and three substitutions (DBDPE and two DPs) were analyzed in 16 wild fish species sampled from the open SCS to investigate their spatial and species-specific variations. The results showed that the total concentrations of PBDEs, DBDPE, and DPs in fish samples were in the range of 1.69-47.6, not detected (nd) to 21.0, and nd to 3.80 ng/g lipid weight (lw), respectively. BDEs 47, 209 and 100 were the dominant target PBDE congeners, representing 49.2%, 17.2% and 9.93% of the total PBDE concentrations, respectively. Higher concentrations of PBDEs, DBDPE, and DPs were found in fish species from the Wanshan Archipelago compared to those from the Mischief Reef and the Yongxing Island, suggesting the significant influence of anthropogenic activities. Species-specific differences in levels of PBDEs were observed, with the order of bathydemersal > demersal > pelagic ≈ reef-associated > benthopelagic species. The average f anti value of all fish samples was 0.68, suggesting commercial DP products as a contamination source. The levels of PBDEs, DPs, and DBDPE in fish samples were relatively low compared with those from other locations around the globe. Finally, the health risks concerning the ingestion of BDEs 47, 99, 153 and 209 via fish consumption collected from the SCS are negligible., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Despite their ban, polybrominated diphenyl ethers (PBDEs) are frequently detected in various environmental compartments including marine and coastal ecosystems due to their persistence, bio-accumulative, high production volumes, and widespread use. One of the major concerns from PBDEs is the transformation products, such as hydroxylated polybrominated diphenyl ethers (OH-BDEs), which are more bioactive than the parent compounds. For example, 6-hydroxy-2,2',4',4-tetrabromodiphenyl ether (6-OH-BDE-47) is a typical metabolite of PBDEs and cause endocrine system disruption, developmental toxicity, and neurotoxicity in different species. Despite being widely detected in marine environments, investigations on the toxicological mechanisms of 6-OH-BDE-47 in cetaceans remain scarce. High concentrations of PBDEs accumulate in cetaceans due to the long lifespan and large fat reserve. The accumulated PBDEs have become the major source of OH-BDEs in cetaceans. We exposed immortalized fibroblast cell lines from the skin of pygmy killer whales (PKW-LWHT) and Indo-Pacific finless porpoises (FP-LWHT) to 6-OH-BDE-47 and analyzed changes in cellular function using transcriptomic data, along with enzymatic activity. Exposure to the body-relevant body burdens of 6-OH-BDE-47 (250 and 500 ng mL -1 ) significantly decreased cell viability. Differentially expressed genes in FP-LWHT exposed to 6-OH-BDE-47 were primarily enriched in the pathways associated with steroid metabolism. Total cholesterol was decreased by 6-OH-BDE-47, whereas low-density lipoprotein cholesterol and triglyceride levels were significantly increased in FP-LWHT cells. In contrast, glycolysis was the main enriched function of differentially expressed genes in PKW-LWHT cells exposed to 6-OH-BDE-47, and the enzyme activity of phosphofructokinase and hexokinase was upregulated. Thus, even though the cell viability of both cell lines from these two species was significantly suppressed by 6-OH-BDE-47, the cellular response or affected cellular function was different between the Pygmy killer whale and the Indo-Pacific Finless Porpoise, suggesting a diverse response towards OH-BDEs exposure., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could influence the work reported in this study., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Halogenated flame retardants in farmlands were observed to inhibit the growth of exposed crops. This study aimed to elucidate the mechanism of inhibition on rice by employing four representative polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs). The exposure to these contaminants at 200 nM led to a decrease of 0.63-0.95 fold in rice below-ground biomass and 0.49-0.66 fold in yield, and a corresponding 4%-10% increase in soluble sugars in leaves. PBDEs and PCBs were found to significantly disrupt the synthesis, decomposition, and transport of sugars in leaves, the three pivotal determinants of crop growth. Notably, these compounds promoted a 1.41- to 7.60-fold upregulation of the triose phosphate translocator, significantly enhancing soluble sugar synthesis. Conversely, a 0.45-0.97 fold downregulation was observed for sucrose transporters, thus impeding the leaf-to-shoot efflux of soluble sugars. Furthermore, PBDEs and PCBs were favorably bound to fructose-1,6-bisphosphate aldolase (FBA), inducing its substrate-specific dysfunction in fructose-1,6-diphosphate decomposition (3%-14%). Overall, PBDE and PCB exposure promoted a notable intracellular accumulation of soluble sugars in rice leaves, a typical symptom of plant diabetes, since the intensified synthesis of soluble sugars in leaves and the repressed decomposition and transportation of soluble sugars to other storage organs, thus impeding crop growth. This study provided an insightful understanding of the toxic effects and molecular mechanisms of halogenated flame retardants, highlighting their role in abnormal sugar accumulation and growth inhibition in crops and offering vital information for the risk assessment and administration of these compounds to guarantee the safety of agricultural products., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Bromophenols has been proven to synthesize hydroxylated polybrominated diphenyl ethers (OH-PBDEs), which may pose additional environmental and health risks in the process of bioremediation. In this study, the removal of 2,4-dibromophenol (2,4-DBP) and 2,4,6-tribromophenol (2,4,6-TBP) and the biosynthetic of OH-PBDEs by Prorocentrum donghaiense were explored. The removal efficiencies of 2,4-DBP and 2,4,6-TBP ranged from 32.71% to 76.89% and 31.15%-78.12%, respectively. Low concentrations of 2,4-DBP stimulated algal growth, while high concentrations were inhibitory. Furthermore, exposure to 10.00 mg L -1 2,4-DBP resulted in the detection of 2'-hydroxy-2,3',4,5'-tetrabromodiphenyl ether (2'-OH-BDE-68) within P. donghaiense. In contrast, increasing concentrations of 2,4,6-TBP considerably inhibited P. donghaiense growth, with 4'-hydroxy-2,3',4,5',6-pentabromodiphenyl ether (4'-OH-BDE-121) detected within P. donghaiense under 5.00 mg L -1 2,4,6-TBP. Metabolomic analysis further revealed that the synthesized OH-PBDEs exhibited higher toxicity than their precursors and identified the oxidative coupling as a key biosynthetic mechanism. These findings confirm the capacity of P. donghaiense to remove bromophenols and biosynthesize OH-PBDEs from bromophenols, offering valuable insights into formulating algal bioremediation to mitigate bromophenol contamination., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The contamination status on persistent organic pollutants (POPs) in the Croatian terrestrial ecosystem was investigated by analyzing two classes of contaminants in adipose tissue of male European brown bear (Ursus arctos, N = 27) collected in 2021 and 2022. In addition to seven indicator polychlorinated biphenyls (PCBs), for the first time seven polybrominated diphenyl ethers (PBDEs) were analyzed in terrestrial species from this region. Sum of mass fractions detected in adipose tissue ranged from 0.011 to 0.463 ng g -1 lipid weight (lw) for the PBDEs, and from 0.652 to 30.17 ng g -1 lw for PCBs, with two orders of magnitude difference in the median value for these two groups of POPs (PBDEs: 0.022 ng g -1 lw; PCBs: 2.307 ng g -1 lw). PCBs dominated over PBDEs with a share of over 94 % of the total mass fractions of both groups of analyzed POPs. Results of the comparison of the PCB levels in the adipose tissue of brown bears reported here and in previous investigation from this region showed decrease in PCB-28, but increase of PCB-118 and PCB-180, while other congeners seemed to have reached a steady-state level in the environment over a ten-year period. Among the compounds analyzed in this study, BDE-47, PCB-153 and PCB-180 were the dominant congeners. Somewhat higher sum of PCBs was measured in April compared to October, although not statistically significant, indicating possible impact of winter hibernation causing concentration of lipophilic compounds due to body fat loss. Revealed POP levels in brown bears are consistent with the data on the low contamination of the Croatian terrestrial ecosystem in general., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Polybrominated diphenyl ethers (PBDEs) in soils posed potential risks to crop growth and food safety due to their prevalence and persistence. PBDEs were capable of being absorbed and accumulated into crops, impacting their growth, whereas the interference on metabolic components and nutritional composition deserves further elucidation. This study integrated a combined non-targeted and targeted metabolomics method to explore the influences of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), 2,2',4,4',5-pentabromodiphenyl ether (BDE-99) and decabromodiphenyl ether (BDE-209) on the metabolic responses of rice (Oryza sativa). Metabolic pathways, which were associated with sugars, organic acids, and amino acids, were significantly disturbed under PBDE stresses. Particularly, 75% of the marked altered pathways belonged to amino acid metabolism, with alanine/aspartate/glutamate metabolism being commonly enhanced. The degradation of aspartic acid promoted the formation of downstream amino acids, among which the levels of lysine, methionine, isoleucine, and asparagine were increased by 1.31-3.15 folds compared to the control. Thus, the antioxidant capacity in rice plants was enhanced, particularly through the significant promotion of ascorbic acid-glutathione (AsA-GSH) cycle in rice leaves. The amino acids were promoted to resist reactive oxygen species (ROS) efficiently, thus were deficient for nutrient storage. When exposed to 4 μmol/kg PBDEs, the contents of amino acids and proteins in grains decreased by 9.1-32.1% and 8.6-34.8%, respectively. In particular, glutelin level was decreased by 5.6-41.2%, resulting in a decline in nutritional quality. This study demonstrated that PBDEs deteriorated the protein nutrition in rice grains by affecting amino acid metabolism, providing a new perspective for evaluating the ecological risks of PBDEs and securing agricultural products., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Adipose tissue compromises one of the principal depots where brominated flame retardants (BFR) accumulate in vivo, yet whether BFR disturb thermogenic brown/beige adipocytes is still not referred to date. Herein, effects of BDE-99, a major congener of polybrominated diphenyl ethers (PBDEs) detected in humans, on brown/beige adipocytes were explored for the first time, aiming to provide new knowledge evaluating the obesogenic and metabolic disrupting effects of BFR. Our results firstly demonstrated that exposure to BDE-99 during the lineage commitment period significantly promoted C3H10T1/2 MSCs differentiating into brown/beige adipocytes, evidenced by the increase of brown/beige adipocyte marker UCP1, Cidea as well as mitochondrial membrane potential and basal respiration rate, which was similar to pharmacological PPARγ agonist rosiglitazone. Unexpectedly, the mitochondrial maximal respiration rate of BDE-99 stimulated brown/beige adipocytes was not synchronously enhanced and resulted in a significant reduction of mitochondrial spare respiration capacity (SRC) compared to control or rosiglitazone stimulated adipocytes, indicating a deficient energy-dissipating capacity of BDE-99 stimulated thermogenic adipocytes. Consistently with compromised mitochondrial SRC, lipidomic analysis further revealed that the lipids profile of mitochondria derived from BDE-99 stimulated brown/beige adipocytes were quite different from control or rosiglitazone stimulated cells. In detail, BDE-99 group contains more free fatty acid (FFA) and lyso-PE in mitochondria. In addition to energy metabolism, our results also demonstrated that BDE-99 stimulated brown/beige adipocytes were deficient in endocrine, which secreted more adverse adipokine named resistin, coinciding with comparable beneficial adipokine adiponectin compared with that of rosiglitazone. Taken together, our results showed for the first time that BDE-99 stimulated brown/beige adipocytes were aberrant in energy metabolism and endocrine, which strongly suggests that BDE-99 accumulated in human adipose tissue could interfere with brown/beige adipocytes to contribute to the occurrence of obesity and relevant metabolic disorders., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

