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Although firefighters are at an increased risk of occupational exposure to chemicals, such as flame retardants, research on the exposure of Korean firefighters to organophosphate esters (OPEs)-a group of emerging flame retardants-remains limited. Therefore, in the present study, OPE metabolite concentrations in the urine samples of 149 former and current Korean firefighters were measured. Based on the data obtained, the estimated daily intakes (EDIs) of OPEs were calculated. Subsequently, the association between the urinary concentrations of OPE metabolites and the potential determinants of OPE exposure and health outcomes (e.g., obesity and serum lipids) was investigated. We found that bis(1-chloro-2-propyl) phosphate (BCIPP) and bis(2-chloroethyl) phosphate (BCEP) were the most prevalent urinary OPE metabolites, with median concentrations of 2.33 and 1.80 ng/mL, respectively; these concentrations were higher than those reported previously in other countries, such as the USA and China. Moreover, their parent compounds-tris(1-chloro-2-propyl) phosphate (TCIPP) and tris(2-chloroethyl) phosphate (TCEP)-exhibited EDIs of 126 and 94.8 ng/kg bw/day, respectively. Unlike the high detection rate of bis(1,3-dichloro-2-propyl) phosphate (BDCIPP) in other populations, its detection rate in this study was low (6.7%), suggesting regional differences in the exposure pattern of OPEs among countries. Furthermore, occupational characteristics, such as recent participation in firefighting activity, were identified as determinants of the urinary concentrations of OPE metabolites. Total OPE metabolites were inversely associated with body mass index and positively associated with high-density lipoprotein cholesterol. Overall, our findings demonstrate that Korean firefighters are highly exposed to several occupation-related OPEs. Further prospective studies will help elucidate the potential health implications of occupational exposure to OPEs among firefighters., 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.)

Settled house dust (SHD) is a reservoir for various contaminants, including endocrine-disrupting chemicals (EDCs), trace metals, and house dust mite allergens. This study aimed to characterize various chemical and biological contaminants in SHD and identify determinants governing the indoor contaminants. In total, 106 SHD samples were collected from 106 houses in Seoul and Gyeonggi Province, Korea, in 2021. Bedding dust samples were collected from 30 of these 106 houses. All participants completed a questionnaire comprised of housing and lifestyle-related factors. The samples were analyzed for 18 organophosphate flame retardants (OPFRs), 16 phthalates, five alternative plasticizers (APs), seven trace metals, and two house dust mite allergens (Dermatophagoides farinae type 1 [Der f1] and Dermatophagoides pteronyssinus type 1 [Der p1]). A multiple regression analysis was conducted to identify the determinants governing the concentrations and profiles of various contaminants. OPFRs, phthalates, APs, and trace metals were detected in all SHD samples, indicating ubiquitous contamination in indoor environments. Among the three EDC groups, APs were detected at the highest concentrations (geometric mean [GM] (geometric standard deviation, [GSD]): 1452 (1.6) μg/g in total), followed by phthalates (GM (GSD): 676 (1.4) μg/g in total) and OPFRs (GM (GSD): 10 (1.4) μg/g in total). Der f1 was detected in all bedding dust samples with significantly higher levels than Der p1 (GM (GSD): 0.1 (1.8) μg/g vs. 1.4 × 10 -3 (2.3) μg/g). The concentrations of OPFRs, plasticizers, and trace metals in SHD were significantly associated with the type and number of electronic appliances and combustion activities. Der f1 was significantly associated with the number of occupants and water penetration. Ventilation, vacuum cleaning, and wet cleaning or dry mopping significantly reduced the levels of most contaminants in SHD. As residents are persistently exposed to a wide array of pollutants, comprehensive and adequate measures are required to prevent potential exposures., (© 2022 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.)

