Pharmaceuticals and personal care products (PPCPs) in surface water and fish from three Asian countries: Species-specific bioaccumulation and potential ecological risks.

In Asian developing countries, undeveloped and ineffective sewer systems are causing surface water pollution by a lot of contaminants, especially pharmaceuticals and personal care products (PPCPs). Therefore, the risks for freshwater fauna need to be assessed. The present study aimed at: i) elucidating the contamination status; ii) evaluating the bioaccumulation; and iii) assessing the potential risks of PPCP residues in surface water and freshwater fish from three Asian countries. We measured 43 PPCPs in the plasma of several fish species as well as ambient water samples collected from India (Chennai and Bengaluru), Indonesia (Jakarta and Tangerang), and Vietnam (Hanoi and Hoa Binh). In addition, the validity of the existing fish blood-water partitioning model based solely on the lipophilicity of chemicals is assessed for ionizable and readily metabolizable PPCPs. When comparing bioaccumulation factors calculated from the PPCP concentrations measured in the fish and water (BAFmeasured) with bioconcentration factors predicted from their pH-dependent octanol-water partition coefficient (BCFpredicted), close values (within an order of magnitude) were observed for 58-91 % of the detected compounds. Nevertheless, up to 110 times higher plasma BAFmeasured than the BCFpredicted were found for the antihistamine chlorpheniramine in tilapia but not in other fish species. The plasma BAFmeasured values of the compound were significantly different in the three fish species (tilapia > carp > catfish), possibly due to species-specific differences in toxicokinetics (e.g., plasma protein binding and hepatic metabolism). Results of potential risk evaluation based on the PPCP concentrations measured in the fish plasma suggested that chlorpheniramine, triclosan, haloperidol, triclocarban, diclofenac, and diphenhydramine can pose potential adverse effects on wild fish. Results of potential risk evaluation based on the PPCP concentrations measured in the surface water indicated high ecological risks of carbamazepine, sulfamethoxazole, erythromycin, and triclosan on Asian freshwater ecosystems.

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.

Seasonal variation of atmospheric organochlorine pesticides and polybrominated diphenyl ethers in Parangipettai, Tamil Nadu, India: Implication for atmospheric transport.

Past studies have reported several persistent organic pollutants (POPs) in different environmental matrices from a tropical coastal site, Parangipettai (PI), located along the bank of the Vellar River in Tamil Nadu, south India. Hence to fill the data gap after the strict ban on several POPs, high volume air sampling was conducted in PI to study the variability of atmospheric organochlorine pesticides (OCPs) and polybrominated diphenyl ethers (PBDEs) during summer, pre-monsoon and monsoon seasons. Emission source regions were tracked by using five days back trajectory analysis. Range of air concentrations in pg/m3 were: dichlorodiphenyltrichloroethane (DDT), 13 - 1976; hexachlorocyclohexane (HCH), 260-1135, hexachlorocyclobenzene (HCB), 52-135, chlordanes, 36-135 and endosulfans, 66-1013. Six PBDE congeners ranged between 25 and 155 pg/m3 with the highest concentration in summer followed by pre-monsoon and monsoon. Atmospheric DDT and HCH in PI have drastically reduced from the past report thereby showing the strict ban on agricultural use of these compounds. During monsoon, fresh source of o,p'-DDT, trans-chlordane and α-endosulfan was evident. Higher level of endosulphan sulfate in PI seems to be likely affected by the air mass, originating from a neighbouring state Kerela, where endosulfan has been extensively used for cashew plantations. Similarly in summer, the day recorded with the highest level of PBDEs, the sample was concurrently impacted by air parcel comprised of two major clusters, 1 (25%) and 2 (49%) that traversed through the metropolitan cities like Bangalore and Chennai. Dominance of BDE-99 over BDE-47 in PI is in line with the PBDE profile reported from Chennai city during similar time frame. Average concentration of tetra and penta BDE congeners in summer samples were nearly 2-3 folds higher than pre-monsoon or monsoon. Given the fact that strong localised sources for heavier BDE congeners are lacking in PI, regional atmospheric transport from the strong emission source regions in Chennai might have impacted PBDE concentration in PI.

Occurrence of triclocarban and benzotriazole ultraviolet stabilizers in water, sediment, and fish from Indian rivers.

