Multi-level assessment of the origin, feeding area and organohalogen contamination on salmon from the Baltic Sea.

The Atlantic salmon (Salmo salar) population in the Baltic Sea consists of wild and hatchery-reared fish that have been released into the sea to support salmon stocks. During feeding migration, salmon migrate to different parts of the Baltic Sea and are exposed to various biotic and abiotic stressors, such as organohalogen compounds (OHCs). The effects of salmon origin (wild or hatchery-reared), feeding area (Baltic Main Basin, Bothnian Sea, and Gulf of Finland), and OHC concentration on the differences in hepatic proteome of salmon were investigated. Multi-level analysis of the OHC concentration, transcriptome, proteome, and oxidative stress biomarkers measured from the same salmon individuals were performed to find the key variables (origin, feeding area, OHC concentrations, and oxidative stress) that best account for the differences in the transcriptome and proteome between the salmon groups. When comparing wild and hatchery-reared salmon, differences were found in xenobiotic and amino acid metabolism-related pathways. When comparing salmon from different feeding areas, the amino acid and carbohydrate metabolic pathways were notably different. Several proteins found in these pathways are correlated with the concentrations of polychlorinated biphenyls (PCBs). The multi-level analysis also revealed amino acid metabolic pathways in connection with PCBs and oxidative stress variables related to glutathione metabolism. Other pathways found in the multi-level analysis included genetic information processes related to ribosomes, signaling and cellular processes related to the cytoskeleton, and the immune system, which were connected mainly to the concentrations of Polychlorinated biphenyls and Dichlorodiphenyltrichloroethane and their metabolites. These results suggest that the hepatic proteome of salmon in the Baltic Sea, together with the transcriptome, is more affected by the OHC concentrations and oxidative stress of the feeding area than the origin of the salmon.

A review on management practices, environmental impacts, and human exposure risks related to electrical and electronic waste in Vietnam: findings from case studies in informal e-waste recycling areas.

Electrical and electronic waste (e-waste) has become a global concern, especially in developing countries. In this review, we conducted a literature survey of e-waste management practices, processing activities, and adverse effects in Vietnam, an emerging country in Southeast Asia, by gathering data from peer-reviewed articles published between 2009 and 2021. This is the first review paper to comprehensively discuss management and research aspects regarding e-waste in an Asian developing country. Due to the lack of an effective management and recycling system, a certain portion of Vietnamese e-waste has been processed by informal sectors without appropriate recycling and pollution control technology, resulting in localized contamination and human exposure to toxic chemicals. Primitive processing activities, such as manual dismantling, open burning, and plastic recycling, have been identified as important contributors to the environmental emission and human exposure to toxic elements (notably As, Mn, Ni, Pb, Zn) and organic pollutants like flame retardants, PAHs, PCBs, and dioxin-related compounds. Informal e-waste processing from these small-scale workshops can release pollutants at similar levels compared to large-scale facilities in developed countries. This fact suggests an urgent need to develop management best practices for e-waste in Vietnam as well as other emerging and developing countries, in order to increase recycling efficiency and minimize their adverse impacts on environmental and human health.

Polycyclic Aromatic Hydrocarbons in Air and Dust Samples from Vietnamese End-of-life Vehicle Processing Workshops: Contamination Status, Sources, and Exposure Risks.

Concentrations of 18 unsubstituted polycyclic aromatic hydrocarbons (PAHs) and 11 methylated derivatives (Me-PAHs) were measured in polyurethane foam-based passive air (PUF-PAS) and settled dust samples collected from end-of-life vehicle (ELV) processing workshops in northern Vietnam. Concentrations of total 29 PAHs ranged from 42 to 95 (median 57) ng/m3 and from 860 to 18,000 (median 5700) ng/g in air and dust samples, respectively. PAH levels in ELV air and dust samples were 1.5 ± 0.4 and 9.4 ± 7.9 times higher than levels found in a control house, suggesting ELV processing as potential PAH emission sources. Concentrations and proportions of Me-PAHs in total PAHs of the ELV air (26% ± 7%) and dust (41% ± 14%) were higher than those found in control house (18% in both air and dust). The occurrence of PAHs and Me-PAHs in the ELV workshops are attributed to not only pyrogenic but also petrogenic sources (i.e., improper treatment and management of fuels, lubricants, and vehicle oils).

