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.

Antiandrogenic and Estrogenic Activity Evaluation of Oxygenated and Nitrated Polycyclic Aromatic Hydrocarbons Using Chemically Activated Luciferase Expression Assays.

To establish the risk of the endocrine disrupting activity of polycyclic aromatic compounds, especially oxygenated and nitrated polycyclic aromatic hydrocarbons (oxy-PAHs and nitro-PAHs, respectively), antiandrogenic and estrogenic activities were determined using chemically activated luciferase expression (CALUX) assays with human osteoblast sarcoma cells. A total of 27 compounds including 9 oxy-PAHs (polycyclic aromatic ketones and quinones) and 8 nitro-PAHs was studied. The oxy-PAHs of 7H-benz[de]anthracen-7-one (BAO), 11H-benzo[a]fluoren-11-one (B[a]FO), 11H-benzo[b]fluoren-11-one (B[b]FO), and phenanthrenequinone (PhQ) exhibited significantly the potent inhibition of AR activation. All nitro-PAHs exhibited high antiandrogenic activities (especially high for 3-nitrofluoranthene (3-NFA) and 3-nitro-7H-benz[de]anthracen-7-one (3-NBAO)), and the AR inhibition was confirmed as noncompetitive for 3-NFA, 3-NBAO, and 1,3-dinitropyrene (1,3-DNPy). Antiandrogenic activity of 3-NFA demonstrated characteristically a U-shaped dose-response curve; however, the absence of fluorescence effect on the activity was confirmed. The prominent estrogenic activity dependent on dose-response curve was confirmed for 2 oxy-PAHs (i.e., B[a]FO and B[b]FO). Elucidating the role of AR and ER on the effects of polycyclic aromatic compounds (e.g., oxy- and nitro-PAHs) to endocrine dysfunctions in mammals and aquatic organisms remains a challenge.

Polycyclic aromatic hydrocarbons in airborne particulate matter samples from Hanoi, Vietnam: Particle size distribution, aryl hydrocarbon ligand receptor activity, and implication for cancer risk assessment.

Concentrations and profiles of unsubstituted and methylated polycyclic aromatic hydrocarbons (PAHs and Me-PAHs) were analyzed in airborne particulate matter (PM) samples collected from high-traffic roads in Hanoi urban area. Levels of PAHs and Me-PAHs ranged from 210 to 660 (average 420) ng/m3 in total PM, and these pollutants were mainly associated with fine particles (PM2.5) rather than coarser ones (PM > 10 and PM10). Proportions of high-molecular-weight compounds (i.e., 5- and 6-ring) increased with decreasing particle size. Benzo[b+k]fluoranthene, indeno[1,2,3-cd]pyrene, and benzo[ghi]perylene were the most predominant compounds in the PM2.5 samples. In all the samples, Me-PAHs were less abundant than unsubstituted PAHs. The PAH-CALUX assays were applied to evaluate aryl hydrocarbon receptor (AhR) ligand activities in crude extracts and different fractions from the PM samples. Benzo[a]pyrene equivalents (BaP-EQs) derived by the PAH-CALUX assays for low polar fractions (mainly PAHs and Me-PAHs) ranged from 300 to 840 ng/m3, which were more consistent with theoretical values derived by using PAH-CALUX relative potencies (270-710 ng/m3) rather than conventional toxic equivalency factor-based values (22-69 ng/m3). Concentrations of PAHs and Me-PAHs highly correlated with bioassay-derived BaP-EQs. AhR-mediated activities of more polar compounds and interaction effects between PAH-related compounds were observed. By using PAH-CALUX BaP-EQs, the ILCR values ranged from 1.0 × 10-4 to 2.8 × 10-4 for adults and from 6.4 × 10-5 to 1.8 × 10-4 for children. Underestimation of cancer risk can be eliminated by using effect-directed method (e.g., PAH-CALUX) rather than chemical-specific approach.

Characterization of unsubstituted and methylated polycyclic aromatic hydrocarbons in settled dust: Combination of instrumental analysis and in vitro reporter gene assays and implications for cancer risk assessment.