Triclocarban and benzotriazole ultraviolet stabilizers (BUVSs) are listed as high production volume synthetic chemicals, used extensively in personal care products. Many of these chemicals persist in the aquatic environment as micropollutants. Knowledge on their fate in freshwater ecosystems is still lacking, especially in the Indian Rivers. Our intention is to study the seasonal distribution, hazard quotient, risk assessment, and bioaccumulation of triclocarban and BUVSs (UV-9, UV-P, UV-326, UV-327, UV-328, and UV-329) during wet and dry seasons in water, sediment and fish from the Kaveri, Vellar, and Thamiraparani rivers in Tamil Nadu State, India. Triclocarban and BUVSs were identified in all matrices analysed. Triclocarban was found in water, sediment, and fish up to 1119ng/L, 26.3ng/g (dry wt.), and 692ng/g (wet wt.), respectively. Among BUVSs, UV-329 was found up to 31.3ng/L (water samples), UV-327 up to 7.3ng/g (sediment samples), and UV-9 up to 79.4ng/g (fish samples). The hazard quotient (HQenv.) for triclocarban in surface water was found to be at risk level (HQenv. >1) in the Kaveri, and Thamiraparani rivers during dry season. Bioaccumulation factors indicate that target compounds (triclocarban and BUVSs) could bio-accumulate in organisms.

GC-MS determination of phthalate esters in human urine: A potential biomarker for phthalate bio-monitoring.

Six phthalic acid esters (PAEs) in human urine sampled randomly from three districts (Erode, Thanjavur, and Perambalur) in Tamil Nadu State and a Union Territory (Pondicherry) in India were quantified. We determined gender-wise, age-wise and location-wise distribution of PAEs and measured estrogenic activity of urine by molecular docking. Bis(2­ethylhexyl) phthalate (DEHP) was the predominant phthalic acid ester found and had a recovery of 104.5% (ultrasonic extraction at 15 min). Gender-wise (pregnant women: 185 ng/mL, children: 156 ng/mL, female: 151 ng/mL, and male: 138 ng/mL), age-wise (1-20 y: 157 ng/mL, 21-40 y: 156 ng/mL, and >40 y: 146 ng/mL), location-wise (urban: 154 ng/mL, and rural: 151 ng/mL), and region-wise (Erode district: 185 ng/mL, Thanjavur district: 155 ng/mL, Perambalur district: 117 ng/mL, and Pondicherry: 135 ng/mL) differences with total mean of Σ6 PAEs were found. The molecular docking study showed a high negative binding energy of PAEs with microbial receptors. Based on the results we conclude that urine could be used as an ideal biomarker to understand PAEs exposure in humans.

Edward D. Goldberg's proposal of "the Mussel Watch": Reflections after 40years.

We chronicle the extensive influence over the past forty years of Professor Edward D. Goldberg and his call in 1975 for a "Mussel Watch" or bivalve sentinel organism approach to assess geographic status and temporal trends of several chemicals of environmental concern in the coastal ocean. Examples of local, regional, national and international programs are discussed briefly as are examples of interesting useful findings and limitations to the Mussel Watch concept. Mussel Watch continues to provide useful data about status and trends of chemical contamination in coastal ecosystems.

Recent status of organohalogens, heavy metals and PAHs pollution in specific locations in India.

Our group of scientists at the Center for Marine Environmental Studies (CMES), Ehime University, Japan has been carrying-out studies in India from the 1980s on chemicals contamination. Due to its agrarian economy, use of fossil fuels, industries, growing population and urbanization, chemicals such as pesticides, dioxins and related chemicals (DRCs), brominated flame retardants (BFRs), heavy metals, and polyaromatic hydrocarbons (PAHs) are widely spread in India. We have published a review (Subramanian and Tanabe, 2007) covering papers published until 2005, on India. A decade had passed and this is the time to provide an update of the spatial and temporal changes during this period and hence this review. At many instances organochlorines such as DDTs and HCHs showed decreasing trends even though they are still at considerable levels. Novel chemicals such as PCDDs/Fs are seen at municipal solid waste dumping sites of India at levels equivalent to similar locations of the developed world. In the e-waste processing sites in India, especially the informal ones, apart from PCDDs/Fs, some brominated flame retardants (BFRs) and heavy metals were present as contaminants. Metro cities of India showed location specific contamination by HCHs, DDTs, PCDDs/Fs, BFRs, PAHs, etc. Coastal regions of India seem to be still unpolluted when compared to the nearby inland locations. This review is concerned mainly with the chemicals that we (CMES) have been evaluating in India in the past three decades. We suggest the importance of further studies, future directions for policy decisions and also for implementing control measures.