From 2005 to 2019, three gadoid species, Atlantic cod (Gadus morhua), haddock (Melanogrammus aeglefinus) and saithe (Pollachius virens), were sampled approximately every third year in the northeastern part of the North Sea. Liver samples were analyzed to investigate levels and temporal trends of six groups of persistent organic pollutants (POPs): polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane (DDT) and its degradation products, hexachlorocyclohexanes (HCHs), hexachlorobenzene (HCB), trans-nonachlor (TNC), and polybrominated diphenyl ethers (PBDEs). Some of the highest average concentrations were found in cod, the levels otherwise being similar between the three species and mostly below established threshold values. The levels of all the contaminants except HCB and TNC were higher than previously reported for cod and haddock in the Barents Sea. Significantly decreasing levels were found for Σ7PCBs, ΣDDTs, ΣHCHs and Σ15PBDEs in all three species, and for TNC in haddock and saithe, while there was no significant trend for TNC in cod. HCB levels increased significantly in cod and haddock and showed only a minor decrease in saithe. The observed time trends of legacy POPs demonstrate the persistence of some of the studied pollutants despite efforts to eliminate them from the marine environment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

The persistent organic pollutant 2,2',4,4'-Tetrabromodiphenyl ether (BDE-47), a prevalent congener among polybrominated diphenyl ethers (PBDEs), exhibits potent bioaccumulation and toxicity. Despite extensive research into the adverse effects of BDE-47, its neurotoxicity in sea cucumbers remains unexplored. Given the crucial role of the sea cucumber's nervous system in survival and adaptation, evaluating the impacts of BDE-47 is vital for sustainable aquaculture and consumption. In this study, we employed ultra-high-performance liquid chromatography-quadrupole time-of-flight mass spectrometry (UPLC-Triple-TOF-MS) to analyze metabolomic changes in neuro-related tissues of Apostichopus japonicus exposed to low (0.1 µg/L), medium (1.0 µg/L), and high (10.0 µg/L) BDE-47 concentrations. We identified significantly changed metabolites in each exposure group (87 in low, 79 in medium, and 102 in high), affecting a variety of physiological processes such as steroid hormone balance, nucleotide metabolism, energy metabolism, neurotransmitter levels, and neuroprotection. In addition, we identified concentration-dependent, common, and some other metabolic responses in the neuro-related tissues. Our findings reveal critical insights into the neurotoxic effects of BDE-47 in sea cucumbers and contribute to risk assessment related to BDE-47 exposure in the sea cucumber industry, paving the way for future neurotoxicological research in invertebrates., Competing Interests: Declaration of Competing Interest The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

Polybrominated diphenyl ether (PBDE) contamination is common in aquatic environments and can severely damage aquatic organisms. However, there is a lack of information on the response and self-adaptation mechanisms of these organisms. Chlorella pyrenoidosa was treated with 2,2',4,4'-tetrabromodiphenyl ether (BDE47), causing significant growth inhibition, pigment reduction, oxidative stress, and chloroplast atrophy. Photosynthetic damage contributed to inhibition, as indicated by Fv/Fm, Chl a fluorescence induction, photosynthetic oxygen evolution activity, and photosystem subunit stoichiometry. Here, Chl a fluorescence induction and quinone electron acceptor (Q A - ) reoxidation kinetics showed that the PSII donor and acceptor sides were insensitive to BDE47. Quantitative analyses of D1 and PsaD proteins illustrated that PSII and PSI complexes were the main primary targets of photosynthesis inhibition by BDE47. Significant modulation of PSII complex might have been caused by the potential binding of BDE47 on D1 protein, and molecular docking was performed to investigate this. Increased activation of antioxidant defense systems and photosystem repair as a function of exposure time indicated a positive resistance to BDE47. After a 5-day exposure, 23 % of BDE47 was metabolized. Our findings suggest that C. pyrenoidosa has potential as a bioremediator for wastewater-borne PBDEs and can improve our understanding of ecological risks to microalgae., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

This study was conducted to assess the mitigating effects of curcumin (Cur) on immunotoxicity in the spleen of broilers induced by the polybrominated diphenyl ether BDE-209. Eighty one-day-old broilers were allocated to the following four groups: control group, BDE-209 (0.4 g/kg) group, BDE-209 (0.4 g/kg) + Cur (0.3 mg/kg) group, and Cur (0.3 mg/kg) group. Growth performance, immunological function, inflammation, and apoptosis were assessed after 42 days of treatment. The findings demonstrate that firstly, Cur restored spleen damage caused by BDE-209 by increasing body weight, decreasing feed-to-gain ratio, correcting the spleen index, and improving the histopathological structure of the spleen. Secondly, Cur relieved BDE-209-induced immunosuppression by increasing the levels of the immunoglobulins IgG, IgM, and IgA in the serum, as well as the levels of white blood cells and lymphocytes. The levels at which GATA binding protein 3, T-box expressed in T cells, interferon-γ, and interleukin (IL)- 4 are expressed were controlled. The ratio of T helper (Th) type 1 (Th1) to Th2 cells in the spleen of broilers was also controlled. Thirdly, Cur reduced the expression of Toll like receptor (TLR) 2, TLR4, nuclear factor (NF)-κB, IL-8, IL-6, and IL-1β, which alleviated BDE-209-induced inflammation in broilers. Cur reduced BDE-209-induced apoptosis by increasing the expression of the bcl-2 protein, decreasing the expression of cleaved caspase-3 and bax proteins, decreasing the bax/bcl-2 protein ratio, and decreasing the mean optical density of TUNEL. These results suggest that Cur protects broiler spleens from BDE-209-induced immunotoxicity via modulating humoral immunity, the equilibrium between Th1 and Th2 cells, the TLRs/NF-κB inflammatory pathway, and the apoptotic pathway., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

2,2',4,4'-Tetrabromodiphenyl ether (BDE-47) is a persistent organic pollutant that spreads widely in the marine environment. Our previous studies found that it had adverse effects on the marine rotifer Brachionus plicatilis and caused a series of stress responses. The present study was performed to verify the occurrence of autophagy and explore its role in B. plicatilis' coping with BDE-47 exposure. Rotifers were exposed to 0.05, 0.2, 0.8, and 3.2 mg/L BDE-47 for 24 h, respectively. Detections of the autophagy marker protein LC3 by western blot and autophagosomes by MDC staining demonstrated the occurrence of autophagy. The levels of autophagy were significantly increased in BDE-47-treated groups with a peak in 0.8 mg/L group. A series of indicators responded to BDE-47 exposure, including reactive oxygen species (ROS), GSH/GSSG ratio, superoxide dismutase (SOD) activity, and malonaldehyde (MDA), collectively indicating the occurrence of oxidative stress. The potential interplay between autophagy and oxidative stress in B. plicatilis was explored in the 0.8 mg/L group through a series of additions. The ROS level was significantly decreased by the addition of the ROS generation inhibitor diphenyleneiodonium chloride, to a level even lower than that in the blank control, and concomitantly, autophagosome was almost undetectable, indicating that a certain level of ROS was essential for the occurrence of autophagy. Autophagy was weakened by the addition of the autophagy inhibitor 3-methyladenine coincident with the great elevation of ROS, indicating that activated autophagy contributed to reducing the ROS level. Additional proof of this relation was obtained from the direct opposite effects of the autophagy inhibitor bafilomycin A1 and the autophagy activator rapamycin: the former increased the MDA content significantly, whereas the latter decreased it significantly. The combined results suggested that autophagy alleviated oxidative stress and might be a newly discovered protective mechanism in B. plicatilis coping with BDE-47 exposure., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier B.V.)