Effects of 1,3,7-tribromodibenzo-p-dioxin, a natural dioxin on chicken embryos: Comparison with effects of 2,3,7,8-tetrachlorodibenzo-p-dioxin.

Several naturally occurring dioxins, including 1,3,7-tribromodibenzo-p-dioxin (1,3,7-TriBDD), synthesized by red algae, have been detected in the marine environment. As 1,3,7-TriBDD is accumulated in mussels and fish, predators, such as marine birds, are exposed to this congener, similar to anthropogenic dioxins (including 2,3,7,8-tetrachlorodibenzo-p-dioxin TCDD). However, little is known about the impact of 1,3,7-TriBDD exposure on the bird health. To understand the effects of 1,3,7-TriBDD on birds, the phenotypic effects and hepatic transcriptome were investigated in chicken (Gallus gallus) embryos treated with 27 µM (2.9 ng/g egg) and 137 µM (14.4 ng/g egg) 1,3,7-TriBDD. The blood glucose levels in the 1,3,7-TriBDD-treated groups were lower than those in the control group. The transcriptome analysis of 6520 sequences in the 27 and 137 µM 1,3,7-TriBDD-treated groups identified 733 and 596 differentially expressed genes (DEGs). Cytochrome P450 1A4 and 1A5 were also identified as DEGs, suggesting that the aryl hydrocarbon receptor is activated by this congener. Pathway and network analyses with DEGs suggested that 1,3,7-TriBDD may induce carcinogenic effects and metabolic alterations. These results were similar to the effects on TCDD-treated embryos. Nevertheless, the overall transcriptome results suggested that compared with TCDD, 1,3,7-TriBDD has a unique impact on insulin- and peroxisome-signaling pathways in chicken embryos. Differences in altered transcriptome profiles between 1,3,7-TriBDD- and TCDD-treated embryos may lead to different phenotypic effects: less severe effects of 1,3,7-TriBDD and more fatal effects of TCDD. Collectively, these findings warrant the further assessment of the hazard and risk of 1,3,7-TriBDD on marine animals, considering increased exposure due to climate change.

Determination of the relative potencies of brominated dioxins for risk assessment in aquatic environments using the early-life stage of Japanese medaka.

World Health Organization toxic equivalency factors (WHO-TEFs) are recommended for risk management of brominated dioxins in aquatic environments because limited information is available on their toxicity to fish. To validate this approach, we obtained the relative potencies of polybrominated dibenzo-p-dioxins and polybrominated dibenzofurans and mixed-halogenated furans (PXDF, X = Cl/Br) against 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) based on their toxicity to the early-life stage of Japanese medaka (Oryzias latipes). 2,3,7,8-substituted brominated dibenzofurans caused typical dioxin exposure effects, such as blue-sac disease. The TCDD-relative potency factors (REPs) of test substances were calculated based on the concentrations in water and eggs that caused 20% lethality on day 28 post-fertilization, and were in the order of: 2-chloro-3,7,8-tribromodibenzofuran (REPwater 3.3, REPegg 4.6) > 2,3,7,8-tetrabromodibenzofuran (0.85, 0.92) > 2,3,4,7,8-pentabromodibenzofuran (0.053, 0.55) > 1,2,3,7,8-pentabromodibenzofuran (0.0091, 0.19). The transfer rate from water to eggs was lower for pentabrominated furans than tetrabrominated congeners, and was expected to decrease with the log Kow of the test substance. Although the REPegg value can be used to compare the toxicity potential of brominated dioxins, REPwater may be more suitable for environmental risk assessment because the uptake potential of these compounds from water should be considered. This study is the first to report higher toxicity of a PXDF congener compared with TCDD in vivo, further investigations of the toxicity of mixed-halogenated dioxins and environmental behavior are necessary for environmental risk assessment.

