Polybrominated diphenyl ethers (PBDEs) were measured in surface sediment samples collected from urban canals or rivers in Lao PDR, Cambodia, Vietnam, India, Indonesia, Thailand, the Philippines, Malaysia and Japan. The total PBDE concentrations in the sediments ranged from 0.83 to 3140 ng/g dry wt. BDE-209 was predominant, ranging from 43% to 97% of total PBDEs, followed by nona-BDEs and some detectable concentrations of BDEs 47, 49, 99, 100, 153, 154 and 183. Sedimentary PBDE levels in Malaysia, Cambodia, the Philippines and Thailand were generally higher than those reported for highly industrialized countries. Spatial distribution of PBDEs indicated that inland sources may impact coastal areas. The presence of BDE congeners which are not contained in technical mixtures and the higher proportions of nona-BDEs relative to BDE-209 in the sediments were identified as indicators of debromination. BDE-209 was possibly debrominated under anaerobic conditions in some of the sediment samples.
Plastic resin pellets collected at Minh Chau island and Ba Lat estuary between 2007 and 2014 in Vietnam were analyzed for dichloro-diphenyl-trichloroethanes (DDTs), polychlorinated biphenyls (PCBs) and hexachlorocyclohexanes (HCHs). The study was carried out as part of the International Pellet Watch program for monitoring the global distribution of persistent organic pollutants (POPs). Higher levels of DDTs compared to PCBs indicated agricultural inputs rather than industrial discharges in the region. Most POP concentrations on both beaches decreased over the period, with the exception of HCH isomers. Though the concentration of DDTs showed a drastic decline on both beaches between 2007/2008 and 2014, DDTs accounted for 60-80% of total DDTs, suggesting that there is still a fresh input of these chemicals in the region. This study strongly recommends further investigations to track temporal and spatial patterns of POP levels in the marine environment using plastic resin pellets.
Polybrominated diphenyl ethers (PBDEs) are extensively used as flame retardants in many consumer products, and leachates from landfills have been identified as one of the possible sources of PBDEs in the environment. Meanwhile, the unprecedented economic and population growths of some Asian countries over the last decade have led to significant increases in the amount of waste containing PBDEs in that region. This study investigates the status of PBDEs in leachates from municipal solid waste dumping sites (MSWDS) in tropical Asian countries. A total of 46 PBDE congeners were measured, both in the adsorbed (n=24) and dissolved (n=16) phases, in leachate samples collected, from 2002 to 2010, from ten MSWDS distributed among the eight countries of Lao PDR, Cambodia, Vietnam, India, Indonesia, Thailand, the Philippines, and Malaysia. PBDEs were predominantly found in the adsorbed phase. Partitioning of PBDEs in the dissolved phase was associated with the presence of dissolved organic matter; the apparent organic carbon-normalized partition coefficients (K'oc) of the BDE congeners were lower by two to four orders of magnitude than the K oc predicted from the octanol-water partition coefficients (K ow). The total PBDE concentrations from mono- to deca-BDEs ranged from 3.7 to 133,000 ng/L, and showed a trend toward higher concentrations in the more populous and industrialized Asian countries. The congener profiles in the leachates basically reflected the composition of PBDE technical mixtures. The occurrence of congeners not contained, or in trace concentrations, in technical products (e.g., BDEs 208, 207, 206, 202, 188, 179, 49, 17/25, 8, 1) was observed in most of the leachate samples, suggesting the debromination of technical mixtures, including BDE-209, in the MSWDS of tropical Asian countries. Moreover, the temporal trend indicated the reduction of BDE-209 over time, with a corresponding increase in and/or emergence of lower brominated PBDE congeners. The results indicated that MSWDS of tropical Asian countries are potential sources of environmental PBDEs, which may be transported to the aquatic environment via dissolution with dissolved organic matter. MSWDS could be amplifiers of PBDE toxicity in the environment, possibly through debromination.