Legacy and alternative halogenated flame retardants (HFRs), such as polybrominated diphenyl ethers (PBDEs), novel brominated flame retardants (NBFRs), and dechlorane plus (DP), were measured in dated sediments from a highly industrialized lake in Korea. All HFRs were detected in almost all of the sediment depth layers for more than 70 years, indicating a history of long-term contamination. Similar historical trends in PBDEs, 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), and DP were observed in dated sediments, whereas decabromodiphenylethane (DBDPE), and 2-ethylhexyl-2,3,4,5-octabromo-1,3,3-trimethyl-1-phenylindane (OBIND) concentrations sharply increased since the 1990s. Moreover, the concentration ratios of DBDPE/BDE 209 increased from the early 1990s to the present. Our findings suggest that DBDPE and OBIND have been used as HFR alternatives. The historical record of the concentrations and profiles of legacy and alternative HFRs corresponded with industrial activities, consumption of FRs, and coastal development activities. Inventories of legacy and alternative HFRs were similar to those reported for highly industrialized regions around the globe., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

South Korea is one of the largest consumers of flame-retardants worldwide. In this study, water, sediment, and biota samples were collected from a highly industrialized lake to investigate contamination, isomeric profiles, source, and the bioaccumulation potential of hexabromocyclododecanes (HBCDDs). Almost all of the sediments were severely contaminated by HBCDDs, which were some of the highest global levels compared to those found in previous studies. The highest concentrations and similar profiles to those of technical mixtures of HBCDDs were observed in creeks passing through industrial complexes, indicating on-going contamination by high consumption of HBCDDs from industrial activities. γ-HBCDD was dominant in water and sediment, whereas α-HBCDD was dominant in fish and shellfish. The diastereoisomeric profiles of HBCDDs in multiple matrices were influenced by proximity to industry and chemical properties. In-situ biota-sediment accumulation factors of α-HBCDDs were > 1 in benthic species, implying that HBCDDs are of great concern in sedimentary environments., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Novel halogenated flame retardants (HFRs) were introduced to industrial markets as alternatives to legacy brominated FRs (BFRs), such as polybrominated diphenyl ethers (PBDEs). In the present study, PBDEs and their brominated and chlorinated alternatives, novel BFRs (NBFRs) and dechlorane plus (DP), were measured in multiple environmental matrices in a highly industrialized lake in Korea. Legacy and novel HFRs were detected in multiple samples, indicating ubiquitous contamination. Concentrations of HFRs in water and sediment observed in creeks running through machine, textiles, and automobile industrial complexes were significantly higher than those observed in inside and outside of the lake. Higher bioaccumulation levels of HFRs were observed in inshore compared with offshore waters. Results suggest that multi-matrix distribution of legacy and novel HFRs was dependent on the geographical proximity to industrial sources. Compared with previous studies, the highest levels of PBDEs and NBFRs were recorded in water samples on a global scale, implying on-going emissions from industrial activities. Decabromodiphenyl ethane (DBDPE) was a dominant compound in water samples, whereas the concentrations of PBDEs, NBFRs, and DP in sediment were similar to each other. This suggests a shift in consumption from legacy to novel HFRs, preferentially in water environments. A significant declining trend in PBDEs was observed in water and sediment collected between 2008 and 2015, indicating the effectiveness of regulatory actions. Based on their environmental occurrence and bioaccumulation potential, pentabromoethylbenzene and bis(2-ethylhexyl) tetrabromophthalate may pose emerging concerns regarding contamination of aquatic environments., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Cresyl diphenyl phosphate (CDP), as a kind of aryl substituted organophosphate esters (OPEs), is commonly used as emerging flame retardants and plasticizers detected in environmental media. Due to the accumulation of CDP in organisms, it is very important to discover the toxicological mechanism and metabolic process of CDP. Hence, liver microsomes of crucian carps (Carassius carassius) were prepared for in vitro metabolism kinetics assay to estimate metabolism rates of CDP. After 140 min incubation, the depletion of CDP accounted for 58.1%-77.1% (expect 0.5 and 2 μM) of the administrated concentrations. The depletion rates were best fitted to the Michaelis-Menten