Nontarget Screening of Organohalogen Compounds in the Liver of Wild Birds from Osaka, Japan: Specific Accumulation of Highly Chlorinated POP Homologues in Raptors.

Nontarget screening studies have recently revealed the accumulation of typically unmonitored organohalogen compounds (OHCs) in various marine animals, but information for terrestrial food chains is still lacking. This study investigated the accumulation profiles of known and unknown OHCs in the liver of representative wild bird specimens from Osaka, Japan using nontarget analysis based on two-dimensional gas chromatography-time-of-flight mass spectrometry. A large number of unmonitored OHCs were identified, including anthropogenic contaminants and marine halogenated natural products (HNPs), and their accumulation profiles were considered to be influenced by terrestrial and brackish water-based diets. Anthropogenic OHCs were highly accumulated in terrestrial predator species (peregrine falcon, hawks, and black kite), and some unmonitored highly chlorinated contaminants reached the levels of microgram per gram lipid in the liver, i.e., C10-/C15-based chlordane related compounds (CHLs) and their epoxides, dichlorodiphenyldichloroethylene (DDE) homologues, and polychlorinated terphenyls (PCTs). In contrast, HNPs were accumulated at higher levels in piscivorous birds (gray heron and common cormorant). Considering the enrichment of the unmonitored C10-/C15-based CHLs, PCTs, and DDE homologues relative to structurally similar persistent organic pollutants (POPs) in high trophic-level species such as raptors, further studies are needed to elucidate their environmental levels, behavior in terrestrial food chains, and ecotoxicological impacts.

Effects on the Liver Transcriptome in Baltic Salmon: Contributions of Contamination with Organohalogen Compounds and Origin of Salmon.

Hatchery-reared Atlantic salmon (Salmo salar) has been released to support the wild salmon stocks in the Baltic Sea for decades. During their feeding migration, salmon are exposed to organohalogen compounds (OHCs). Here, we investigated the OHC levels and transcriptome profiles in the liver of wild and hatchery-reared salmon collected from the Baltic main basin (BMB), the Bothnian Sea (BS), and the Gulf of Finland (GoF) and examined whether salmon origin and OHC levels contributed to the hepatic transcriptome profiles. There were no differences in the OHC concentrations between wild and reared fish but larger differences between areas. Several transcript levels were associated with non-dioxin-like polychlorinated biphenyls, polybrominated diphenylethers, chlordanes, and dichlorodiphenyltrichloroethane in a concentration-dependent manner. Between wild and reared salmon, lipid metabolism and related signaling pathways were enriched within the BMB and BS, while amino acid metabolism was altered within the GoF. When comparing the different areas, lipid metabolism, environmental stress and cell growth, and death-related pathways were enriched. Class coinertia analysis showed that the covariation in the OHC levels and the transcriptome were significantly similar. These results suggest that the hepatic transcriptomes in wild and hatchery-reared salmon are more affected by the OHC levels rather than the origin of salmon.

Nontarget and Target Screening of Organohalogen Compounds in Mussels and Sediment from Hiroshima Bay, Japan: Occurrence of Novel Bioaccumulative Substances.