Polybrominated diphenyl ethers (PBDEs) are a class of persistent organic pollutants being widely distributed and harmful to human health and wildlife, and the development of sustainable rehabilitation strategies including microbial degradation is of great concern. Although the increasing number of bacteria, especially the broad-spectrum and potent aerobes have been isolated for the efficient removal of PBDEs, the external influences and the corresponding influential mechanism on biodegradation are not fully understood yet. Given the wide-spectrum biodegradability of aerobic bacterial isolate, B. xenovorans LB400 for PBDEs, the dual impacts of many pivotal factors including pH, temperature, presence of dissolved organic matter (DOM) and cadmium ion etc. were comprehensively revealed on biodegradation of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47). Due to the structural resemblance and stimulation of specific enzyme activity in bacteria, the biphenyl as substrates showed the greater capacity than non-aromatic compounds in improving biodegradation. The individual adaptation to neutrality and cultivation at about 30 °C was beneficial for biodegradation since the bacterial cellular viability and enzyme activity was mostly preserved. Although it was possibly good for the induction of hormesis and favorable to enhance the permeability or bioavailability of pollutant, the exceeding increase of Cd 2+ or DOM may not give the profitable increase of biodegradation yet for the detrimental effect. For biodegradation, the mechanistic relationship that took account of the integrative correlation with the influential factors was artfully developed using partial least square (PLS) regression technique. Relative to the most significant influence of culture time and initial concentration of BDE-47, the larger relevance of other factors primarily marked as pH and DOM was consecutively shown after the quantitative prioritization. This may not only help understand the influential mechanism but provide a prioritizing regulation strategy for biodegradation of BDE-47. The PLS-derived relationship was validated with the certain predictability in biodegradation, and could be used as an alternative to accelerate a priori evaluation of suitability or improve the feasibility of such bacteria in remediation of PBDEs in the environment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Glucuronoyl esterase (GE) is a promising agent for the delignification of plant biomass since it has been shown to cleave the linkage between xylan and lignin in vitro. In this study, we demonstrate that NcGE, a GE from Neurospora crassa, stimulates plant biomass degradation. In vitro, NcGE synergistically increased the release of reducing sugars from plant biomass when added together with cellulase or xylanase. In vivo, overexpression of NcGE in N. crassa resulted in an increase in xylanolytic activity. Consistently, elevated transcription of genes encoding the major plant biomass degrading-enzymes (PBDEs) was observed in the NcGE overexpression strain. Increased xylanolytic activity and transcription of PDBE genes were largely abolished when the transcription factors clr-1, clr-2, or xlr-1 were deleted. Interestingly, the expression of some PBDE genes was increased when the hydrolysate of plant biomass by NcGE was added to the culture medium. We propose that NcGE boosts the production of PBDEs through the activation of key transcription factors, which is presumably caused by NcGE-mediated generation of hypothetical inducer(s) from plant biomass.

Polybrominated diphenyl ethers (PBDEs) are persistent environmental contaminants with developmental neurotoxicity, the mechanism of which remains obscure. The present study aimed to evaluate cognitive deficits and microglia-originated neuroinflammation in the hippocampus of offspring rats exposed to BDE-209 (30 and 100 mg/kg) during perinatal period. Compared to the control, BDE-209-treated rats showed significant longer escape latency and less platform crossings in tests of Morris water maze. Besides obvious hippocampal neuron damage, increased microglial activation and pro-inflammatory markers (CD86, TNFα, and IL-1β), meanwhile, decreased anti-inflammatory molecules (CD206, IL-10, and Arg1) were induced by BDE-209. Furthermore, we investigated the neuroprotection of melatonin against BDE-209 and whether through sirtuin 1 (SIRT1). Consistent with restored SIRT1 activity, enhanced deacetylation of HMGB1 and inhibited cytoplasmic translocation of HMGB1, reduced expression of proteins involved in TLR4-NF-κB pathway and nuclear transfer of phosphorylated-NF-κB p65, and ultimately suppressed microglial activation and improved spatial memory were observed in 10 mg/kg melatonin-pretreated rats, compared with BDE-209-exposed alone. These results demonstrated that melatonin ameliorated BDE-209-caused cognitive impairment partially through shifting microglia polarization towards anti-inflammatory phenotype in a SIRT1-dependent manner, suggesting a potential mechanism for prevention., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Microalgae act as the entrance of polybrominated diphenyl ethers (PBDEs) from abiotic to biotic environments, which controlled the environmental fate of PBDEs in aquatic environments. Combing with typical coastal environmental characteristics including extracellular polymer substances (EPS) enrichment, light limitation and nitrogen starvation, the changes of adsorption and absorption kinetics of BDE-47 by Chlorella sp. and the role of EPS therein were investigated. The results quantified the adsorption and absorption kinetics of BDE-47 by Chlorella sp. cells and fitted it by the Lagergren pseudo first order model. Furthermore, we found the adsorption and absorption kinetics could be changed by the above mentioned environmental factors. To be specific, the total BDE-47 adsorption amounts per microalgal cell were increased as the increase of ambient EPS (proteins or carbohydrates), attributing to the increase of soluble (SL)-EPS contents; increased total BDE-47 adsorption amounts but decreased absorption rates were found under light limitation and nitrogen starvation, which were attributed to increased bound (B)-EPS contents and protein/carbohydrates (P/C) ratios therein, respectively. Therefore, our study elucidated the adsorption and absorption kinetics of PBDEs by microalgae could be influenced by ambient environmental changes, clarified the roles of SL-EPS, B-EPS contents and P/C ratios, providing a solid basis for evaluating the environmental fate of PBDEs in the marine environments., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) have been identified as the strong endocrine disrupting chemicals to humans, which show structural similarity with endogenous thyroid hormones (THs) and thus disrupt the functioning of THs through competitive binding with TH receptors (TRs). Although previous studies have reported the hormone activities of some OH-PBDEs on TH receptor β (TRβ), the interaction mechanism remains unclear. Furthermore, hydroxyl dissociation of OH-PBDEs may alter their TR disrupting activities, which has not yet been investigated in depth. In this work, we selected 18 OH-PBDEs with neutral and anionic forms and performed molecular dynamics (MD) simulations to estimate their binding interactions with the ligand binding domain (LBD) of TRβ. The results demonstrate that most of OH-PBDEs have stronger binding affinities to TRβ-LBD than their anionic counterparts, and the hydroxyl dissociation of ligands differentiate the major driving force for their binding. More Br atoms in OH-PBDEs can result in stronger binding potential with TRβ-LBD. Moreover, 5 hydrophobic residues, including Met313, Leu330, Ile276, Leu346, and Phe272, are identified to have important contributions to bind OH-PBDEs. These results clarify the binding mechanism of OH(O - )-PBDEs to TRβ-LBD at the molecular level, which can provide a solid theoretical basis for accurate assessment of TH disrupting effects of these chemicals., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Decabromodiphenyl ether (BDE-209), as a brominated flame retardant (BFR), is widely applied to various consumer products due to its superior performance and affordable pricing to improve the flame resistance of materials. To better comprehend the pyrolysis behavior of BDE-209 and the evolution process of main pyrolysis products, the thermal degradation mechanism of BDE-209 was studied using density functional theory (DFT) method at the theoretical level of M06/cc-pVDZ, and thermodynamic parameters were calculated in this paper. Unimolecular degradation was dominated by cleavage of the ether linkage, which results in a high yield of hexabromobenzene, and fission of the ortho-position C-Br bond is the main competitive reaction channel. In the system of BDE-209 + H, the pyrolysis reaction is majorly characterized by debromination, leading to the formation of considerable HBr and low-brominated diphenyl ethers. Additionally, the hydrogen-derived splitting of the ether bond acts as a mainly competitive channel, which is the source of polybromophenols and polybromobenzenes. The formation of polybrominated dibenzofuran (PBDF) derives from the cyclization reaction of ortho-phenyl-type radicals, which are readily generated through the ortho-position Br atom abstraction by H radical. The formation of polybrominated dibenzo-p-dioxin (PBDD) involves the ortho-C-O coupling reaction of polybromophenoxy radicals, debromination reaction, and cyclization reaction. And the total yield of PBDD/Fs was significantly increased when H was involved. Results presented in this work will provide the helpful information for the treatment and reuse of BDE-209-containing waste plastics through using pyrolysis technology., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Several halogenated flame retardants (HFRs) have been identified as thyroid disruptors in birds including the polybrominated diphenyl ether (PBDE) mixtures, which have been replaced with other HFRs such as Dechlorane-604 (Dec-604). Dec-604 Component B (Dec-604 CB), a putative debrominated product of Dec-604, has been frequently reported in urban-adapted ring-billed gulls (Larus delawarensis) breeding in the Montreal area (QC, Canada). The metabolic pathways of Dec-604 are yet to be characterized, although the occurrence of Dec-604 CB in gulls may suggest that enzyme-mediated dehalogenation may occur, potentially involving the thyroid deiodinases. The objective of this study was to investigate the effect of Dec-604 on type 1 deiodinase (DIO1) in the presence of thyroxine (T 4 ) in an in vitro DIO1 assay using liver microsomes of ring-billed gulls that are highly exposed to HFRs in the Montreal area, and to determine whether DIO1 is involved in the in vitro debromination of Dec-604. We tested the in vitro activity of DIO1 in gull liver microsomes in the presence of five concentrations of Dec-604 ranging from 0.86 to 86.21 nM. HFR concentrations (Σ 40 HFR) were also determined in liver samples of gulls. Results showed that total DIO1 activity in gull liver microsomes was increased by three of the five concentrations of Dec-604. No relationship between liver Σ 40 HFR concentrations and DIO1 activity was observed, except for T 2 formation rates that significantly decreased with increasing liver HFR concentrations. Moreover, greater Dec-604 CB to Dec-604 concentration ratios in activated gull microsomes (with the DIO1 cofactor dithiothreitol) were found at the intermediate Dec-604 concentration compared to controls. These results suggested that liver microsome DIO1 activity may be perturbed in ring-billed gulls exposed to Dec-604, and be involved at least in part, in the debromination of Dec-604 leading to the formation of Dec-604 CB., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Inc. All rights reserved.)