model (R 2  = 0.995), where maximum velocity (V max ) and Michaelis-Menten constant (K m ) were 12,700 ± 2120 pmol min -1 ·mg -1 protein and 1030 ± 212 μM, respectively. Moreover, the in vitro hepatic clearance (C Lint ) of CDP was 12.3 μL min -1 ·mg -1 protein. Log K ow and bioconcentration factor (BCF) of aryl-OPEs were both higher than those of alkyl- and chlorinated-OPEs, indicating that CDP may easily accumulate in aquatic organisms. The results made clear that the metabolism rate of CDP was greater than those of other OPEs detected in liver microsomes in previous research. This paper was first of its kind to comprehensively investigate the in vitro metabolic kinetics of CDP in fish liver microsomes. The present study might provide useful information to understand the environmental fate and metabolic processes of these kinds of substances, and also provide a theoretical basis for the ecological risk assessment of emerging contaminants., Competing Interests: Declaration of competing interest The authors declare that there were no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Legacy and novel flame retardants (FRs) such as polybrominated diphenyl ethers (PBDEs), novel BFRs, and organophosphate flame retardants (OPFRs) were measured in water and sediment collected from highly industrialized bays of Korea. Predominant compounds in sediment were BDE 209, DBDPE, and BTBPE for BFRs, and TCPP and TBOEP for OPFRs, respectively. Higher alternative FR concentrations were observed compared to those reported for previous studies. The highest BFR concentrations were found in locations close to industrial complexes, while the OPFR concentrations were highest in locations close to domestic regions and a wastewater treatment plant. Different contamination sources were observed for BFRs and OPFRs. The ratio of DBDPE/BDE 209 in sediment ranged from 0.84 to 28, indicating a shift in consumption of BFRs. A significant decline in PBDEs suggests the effectiveness of domestic and global regulations. Despite this, sedimentary PBDE concentrations may pose adverse health risks to benthic organisms and humans., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Environmental contamination by organophosphate flame retardants (OPFRs) and plasticizers are environmental concerns. In this study, 18 OPFRs were analyzed in sediment and bivalves collected from 50 locations along the Korean coast to assess occurrence, geographical distribution, contamination source, and bioaccumulation potential. Tris(1-chloro-2-propanyl) phosphate (TCPP) and tris(2-ethylhexyl) phosphate (TEHP) were highly detected (>80%) OPFRs in sediment and bivalves. Total concentrations of OPFRs and plasticizers in sediment and bivalves ranged from 2.18 to 347 ng/g dry weight and from 6.12 to 206 ng/g dry weight, respectively, which were within the ranges reported for previous studies. Sedimentary organic carbon was a primary factor governing the OPFR distribution. Concentrations of OPFRs and plasticizers in sediments from harbor zones were significantly higher than non-harbor zones, indicating that shipping activity is a contamination source of OPFRs and plasticizers in coastal environments. Biota-sediment accumulation factors <1 for several OPFRs indicated limited potential for bioaccumulation., 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.)

Numerous chemicals have been manufactured through industrial activities and used as consumer products since the late 18th century. Non-target analysis is a new analytical tool to detect many chemicals in environmental samples and to prioritize emerging contaminants. In this study, suspect and non-target analytical methods were optimized using gas chromatography coupled with time-of-flight (GC/TOF) to propose contaminants of emerging concern for the Arctic environment. A suspect analytical method was developed with qualification and qualifier ions, isotopic ratios, and retention times of 215 contaminants including persistent organic pollutants (POPs) to establish an in-house library. Non-target analytical method was also optimized with a deconvoluted ion chromatogram, which is a form that can possibly match the mass spectrum of the NIST library. Multiple environmental samples, such as seawater, air, soil, sediment, sludge, and iceberg, collected from the Arctic region were analyzed with suspect and non-target analysis of GC/TOF after the clean-up procedure with a solid phase extraction (SPE) cartridge. The commonly detected contaminants in the Arctic environmental samples were siloxanes, organophosphate flame retardants, phthalates, synthetic musk compounds, polychlorinated biphenyls, and polycyclic aromatic hydrocarbons. Among them, siloxanes and organophosphate flame retardants were proposed to be contaminants of emerging concerns for the Arctic