Recent screening surveys have shown the presence of unknown halogenated compounds in the marine environment at comparable levels to persistent organic pollutants (POPs). However, their exposure levels and profiles in marine organisms and bioaccumulative potentials remain unclear. The present study performed nontarget/target screening of organohalogen compounds (OHCs) in mussel and sediment samples collected from Hiroshima Bay, Japan, in 2012 and 2018 by using integrated analyses of two-dimensional gas chromatography-high resolution time-of-flight mass spectrometry (GC×GC-HRToFMS) and magnetic sector GC-HRMS. Nontarget analysis by GC×GC-HRToFMS revealed the detection of approximately 60 OHCs including unknown mixed halogenated compounds (UHC-Br3-5Cl) with molecular formulae of C9H6Br3ClO, C9H5Br4ClO, and C9H4Br5ClO in the mussel. Interestingly, UHC-Br3-5Cl concentrations in the mussel samples, which were semi-quantified by GC-HRMS, were comparable to or higher than those of POPs at all the locations surveyed, and their geographical distribution patterns differed from those of other OHCs. These results suggest that UHC-Br3-5Cl are ubiquitous in coastal waters of Hiroshima Bay and derived from a specific source(s). The biota-sediment accumulation factors (BSAFs) of UHC-Br3-5Cl, estimated for a paired sample set of mussel (ng/g lw) and sediment (ng/g TOC), were 1 order of magnitude higher than those for POPs with similar log Kow values, indicating their high bioaccumulative potential.

Complex Mixtures of Brominated/Chlorinated Diphenyl Ethers and Dibenzofurans in Soils from the Agbogbloshie e-Waste Site (Ghana): Occurrence, Formation, and Exposure Implications.

The distribution and toxic equivalents (TEQs) of brominated and chlorinated dibenzo- p-dioxins/dibenzofurans (PBDD/Fs and PCDD/Fs) in soils from Agbogbloshie e-waste site (Ghana) were investigated. The composition of brominated/chlorinated dibenzofurans (PXDFs) and diphenyl ethers (PBDEs, PCDEs, and PXDEs) was examined using two-dimensional gas chromatography-time-of-flight mass spectrometry to elucidate possible formation pathways of dioxins from e-waste recycling. The highest concentrations of PCDD/Fs and PBDD/Fs were found, respectively, in the open burning (1.3-380 ng/g dry weight) and dismantling areas (11-1000 ng/g dry weight) and were comparable to the highest reported for informal e-waste sites. PXDFs and PXDEs were detected at up to the range of hundreds of nanograms per gram. The homologue profiles suggest that PXDFs were formed mainly from PBDFs through successive Br-to-Cl exchange. However, monobromo-PCDFs were also derived from de-novo-generated PCDFs in open burning areas. PBDFs contributed similar or higher TEQs (7.9-5400 pg/g dry weight) compared with PCDD/Fs (6.8-5200 pg/g dry weight), whereas PXDFs were also substantial TEQ contributors in open burning areas. The high TEQs of PBDFs in the dismantling area (120-5200 pg/g dry weight) indicate the need to consider brominated dioxins besides chlorinated dioxins in future studies on health implications for e-waste workers and local residents.

A preliminary investigation of 942 organic micro-pollutants in the atmosphere in waste processing and urban areas, northern Vietnam: Levels, potential sources, and risk assessment.

Of 942 organic micro-pollutants screened, 167 compounds were detected at least once in the atmosphere in some primitive waste processing sites and an urban area in northern Vietnam by using a polyurethane foam-based passive air sampling (PUF-PAS) method and an Automated Identification and Quantification System with a Database (AIQS-DB) for GC-MS. Total concentrations of organic pollutants were higher in samples collected from an urban area of Hanoi city (2300-2600 ng m-3) as compared with those from an end-of-life vehicle (ELV) dismantling area in Bac Giang (900-1700 ng m-3) and a waste recycling cooperative in Thai Nguyen (870-1300 ng m-3). Domestic chemicals (e.g., n-alkanes, phthalate ester plasticizers, and synthetic phenolic antioxidants) dominated the organic pollutant patterns in all the samples, especially in the urban area. Pesticides (e.g., permethrins, chlorpyrifos, and propiconazole) were found in the atmosphere around the ELV sites at more elevated concentrations than the other areas. Levels of polycyclic aromatic hydrocarbons and their derivatives in the Bac Giang and Thai Nguyen facilities were significantly higher than those measured in Hanoi urban houses, probably due to the waste processing activities. Daily intake doses of organic pollutants via inhalation were estimated for waste processing workers and urban residents. This study shall provide preliminary data on the environmental occurrence, potential emission sources, and effects of multiple classes of organic pollutants in urban and waste processing areas in northern Vietnam.