Organohalogens and their hydroxylated metabolites in the blood of pigs from an open waste dumping site in south India: association with hepatic cytochrome P450.

The concentrations of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and their hydroxylated metabolites (OH-PCBs and OH-PBDEs) were measured in the blood of Eurasian wild pigs (Sus scrofa) from a municipal waste open dumping site (DS) and a reference site (RS) in South India. We showed that contamination with OH-PCBs was higher in female pigs from the DS than in all other adult pigs. The highest OH-PCB concentrations were found in piglets from the DS. Moreover, the hepatic expression levels of CYP1A and CYP2B were higher in piglets than in their dam, implying metabolism of PCBs by cytochrome P450 (CYP) enzymes. The OH-PCB congener profiles differed according to sex and collection sites, possibly because of variations in the expression levels of phase I and phase II enzymes among individual pigs, differences in the exposure sources, and maternal transfer of parent PCBs. The hepatic CYP1A expression levels were positively correlated with the blood concentrations of 4OH-CB107, 4OH-CB162, and 4OH-CB187, implying CYP1A-dependent formation of these OH-PCBs in the pig liver. We found no significant correlations between the blood concentrations of OH-PCBs and thyroid hormones (THs); however, the thyroxin (T4) levels were lower in pigs from the DS than in pigs from the RS. Our limited dataset suggest that induced CYP enzymes accelerate the metabolism of xenobiotics and endogenous molecules in pigs. Thus, besides parental compounds, the risk of hydroxylated metabolites entering wildlife and humans living in and around municipal open waste dumping sites should be considered.

Methylated and unsubstituted polycyclic aromatic hydrocarbons in street dust from Vietnam and India: occurrence, distribution and in vitro toxicity evaluation.

Methylated polycyclic aromatic hydrocarbons (MePAHs), unsubstituted PAHs and AhR-mediated activities were determined in street dust collected from Vietnam and India using a combined approach of chemical analysis and in vitro reporter gene assay. MePAHs and PAHs diagnostic ratios indicated that the main sources of MePAHs in Vietnam were pyrogenic emissions, whereas in India there were mixed sources of pyrogenic and petrogenic emissions. AhR-mediated activities determined by using DR-CALUX assay were observed in urban street dust at mean 40, 29 and 20 ng CALUX-TEQ/g dw for Hanoi, Bangalore and New Delhi, respectively. MePAHs and PAHs contributed only 5% or less to AhR-mediated activity in street dust, indicating the occurrence of unknown AhR agonists. The principal contributors to Theoretical-TEQs among target compounds were methyl benz[a]anthracene, benzo[b]- and benzo[k]fluoranthene. The present study indicates importance of MePAHs in evaluation of toxic risk related to AhR-mediated activity in urban polluted areas.

Environmental contamination and human exposure to dioxin-related compounds in e-waste recycling sites of developing countries.

E-waste recycling using uncontrolled processes is a major source of dioxin-related compounds (DRCs), including not only the regulated polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) but also non-regulated brominated and mixed halogenated compounds (PBDD/Fs and PXDD/Fs). Various studies at informal e-waste recycling sites (EWRSs) in Asian developing countries found the soil contamination levels of PCDD/Fs from tens to ten thousand picogram TCDD-equivalents (TEQ) per gram and those of DL-PCBs up to hundreds of picogram TEQ per gram. The air concentration of PCDD/Fs was reported as high as 50 pg TEQ per m(3) in Guiyu, the largest Chinese EWRS. Non-regulated compounds also contributed substantially to the total DL toxicity of the DRC mixtures from e-waste, as evidenced by the high TEQ levels estimated for the currently identifiable PBDD/Fs as well as the large portion of unexplained bioassay-derived TEQ levels in soils/dusts from EWRSs. Considering the high exposure levels estimated for EWRS residents, especially children, comprehensive emission inventories of DRCs from informal e-waste recycling, the identities and toxic potencies of unidentified DRCs released, and their impacts on human health need to be investigated in future studies.