2,2',4,4'-tetrabrominated diphenyl ether (BDE-47) is one of the most widely distributed PBDEs. BDE-47 is also the most abundant in organisms and the most toxic to humans and animals. Herein, we have studied the pathway of BDE-47 degradation and gene involvement in Acinetobacter pittii GB-2. This degradation is dominated by hydroxylation, resulting in hydroxylated products 6-OH-BDE-47, 5-OH-BDE-47 and 2'-OH-BDE-28, and bromophenol products 2,4-DBP and 4-BP. Transcriptome sequencing results showed 359 differentially expressed genes (DEGs) induced by BDE-47, of which 159 were up-regulated and 200 were down-regulated. The up-regulated ones were mainly related to substance transport, degradation and cell stress. From these results, we suggest that 1,2-dioxygenase, phenol hydroxylase and monooxygenase are involved in BDE-47 degradation. The function of AntA gene was identified by constructing a prokaryotic expression vector. Our study contributes to understanding how the metabolism of strain GB-2 changes under BDE-47 stress conditions, and sheds light on the mechanism of BDE-47 degradation., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

The influence of biochar on the biodegradation of persistent organic pollutants (POPs) has been extensively studied. However, the underlying mechanisms behind the response of functional microbial consortia to biochar remain poorly understood. Herein, we systematically explored the effect of biochar on 2,2',4,4'-tetrabrominated ether (BDE-47) biodegradation, and investigated the interaction and assembly mechanism of the functional bacterial consortium QY2. The results revealed that the biodegradation efficiency of QY2 for BDE-47 increased from 53.85% to 94.11% after the addition of biochar. Fluorescence excitation-emission matrix and electrochemical analysis showed that biochar-attached biofilms were rich in redox-active extracellular polymeric substances (EPS, 3.03-fold higher than free cell), whose strong interaction with biochar facilitated the electron transfer of the biofilm, thus enhancing the debromination degradation of BDE-47. Meanwhile, the assembly model and molecular ecological networks analysis indicated that bacterial community assembly in biofilms was more driven by deterministic processes (environmental selection >75.00%) upon biochar stimulation and exhibited closer interspecific cooperative interactions, leading to higher biodiversity and broader habitat niche breadth for QY2 in response to BDE-47 disturbance. Potential degraders (Methylobacterium, Sphingomonas, Microbacterium) and electrochemical bacteria (Ochrobactrum) were selectively enriched, whose role as keystone bacteria may be participated in biofilm formation and redox-active EPS secretion (r > 0.5, P < 0.05). These findings deepen the understanding of the mechanisms by which biochar promotes microbial degradation of PBDEs and provided a theoretical basis for better regulation of functional bacterial communities during environmental remediation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Polybrominated diphenyl ethers (PBDEs) are persistent organic pollutants (POPs) that pose serious challenges to aquatic animals and environments. Compared with BDE-47 which was one of the most toxic congeners known to date, BDE-209 is less toxic with higher abundance in biotic and abiotic samples. In this study, we have explored the effects of BDE-47 and BDE-209 at different concentrations on the radical oxygen species (ROS) levels and the antioxidant defense system of Brachionus plicatilis. Antioxidant indexes were measured, including total protein content (TSP), the activities of antioxidant enzymes, lipid peroxidation and DNA damage. The results indicated that while low concentrations of PBDEs could activate the antioxidant defense mechanisms, prolonged exposure to higher concentrations of PBDEs could impair the antioxidative capacity of B.plicatilis (P < 0.05). The overwhelming of the B.plicatilis antioxidant defense mechanism led to an accumulation of free radicals, resulting in the overactivation of lipid peroxidation and the increased frequency of DNA damage (P < 0.05). By studying the toxicity of PBDEs and the detoxification mechanism of B.plicatilis, our research has revealed useful indexes for detecting and monitoring the level of BDE-47 and BDE-209 in the future. Altogether, this study holds immense value in the field of ecotoxicology and environmental safety and will aid in the proper management of PBDEs pollution., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Environmental pollution often releases multiple contaminants resulting in as yet largely uncharacterized additive toxicities. Cadmium (Cd) is a widespread pollutant that induces nephrotoxicity in animal models and humans. However, the combined effect of Cd in causing nephrotoxicity with 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), a typical congener of polybrominated diphenyl ethers (PBDEs), has not been evaluated and mechanisms are not completely clear. Here, we applied transcriptome sequencing analysis to investigate the combined toxicity of Cd and BDE-47 in the renal tubular epithelial cell lines HKCs. Cd or BDE-47 exposure decreased cell viability in a dose-dependent manner, and exhibited cell swelling and rounding similar to necrosis, which was exacerbated by co-exposure. Transcriptomic analysis revealed 2191, 1331 and 3787 differentially-expressed genes following treatment with Cd, BDE-47 and co-exposure, respectively. Interestingly, functional annotation and enrichment analyses showed involvement of pathways for oxidative stress, NOD-, LRR- and pyrin domain-containing protein 3 (NLRP3) inflammasome and inflammatory cell death for all three treatments. Examination of indices of mitochondrial function and oxidative stress in HKC cells showed that the levels of reactive oxygen species (ROS), malondialdehyde (MDA) and intracellular calcium ion concentration [Ca 2+ ]i were elevated, while superoxide dismutase (SOD) and mitochondrial membrane potential (MMP) were decreased. The ratio of apoptotic and necrotic cells and intracellular lactate dehydrogenase (LDH) release were increased by Cd or BDE-47 exposure, and was aggravated by co-exposure, and was attenuated by ROS scavenger N-Acetyl-L-cysteine (NAC). NLRP3 inflammasome and pyroptosis pathway-related genes of NLRP3, adaptor molecule apoptosis-associated speck-like protein (ASC), caspase-1, interleukin-18 (IL-18) and IL-1β were elevated, while gasdermin D (GSDMD) was down-regulated, and protein levels of NLRP3, cleaved caspase-1 and cleaved GSDMD were increased, most of which were relieved by NAC. Our data demonstrate that exposure to Cd and BDE-47 induces mitochondrial dysfunction and triggers NLRP3 inflammasome and GSDMD-dependent pyroptosis leading to nephrotoxicity, and co-exposure exacerbates this effect, which could be attenuated by inhibiting ROS. This study provides a further mechanistic understanding of kidney damage, and co-exposure impact is worthy of concern and should be considered to improve the accuracy of environmental health assessment., (Copyright © 2022. Published by Elsevier Inc.)

Degradation experiments are conducted to specifically compare the degradation of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) by aerobic and anaerobic strains isolated from real e-waste sites contaminated by BDE-47. The effect of carbon sources, inducers and surfactants on the degradation was examined to strengthen such a comparison. An aerobic strain, B. cereus S1, and an anaerobic strain, A. faecalis S4, were obtained. The results indicated that BDE-47 could be used as the sole carbon source by B. cereus S1 and A. faecalis S4 under aerobic and anaerobic conditions, respectively. The degradation of BDE-47 by B. cereus S1 and A. faecalis S4 was illustrated a first-order kinetics process obtaining a removal efficiency of 61.6% and 51.6% with a first-order rate constant of 0.0728 d -1 and 0.0514 d -1 , and corresponding half-life of 8.7 d and 13.5 d, respectively. The addition of carbon sources (yeast extract, glucose, acetic acid and ethanol) and inducers (2,4-dichlorophenol, bisphenol A and toluene) promoted BDE-47 degradation by both B. cereus S1 and A. faecalis S4 under aerobic and anaerobic conditions, while hydroquinone as the inducer inhibited the degradation. All of the surfactants tested (CTAB, Tween 80, Triton X-100, rhamnolipid and SDS) showed inhibitory effect. BDE-47 degradation by B. cereus S1 under aerobic condition was more efficient than A. faecalis S4 under anaerobic condition whether with or without the additives. The results of the study indicated that in the field sites contaminated by BDE-47, the aerobic condition can be more favorable for BDE-47 removal and the degradation can be further enhanced by applying suitable carbon sources and inducers., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

2,2',4,4'-Tetrabromodiphenyl ether (BDE-47) is a biotoxin of polybrominated diphenyl ether (PBDEs) frequently detected in the environment. Apoptosis and cell cycle arrest are important toxic phenomena of xenobiotics that inhibit cell proliferation. In this study, we investigated the effects of BDE-47 (5 μM, 10 μM, 20 μM, 40 μM) on cell viability, morphology, cell cycle and apoptosis. BDE-47 significantly decreased cell viability, and morphological alterations were observed. The significant increase in cells at G1 phase indicated the occurrence of G1 phase cell cycle arrest in RTG-2 cells. An acridine orange and ethidium bromide (AO/EB) staining assay was employed and revealed the induction of apoptosis in RTG-2 cells. The results indicated that BDE-47 exposure inhibits cell proliferation. Transcriptome analysis was applied for further evidence. A total of 1300 differentially expressed genes (DEGs) were identified in RTG-2 cells, among which 26 DEGs were associated with the cell cycle and apoptosis. Western blotting and qPCR analyses also showed the expression of cell cycle- and apoptosis-related proteins and genes. Mapping the Kyoto Encyclopedia of Genes and Genomes (KEGG) database, p53, Tumor necrosis factor (TNF), Mitogen-activated protein kinase (MAPK), phosphatidylinositide 3-kinase-AKT (PI3K-AKT), and reaction oxygen species (ROS)-mediated signaling pathways were determined to be the major pathways involved in modulating the cell cycle and apoptosis. Since we demonstrated simultaneous ROS overproduction during BDE-47 exposure in a previous study, we speculated a possible explanation for the observation: BDE-47-induced ROS overproduction was the initiating signal, which activated cell cycle arrest and apoptosis and finally inhibited cell proliferation., (Copyright © 2022. Published by Elsevier B.V.)