Occurrence of Natural Mixed Halogenated Dibenzo-p-Dioxins: Specific Distribution and Profiles in Mussels from Seto Inland Sea, Japan.

In addition to unintentional formation of polychlorinated (PCDD/Fs), polybrominated (PBDD/Fs), and mixed halogenated (PXDD/Fs) dibenzo-p-dioxins/dibenzofurans during industrial activities, recent studies have shown that several PBDD and PXDD congeners can be produced by marine algal species from the coastal environment. However, multiple exposure status of anthropogenic and naturally derived dioxins in marine organisms remains unclear. The present study examined the occurrence, geographical distribution, and potential sources of PCDD/Fs, PBDD/Fs, and PXDD/Fs using mussels and brown algae collected in 2012 from Seto Inland Sea, Japan. The results showed the widespread occurrence of not only PCDD/Fs but also PBDDs and PXDDs in Seto Inland Sea. The geographical distribution pattern of PBDDs was similar to that of PXDDs, which were obviously different from that of PCDDs and PCDFs, and a significant positive correlation was observed between the levels of their predominant congeners, i.e., 1,3,7-/1,3,8-TrBDDs and DiBMoCDDs. Interestingly, potential precursors of 1,3,7-/1,3,8-TrBDDs and DiBMoCDDs, hydroxylated tetrabrominated diphenyl ethers (6-HO-BDE-47 and 2'-HO-BDE-68) and their mixed halogenated analogue (HO-TrBMoCDE), were also identified in the mussel and brown alga samples collected at the same site, by comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (GC × GC-ToFMS) analyses. It is noteworthy that residue levels of 1,3,7-/1,3,8-TrBDDs and DiBMoCDDs in the mussel were 30 times higher than those in the brown alga, suggesting the bioaccumulation of these natural dioxins.

Toxic Identification and Evaluation of Androgen Receptor Antagonistic Activities in Acid-Treated Liver Extracts of High-Trophic Level Wild Animals from Japan.

Sulfuric acid-treated liver extracts of representative high-trophic level Japanese animals were analyzed by toxic identification and evaluation (TIE) with chemically activated luciferase expression (CALUX) and chemical analysis to elucidate androgen receptor (AR) antagonistic activities and potential contributions of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs). The activities were detected in striped dolphins (n = 5), Stejneger's beaked whales (n = 6), golden eagle (n = 1), and Steller's sea eagle (n = 1) with CALUX-flutamide equivalents (FluEQs) as follow: 38 (20-52), 47 (21-96), 5.0, and 80 µg FluEQ/g-lipid, respectively. The AR antagonism was detected in limited number of specimens at lower levels for finless porpoise, raccoon dog, and common cormorant. Theoretical activities (Theo-FluEQs) were calculated using the concentration of OCPs and PCBs and their IC25-based relative potency (REP) values. These total contribution to CALUX-FluEQ was 126%, 84%, 53%, 55%, and 44% for striped dolphin, Steller's sea eagle, Stejneger's beaked whale, finless porpoise, and golden eagle, respectively, and the main contributor was p,p'-DDE. However, most of the activities for raccoon dog (7.6%) and common cormorant (17%) could not be explained by OCPs and PCBs. This suggests other unknown compounds could function as AR antagonists in these terrestrial species.

Dioxin-related compounds in breast milk of women from Vietnamese e-waste recycling sites: levels, toxic equivalents and relevance of non-dietary exposure.

