Maricar Prudente

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 µg 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 µg l–1 to mg l–1 and were correlated with the level of economic development.

Mussel watch: marine pollution monitoring of butyltins and organochlorines in coastal waters of Thailand, Philippines and India

Contamination by butyltin (BTs) and organochlorine compounds (OCs) in green mussels collected along the coastal areas of Thailand, Philippines and India during the period of 1994–1997 was examined. The BT residues in green mussel were widely detected, suggesting a widespread contamination along the coastal waters of Asian developing countries. Relatively high concentrations of BTs in green mussel were found in high boating activity and coastal aquaculture areas, implying the usage of TBT as a biocide in antifouling paints used on boat hulls and marine aquaculture facilities. The composition of BT derivatives in mussel was in the order of TBT>DBT>MBT, suggesting also the presence of significant butyltin source in Asian coast. BT residues pattern in green mussels from Thailand revealed higher levels in aquaculture than in boating activity sites. This result may indicate that the developing countries showing high economic growth rate (like Thailand) tend to increase the usage of TBT for aquaculture activities. BT contamination levels in Asian developing countries were lower than those in developed nations. However, considering the fact that the unregulated usage of organotins in Asian developing countries and the increasing demand for antifouling paints in Asia–Pacific regions, BTs contamination in aquatic environment may be serious in future. Concentrations of OCs detected in green mussels were lower than BTs. Considerable residues of p,p′-DDT found in mussel indicated the current usage of DDTs in Asian regions. HCHs and DDTs contamination in India is apparently higher than in other Asian developing countries. The present study clearly indicates that the aquatic environment in Asia–Pacific regions is still being contaminated by some OCs. To our knowledge, this is a first report on the detection of butyltin compounds in green mussels (Perna viridis) from Thailand, Philippines and India.

Sources of sedimentary PAHs in tropical Asian waters: Differentiation between pyrogenic and petrogenic sources by alkyl homolog abundance

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.

Accumulation features of persistent organochlorines in resident and migratory birds from Asia.

Concentrations of organochlorine contaminants including polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane and its metabolites (DDTs), hexachlorocyclohexane isomers (HCHs), chlordane compounds (CHLs), hexachlorobenzene (HCB) were determined in the resident and migratory birds, which were collected from India, Japan, Philippines, Russia (Lake Baikal) and Vietnam. Accumulation patterns of organochlorine concentrations in resident birds suggested that the predominant contaminants of each country were as follows: Japan--PCBs Philippines--PCBs and CHLs, India--HCHs and DDTs, Vietnam--DDTs, and Lake Baikal--PCBs and DDTs. The migratory birds from Philippines and Vietnam retained mostly the highest concentrations of DDTs among the organochlorines analyzed, indicating the presence of stopover and breeding grounds of those birds in China and Russia. On the other hand, migratory birds from India and Lake Baikal showed different patterns of organochlorine residues, reflecting that each species has inherent migratory routes and thus has exposure to different contaminants. Species which have breeding grounds around the Red Sea and Persian Gulf showed high levels of PCBs, indicating the presence of areas heavily polluted by PCBs in the Middle East.

ORGANOCHLORINE CONTAMINATION IN SOME ODONTOCETI SPECIES FROM THE NORTH PACIFIC AND INDIAN OCEAN

Abstract Concentrations of persistent organochlorines were determined in the blubber and melon of 11 species of adult male odontocetis collected from the North Pacific, Indian Ocean and nearby seas. Mean concentrations of DDs (33 μg/g wet wt) were the highest followed by PCBs (32 μg/g wet wt), chlordane compounds (CHLs: 3.7 μg/g wet wt), HCHs (1.1 μg/g wet wt), and HCB (0.32 μg/g wet wt). Odontoceti species inhabiting temperate waters revealed maximum residual concentrations of these contaminants, and the elevated DDT and PCB residues detected seem to suggest that some of the present species might potentially be at high risk. Relatively high DDT concentrations were found in tropical water species, which could be attributed to the current usage of DDT in the tropics and the less movable nature of this compound via long-range atmospheric transport. The HCH levels in animals inhabiting cold and temperate waters were higher than those inhabiting tropical waters, a result that was perhaps reflective of atmospheric transport from the tropical source to the northern sinks. A similar pattern was also observed in PCBs, CHLs and HCB, probably indicating the ongoing discharge of these compounds from mid-latitudes as well as those originating in tropical regions.

Organophosphorus flame retardants (PFRs) in human breast milk from several Asian countries

In this study, the concentrations of 10 organophosphorus flame retardants (PFRs) were determined in 89 human breast milk samples collected from Japan, the Philippines and Vietnam. Among the targeted PFRs, tris(2-chloroexyl) phosphate (TCEP) and triphenyl phosphate (TPHP) were the predominant compounds and were detected in more than 60% of samples in all three countries. The concentrations of PFRs in human breast milk were significantly higher (p<0.05) in the Philippines (median 70 ng g(-1) lipid wt.) than those in Japan (median 22 ng g(-1) lipid wt.) and Vietnam (median 10 ng g(-1) lipid wt.). The present results suggest that the usage of products containing PFRs in the Philippines is higher than those of Japan and Vietnam. Comparing with a previous literature survey in Sweden, the levels of PFRs in human breast milk from the Philippines were 1.5-2 times higher, whereas levels in Japan and Vietnam were 4-20 times lower, suggesting that these differences might be due to their variation in the usage of flame-retarded products utilized in each country. When daily intake of PFRs to infants via human breast milk was estimated, some individuals accumulated tris(2-butoxyethyl) phosphate (TBOEP) and TCEP were close to reference dose (RfD). This is the first report to identify PFRs in human breast milk samples from Asian countries.