Historical trends of the accumulation of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in a typical tropical Asian environment were investigated using radio-dated sediment cores from Manila Bay, the Philippines and from the upper Gulf of Thailand. Vertical profiles indicated earlier usage of PCBs than of PBDEs which coincided with their industrial production. The increasing concentrations of total PBDEs and PCBs toward the surface suggested an increased consumption of PBDEs; and possible leakage of PCBs from old machineries into the aquatic environment in recent years. Current input of PCBs to the catchment of Manila Bay was supported by the analyses of air samples and plastic resin pellets. The vertical profiles of total PBDEs in the cores (i.e., rapidly increasing concentrations corresponding to the mid-1980s until mid-1990s, followed by a decrease until the early 2000s, and increasing again toward the surface) likely corresponded to the rapid economic growth in Asia in the 1990s, the Asian financial crisis in 1997, and the economic recovery since early 2000s. BDE-209 was predominant especially on the surface layers. BDEs 47 and 99 generally decreased toward the surface, reflecting the phase-out of the technical penta-PBDE products and the regulation by the Stockholm Convention in recent years. Increasing ratios of BDE-202/209, 206/209, 207/209 and decreasing % of BDE-209 down the core layers may provide evidence for the anaerobic debromination of BDE-209 in the sediment cores. Inventories in ng/cm(2) of total PCBs were higher than total PBDEs (92 vs. 34 and 47 vs. 11 in the Philippines; 47 vs. 33 in Thailand). However, the doubling times indicated faster accumulation of total PBDEs (6-7 years) and BDE-209 (6-7.5 years) than of PCBs (8-11 years). Furthermore, the temporal increase in BDE-209 was comparable to or faster than those reported in other water bodies around the world.
We collected surface sediment samples from 174 locations in India, Indonesia, Malaysia, Thailand, Vietnam, Cambodia, Laos, and the Philippines and analyzed them for polycyclic aromatic hydrocarbons (PAHs) and hopanes. PAHs were widely distributed in the sediments, with comparatively higher concentrations in urban areas (Sigma PAHs: approximately 1000 to approximately 100,000 ng/g-dry) than in rural areas ( approximately 10 to approximately 100g-dry), indicating large sources of PAHs in urban areas. To distinguish petrogenic and pyrogenic sources of PAHs, we calculated the ratios of alkyl PAHs to parent PAHs: methylphenanthrenes to phenanthrene (MP/P), methylpyrenes+methylfluoranthenes to pyrene+fluoranthene (MPy/Py), and methylchrysenes+methylbenz[a]anthracenes to chrysene+benz[a]anthracene (MC/C). Analysis of source materials (crude oil, automobile exhaust, and coal and wood combustion products) gave thresholds of MP/P=0.4, MPy/Py=0.5, and MC/C=1.0 for exclusive combustion origin. All the combustion product samples had the ratios of alkyl PAHs to parent PAHs below these threshold values. Contributions of petrogenic and pyrogenic sources to the sedimentary PAHs were uneven among the homologs: the phenanthrene series had a greater petrogenic contribution, whereas the chrysene series had a greater pyrogenic contribution. All the Indian sediments showed a strong pyrogenic signature with MP/P approximately 0.5, MPy/Py approximately 0.1, and MC/C approximately 0.2, together with depletion of hopanes indicating intensive inputs of combustion products of coal and/or wood, probably due to the heavy dependence on these fuels as sources of energy. In contrast, sedimentary PAHs from all other tropical Asian cities were abundant in alkylated PAHs with MP/P approximately 1-4, MPy/Py approximately 0.3-1, and MC/C approximately 0.2-1.0, suggesting a ubiquitous input of petrogenic PAHs. Petrogenic contributions to PAH homologs varied among the countries: largest in Malaysia whereas inferior in Laos. The higher abundance of alkylated PAHs together with constant hopane profiles suggests widespread inputs of automobile-derived petrogenic PAHs to Asian waters.