Although informal e-waste recycling sites (EWRSs) are hotspots of both polychlorinated and polybrominated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs and PBDD/Fs), human exposure to the latter has not been studied in details. This study investigated the accumulation levels and profiles of dioxin-related compounds (DRCs) in breast milk samples from women living in two Vietnamese EWRSs and estimated the intake contribution from e-waste-related exposure. Screening results using Dioxin-Responsive Chemically Activated LUciferase gene eXpression assay (DR-CALUX) showed higher dioxin-like (DL) activities in samples from the EWRS Bui Dau than in those from the EWRS Trang Minh and a reference site (2.3-10 vs 1.7-4.8 and 0.60-5.7 pg CALUX-TEQ/g lipid, n=10, 6 and 9, respectively). Chemical analysis results of selected samples show that the WHO-TEQ levels of PCDD/Fs, DL-PCBs and PBDD/Fs in EWRS samples were not significantly higher than in those from the reference site (0.22-7.4 vs 1.1-3.0 pg/g lipid) and within the Vietnamese background range, but women involved in recycling accumulated higher concentrations of PCDFs (13-15 vs 2.3-8.8 pg/g lipid) and PBDFs (1.1-1.5 vs <1.1 pg/g lipid). By comparing the DRC profile in milk of these women with the reported profile in house dust from the same site, dust ingestion was estimated to contribute most of the intake for tetraBDF, 37 per cent to 55 per cent for penta-octaCDFs, but less than twenty per cent for PCDDs and DL-PCBs, and 26 per cent for total WHO-TEQs. The DL activities in some EWRS milk samples were not fully explained by chemical data, suggesting contribution from unidentified compounds. The estimated WHO-TEQ intake doses for breastfed infants (1.3-33 pg/kg/d) mostly exceeded the tolerable value, especially for those living in the EWRSs; and unidentified DRCs might increase further the dioxin-related health risk.

Uptake, Elimination and Metabolism of Brominated Dibenzofurans in Mice.

Polybrominated dibenzofurans (PBDFs) are major brominated dioxins in the environment, but information on their bioaccumulation potential and toxicokinetics is limited. This study conducted oral exposure experiments with C57BL/6J mice to investigate the uptake ratios, distribution in the liver, plasma and brain, metabolism, and elimination kinetics of four bromine/chlorine-substituted dibenzofurans (TrBDF: 2,3,8-tribromo, TeBDF: 2,3,7,8-tetrabromo, PeBDF: 1,2,3,7,8-pentabromo, TrBCDF: 2,3,7-tribromo-8-chloro) in comparison with 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). The hepatic uptake ratios of 2,3,7,8-substituted dibenzofurans were lower than that of TCDD (up to 84% of the administered doses) and decreased with the number of Br substitutions (42%, 33%, and 29% for TrBCDF, TeBDF, and PeBDF, respectively). The brain uptake ratios of these dibenzofurans were less than 0.05%, and the plasma-to-brain transfer ratio also decreased with the Br number. All 2,3,7,8-substituted compounds were eliminated from the liver following first-order kinetics, with half-times in the order of TrBCDF (5.6 days) < TeBDF (8.8 days) ≈ TCDD (8.7 days) < PeBDF (13 days). The non-2,3,7,8-substituted TrBDF was poorly retained in the liver (<0.01% of the dose at 1 day) and rapidly eliminated following two-phase kinetics. All dibenzofurans were metabolised into monohydroxylated products in the liver, but the contribution of this metabolic pathway to hepatic elimination was only significant for TrBDF. As the toxic effects of dioxin-like compounds are influenced by their biological persistence, the slow elimination of TrBCDF, TeBDF, and PeBDF observed in this study suggests that exposure risk of brominated dibenzofurans may be underestimated using the toxic equivalency factors of the less persistent chlorinated analogues.

