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.

Microplastics in dumping site soils from six Asian countries as a source of plastic additives.

The ubiquitous distribution of microplastics (MP) is a serious environmental issue in Asian countries. In this study, 54 open-dumping site soils collected from Cambodia, India, Indonesia, Laos, the Philippines, and Vietnam were analyzed for MP. Soil samples were also divided into light (floating) and heavy (sedimentation) fractions by density separation and analyzed for plastic additives. The highest abundance of MP was found in a soil from Cambodia at 218,182 pieces/kg. The median of MP in soils ranged from 1411 pieces/kg in India to 24,000 pieces/kg in the Philippines, suggesting that dumping sites are a major source of MP into the environment. Polyethylene, polypropylene, and polyethylene terephthalate were dominant polymers in soil samples analyzed. This indicates that daily-used plastic products are main sources of MP in dumping site soils in Asian countries. The high concentrations and burdens of phthalates and an antioxidant were detected in floating fraction accounting for 40 to 60% of the total additives in soils. Previous studies on soil pollution have assumed that the organic hydrophobic chemicals analyzed are adsorbed on the surface of soil particles. However, this result indicates that approximately half of the additives in dumping site soils were derived from MP, not soil particle. Monitoring study on soil pollution should be considered the occurrence of MP in the matrices.

Mercury, cadmium, and lead in cigarettes from international markets: concentrations, distributions and absorption ability of filters.

Mercury (Hg), cadmium (Cd), and lead (Pb) concentrations in marketed cigarettes from South Korea, Vietnam, Japan, Indonesia, Taiwan, Thailand, the United Kingdom (UK), Belgium, Italy, Finland, and France were investigated. The cigarettes from Vietnam and Thailand had the highest trend of Hg. Meanwhile, Cd was found higher in cigarettes from Thailand, the UK, and Belgium. Pb concentrations in cigarettes from Belgium, the UK, and Korea were higher than others. The average of these heavy metals concentrated in cigarettes was in the order of Pb > Cd > Hg. Furthermore, the contents of these heavy metals in cigarette leaves were much higher than in filter and rolling paper. There was a significant positive correlation between Hg and Cd, but no correlation between Cd and Pb and between Hg and Pb. Significant positive correlations of nicotine with Hg and Cd but not Pb in the cigarette were observed. Activated carbon filters (Ce-C) absorb Cd and Pb from cigarette leaves and rolling paper indicated a higher trapping trend than cellulose acetate filter without activated carbon (Ce). The trapping ratios of Ce-C (Cd: 5.53%, Pb:5.41%) were higher than Ce (Cd:3.09%, Pb:5.49%). On the other hand, Hg had lower absorption by both types of filters (Ce:0.15%, Ce-C:0.02%). This revealed that Hg, Cd and Pb absorption ability by both filters was relatively lower to the total concentration of these metals in tobacco leaves and rolling paper. The concern was that the higher concentrations of metals such as Hg, Cd and Pb in cigarettes might exist in mainstream smoke.

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.

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.

Exposure, metabolism, and health effects of arsenic in residents from arsenic-contaminated groundwater areas of Vietnam and Cambodia: a review.

In this review, we summarize the current knowledge on exposure, metabolism, and health effects of arsenic (As) in residents from As-contaminated groundwater areas of Vietnam and Cambodia based on our findings from 2000 and other studies. The health effects of As in humans include severe gastrointestinal disorders, hepatic and renal failure, cardiovascular disturbances, skin pigmentation, hyperkeratosis, and cancers in the lung, bladder, liver, kidney, and skin. Arsenic contamination in groundwater is widely present at Vietnam and Cambodia and the highest As levels are frequently found in groundwater from Cambodia. Sand filter system can reduce As concentration in raw groundwater. The results of hair and urine analyses indicate that residents from these As-contaminated areas are exposed to As. In general, sex, age, body mass index, and As exposure level are significantly associated with As metabolism. Genetic polymorphisms in arsenic (+III) methyltransferase and glutathione-S-transferase isoforms may be influenced As metabolism and accumulation in a Vietnamese population. It is suggested oxidative DNA damage is caused by exposure to As in groundwater from residents in Cambodia. An epidemiologic study on an association of As exposure with human health effects is required in these areas.

Kinetic differences of legacy organochlorine pesticides and polychlorinated biphenyls in Vietnamese human breast milk.

The present study investigated the current contamination status and evaluated several kinetic-related features of organochlorine pesticides (OCPs) and PCBs in human breast milk collected from northern Vietnam. The variation in the levels of these contaminants was found to be strongly associated with total lactation time and dietary habits. OCPs exhibited the characteristics of steadily declining compounds: the overall levels of DDTs and HCHs in the population decreased with a half-time of only 5years and it can be suggested that OCPs depurated relatively fast with breastfeeding (5% per month). PCBs were slower in both regards, with a temporal decrease half-time of 12years and a suggested depuration rate via breastfeeding of 2.5% per month, indicating that the exposure level was still high relative to the human body burden. It was found that the PCB exposure levels of infant from breastfeeding exceeded the reference dose, and this situation may continue for the next two or three decades. Knowledge of these kinetic-related characteristics not only is useful for risk assessment and prediction of future trends of legacy contaminants but also may provide insight regarding similar kinetic processes of emerging persistent pollutants.

Recent levels of organochlorine pesticides and polychlorinated biphenyls in sediments of the sewer system in Hanoi, Vietnam.