Several epidemiological studies have reported significant associations between prenatal polybrominated diphenyl ethers (PBDEs) exposure and adverse birth outcomes. Placental injury is thought to mediate these associations. However, few study has investigated the adverse effects of PBDEs exposure on placental growth and development. We examined the impacts of gestational exposure to BDE-209, the most abundant PBDE conger detected in human samples, on placental structure and function, and its model of action in vivo and in vitro. Pregnant mice were exposed to 0, 2, 20, 200 mg/kg/day of BDE-209 by gavages from gestational day (GD) 0 to GD18. Results showed that gestational BDE-209 exposure significantly reduced placental weight, impaired placental vascular development and induced placental cell apoptosis. In addition, gestational BDE-209 exposure impaired placental transport and endocrine function as demonstrated by markedly downregulated expression of Glut1, Znt1, Pgf and Igf2 in BDE-209-treated placentas. Mechanistically, gestational exposure to BDE-209 upregulated the expression of GRP78, and 3 downstream proteins (p-eIF2α, ATF4 and CHOP) of the PERK signaling, suggesting the activation of endoplasmic reticulum (ER) stress and PERK signaling pathway in mouse placentas. Further in vitro study showed that PERK siRNA pretreatment markedly reversed BDE-209-induced cell apoptosis in human JEG-3 cells. Collectively, our results suggest that the activation of the ER stress-mediated PERK/ATF4/CHOP signaling pathway played a role in BDE-209-induced placental injury. Our findings provide new insight into the mechanisms of BDE-209 induced reproductive and developmental toxicity., (Copyright © 2022 The Authors. Published by Elsevier Inc. All rights reserved.)

Polybrominated diphenyl ethers (PBDEs) exist in aquatic environments with nephrotoxicity to non-target aquatic species. Melatonin (MT) exhibits an inhibitory effect of oxidative stress and apoptosis in various diseases. 2, 2', 4, 4'-tetrabromodiphenyl ether (BDE-47) is the main homolog of PBDE samples. Therefore, we investigated the toxic mechanism of BDE-47 and the alleviation effect of MT, the ctenopharyngodon idellus kidney (CIK) cells were treated with BDE-47 (100 μM) and/or MT (60 μM) for 24 h. Firstly, BDE-47 exposure could inhibit oxidative stress-related antioxidant enzymes (T-AOC, SOD, CAT and GPx) and increase the content of malondialdehyde (MDA) to cause oxidative stress. Secondly, BDE-47 enhanced mitochondrial division and inhibited fusion to induce mitochondrial membrane potential in CIK cells. BDE-47 enhanced the mRNA and protein levels of mitochondrial-pathway apoptosis related genes (Cas 3, Cyt-c, and BAX). Thirdly, BDE-47 treatment decreased the expression levels of mitochondrial-related regulatory factors AMPK-Sirt1-PGC-1α signal pathway. Intriguingly, BDE-47-induced oxidative stress, mitochondrial pathway apoptosis and mitochondrial dynamics disorder could be alleviated by MT treatment. Overall, we concluded that MT could relieve BDE-47-induced oxidative stress, mitochondrial dysfunction and apoptosis through the AMPK-Sirt1-PGC-1α axis. These results enrich the mechanisms of BDE-47 poisoning and reveal that MT treatment may be a potential strategy for solving BDE-47 poisoning., (Copyright © 2022 The Authors. Published by Elsevier Inc. All rights reserved.)

Decabromodiphenyl ether (BDE-209) has drawn significant attention due to its suppression of immune functions in animals and even humans. In order to explore the mechanism through which BDE-209 affects the immune system, broiler chicks were fed a diet containing various concentrations of BDE-209 (0, 0.004, 0.04, 0.4, and 4 g/kg) for 42 days. Histopathological observations of immune organs found damaged and necrotic lymphocytes in the spleen and bursa, and losses of lymphoid cells in thymic gland. The activities of catalase, glutathione, glutathione peroxidase, and superoxide dismutase in both the spleen and serum were affected by BDE-209. Obvious bioaccumulation effect was found in spleen tissues (high to 1339 ± 181.9 μg/kg). Furthermore, transcriptome sequencing analyses of the spleen identified 424 upregulated and 301 downregulated DEGs, and the cytokine-cytokine receptor interaction signal pathway was most significantly enriched based on the Kyoto Encyclopedia of Genes and Genomes database. Quantitative real-time PCR affirmed the decreased expressions of interleukin IL18, IL18R1, IL18RAP, IL21, as well as interferon gamma IFNG and tumor necrosis factor superfamily members TNFSF8, indicating significant interference to immunomodulation function and possible disease progression in inflammatory effects resulting from BDE-209 exposure. The immunotoxicity of BDE-209 may cause the suppression of immune and physiological functions of spleen cells, leading to inflammation and apoptosis and ultimately spleen atrophy., (Copyright © 2022 The Authors. Published by Elsevier Inc. All rights reserved.)

Network pharmacology was used to illuminate the targets and pathways of polybrominated diphenyl ethers (PBDEs) causing thyroid dysfunction. A protein-protein interaction (PPI) network was constructed. Molecular docking was applied to analyze PBDEs and key targets according to the network pharmacology results. A total of 247 targets were found to be related to 16 PBDEs. Ten key targets with direct action were identified, including the top five PIK3R1, MAPK1, SRC, RXRA, and TP53. Gene Ontology (GO) functional enrichment analysis identified 75 biological items. Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway analysis identified 62 pathways mainly related to the regulation of the thyroid hormone signaling pathway, MAPK signaling pathway, PI3K-Akt signaling, pathways in cancer, proteoglycans in cancer, progesterone-mediated oocyte maturation, and others. The molecular docking results showed that BDE-99, BDE-153, 5-OH-BDE47, 5'-OH-BDE99, 5-BDE47 sulfate, and 5'-BDE99 sulfate have a good binding effect with the kernel targets. PBDEs could interfere with the thyroid hormone endocrine through multiple targets and biological pathways, and metabolites demonstrated stronger effects than the prototypes. This research provides a basis for further research on the toxicological effects and molecular mechanisms of PBDEs and their metabolites. Furthermore, the application of network pharmacology to the study of the toxicity mechanisms of environmental pollutants provides a new methodology for environmental toxicology., Competing Interests: The authors declare that there is no conflict of interest., (Copyright © 2021 Qiaoyu He et al.)

Polybrominated diphenyl ethers (PBDEs) are persistent, highly toxic, and widely distributed environmental pollutants. The microbial populations and functional reductive dehalogenases (RDases) responsible for PBDE debromination in anoxic systems remain poorly understood, which confounds bioremediation of PBDE-contaminated sites. Here, we report a PBDE-debrominating enrichment culture dominated by a previously undescribed Dehalococcoides mccartyi population. A D. mccartyi strain, designated TZ50, whose genome contains 25 putative RDase-encoding genes, was isolated from the debrominating enrichment culture. Strain TZ50 dehalogenated a mixture of pentabrominated diphenyl ether (penta-BDE) and tetra-BDE congeners (total BDEs, 1.48 μM) to diphenyl ether within 2 weeks (0.58 μM Br - /day) via ortho - and meta -bromine elimination; strain TZ50 also dechlorinated tetrachloroethene (PCE) to vinyl chloride and ethene (260.2 μM Cl - /day). Results of native PAGE, proteomic profiling, and in vitro enzymatic activity assays implicated the involvement of three RDases in PBDE and PCE dehalogenation. TZ50&#95;0172 (PteA TZ50 ) and TZ50&#95;1083 (TceA TZ50 ) were responsible for the debromination of penta- and tetra-BDEs to di-BDE. TZ50&#95;0172 and TZ50&#95;1083 were also implicated in the dechlorination of PCE to trichloroethene (TCE) and of TCE to vinyl chloride/ethene, respectively. The other expressed RDase, TZ50&#95;0090 (designated BdeA), was associated with the debromination of di-BDE to diphenyl ether, but its role in PCE dechlorination was unclear. Comparatively few RDases are known to be involved in PBDE debromination, and the identification of PteA TZ50 , TceA TZ50 , and BdeA provides additional information for evaluating debromination potential at contaminated sites. Moreover, the ability of PteA TZ50 and TceA TZ50 to dehalogenate both PBDEs and PCE makes strain TZ50 a suitable candidate for the remediation of cocontaminated sites. IMPORTANCE The ubiquity, toxicity, and persistence of polybrominated diphenyl ethers (PBDEs) in the environment have drawn significant public and scientific interest to the need for the remediation of PBDE-contaminated ecosystems. However, the low bioavailability of PBDEs in environmental compartments typically limits bioremediation of PBDEs and has long impeded the study of anaerobic microbial PBDE removal. In the current study, a novel Dehalococcoides mccartyi strain, dubbed strain TZ50, that expresses RDases that mediate organohalide respiration of both PBDEs and chloroethenes was isolated and characterized. Strain TZ50 could potentially be used to remediate multiple cooccurring organohalides in contaminated systems.