Organohalogen compounds in human breast milk from mothers living in Payatas and Malate, the Philippines: Levels, accumulation kinetics and infant health risk

Human breast milk samples (n=33) from primipara and multipara mothers from Payatas a waste dump site, and Malate a reference site in the Phillipines were collected in 2004 and analyzed for eight organohalogen compounds, viz., PCBs, DDTs, CHLs, HCHs, HCB, TCPMe, PBDEs and HBCDs. DDTs and PCBs were predominant in all the samples. Overall mean concentrations of PBDEs found in our study were higher (7.5 ng/g lipid wt.) than those reported for Japan and many other Asian countries. Primipara mothers had significantly higher levels of DDTs, CHLs and HCHs than multipara mothers, but not PBDEs and HBCDs. A few individuals accumulated CHLs close to or even higher than the tolerable daily intake guidelines proposed by Health Canada.

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.

Global pollution monitoring of butyltin compounds using skipjack tuna as a bioindicator

Butyltin compounds (BTs) including mono- (MBT), di- (DBT), tri-butyltin (TBT) and total tin (sigmaSn), were determined in the liver of skipjack tuna (Katsuwonus pelamis) collected from Asian offshore waters (off-Japan, the Japan Sea, off-Taiwan, the East China Sea, the South China Sea, off-Philippines, off-Indonesia, the Bay of Bengal), off-Seychelles, off-Brazil and open seas (the North Pacific). BTs were detected in all the skipjack tuna collected, suggesting widespread contamination of BTs even in offshore waters and open seas on a global scale. Considering specific accumulation, Sex-, body length- differences and migration of skipjack tuna did not seem to affect BT concentrations, indicating rapid reflection of the pollution levels in seawater where and when they were collected. Skipjack tuna is a suitable bioindicator for monitoring the global distribution of BTs in offshore waters and open seas. High concentrations of BTs were observed in skipjack tuna from offshore waters around Japan, a highly developed and industrialized region (up to 400 ng/g wet weight). Moreover skipjack tuna collected from offshore waters around Asian developing countries also revealed the levels comparable to those in Japan (up to 270 ng/g wet weight) which may be due to the recent improvement in economic status in Asian developing countries. High percentages (almost 90%) of BTs in total tin (sigmaSn: sum of inorganic tin+organic tin) were found in the liver of skipjack tuna from offshore waters around Asian developing countries. This finding suggests that the anthropogenic BTs represent the major source of Sn accumulation in skipjack tuna from these regions.

Accumulation of brominated flame retardants and polychlorinated biphenyls in human breast milk and scalp hair from the Philippines: levels, distribution and profiles.

Paired human breast milk and scalp hair samples (n=30) were obtained in 2008 from primipara and multipara mothers living in two locations in the Philippines viz., Payatas, a waste dumpsite, and Malate, a non-dumpsite. Samples were analyzed for three groups of organohalogenated compounds, such as polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs). PCBs were the predominantly identified compounds (median: 70 ng/g lipid wt.) in all the breast milk samples. In the human milk, CB-153 was the most dominant PCB congener (17-44% contribution to the sum PCB), closely followed by CB-138 (12-35%), CB-118 (4-12%), CB-180 (2-13%), CB-187 (3-13%), and CB-170 (1.5-10%). Levels of PBDEs (median: 3.0 ng/g lipid wt.) in human milk samples from the Philippines were similar to other Asian or European countries. BDE-47, -99, -100 and -153 were the major PBDE congeners. For HBCDs, the α-isomer was predominant followed by the γ-HBCD isomer in the both locations. PBDE levels in human milk were significantly higher in the dumpsite (3.9 ng/g lipid wt.) than in the non-dump site (2.2 ng/g lipid wt.). PBDE concentrations (including BDE-209) were significantly higher (median: 70 ng/g hair) than those of PCBs (median: 30 ng/g hair) and HBCDs (median: 1.0 ng/g hair) in all the scalp hair samples. To our knowledge, this is the first report on HBCDs in human scalp hair. PBDE congeners in scalp hair were dominated by BDE-209 and BDE-47. On a congener basis, the levels of PBDEs found in scalp hair were higher than those in Spain (children and adults) and China (general people). PCB levels found in scalp hair were higher than those in Greece, Romania and Belgium, but lower than those in China. In this study, there were no significant differences in the concentration of PCBs and HBCDs in human milk; and PCBs, HBCDs and PBDEs in human scalp hair from the two different locations. No significant correlations were observed between PCBs, PBDEs and HBCDs levels and age of mothers in this study, which may be due to the small number of samples. Furthermore, there was no correlation between milk and hair levels for more persistent compounds (PCB-153, PCB-138, or BDE-47), and thus it is worthy to follow-up in future studies along with more number of samples. This is the first report to provide measurement data for PCBs, PBDEs and HBCDs in paired milk and hair of populations in the Philippines.