The occurrence, temporal trend, sources and toxicity of PCBs and organochlorine pesticides were investigated in sediment samples from the sewer system of Hanoi City, including the rivers Nhue, To Lich, Lu, Set, Kim Nguu and the Yen So Lake. In general, the concentrations of the pollutants followed the order DDTs>PCBs>HCHs (beta-HCH)>HCB. However, the pollution pattern was different for the DDTs and PCBs when the sampling locations were individually evaluated. The concentrations of the DDTs, PCBs, HCHs, and HCB ranged from 4.4 to 1100, 1.3 to 384, <0.2 to 36 and <0.2 to 22 ng/g d.w., respectively. These levels are higher than at any other location in Vietnam. Compared to measurements from 1997, the DDTs, PCBs, beta-HCH and HCB levels show an increasing trend with DDT/DDE ratios, indicating very recent inputs into the environment although these persistent compounds are banned in Vietnam since 1995.

Transport and release of chemicals from plastics to the environment and to wildlife.

Plastics debris in the marine environment, including resin pellets, fragments and microscopic plastic fragments, contain organic contaminants, including polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons, petroleum hydrocarbons, organochlorine pesticides (2,2'-bis(p-chlorophenyl)-1,1,1-trichloroethane, hexachlorinated hexanes), polybrominated diphenylethers, alkylphenols and bisphenol A, at concentrations from sub ng g(-1) to microg g(-1). Some of these compounds are added during plastics manufacture, while others adsorb from the surrounding seawater. Concentrations of hydrophobic contaminants adsorbed on plastics showed distinct spatial variations reflecting global pollution patterns. Model calculations and experimental observations consistently show that polyethylene accumulates more organic contaminants than other plastics such as polypropylene and polyvinyl chloride. Both a mathematical model using equilibrium partitioning and experimental data have demonstrated the transfer of contaminants from plastic to organisms. A feeding experiment indicated that PCBs could transfer from contaminated plastics to streaked shearwater chicks. Plasticizers, other plastics additives and constitutional monomers also present potential threats in terrestrial environments because they can leach from waste disposal sites into groundwater and/or surface waters. Leaching and degradation of plasticizers and polymers are complex phenomena dependent on environmental conditions in the landfill and the chemical properties of each additive. Bisphenol A concentrations in leachates from municipal waste disposal sites in tropical Asia ranged from sub microg l(-1) to mg l(-1) and were correlated with the level of economic development.

Contamination of groundwater and risk assessment for arsenic exposure in Ha Nam province, Vietnam.

The characteristics of arsenic-contaminated groundwater and the potential risks from the groundwater were investigated. Arsenic contamination in groundwater was found in four villages (Vinh Tru, Bo De, Hoa Hau, Nhan Dao) in Ha Nam province in northern Vietnam. Since the groundwater had been used as one of the main drinking water sources in these regions, groundwater and hair samples were collected in the villages. The concentrations of arsenic in the three villages (Vinh Tru, Bo De, Hoa Hau) significantly exceeded the Vietnamese drinking water standard for arsenic (10 microg/L) with average concentrations of 348, 211, and 325 microg/L, respectively. According to the results of the arsenic speciation testing, the predominant arsenic species in the groundwater existed as arsenite [As(III)]. Elevated concentrations of iron, manganese, and ammonium were also found in the groundwater. Although more than 90% of the arsenic was removed by sand filtration systems used in this region, arsenic concentrations of most treated groundwater were still higher than the drinking water standard. A significant positive correlation was found between the arsenic concentrations in the treated groundwater and in female human hair. The risk assessment for arsenic through drinking water pathways shows both potential chronic and carcinogenic risks to the local community. More than 40% of the people consuming treated groundwater are at chronic risk for arsenic exposure.

Simultaneous determination of degradation products of nonylphenol polyethoxylates and their halogenated derivatives by solid-phase extraction and gas chromatography-tandem mass spectrometry after trimethylsilylation.

An efficient method for the simultaneous determination of the degradation products of nonylphenol polyethoxylates (NPnEOs, n = number of ethoxy units), i.e., nonylphenol (NP), NPnEOs (n = 1-3), nonylphenoxy carboxylic acids (NPnECs, n = 1-2, number of ethoxy units plus an acetate) and their halogenated derivatives (XNP, XNP1EO and XNP1EC; X = Br or Cl), in water samples were developed. After trimethylsilylation with N,O-bis(trimethysilyl)acetamide, all the analytes were determined by gas chromatography-tandem mass spectrometry (GC-MS-MS) with electron ionization (EI). The ion peaks of [M - 85]+ of the derivatives were selected as precursor ions and their product ions showing the highest intensities were used for the quantitative analysis. The instrumental detection limits were in the range from 2.1 to 11 pg. The recoveries of the analytes from the water samples were optimized by using solid-phase extraction (SPE). The deuterated reagents of octylphenol, octylphenol monoethoxylate and octylphenoxyacetic acid were used as the surrogates. The method detection limits (500 ml water sample) using C18 SPE were from 2.5 to 18 ng/l. The recoveries from spiked pure water and the environmental water samples were greater than 78%. The method was successfully applied to environmental samples. Remarkably, the concentrations of the halogenated compounds (CINP, CINP1EO and BrNP1EO) were detected at the hundreds of ng/l levels in the Neya river.