environment. This is the first report to prioritize emerging contaminants in the Arctic environment with suspect and non-target analysis of GC/TOF., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Contamination by organophosphate flame retardants (OPFRs) is an emerging concern in aquatic environments. Concentrations of 18 OPFRs were measured in water and sediments collected from the artificial Lake Shihwa. OPFR concentrations in sediments measured in this study were the highest reported worldwide, implying severe OPFR contamination. The highest concentrations of OPFRs were found in creeks taken near industrial complexes, and OPFR concentrations decreased with increasing distance from creeks to inshore or offshore lake waters. On-going OPFR contamination by wastewater treatment plant (WWTP) discharge was evidenced by the clear decrease in OPFRs in water samples collected moving away from WWTP outfall. TBEP and TEP were dominant in water samples, while TDCPP and TCPP were dominant in sediment samples. Differences in contamination profiles with sample matrices are likely due to hydrophobicity of individual OPFRs. Non-parametric multidimensional scaling ordination showed that OPFR contamination was affected by pollution inflow and proximity to industrial complexes., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

This study was undertaken to investigate levels of organophosphorus flame retardants (PFRs) and phthalates in floor and road dust from a manual e-waste dismantling facility and nearby communities in Thailand. Concentrations of Σ10 PFRs and Σ6 phthalates in floor dust from the facility were approximately 36-1,700 and 86,000-790,000 ng g -1 , whereas those from the communities were about 13-9,200 and 44,000-2,700,000 ng g -1 , respectively. The highest content of Σ10 PFRs (9,200 ng g -1 ) and Σ6 phthalates (2,700,000 ng g -1 ) in indoor dust was both detected in the dust sampled from a house with no prevailing winds located 350 m northeast of the facility. Levels of Σ10 PFRs and Σ6 phthalates in road dust from the facility were around 1,100-2,100 and 40,000-670,000 ng g -1 , while those from the residences were about 650-2,000 and 27,000-650,000 ng g -1 , respectively. Concentrations of Σ10 PFRs (2,100 ng g -1 ) and Σ6 phthalates (670,000 ng g -1 ) in road dust were greatest in the dust collected from the facility. For the distributional pattern, TBEP (tris (2-butoxyethyl) phosphate) was the main PFR in residential dust, whereas TPP (triphenyl phosphate) was the major PFR in facility dust. TBEP was also found to be the most prominent PFR in all road dust samples. Furthermore, DEHP (di-2-ethylhexyl phthalate) was the most abundant phthalate congener in both floor and road dust samples. Under realistic high-end scenarios of environmental exposure to DEHP, Thai toddlers (25.29 µg kg -1 bw day -1 ) in the adjacent communities were exposed above the US EPA's (United States Environmental Protection Agency) reference dose (RfD) for this congener (20 µg kg -1 bw day -1 ). Our data reveal that the PFR and phthalate-containing products at the residences are a likely substantial source of PFRs and phthalates to the surrounding indoor environment, and humans can be exposed to PFRs and phthalates in their dwellings via the settled floor dust.

This paper presents the first comprehensive survey of 19 novel brominated flame retardants (NBFRs) in soil samples collected among five Asian countries. High variability in concentrations of all NBFRs was found in soils with the geometric mean (GM) values ranging from 0.50 ng/g dry weight (dw) in Vietnam to 540 ng/g dw in the vicinity of a BFR manufacturer in China. In urban, rural, and background locations, the GM concentrations of ∑ 19 NBFRs decreased in the order of Japan > South Korea > China > India > Vietnam. Correlations among different NBFR compounds were positive and statistically significant (p < 0.05), suggesting that they originate from similar sources. Evidence for simultaneous application between polybrominated diphenyl ethers (PBDEs) and NBFRs were also noted. Principal component analysis of NBFR concentrations revealed specific pollution sources for different NBFRs coming from urban, BFR-related industrial, and e-waste sites. For the first time, this study demonstrates a "point source fractionation effect" for NBFRs and PBDEs. The concentrations of all NBFRs and PBDEs were negatively and significantly correlated with the distance from BFR-related industrial and e-waste regions. Positive and significant correlation between population density and NBFR concentrations in soils was identified. Our study revealed that the primary sources effects were stronger than the secondary sources effects in controlling the levels and distribution of NBFRs and PBDEs in soils in these five Asian countries.