Concentrations of 34 unsubstituted and methylated polycyclic aromatic hydrocarbons (PAHs and Me-PAHs) and AhR-mediated activities in settled dust samples were determined by a combination of gas chromatography-mass spectrometry and an in vitro reporter gene assay (PAH-CALUX). The levels of Σ34PAHs and bioassay-derived benzo[a]pyrene equivalents (CALUX BaP-EQs) were significantly higher in workplace dust from informal end-of-life vehicle dismantling workshops than in common house dust and road dust. In all the samples, the theoretical BaP-EQs of PAHs (calculated using PAH-CALUX relative potencies) accounted for 28 ± 19% of the CALUX BaP-EQs, suggesting significant contribution of aryl hydrocarbon receptor (AhR) agonists and/or mixture effects. Interestingly, the bioassay-derived BaP-EQs in these samples were significantly correlated with not only unsubstituted PAHs with known carcinogenic potencies but also many Me-PAHs, which should be included in future monitoring and toxicity tests. The bioassay responses of many sample extracts were substantially reduced but not suppressed with sulfuric acid treatment, indicating contribution of persistent AhR agonists. Cancer risk assessment based on the CALUX BaP-EQs has revealed unacceptable level of risk in many cases. The application of bioassay-derived BaP-EQs may reduce underestimation in environmental management and risk evaluation regarding PAHs and their derivatives (notably Me-PAHs), suggesting a consideration of using in vitro toxic activity instead of conventional chemical-specific approach in such assessment practices.

Inhalation bioaccessibility and health risk assessment of flame retardants in indoor dust from Vietnamese e-waste-dismantling workshops.

Although bioaccessibility testing is applied worldwide for appropriate chemical risk assessment, few studies have focused on the bioaccessibility of flame retardants (FRs), especially inhalation exposure. This study assessed inhalation exposure to FRs in indoor dust by workers at e-waste-dismantling workshops in northern Vietnam, by using modified simulated epithelial lung fluid (SELF) and artificial lysosomal fluid (ALF). The average mass concentrations of FRs were 130,000 ng/g for workplace dust (n = 3), 140,000 ng/g for floor dust (n = 3), and 74,000 ng/g for settled dust (n = 2), whereas the average bioaccessible concentrations of FRs were 1900, 1400, and 270 ng/g in the SELF condition and 2600, 770, and 490 ng/g in the ALF condition, respectively. Results clearly indicate that the bioaccessible concentrations of FRs are markedly lower than their mass concentrations. Tris(2-chloroethyl) phosphate (TCEP, ~19%), tris(2-chloroisopropyl) phosphate (TCIPP, ~35%), and tris(1,3-dichloroisopropyl) phosphate (TDCIPP, ~22%) showed comparably high bioaccessibility in both SELF and ALF conditions. In contrast, the bioaccessibility of tetrabromobisphenol A (TBBPA, ~20%) was high in the SELF condition, but not in the ALF condition. With regard to the test compounds' physicochemical properties, the inhalation bioaccessibility of FRs in both conditions increased as molecular weight or octanol-water partition coefficient decreased, and it decreased as water solubility decreased. Health risk assessment clearly indicated that the hazard quotient of FRs via inhalation exposure for workers in the e-waste-dismantling workshops was less than 1, suggesting that the inhalation exposure to FRs during indoor dismantling of e-waste at this site was negligible based on the current methodology of non-cancer health risk assessment used in this study.

Contamination of heavy metals in paddy soil in the vicinity of Nui Phao multi-metal mine, North Vietnam.

Nui Phao mine in Thai Nguyen Province, Vietnam, is the second-largest tungsten (W) open-pit mine in the world, but the level of environmental impacts is not well known. In order to examine the heavy metal contamination in the ecosystem of this mining area, we analyzed six trace elements (As, Cd, Cr, Cu, Pb and Zn) in the collected soil samples. The analytical results showed that all the soil samples were contaminated by Cd and As. Most of the soil samples were contaminated by As (mean value 50.93 ± 55.44 mg/kg) and Cd (mean value 15.22 ± 9.51 mg/kg), which figures are up to 16 and 23 times higher, respectively, compared with the Vietnamese soil quality standard for agriculture (QCVN 03-MT:2015/BTNMT) of 15 mg/kg for As and 1.5 mg/kg for Cd. Contamination factor (CF), enrichment factor (EF), geo-accumulation index (Igeo), principal component analysis (PCA) and hierarchical clustering analysis (HCA) were used to identify the influence of mining activity in the contamination. The CF, EF, pollution index (PI) and Igeo indicated that this area was extremely polluted by Cd, severely to moderately-heavily polluted by As and slightly to moderately polluted by other elements such as Cr, Cu, Pb and Zn. The PCA and HCA results also attribute the source of As, Pb and Zn contamination and enrichment of Cd, Cr and Cu in the study area to Nui Phao mining activities. The PI and contamination degree (Cd) values of soil quality indicate that the study area was contaminated with particular reference to Cd and As and the level of contamination was decreased in the order of Pb > Cr > Cu > Zn. The study area had high potential ecological risk, and the carcinogenic risk value was higher than the acceptable value (1 × 10-6 to 1 × 10-4). This means that the local resident health is strongly affected by Nui Phao mining activities both directly and indirectly via food consumption, when rice plant grown in the paddy field is the dominant crop in the study area.