We studied the temperature dependence of accumulation and elimination of two polychlorinated biphenyls (PCBs; PCB-70 and PCB-126) and a commercial mixture of congeners of polybrominated diphenyl ethers (PBDEs; DE-71™)) in Northern leopard frog (Lithobates pipiens) tadpoles. We reared tadpoles at 18, 23, or 27 °C for 5.3 or up to 13.6 weeks (longer at cooler temperature where development is slower) on diets containing the toxicants, each at several different toxicant concentrations, and compared tissue concentrations as a function of food concentration and rearing temperature. Following > 1 month of accumulation, tissue concentrations of all three toxicants in exposed tadpoles were linearly related to dietary concentrations as expected for first order kinetics, with no significant effect of rearing temperature.We also raised free-swimming L. pipiens tadpoles for 14 days on foods containing either toxicant at 18 or 27 °C during an accumulation phase, and then during depuration (declining toxicant) phase of 14 days we provided food without toxicants and measured the decline of toxicants in tadpole tissue. All the congeners were eliminated faster at warmer rearing temperature, as expected. Using Arrhenius' equation, we calculated that the apparent activation energy for elimination of both PCB congeners by tadpoles was 1.21 eV (95% confidence interval 0.6-1.8 eV). We discuss how this value was within the range of estimates for metabolic reactions generally (range 0.2 - 1.2 eV), which might include metabolic pathways for biotransformation and elimination of PCBs. Furthermore, we discuss how the lack of an effect of rearing temperature on tadpole near-steady-state tissue residue levels suggests that faster elimination at the warmer temperature was balanced by faster uptake, which is plausible considering the similar temperature sensitivities (i.e., activation energies) of all these processes. Although interactions between toxicants and temperature can be complex and likely toxicant-dependent, it is plausible that patterns observed in tadpoles might apply to other aquatic organisms. Published data on depuration in 11 fish species eliminating 8 other organic toxicants indicated that they also had similar apparent activation energy for elimination (0.82 ± 0.12 eV; 95% confidence interval 0.56 - 1.08 eV), even though none of those studied toxicants were PCBs or PBDEs. Additional research on toxicant-temperature interactions can help improve our ability to predict toxicant bioaccumulation in warming climate scenarios., (Copyright © 2021. Published by Elsevier B.V.)

Previous research has shown the absorption of polybrominated diphenyl ethers (PBDEs) in the human gastrointestinal tract, but limited attention has been given to the influence of nutrients on PBDE absorption from food matrices. We investigated the effects of nutrients (oil, starch, protein, and dietary fiber) on the absorption and transport of PBDEs in a Caco-2 cell model and bioaccessibility of PBDEs by an in vitro gastrointestinal digestion method. The results showed that the accumulation ratios of PBDE congeners in Caco-2 cells were higher in the nutrient addition groups (oil: 26.7-50.6%, starch: 27.0-58.7%, protein: 12.1-44.1%, and dietary fiber: 28.2-55.1%) than the control group (7.17-36.1%), whereas the transport ratios were lower (oil: 2.30-7.20%, starch: 1.55-9.15%, protein: 1.04-8.78%, and dietary fiber: 0.85-7.04%) than control group (3.78-11.1%). Additionally, the PBDE bioaccessibility could be increased by adding the nutrients, particularly oil and starch. This study clarified the differences in PBDE absorption in the presence of nutrients using the in vitro digestion and Caco-2 cell model. The findings showed that nutrients were an important factor that promoted PBDE absorption in the gastrointestinal tract. Therefore, it is important to focus on a novel dietary strategy of food consumption with contaminant compounds to protect human health., (Copyright © 2020 The Authors. Published by Elsevier Inc. All rights reserved.)

Polybrominated diphenyl ethers (PBDEs) are often suspected to activate the signal transduction pathway of aryl hydrocarbon receptor (AhR), a ligand-activated transcription factor, for the induction of toxicity. Hence, the binding property of PBDEs with AhR is assumed to be associated with the ligand-dependent activation of AhR that may introduce many drug-metabolizing enzymes of genes encoding. However, the binding mechanism and the structural effect of PBDEs on their binding properties of AhR still need to be unraveled for toxicology research. A comprehensive study of the PBDEs-AhR binding mechanism was investigated using an integrated molecular modeling approach with two-dimensional quantitative structure-activity relationships (2D-QSAR), three-dimensional QSAR (3D-QSAR), and molecular docking simulation. Molecular docking revealed the differences in binding domains among 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)-AhR complex and two PBDE-AhR complexes. A 2D-QSAR model was developed to analyze the overall structural effects of PBDEs on the binding affinity of AhR. It provided an insight into major physico-chemical properties by multiple linear regression based on genetic algorithm with reasonable results. The 3D-QSAR modeling discovered the detailed interaction features of binding sites, configurations and interaction fields of AhR with different PBDE ligands. This study demonstrated that the descriptors of Smin69 and MoRSEC15 were related to electronic properties and had a great effect on the relative binding affinities. The position of Br substitutions exhibited a significant influence on the interactions between AhR and PBDEs, including halogen interaction, π-S interaction, π-π stacking interaction, and hydrophobic effect. This integrated molecular modeling approach provided a comprehensive analysis of the structural effects of PBDEs on their binding properties with AhR at molecular level., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Rapid and widespread evolution of multiple herbicide resistance in global weed species endowed by increased capacity to metabolize (degrade) herbicides (metabolic resistance) is a great threat to herbicide sustainability and global food production. Metabolic resistance in the economically damaging crop weed species Lolium rigidum is well known but a molecular understanding has been lacking. We purified a metabolic resistant (R) subset from a field evolved R L. rigidum population. The R, the herbicide susceptible (S) and derived F 2 populations were used for candidate herbicide resistance gene discovery by RNA sequencing. A P450 gene CYP81A10v7 was identified with higher expression in R vs. S plants. Transgenic rice overexpressing this Lolium CYP81A10v7 gene became highly resistant to acetyl-coenzyme A carboxylase- and acetolactate synthase-inhibiting herbicides (diclofop-methyl, tralkoxydim, chlorsulfuron) and moderately resistant to hydroxyphenylpyruvate dioxygenase-inhibiting herbicide (mesotrione), photosystem II-inhibiting herbicides (atrazine and chlorotoluron) and the tubulin-inhibiting herbicide trifluralin. This wide cross-resistance profile to many dissimilar herbicides in CYP81A10v7 transgenic rice generally reflects what is evident in the R L. rigidum. This report clearly showed that a single P450 gene in a cross-pollinated weed species L. rigidum confers resistance to herbicides of at least five modes of action across seven herbicide chemistries., (© 2020 Society for Experimental Biology and John Wiley & Sons Ltd.)

Polybrominated diphenyl ethers (PBDEs) are the ubiquitous contaminants in the coastal wetlands, with high persistence and toxicity. Environmental behaviors of PBDEs in sediment-plant system is a hot research area, where much uncertainties still occurred in field environment. In this study, the sediments and Suaeda heteroptera were synchronously collected to investigate the bioaccumulation and translocation of PBDEs in Liaohe coastal wetland. Mean concentrations of PBDEs in sediments, roots, stems and leaves were 8.37, 6.64, 2.42 and 1.40 ng/g d.w., respectively. Tissue-specific accumulation of PBDEs were detected in Suaeda heteroptera, with predominant accumulation in roots. Congener patterns of PBDEs were similar between sediments and roots, demonstrating root uptake as the key pathway of PBDE bioaccumulation. The proportions of lower brominated congeners increased from roots to leaves, implying the congener-specific translocation. Meanwhile, the lower brominated congeners exhibited higher sediment-tissue bioaccumulation (AFs) and translocation factors (TFs) compared to higher brominated congeners in Suaeda heteroptera, further verifying their preferential translocation. AFs and TFs of PBDEs were both not correlated with their log K ow , which was inconsistent with those of laboratory studies, reflecting the complicated behaviors of PBDEs in field environment. This is the first comprehensive report on bioaccumulation and translocation of PBDEs within Suaeda heteroptera in Liaohe coastal wetland., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Polybrominated diphenyl ethers (PBDEs) are ubiquitously distributed persistent organic pollutants (POPs) in marine environments. Phytoplankton are the entrance of PBDEs entering to biotic environments from abiotic environments, while the responding mechanisms of phytoplankton to PBDEs have not been full established. Therefore, we chose the model diatom Thalassiosira pseudonana in this study, by integrating whole transcriptome analysis with physiological-biochemical data, to reveal the molecular responding mechanisms of T. pseudonana to the toxicity of BDE-47. Our results indicated the changes of genes expressions correlated to the physiological-biochemical changes, and there were multiple molecular mechanisms of T. pseudonana responding to the toxicity of BDE-47: Gene expressions evidence explained the suppression of light reaction and proved the occurrence of cellular oxidative stress; In the meanwhile, up-regulations of genes in pathways involving carbon metabolisms happened, including the Calvin cycle, glycolysis, TCA cycle, fatty acid synthesis, and triacylglycerol synthesis; Lastly, DNA damage was found and three outcome including DNA repair, cell cycle arrest and programmed cell death (PCD) happened, which could finally inhibit the cell division and population growth of T. pseudonana. This study presented the most complete molecular responding mechanisms of phytoplankton cells to PBDEs, and provided valuable information of various PBDEs-sensitive genes with multiple functions for further research involving organic pollutants and phytoplankton., (Copyright © 2020 Elsevier B.V. All rights reserved.)