Few studies have been conducted on the alternatives to legacy flame retardants in avian species worldwide. In this study, polybrominated diphenyl ethers (PBDEs) and alternative flame retardants such as novel brominated flame retardants (NBFRs) and dechlorane plus (DP) were determined in livers of 10 species of birds from Korea to elucidate species-specific accumulation, biological factors that affect accumulation, and bioaccumulation potentials of these contaminants. Among the emerging alternative flame retardants, the highest occurrence was found for bis(2-ethylhexyl)-3,4,5,6-tetrabromo-phthalate (BEHTBP), syn-DP, anti-DP, and decabromodiphenyl ethane (DBDPE). PBDE concentrations (median: 17.1 ng/g lipid wt) measured in our study were within the ranges reported in previous studies, while the concentrations of BEHTBP, BTBPE and DP were greater than those reported earlier. Residential predatory birds showed significantly greater concentrations of PBDEs and NBFRs than migratory predators and passerine birds. The concentrations of PBDEs, BEHTBP, and DP in residential predatory birds were significantly correlated with increasing stable nitrogen isotope ratio (δ 15 N), which indicated biomagnification potentials of these contaminants. Our results suggest that the concentrations and accumulation patterns of PBDEs, NBFRs, and DP depend on the feeding habits and migration patterns of avian species. This is the first report on the accumulation of emerging alternatives to PBDEs in birds from Korea., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Organophosphate flame retardants (OPFRs) have been widely used as flame retardants and plasticizers in commercial products. Limited data are available on the occurrence and exposure of OPFRs via drinking water consumption. In this study, 127 drinking water samples were collected from tap water, purified water (tap water that is passed through in-house filters) and bottled water from major cities in Korea in 2014. The total concentrations of OPFRs (ΣOPFR) in all of the samples ranged from below the method detection limit (MDL) to 1660 (median: 48.7) ng/L. The predominant OPFR compounds in drinking water were tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroethyl) phosphate (TCPP), and tris(2-butoxyethyl) phosphate (TBEP). Significant differences were observed in the levels of TCPP, TBEP and ΣOPFR among various types of drinking water. TCPP is introduced in the drinking water during the water purification process. Regional differences existed in the levels and patterns of OPFRs in water samples, which indicated the existence of diverse sources of these contaminants. Purified water was a significant contributor to the total OPFR intake by humans. The estimated daily intake of OPFRs was lower than the tentative oral reference dose (RfD) values. In comparison with exposure of OPFRs via dust ingestion, water consumption was a significant source of chlorinated PFRs (99% for TCEP and 34% for TCPP to the total intakes) for Koreans., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

With the global decline in the use of polybrominated diphenyl ethers, the demand for alternative flame retardants, such as triphenylphosphate (TPP), has increased substantially. Triphenylphosphate is now detected in various environments including aquatic ecosystems worldwide. However, studies on the toxicological consequences of chronic TPP exposure on aquatic organisms are scarce. The zebrafish model was used to investigate the effects of long-term TPP exposure on the endocrine system. Zebrafish embryos were exposed to 5 µg/L, 50 µg/L, or 500 µg/L TPP for 120 d, and hormonal and transcriptional responses were measured along the hypothalamic-pituitary-gonad (HPG) axis, the hypothalamic-pituitary-interrenal (HPI) axis, and the hypothalamic-pituitary-thyroid (HPT) axis. Exposure to TPP significantly increased plasma 17β-estradiol, but decreased 11-ketotestosterone in both sexes. Gene expression data support these changes. In the HPI axis, plasma cortisol and proopiomelanocortin (pomc) and mineralocorticoid receptor transcripts increased in females, but in males cortisol decreased whereas pomc increased (p < 0.05). Thyroxine and triiodothyronine increased, and thyrotrophin-releasing hormone receptor 2 (trhr2) and trh expression were affected only in females (p < 0.05). In summary, long-term exposure to TPP enhanced estrogenicity in both males and females, potentially through influencing the HPG axis, but modulated the HPI, and HPT axes differently by sex, suggesting that both genomic and nongenomic responses might be involved. Environ Toxicol Chem 2016;35:2288-2296. © 2016 SETAC., (© 2016 SETAC.)