Polychlorinated biphenyls in settled dusts from an end-of-life vehicle processing area and normal house dusts in northern Vietnam: Occurrence, potential sources, and risk assessment.

Concentrations and congener-specific profiles of total 209 polychlorinated biphenyls (PCBs) were investigated in settled dust samples collected from end-of-life vehicle (ELV) processing, urban, and rural areas in northern Vietnam. Concentrations of total 209 PCBs, seven indicator congeners, and twelve dioxin-like PCBs decreased in the order: ELV working > ELV living ≈ urban > rural dusts. Penta- and hexa-CBs dominated the homolog patterns in all the samples with higher proportions in the ELV dusts compared to the urban and rural house dusts. The abundance and pattern of PCBs in the ELV dusts suggest on-going emissions of these compounds related to processing of vehicular oils and lubricants containing PCBs, whereas the presence of PCBs in the urban and rural house dusts indicate long-time releases. However, levels of some PCBs identified as by-products of pigment manufacturing (e.g., PCB-11 and PCB-209) were higher in the urban house dusts than those from other locations, resulting from human activities utilizing paints and pigments. Daily intake doses (ID), non-carcinogenic hazard quotient (HQ), and lifetime cancer risk (CR) of PCBs through dust ingestion were estimated for ELV workers and residents in the studied areas. The workers and children in the ELV sites were estimated to be at higher risk of PCB exposure, however almost all of the HQ < 1 and CR < 10-4 indicate no serious risk related to dust-bound PCBs.

Bioaccessibility and exposure assessment of flame retardants via dust ingestion for workers in e-waste processing workshops in northern Vietnam.

Flame retardants (FRs) from electronic waste (e-waste) are a widespread environmental concern. In our study, in vitro physiologically based extraction tests (PBETs) for FRs were conducted in three different areas where dust remained after processing of e-waste to identify the bioaccessible FRs and quantify their bioaccessibilities of gastrointestinal tract for human as well as to assess the exposure via ingestion of workers in e-waste processing workshops. All 36 FRs were measured and detected in indoor dusts. Among the FRs, the mean concentrations of polybrominated diphenyl ethers (PBDEs) in the floor dust and settled dust were highest, 65,000 ng/g, and 31,000 ng/g, respectively. In contrast, phosphorus-containing flame retardants (PFRs) presented the highest mean concentration in the workplace dust samples, 64,000 ng/g. However, the highest bioaccessible concentrations in workplace dust, floor dust, and settled dust were observed for PFRs: 5900, 1600, and 680 ng/g, respectively. This study revealed that the higher bioaccessibility of PFRs versus other compounds was related to the negative correlation between FR concentrations and log KOW (hydrophobicity) values. The fact that hazard indices calculated using measured bioaccessibilities were less than 1 suggested that the non-cancer risk to human health by the FRs exposure via dust ingestion might be low.

Soil and sediment contamination by unsubstituted and methylated polycyclic aromatic hydrocarbons in an informal e-waste recycling area, northern Vietnam: Occurrence, source apportionment, and risk assessment.

Improper processing activities of e-waste are potential sources of polycylic aromatic hydrocarbons (PAHs) and their derivatives, however, information about the environmental occurrence and adverse impacts of these toxic substances is still limited for informal e-waste recycling areas in Vietnam and Southeast Asia. In this study, unsubstituted and methylated PAHs were determined in surface soil and river sediment samples collected from a rural village with informal e-waste recycling activities in northern Vietnam. Total levels of PAHs and MePAHs decreased in the order: workshop soil (median 2900; range 870-42,000 ng g-1) > open burning soil (2400; 840-4200 ng g-1) > paddy field soil (1200; range 530-6700 ng g-1) > river sediment samples (750; 370-2500 ng g-1). About 60% of the soil samples examined in this study were heavily contaminated with PAHs. Fingerprint profiles of PAHs and MePAHs in the soil and sediment samples indicated that these pollutants were mainly released from pyrogenic sources rather than petrogenic sources. The emissions of PAHs and MePAHs in this area were probably attributed to uncontrolled burning of e-waste and agricultural by-products, domestic coal and biomass combustion, and traffic activities. Carcinogenicity and mutagenicity of PAHs in the e-waste workshop soils were significantly higher than those of the field soils; however, the incremental lifetime cancer risk of PAH-contaminated soils in this study ranged from 5.5 × 10-9 to 4.6 × 10-6, implying acceptable levels of human health risk. Meanwhile, concentrations of some compounds such as phenanthrene, anthracene, fluoranthene, benz[a]anthracene, and benzo[a]pyrene in several soil samples exceeded the maximum permissible concentrations, indicating the risk of ecotoxicological effects.