A series of pollutants can be removed from soil using a Fenton-like oxidation and biological treatment. As a natural mineral, tourmaline has been used for as a material of Fenton-like reaction. In the present study, the risks of remediation technology tourmaline catalyzed Fenton-like reaction (TCFR) combined with Phanerochaete chrysosporium (TCFR + P) were assessed through measuring soil properties, physiological response of plant, and PBDEs migration from soil to plant. Batch pot experiments showed that the silicon contents, specific surface area and soil pore size of soil in TCFR and 5%TCFR + P groups increased obviously. TCFR and TCFR + P treatments promoted the lettuce growth compared to control. Moreover, chlorophyll content of lettuce in 2%TCFR + P and 5%TCFR + P group increased by 46.74% and 44.57% than that in the CK, respectively. The treatment of 2%TCFR decreased the total concentration of PBDEs in rhizosphere soil and non-rhizosphere soil by 52.0.2% and 64.17%, respectively, after 60 days compared to the soil of CK, and did not prompt the uptake of lower-brominated PBDEs by lettuce. TCFR and TCFR + P can alter the migration of BDE isomers from soil to plant, the ratio of BDE99/BDE100 in lettuce shoots decreased slightly. BDE-99/BDE-100 ratios in the shoots were lower than those in the roots, while BDE153/BDE154 ratios were higher than 1.0 and ratios in shoots were higher than those in roots. Therefore, our findings illustrated that the TCFR could be applied to remediate the agricultural soil, considering the appropriate doses of tourmaline., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020. Published by Elsevier Ltd.)

Polybrominated diphenyl ethers (PBDEs) comprise a major class of brominated flame retardants and are well-known endocrine disruptors. The dietary route, through contaminated seafood consumption, is a main contributor to human exposure. Hence, the aim of this work was to provide thorough information on the dietary pathway of PBDEs and their methoxylated metabolites (MeO-PBDEs) after consumption of contaminated cooked seafood. The analyses were performed by gas chromatography (tandem) mass spectrometry using environmental-friendly extractive methods validated for fish and samples from several digestion segments with limits of detection at the pictogram level (per gram or milliliter of sample). Selected fish species were artificially contaminated and cooked using common household practices (steamed, grilled and microwaved), resulting in considerable loss of pollutants (up to 32% loss), with significant differences between cooking methods and species. Finally, an in vitro method that simulates four human adult digestion steps (oral, gastric digestion, small and large intestinal digestion) was applied to raw and cooked fish. Bioaccessibility of PBDEs and MeO-PBDEs in small intestinal was low (below 24%), pointing to a heavy impact in gut microbiota. Nevertheless, gut microbiota was able to reduce the amounts of targeted contaminants (up to 82%) in the large intestine. The results achieved herein are of great value to predict both amounts and nature of PBDEs and MeO-PBDEs that seafood consumers may be exposed after the ingestion of contaminated food as to ascertain more accurately the impact on human and environmental health., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Novel brominated flame retardants (NBFRs) have been widely used and frequently detected in various environmental matrices. In this study, 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB), bis-(2-ethylhexyl) tetrabromophthalate (TBPH) and their metabolites (namely 2,3,4,5-tetra-bromo benzoic acid (TBBA) and mono(2-ethylhexyl) tetrabromophthalate (TBMEHP)) were exposed to human umbilical vein endothelial cells (HUVECs). Metabolites can induce stronger cytotoxicity than parent compounds with EC50 at 47.3 (TBBA), 8.6 μg/ml (TBMEHP) vs > 200 μg/mL for parent compounds. Gene expression of platelet endothelial cell adhesion molecule-1, the gene associated with blood platelet kinetics, was significantly induced under TBBA and TBMEHP exposure. The in vivo test was consistent with gene expression result that the number of platelets in mouse blood was significantly increased after gavaged with 0.8 μg/mL TBBA and TBMEHP. In addition, TBB or TBPH were exposed to mice via gavage, and higher concentrations of TBBA (4 h, 60.8 ± 12.9 ng/mL, 8 h, 69.4 ± 2.24 ng/mL) in mouse blood were found than those of TBMEHP (4 h, 17.2 ± 4.01 ng/mL, 8 h, 12.8 ± 3.20 ng/mL), indicating that TBB was more readily in vivo metabolized than TBPH. The in vivo metabolism of TBB and TBPH and the stronger toxicity of their metabolites underscore the potential risk through NBFR exposure and the importance of understanding NBFR metabolism process., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Prenatal polybrominated diphenyl ether (PBDE) exposures are a public health concern due to their persistence and potential for reproductive and developmental harm. However, we have little information about the extent of fetal exposures during critical developmental periods and the variation in exposures for groups that may be more highly exposed, such as communities of color and lower socioeconomic status (SES). To characterize maternal-fetal PBDE exposures among potentially vulnerable groups, PBDE levels were examined in the largest sample of matched maternal serum, placenta, and fetal liver tissues during mid-gestation among a geographically, racially/ethnically, and socially diverse population of pregnant women from Northern California and the Central Valley (n = 180; 2014-16). Maternal-fetal PBDE levels were compared to population characteristics using censored Kendall's tau correlation and linear regression. PBDEs were commonly detected in all biomatrices. Before lipid adjustment, wet-weight levels of all four PBDE congeners were highest in the fetal liver (p < 0.001), whereas median PBDE levels were significantly higher in maternal serum than in the fetal liver or placenta after lipid-adjustment (p < 0.001). We also found evidence of racial/ethnic disparities in PBDE exposures (Non-Hispanic Black > Latina/Hispanic > Non-Hispanic White > Asian/Pacific Islander/Other; p < 0.01), with higher levels of BDE-100 and BDE-153 among non-Hispanic Black women compared to the referent group (Latina/Hispanic women). In addition, participants living in Fresno/South Central Valley had 34% (95% CI: - 2.4 to 84%, p = 0.07) higher wet-weight levels of BDE-47 than residents living in the San Francisco Bay Area. PBDEs are widely detected and differentially distributed in maternal-fetal compartments. Non-Hispanic Black pregnant women and women from Southern Central Valley geographical populations may be more highly exposed to PBDEs. Further research is needed to identify sources that may be contributing to differential exposures and associated health risks among these vulnerable populations.