Bioaccessibility of halogenated flame retardants and organophosphate esters in settled dust: Influences of specific dust matrices from informal e-waste and end-of-life vehicle processing areas in Vietnam.

Bioaccessibility of halogenated flame retardants (HFRs) and organophosphorus esters (OPEs) is necessarily investigated to provide more accurate risk assessment and information about absorption behavior of these pollutants. In this study, total and bioaccessible concentrations of HFRs (including legacy and alternative substances) and OPEs were determined in settled dust samples collected from Vietnamese e-waste and end-of-life vehicle (ELV) processing areas. Concentrations of both HFRs and OPEs were significantly higher in the e-waste dust than ELV dust. Bioavailability of HFRs and OPEs in dust was determined by using an in vitro assay with human-simulated digestive fluids, dialysis membrane, and Tenax® TA sorptive sink. Bioaccessibility of HFRs was markedly lower than that of OPEs, which could be largely due to higher hydrophobicity of HFRs compared to OPEs. Bioaccessibility of almost hydrophobic compounds were markedly lower in the e-waste dust (containing micronized plastic debris) than in the ELV dust (containing oily materials), suggesting the influence of specific dust matrices on pollutant bioaccessibility. Although the daily uptake doses of selected HFRs and OPEs from dust were markedly higher in the e-waste sites compared to the ELV sites, the direct exposure risk was not significant. Our results suggest that bioaccessibility can partly explain the differences between dust and uptake profiles, which may relate to accumulation profiles of HFRs and OPEs in human samples.

Results of an international interlaboratory study on dioxin-like activities in drinking-, river surface- and wastewater using DR CALUX bioassay.

Aquatic animals and consumers of aquatic animals are exposed to increasingly complex mixtures of known and as-yet-unknown chemicals with dioxin-like toxicities in the water cycle. Effect- and cell-based bioanalysis can cover known and yet unknown dioxin and dioxin-like compounds as well as complex mixtures thereof but need to be standardized and integrated into international guidelines for environmental testing. In an international laboratory testing (ILT) following ISO/CD 24295 as standard procedure for rat cell-based DR CALUX un-spiked and spiked extracts of drinking-, surface-, and wastewater were validated to generate precision data for the development of the full ISO-standard. We found acceptable repeatability and reproducibility ranges below 36 % by DR CALUX bioassay for the tested un-spiked and spiked water of different origins. The presence of 17 PCDD/Fs and 12 dioxin-like PCBs was also confirmed by congener-specific GC-HRMS analysis. We compared the sum of dioxin-like activity levels measured by DR CALUX bioassay (expressed in 2,3,7,8-TCDD Bioanalytical Equivalents, BEQ; ISO 23196, 2022) with the obtained GC-HRMS chemical analysis results converted to toxic equivalents (TEQ; van den Berg et al., 2013).

Similarities in the endocrine-disrupting potencies of indoor dust and flame retardants by using human osteosarcoma (U2OS) cell-based reporter gene assays.

Indoor dust is a sink for many kinds of pollutants, including flame retardants (FRs), plasticizers, and their contaminants and degradation products. These pollutants can be migrated to indoor dust from household items such as televisions and computers. To reveal high-priority end points of and contaminant candidates in indoor dust, using CALUX reporter gene assays based on human osteosarcoma (U2OS) cell lines, we evaluated and characterized the endocrine-disrupting potencies of crude extracts of indoor dust collected from Japan (n = 8), the United States (n = 21), Vietnam (n = 10), the Philippines (n = 17), and Indonesia (n = 10) and for 23 selected FRs. The CALUX reporter gene assays used were specific for compounds interacting with the human androgen receptor (AR), estrogen receptor α (ERα), progesterone receptor (PR), glucocorticoid receptor (GR), and peroxisome proliferator-activated receptor γ2 (PPARγ2). Indoor dust extracts were agonistic to ERα, GR, and PPARγ2 and antagonistic against AR, PR, GR, and PPARγ2. In comparison, a majority of FRs was agonistic to ERα and PPARγ2 only, and some FRs demonstrated receptor-specific antagonism against all tested nuclear receptors. Hierarchical clustering clearly indicated that agonism of ERα and antagonism of AR and PR were common, frequently detected end points for indoor dust and tested FRs. Given our previous results regarding the concentrations of FRs in indoor dust and in light of our current results, candidate contributors to these effects include not only internationally controlled brominated FRs but also alternatives such as some phosphorus-containing FRs. In the context of indoor pollution, high-frequency effects of FRs such as agonism of ERα and antagonism of AR and PR are candidate high-priority end points for further investigation.