Polycyclic aromatic hydrocarbons and their methylated derivatives in settled dusts from end-of-life vehicle processing, urban, and rural areas, northern Vietnam: Occurrence, source apportionment, and risk assessment.

The occurrence and profiles of 19 polycyclic aromatic hydrocarbons (PAHs) and 15 methylated derivatives (Me-PAHs) were examined in settled dust samples collected from workplaces and living areas of an informal end-of-life vehicle (ELV) processing village, and house dusts from urban and rural areas in northern Vietnam. Concentrations of total PAHs and Me-PAHs decreased in the order: ELV workplace (median 5700, range 900-18,000 ng g-1) > rural house (3700, 1800-6200 ng g-1) > urban house (1800, 620-3100 ng g-1) ≈ ELV living dusts (1000, 600-3900 ng g-1). PAHs with 4 rings or more dominated in almost all the samples, indicating the abundance of pyrogenic sources (e.g., vehicular emissions and domestic thermal processes). Levels of Me-PAHs were exceeded those of PAHs in several ELV samples, revealing specific petrogenic sources derived from vehicle processing activities. Results from source apportionment analysis have partially identified traffic emission, biomass and coal combustion, and mixed petrogenic-pyrogenic sources related to ELV waste as the major sources of PAHs and Me-PAHs in the urban, rural, and ELV areas, respectively. Daily intake doses and health risk related to PAHs and Me-PAHs in settled dusts were estimated for ELV workers and residents living in the study areas. The worst exposure scenario of dust-bound PAHs showed a potential cancer risk for the ELV workers, meanwhile, no significant non-cancer and cancer risk was expected for other exposed groups. A more comprehensive and accurate risk assessment of PAHs and related compounds should be conducted in Vietnam.

Aryl hydrocarbon receptor mediated activities in road dust from a metropolitan area, Hanoi-Vietnam: contribution of polycyclic aromatic hydrocarbons (PAHs) and human risk assessment.

Dioxin-Responsive Chemical-Activated LUciferase gene eXpression assay (DR-CALUX) was applied to assess the total toxic activity of the mixture of PAHs and related compounds as well as dioxin-related compounds in road dust from urban areas of Hanoi, Vietnam. Road dust from Hanoi contained significantly higher DR-CALUX activities (3 to 39, mean 20 ng CALUX-TEQ/g dw) than those from a rural site (2 to 13, mean 5 ng CALUX-TEQ/g dw). The total concentrations of 24 major PAHs (Σ24PAHs) in urban road dust (0.1 to 5.5, mean 2.5 µg/g dw) were also 6 times higher than those in rural road dust (0.08 to 1.5, mean 0.4 µg/g dw). Diagnostic ratios of PAHs indicated vehicular engine combustion as the major PAH emission source in both sites. PAHs accounted for 0.8 to 60% (mean 10%) and 2 to 76% (mean 20%) of the measured CALUX-TEQs in road dust for Hanoi the rural site, respectively. Benzo[b]-/benzo[k]fluoranthenes were the major TEQ contributors among PAHs, whereas DRCs contributed <0.1% to CALUX-TEQs for both rural and urban sites. These results suggest TEQ contribution of other aryl hydrocarbon receptor agonists in road dust. Significant PAH concentrations in urban dust indicated high mutagenic and carcinogenic potencies. Estimated results of incremental life time cancer risk (ILCR) indicated that Vietnamese populations, especially those in urban areas such as Hanoi, are potentially exposed to high cancer risk via both dust ingestion and dermal contact. This is the first study on the exposure risk of AhR agonists, including PAHs and DRCs, in urban road dust from a developing country using a combined bio-chemical analytical approach.