Occurrence of halogenated contaminants in inland and coastal fish from Ghana: levels, dietary exposure assessment and human health implications.

Fish consumption is known to have several health benefits for humans. However, the accumulation of toxic contaminants, such as PCBs, PBDEs and HBCDs in fish could pose health hazards. These contaminants were measured in tilapia fish species collected from Ghana. Mean levels were PCBs (62 ng/g lw), PBDEs (7.3 ng/g lw) and HBCDs (1.2 ng/g lw) and the predominance of CB-153, CB-138, CB-180, BDE-47 and α-HBCD is in concordance with scientific literature. The congener profiles of PBDEs and PCBs in the fish suggest that sources of Penta- and Deca-BDE technical mixtures as well as technical PCB mixture (Clophen A60) exist in Ghana, while textile operations and associated release of untreated wastewater are likely to be significant sources of HBCDs. Comparison of the results with some reported studies showed moderate contamination in Ghana although Ghana is a developing country in Africa. Concentrations of PCBs measured in all the specimens in this study were below the food safety guidelines issued by the Food and Drug Administration, USA and the European Commission. The calculated hazard index levels of the target contaminants were below the threshold value of one, indicating that the levels of the target contaminants do not seem to constitute a health risk via fish consumption, with regard to PCBs, PBDEs and HBCDs, based on the limited number of samples that was accounted for in this study. However, due to the continuous discharge of untreated effluents, follow up studies are warranted as the consumption of fish is the primary route of human exposure to PCBs. This maiden report on the status of PBDEs and HBCDs in fish from Ghana will contribute to the knowledge about environmental contamination by POPs in a less industrialized region of the world so far sparsely covered in the literature.

Perchlorate contamination of groundwater from fireworks manufacturing area in South India.

Perchlorate contamination was investigated in groundwater and surface water from Sivakasi and Madurai in the Tamil Nadu State of South India. Sensitive determination of perchlorate (LOQ = 0.005 µg/L) was achieved by large-volume (500 µL) injection ion chromatography coupled with tandem mass spectrometry. Concentrations of perchlorate were <0.005-7,690 µg/L in groundwater (n = 60), <0.005-30.2 µg/L in surface water (n = 11), and 0.063-0.393 µg/L in tap water (n = 3). Levels in groundwater were significantly higher in the fireworks factory area than in the other locations, indicating that the fireworks and safety match industries are principal sources of perchlorate pollution. This is the first study that reports the contamination status of perchlorate in this area and reveals firework manufacture to be the pollution source. Since perchlorate levels in 17 out of 57 groundwater samples from Sivakasi, and none from Madurai, exceeded the drinking water guideline level proposed by USEPA (15 µg/L), further investigation on human health is warranted.

Soil contamination by brominated flame retardants in open waste dumping sites in Asian developing countries.

In Asian developing countries, large amounts of municipal wastes are dumped into open dumping sites each day without adequate management. This practice may cause several adverse environmental consequences and increase health risks to local communities. These dumping sites are contaminated with many chemicals including brominated flame retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs). BFRs may be released into the environment through production processes and through the disposal of plastics and electronic wastes that contain them. The purpose of this study was to elucidate the status of BFR pollution in municipal waste dumping sites in Asian developing countries. Soil samples were collected from six open waste dumping sites and five reference sites in Cambodia, India, Indonesia, Malaysia, and Vietnam from 1999 to 2007. The results suggest that PBDEs are the dominant contaminants in the dumping sites in Asian developing countries, whereas HBCD contamination remains low. Concentrations of PBDEs and HBCDs ranged from ND to 180 µg/kg dry wt and ND to 1.4 µg/kg dry wt, respectively, in the reference sites and from 0.20 to 430 µg/kg dry wt and ND to 2.5 µg/kg dry wt, respectively, in the dumping sites. Contamination levels of PBDEs in Asian municipal dumping sites were comparable with those reported from electronic waste dismantling areas in Pearl River delta, China.

Asia-Pacific mussel watch for emerging pollutants: Distribution of synthetic musks and benzotriazole UV stabilizers in Asian and US coastal waters.