Contamination by perfluorinated compounds in water near waste recycling and disposal sites in Vietnam.

There are very few reports on the contamination by perfluorinated chemicals (PFCs) in the environment of developing countries, especially regarding their emission from waste recycling and disposal sites. This is the first study on the occurrence of a wide range of PFCs (17 compounds) in ambient water in Vietnam, including samples collected from a municipal dumping site (MD), an e-waste recycling site (ER), a battery recycling site (BR) and a rural control site. The highest PFC concentration was found in a leachate sample from MD (360 ng/L). The PFC concentrations in ER and BR (mean, 57 and 16 ng/L, respectively) were also significantly higher than those detected in the rural control site (mean, 9.4 ng/L), suggesting that municipal solid waste and waste electrical and electronic equipment are potential contamination sources of PFCs in Vietnam. In general, the most abundant PFCs were perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), and perfluoroundecanoic acid (PFUDA; <1.4-100, <1.2-100, and <0.5-20 ng/L, respectively). Interestingly, there were specific PFC profiles: perfluoroheptanoic acid and perfluorohexanoic acid (88 and 77 ng/L, respectively) were almost as abundant as PFOA in MD leachate (100 ng/L), whereas PFNA was prevalent in ER and BR (mean, 17 and 6.2 ng/L, respectively) and PFUDA was the most abundant in municipal wastewater (mean, 5.6 ng/L), indicating differences in PFC contents in different waste materials.

Occurrence, emission sources, and risk assessment of polybrominated diphenyl ethers and current-use brominated flame retardants in settled dust from end-of-life vehicle processing, urban, and rural areas, northern Vietnam.

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

Estrogenic, androgenic, and glucocorticoid activities and major causative compounds in river waters from three Asian countries.

Estrogen, androgen, and glucocorticoid receptors (ER, AR, and GR) agonist activities in river water samples from Chennai and Bangalore (India), Jakarta (Indonesia), and Hanoi (Vietnam) were evaluated using a panel of chemical-activated luciferase gene expression (CALUX) assays and were detected mainly in the dissolved phase. The ER agonist activity levels were 0.011-55 ng estradiol (E2)-equivalent/l, higher than the proposed effect-based trigger (EBT) value of 0.5 ng/l in most of the samples. The AR agonist activity levels were < 2.1-110 ng dihydrotestosterone (DHT)-equivalent/l, and all levels above the limit of quantification exceeded the EBT value of 3.4 ng/l. GR agonist activities were detected in only Bangalore and Hanoi samples at dexamethasone (Dex)-equivalent levels of < 16-150 ng/l and exceeded the EBT value of 100 ng/l in only two Bangalore samples. Major compounds contributing to the ER, AR, and GR agonist activities were identified for water samples from Bangalore and Hanoi, which had substantially higher activities in all assays, by using a combination of fractionation, CALUX measurement, and non-target and target chemical analysis. The results for pooled samples showed that the major ER agonists were the endogenous estrogens E2 and estriol, and the major GR agonists were the synthetic glucocorticoids Dex and clobetasol propionate. The only AR agonist identified in major androgenic water extract fractions was DHT, but several unidentified compounds with the same molecular formulae as endogenous androgens were also found.