Polybrominated diphenyl ethers (PBDEs) have been used as flame retardants. Although many reports have indicated an association between exposure to PBDEs and developmental neurotoxicity, the relative contributions of different sources of dust PBDE congeners to the levels in various tissues of mother-baby pairs is not well understood. The aims of this study were thus to measure the quantitative relationship between the level of PBDEs in house dust and tissues of mother-neonate pairs, and to investigate the chemical sources of the PBDEs. Forty-one mother-neonate pairs were recruited and provided samples of maternal serum (n = 29), umbilical cord serum (n = 25), breast milk (n = 50), and house dust (n = 41), where PBDEs were determined with high-resolution gas chromatography coupled with high-resolution mass spectrometry. While deca- (e.g., BDE 209, detected 100%), nona- (BDE 206/207, 95.1%), octa- (BDE 183, 100%), penta- (BDE 99/153, 100%, 98%) and tetra-BDEs (BDE 47, 100%) were detected abundantly in dust, penta- (BDE 99, 76%, 92%) and tetra-BDEs (BDE 47, 84%, 98%) were detected abundantly in umbilical cord serum and breast milk, respectively; tetra-BDEs (BDE 47, 86%) were detected more often relative to other congeners in maternal serum. Spearman's pairwise comparison showed that the levels of BDE 47 (ρ = 0.52, p < 0.001) and -99 (ρ = 0.64, p < 0.01) in umbilical cord serum were associated with BDE 209 levels in dust; BDE 47 in maternal serum also showed correlation with BDE 99 in cord serum (ρ = 0.48, p < 0.01) but there was no significant correlation between maternal BDE 47 and dust BDE 209. On the other hand, a comparison of the distribution among congeners suggested probable associations of BDE 47 in maternal serum, breast milk, and umbilical cord serum with BDE 209 in dust; and of BDE 99 in maternal and umbilical cord serum, breast milk, and dust with BDE 209 in dust. Although further studies are needed, a radar chart-based distributional comparison among congeners supported associations between BDE 47 or -99 in human tissues and BDE 209 in dust.

Tris(2-butoxyethyl) phosphate (TBEOP), a widely used organophosphate flame retardant, has frequently been detected both in the environment and the biota. However, limited information is available on the effects of TBEOP on the endocrine system and its underlying mechanisms. We exposed adult zebrafish pairs to TBEOP at concentrations of 0, 2.1, 11, and 118 μg/L for 21 d, and investigated the effects on gene transcription and hormone production related to the hypothalamic-pituitary-gonadal (HPG) axis, and on reproduction. The adverse effects on the F1 generation were further examined. In male fish, plasma concentrations of 17β-estradiol were significantly increased along with up-regulation of cyp19a. Exposure to TBEOP at 118 μg/L led to a significant decrease in average egg production. Exposure of the F0 generation to TBEOP delayed hatching and lowered hatching rates in the F1 generation. The results demonstrate that exposure to TBEOP at environmentally relevant concentration levels could affect the sex hormone balance by altering regulatory circuits of the HPG axis, eventually leading to disruption of reproductive performance and the development of offspring., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Dechlorane Plus (DP) is a chlorinated flame retardant widely used worldwide, and has been reported in environment and humans. However, only limited information is currently available on its toxicity on aquatic organisms. In this study, we employed zebrafish to evaluate possible toxicological responses including oxidative stress and endocrine disruption following exposure to DP. DP was dissolved in corn oil and was delivered to adult male zebrafish via gavage feeding. Delivery of DP was carried out twice on days 0 and 2, at up to 3 μg/g fish wet weight. Body residue level of DP in the fish at day 6 was within a range that has been reported in hot spot areas of China. On day 6, blood, liver, testis, and brain were collected and were evaluated for oxidative damage and endocrine disruption. Following DP exposure, hepatic catalase activity significantly increased, implying its oxidative damage potential. In addition, plasma