We analyzed 68 green and blue mussels collected from Cambodia, China, Hong Kong, India, Indonesia, Japan, Korea, Malaysia, Philippines, Vietnam and the USA during 2003 and 2007, to elucidate the occurrence and widespread distributions of emerging pollutants, synthetic musks and benzotriazole UV stabilizers (BUVSs) in Asia-Pacific coastal waters. Synthetic musks and BUVSs were detected in mussels from all countries, suggesting their ubiquitous contamination and widespread distribution. High concentrations of musks and BUVSs were detected in mussels from Japan and Korea, where the levels were comparable or greater than those of PCBs, DDTs and PBDEs. Significant correlations were found between the concentrations of HHCB and AHTN, and also between the concentrations of UV-327 and UV-328, which suggest similar sources and compositions of these compounds in commercial and industrial products. To our knowledge, this is the first study of large-scale monitoring of synthetic musks and BUVSs in Asia-Pacific coastal waters.

Different profiles of anthropogenic and naturally produced organohalogen compounds in serum from residents living near a coastal area and e-waste recycling workers in India.

We determined the contamination status and accumulation profiles of polychlorinated biphenyls (PCBs), hydroxylated PCB congeners (OH-PCBs), polybrominated diphenyl ethers (PBDEs), hydroxylated PBDEs (OH-PBDEs), methoxylated PBDEs (MeO-PBDEs), and bromophenols (BPhs) in serum from e-waste recycling workers and residents near a coastal area in India. Residue levels of penta- to octa-chlorinated PCBs, penta- to octa-chlorinated OH-PCBs, 6MeO-BDE47, 6OH-BDE47, and 2,4,6-tri-BPh in serum from residents living near the coastal area were significantly higher than those in serum from e-waste recycling workers. Residue levels of tri- to tetra-chlorinated PCBs, tri- to tetra-chlorinated OH-PCBs, PBDEs, octa-brominated OH-PBDEs, and tetra-BPhs in serum from e-waste recycling workers were higher than those in serum from residents living near the coastal area. Principal component analysis revealed that residents living near the coastal area and e-waste recycling workers had different serum profiles of chlorinated and brominated compounds.

Brominated flame retardants and polychlorinated biphenyls in human breast milk from several locations in India: potential contaminant sources in a municipal dumping site.

This study investigated the status of contamination of organohalogen compounds (OCs) such as polychlorinated biphenyls (PCBs) and brominated flame retardant (BFRs), including polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) in human milk samples from several locations in India. The levels of OCs were significantly higher in the milk of mothers living in and near municipal dumping site than other locations indicating that the open dumping sites for municipal wastes act as potential sources of these contaminants in India. The PCB concentrations observed in this study tended to decrease compared to those in the matched locations reported previously, probably due to the restriction of technical PCB usage in India. PBDE levels in human milk were two to three folds lower than those of PCBs in all the sampling locations investigated. Congener profiles of PCBs and PBDEs were different between samples from the dumping site mothers and general populations in other areas suggesting the presence of region-specific sources and pathways. HBCDs were detected in human milk from only two sites, with much lower concentrations and detection frequencies compared to PCBs and PBDEs. When hazard quotients (HQs) of PCBs and PBDEs were estimated for infant health risk, the HQs in some milk samples from the dumping site exceeded the threshold value (HQ>1) of PCBs, indicating the potential risk for infants in the specific site.

Changes of mercury contamination in red-crowned cranes, Grus japonensis, in East Hokkaido, Japan.

Red-crowned cranes (Grus japonensis) are native to eastern Hokkaido (island population), in contrast to the mainland, which migrates between the Amur River basin and eastern China-Korea peninsula. During the 1990s we found that Red-crowned cranes in Hokkaido were highly contaminated with mercury: however, the source was unknown. We investigated the time trend of mercury contamination in Red-crowned cranes. Total mercury levels in the livers and kidneys from cranes dead in the 2000s were lower than those dead in the 1990s. Feather is a major pathway of mercury excretion for many bird species and is used as an indicator of blood mercury level during feather growth. As internal organs from the specimens collected before 1988 were not available, we analyzed the flight feather shavings from stuffed Red-crowned cranes dead in 1959-1987 and found that the mercury level of feathers from cranes dead in the 1960s and 1970s was not more than those from the cranes dead in the 2000s. These results suggest that mercury contamination in Red-crowned cranes in Hokkaido decreased temporally during the 1990s-2000s. This indicates the possible occurrence of some mercury pollution in Red-crowned cranes' habitat in this region in the 1990s or before.