While persistent organic pollutant (POP) contamination within Antarctica is largely caused by long-range atmospheric transport (LRAT), Antarctic research bases have been shown to be local sources of POPs such as brominated flame retardants (BFRs). This study compared concentrations of seven polybrominated diphenyl ethers (PBDE) congeners and five novel flame retardants (NBFRs) found in Adélie penguin (Pygoscelis adeliae) colony soils near the Australian research stations, Mawson and Davis, to assess the stations as local sources of these contaminants and provide a much needed baseline for contamination of BFRs in East Antarctica. Soil samples (n = 46) were collected from Adélie colonies at close proximity to the research stations as well as further afield during the 2016-17 austral summer. Samples were analysed using selective pressurised liquid extraction (S-PLE) and gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). PBDEs (BDE-28, -47, -99, -100, -153, -154 and -183) were detected in 45/46 samples with ∑ 7 PBDE concentrations ranging from <0.01 to 1.63 ng/g dry weight (dw) and NBFRs (2,3,4,5,6-pentabromotoluene (PBT), 2,3,4,5,6-pentabromoethylbenzene (PBEB), hexabromobenzene (HBB), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB) and bis(2,4,6-tribromophenoxy) ethane (BTBPE)) detected in 20/46 samples, with a range of ∑ 5 NBFR from not detected (ND) to 0.16 ng/g dw. Soils taken from around the Davis and Mawson research stations were more highly contaminated (n = 10) than penguin colonies (n = 27) and control areas not affiliated with breeding seabirds (n = 8). The most common congener detected was BDE-99, reflecting inputs from LRAT. However, the congener profiles of station soils supported the hypothesis that research stations are a local source of PBDEs to the Antarctic environment. In addition, the NBFR pentabromoethylbenzene (PBEB) was quantified for the first time in Antarctic soils, providing essential information for baseline contamination within the region and highlighting the need for ongoing monitoring as global regulations for the use of BFRs continuously change., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Microbial consortium remediation has been considered to be a promising technique for BDE-209 elimination in water, soil and sediment. Herein, we studied malondialdehyde (MDA), membrane potential (MP), and reactive active species (ROS) of a microbial consortium GY1 exposed to BDE-209. The results indicated that the microbial antioxidant defense system was vulnerable by BDE-209. Both early and late apoptosis of microbial consortium induced by BDE-209 were observed. The sequencing results revealed that Stenotrophomonas, Microbacterium and Sphingobacterium in GY1 played major roles in BDE-209 degradation. Moreover, a novel facultative anaerobic BDE-209 degrading strain named Microbacterium Y2 was identified from GY1, by which approximately 56.1% of 1 mg/L BDE-209 was degraded within 7 days, and intracellular enzymes of which contributed great to the result. Overall, the current study provided new insights to deeply understand the mechanisms of BDE-209 degradation by microbial consortium., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Polybrominated diphenyl ethers (PBDEs) are more frequently suspected with the induction of toxicity via signal transduction pathway of cytosolic aryl hydrocarbon receptor (AhR), the initial binding to which is assumed to be an essential prerequisite during the ligand-dependent activation. However, the AhR binding property and associated toxicity of PBDEs is yet to be clearly known for lacking insights into the structural requirements at molecular level. To understand the AhR binding property of PBDEs, the ligand binding domain (LBD) of AhR was simulatively developed on homologous protein after basic validation of geometrical rationality and the binding interaction profile was visually described using molecular docking approach. For AhR binding, the offset or edge-on π-π stackings with aromatic motifs including Phe289, Phe345 and His285 were shown to be structurally required whereas the electrostatic attraction validated for AhR binding to dioxins might be less effective for 2,2',3,4,4'-pentabromodiphenyl ether (BDE-85). Besides the demands of less steric hindrance from alanines and weak formulation of hydrogen bonds, the dispersion force through large contact and polarization of S-π electrons seemed to be impactful when BDE-85 were closer to Cys327, Met334 or Met342. With theoretical computation of AhR binding energies, the more significant correlativity with bioassays was derived especially for the lowly/moderately brominated congeners, and could be used to predict the AhR binding affinity on certain degree. The informative results would thus not only help well understand the molecular basis of AhR-mediated toxicity but give an approach for accelerative evaluation of AhR binding and toxicity of PBDEs., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Hypothyroidism is commonly associated with substantial adverse impacts on human health, and polybrominated diphenyl ether (PBDE), a kind of classic thyroid hormone disruptor, was speculated to be a potential environmental factor, but its effect on thyroxine metabolism has received little attention. In the present study, we investigated the role and mechanism of rno-miR-224-5p in deiodinase-mediated thyroxine metabolism in rats treated with 2,2',4,4'-tetrabromodiphenyl ether (BDE47), a predominant PBDE congener in humans. BDE47 decreased plasma triiodothyronine (T3) and thyroxine (T4) and increased reverse T3 (rT3) in the rats, and the expression of type 1 deiodinase (DIO1) and type 3 deiodinase (DIO3) increased in both the rats and H4-II-E cells. Rno-miR-224-5p was predicted to target dio1 instead of dio3, according to the TargetScan, miRmap.org and microRNA.org databases. Experiments showed that the rno-miR-224-5p level was decreased by BDE47 in a dose-dependent manner and confirmed that rno-miR-224-5p downregulated both DIO1 and DIO3 in the H4-II-E cells and in the rats, as determined using mimics and an inhibitor of rno-miR-224-5p. Furthermore, DIO1 was observed to be a direct functional target of rno-miR-224-5p, whereas DIO3 was indirectly regulated by rno-miR-224-5p via the phosphorylation of the MAPK/ERK (but not p38 or JNK) pathway. Reportedly, DIO1 and DIO3 act principally as inner-ring deiodinases and are responsible for the conversion of T4 to rT3, but not to T3, and the final clearance of thyroxine (mainly in the form of T2). Our results demonstrated that BDE47 induced low levels of T3 conversion through DIO1 and DIO3, which were regulated by rno-miR-224-5p. The findings suggest a novel additional mechanism of PBDE-induced thyroxine metabolism disorder that differs from that of PBDEs as environmental thyroid disruptors., Competing Interests: Declaration of competing interest The authors declare that they have no conflict of interest., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The thermal processes of cement kilns are sources of polybrominated dibenzofurans and dioxins (PBDD/Fs); however, when co-processing decabromodiphenyl ether (BDE-209) soil in cement kilns, very few reports have investigated the mechanism of PBDD/Fs formation from BDE-209. Therefore, the pathways and factors that influence the formation of PBDD/Fs were investigated using Box-Behnken design (BBD) of the response surface methodology (RSM) at lab-scale. The PBDEs, HBr/Br 2 and PBDD/Fs emissions in flue gas from the simulated thermal process were analyzed using gas chromatography/mass spectroscopy (GC/MS), high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS), and ion chromatography (IC). Density functional theory (DFT) was also used to further discuss the formation of PBDD/Fs. The major products of BDE-209 thermal decomposition in flue gas were 97.1% HBr/Br 2 (a.v. 26.6%/70.6%) > 2.7% PBDEs >0.2% PBDD/Fs. Formation of precursors were the main pathways for PBDD/Fs, and those precursors were dominated by higher-brominated PBDEs (heptã deca-BDEs); debromination of BDE-209 was also a crucial pathway for the formation of PBDD/Fs throughout the thermal process. Interestingly, it was easier to form HpBDD/Fs from OBDD/Fs than from PBDEs. The O 2 percentage and interaction factors of O 2 percentage, temperature, and CaCO 3 percentage have the largest influence on PBDD/Fs emissions and formation., (Copyright © 2020 Elsevier Inc. All rights reserved.)

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.

Polybrominated diphenyl ethers (PBDEs) are ubiquitous environmental pollutants with adverse effects on the foetus and infants. This study aimed at assessing in utero exposure levels and transplacental transfer (TPT) characteristics of BDE congeners in primiparous mothers from Kampala, the capital city of Uganda. Paired human samples (30 placenta and 30 cord blood samples) were collected between April and June 2018; and analysed for a suite of 24 tri-to deca-BDE congeners. Extraction was carried out using liquid-liquid extraction and sonication for cord blood and placenta samples, respectively. Clean-up was done on a solid phase (SPE) column and analysis was performed using gas chromatography/mass spectrometry (GC/MS). Total (∑) PBDEs were 0.25-30.9 ng/g lipid weight (lw) (median; 7.11 ng/g lw) in placental tissues and 1.65-34.5 ng/g lw (median; 11.9 ng/g lw) in cord blood serum, with a mean difference of 1.26 ng/g lw between the compartments. Statistical analysis showed no significant difference between the levels of PBDEs in cord blood and placenta samples (Wilcoxon signed rank test, p = 0.665), possibly because foetus and neonates have poorly developed systems to metabolise the pollutants from the mothers. BDE-209 was the dominant congener in both matrices (contributed 40.5% and 51.2% to ∑PBDEs in placenta and cord blood, respectively), suggesting recent and on-going maternal exposure to deca-BDE formulation. Non-significant associations were observed between ∑PBDEs in maternal placenta and maternal age, household income, pre-pregnancy body mass index (BMI), and beef/fish consumption. This suggested on-going exposure to PBDEs through multiple sources such as dust from indoor/outdoor environments and, ingestion of other foods. Based on absolute concentrations, the extent of transplacental transport was greater for higher congeners (BDE-209, -206 and -207) than for lower ones (such as BDE-47), suggesting alternative TPT mechanisms besides passive diffusion. More studies with bigger sample sizes are required to confirm these findings., Competing Interests: Declaration of competing interest The authors declare no conflict of interest., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

As a persistent organic pollutant, 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) has been widely detected in aquatic environments. However, studies on the fate and transfer of BDE-47 in the aquatic food chain remain scarce. In this study, we investigated the bioaccumulation and elimination of BDE-47 in Chlorella pyrenoidosa, as well as the trophic transfer and biomagnification of BDE-47 in the "C. pyrenoidosa-Daphnia magna" food chain, using C-14 radioactive tracer technology. After 96 h of BDE-47 exposure, the algae accumulated 88.98% ± 0.59% of the initial radioactivity from the medium, and 36.09% ± 9.22% of the accumulated residues in the algae occurred in the form of bound residues. During 96 h of elimination, only 13% ± 0.50% of accumulated radioactivity in the algae was released into the medium. After 24 h of exposure, D. magna accumulated 35.99% ± 2.55% of the initial radioactivity via water filtration from the medium, and 31.35% ± 1.92% of the accumulated radioactivity in D. magna occurred as bound residues. However, D. magna accumulated 66.89% ± 2.37% of the accumulated radioactivity in the algae via food uptake from the contaminated algae, with a high portion of radioactivity observed as bound residues (83.40% ± 0.97% of accumulated radioactivity in D. magna). This indicated a reduction in the environmental risk of BDE-47. There was obvious biomagnification in the food chain between C. pyrenoidosa and D. magna (biomagnification factors, BMFs>1), resulting in environmental hazard transfer in the aquatic food chain. However, no metabolite was found during the exposure experiment, and further studies should be carried out to investigate the intrinsic mechanisms of the trophic transfer of BDE-47, especially in multilevel food chains. Therefore, this study elucidated the effect of dietary uptake on the bioaccumulation of BDE-47 in D. magna and provided new insight for future analysis regarding the bioaccumulation and biomagnification of organic pollutants in the food chain., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

While a large body of studies have examined polybrominated diphenyl ethers (PBDEs) and alternative brominated flame retardants (ABFRs) in wildlife, information on the bioaccumulation of these contaminants in reptiles in general, and snakes in particular, are scarce. We investigated the bioaccumulation characteristics of PBDEs and several ABFRs including decabromodiphenyl ethane (DBDPE), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), hexabromobenzene (HBB) and pentabromotoluene (PBT) in a frog-eating snake, the striped keelback snake (Amphiesma stolata), from an e-waste recycling site in South China. The concentrations of ∑PBDEs and ∑ABFRs in the snakes ranged 53-5200 and 3.1-87 ng/g lipid weight, respectively; with higher levels in males than females. Additionally, the concentrations of BDE-28, -47, and -66 were positively correlated with snake size (snout-vent length and body mass), while negative correlations were found for most of the higher brominated PBDE congeners and HBB, PBT and BTBPE. The biomagnification factors (BMFs) estimated in the snake/frog relationship indicated a mild to moderate biomagnification of BDE-28, -47, -66, -100, -153 and -154 (with mean BMFs of 1.1-5.3), while a lack of magnification for the other PBDE congeners and all the ABFRs. This is the first report on the sex- and size-related accumulation and biomagnification potentials of PBDEs and ABFRs in snakes., (Copyright © 2019 Elsevier Ltd. All rights reserved.)