thyroxine (T4) concentrations increased along with up-regulation of corticotropin releasing hormone and thyroid stimulating hormone β genes in brain. Following DP exposure, transcriptional responses of sex hormone related genes in brain were observed, suggesting possible sex hormone disrupting potentials of DP. However, water-borne exposure to DP up to 267 μg/L among the embryo and larval fish did not show any adverse effects on hatching time and transcription of thyroid hormone related genes. Our observations indicate for the first time that DP disrupts thyroid hormone balance of zebrafish by altering regulatory pathways in the brain. Handling editor: David Volz., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Studies on the occurrence of polybrominated diphenyl ethers (PBDEs) and other alternative brominated flame retardants in the environment are scarce. In this study, PBDEs and non-PBDE brominated flame retardants (NBFRs), including decabromodiphenyl ethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), were measured in sludge collected from three types of wastewater treatment plants (WWTPs) in Korea. Total concentrations of PBDEs (∑PBDE) in sludge ranged from 298 to 48,000 (mean: 3240) ng/g dry weight. Among 10 NBFRs analyzed, DBDPE and BTBPE were the only ones detected in sludge samples. Concentrations of DBDPE and BTBPE ranged from 1) of DBDPE/BDE 209 were found in sludge from I-WWTPs, reflecting a shift in the usage pattern of BFRs by the Korean industry. The nationwide annual emission fluxes of ∑PBDE, DBDPE and BTBPE via WWTPs to the environment were estimated to be 7400, 480, and 3.7 kg/year, respectively. This is the first study on the occurrence of alternative brominated flame retardants in sludge from Korea., (© 2013 Elsevier B.V. All rights reserved.)

Tris(1,3-dichloro-2-propyl) phosphate (TDCPP) and triphenyl phosphate (TPP) belong to the group of triester organophosphate flame retardants (OPFRs), which have been used in a wide range of consumer products. These chemicals have been frequently detected in effluents, surface water, and fish, and hence their potential adverse effects on aquatic ecosystem are of concern. The present study was conducted to investigate the reproduction-related effects and possible molecular mechanisms of TDCPP and TPP using a 21 day reproduction test employing adult zebrafish (Danio rerio). After 21 d of exposure to TDCPP or TPP, significant decrease in fecundity along with significant increases of plasma 17β-estradiol (E2) concentrations, vitellogenin (VTG) levels, and E2/testosterone (T) and E2/11-ketotestosterone (11-KT) ratios were observed. The transcriptional profiles of several genes of the hypothalamus-pituitary-gonad (HPG) axis changed as well after the exposure, but the trend was sex-dependent. In male fish, gonadotropin-releasing hormone2 (GnRH2), GnRHR3, cytochrome P450 (CYP) 19B, estrogen receptor α (ERα), ER2 β1, and follicle stimulating hormone β (FSHβ) were upregulated in the brain, while luteinizing hormone β (LHβ) and androgen receptor (AR) were downregulated. Corresponding to the upregulation of FSHβ and downregulation of LHβ in the brain, FSHR was upregulated and LHR was downregulated in the testis. Among the genes that regulate the steroidogenesis pathway, transcription of hydroxyl methyl glutaryl CoA reductase (HMGRA), steroidogenic acute regulatory protein (StAR), and 17β-hydroxysteroid dehydrogenase (17βHSD) decreased, while transcription of CYP11A, CYP17, and CYP19A increased. In female fish, transcription ofGnRH2 and GnRHR3 decreased, but FSHβ, LHβ, CYP19B, ERα, ER2β1, and AR transcription increased in the brain. In the ovary, FSHR and LHR were significantly upregulated, and most steroidogenic genes were significantly upregulated. The observed disruption of GnRH and GtHs could be further related to subsequent disruption in both sex steroid hormone balance and plasma VTG levels, as well as reproductive performance. Overall, our observation indicates that both TDCPP and TPP could disturb the sex hormone balance by altering regulatory mechanisms of the HPG axis, eventually leading to disruption of reproductive performance in fish., (Copyright © 2013 Elsevier B.V. All rights reserved.)