Kaoruko Mizukawa

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.

International Pellet Watch: Global monitoring of persistent organic pollutants (POPs) in coastal waters. 1. Initial phase data on PCBs, DDTs, and HCHs

Samples of polyethylene pellets were collected at 30 beaches from 17 countries and analyzed for organochlorine compounds. PCB concentrations in the pellets were highest on US coasts, followed by western Europe and Japan, and were lower in tropical Asia, southern Africa and Australia. This spatial pattern reflected regional differences in the usage of PCBs and was positively correlated with data from Mussel Watch, another monitoring approach. DDTs showed high concentrations on the US west coast and in Vietnam. In Vietnam, DDT was predominant over its metabolites (DDE and DDD), suggesting the principal source may be current usage of the pesticide for malaria control. High concentrations of pesticide HCHs were detected in the pellets from southern Africa, suggesting current usage of the pesticides in southern Africa. This study demonstrates the utility and feasibility of the International Pellet Watch approach to monitor POPs at a global scale.

Accumulation of plastic-derived chemicals in tissues of seabirds ingesting marine plastics

We analyzed polybrominated diphenyl ethers (PBDEs) in abdominal adipose of oceanic seabirds (short-tailed shearwaters, Puffinus tenuirostris) collected in northern North Pacific Ocean. In 3 of 12 birds, we detected higher-brominated congeners (viz., BDE209 and BDE183), which are not present in the natural prey (pelagic fish) of the birds. The same compounds were present in plastic found in the stomachs of the 3 birds. These data suggested the transfer of plastic-derived chemicals from ingested plastics to the tissues of marine-based organisms.

Organic micropollutants in marine plastics debris from the open ocean and remote and urban beaches

To understand the spatial variation in concentrations and compositions of organic micropollutants in marine plastic debris and their sources, we analyzed plastic fragments (∼10 mm) from the open ocean and from remote and urban beaches. Polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), dichloro-diphenyl-trichloroethane and its metabolites (DDTs), polybrominated diphenyl ethers (PBDEs), alkylphenols and bisphenol A were detected in the fragments at concentrations from 1 to 10,000 ng/g. Concentrations showed large piece-to-piece variability. Hydrophobic organic compounds such as PCBs and PAHs were sorbed from seawater to the plastic fragments. PCBs are most probably derived from legacy pollution. PAHs showed a petrogenic signature, suggesting the sorption of PAHs from oil slicks. Nonylphenol, bisphenol A, and PBDEs came mainly from additives and were detected at high concentrations in some fragments both from remote and urban beaches and the open ocean.

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.

Bioconcentration and biomagnification of polybrominated diphenyl ethers (PBDEs) through lower-trophic-level coastal marine food web.

Bivalves, crabs, fishes, seawater, and sediment collected from the inner part of Tokyo Bay, Japan, were measured for 20 polybrominated diphenyl ether (PBDE) and 5 polychlorinated biphenyl (PCB) congeners. To determine the trophic levels of the organisms, carbon and nitrogen stable isotope ratios (delta(13)C and delta(15)N) were also measured. Bioconcentration factors of PBDE and PCB congeners increased as the octanol-water partition coefficient (K(ow)) rose to log K(ow)=7, above which they decreased again. Biomagnification of PCBs and several PBDE congeners (BDE47, 99, 100, 153 and 154) up the trophic ladder was confirmed by a positive correlation between their concentrations and delta(15)N. Other PBDE congeners showed a negative or no correlation, suggesting their biotransformation through metabolism. The more hydrophobic congeners of both PBDEs (Br=2-6) and PCBs (Cl=6-9) were biomagnified more. It thus appears that PBDEs are less biomagnified than PCBs.

Monitoring of a wide range of organic micropollutants on the Portuguese coast using plastic resin pellets

We analyzed polychlorinated biphenyls (PCBs), dichlorodiphenyl dichloroethane and its metabolites, hexachlorocyclohexanes (HCHs), polycyclic aromatic hydrocarbons (PAHs), and hopanes, in plastic resin pellets collected from nine locations along the Portuguese coast. Concentrations of a sum of 13 PCBs were one order of magnitude higher in two major cities (Porto: 307 ng/g-pellet; Lisboa: 273 ng/g-pellet) than in the seven rural sites. Lower chlorinated congeners were more abundant in the rural sites than in the cities, suggesting atmospheric dispersion. At most of the locations, PAH concentrations (sum of 33 PAH species) were ∼100 to ∼300 ng/g-pellet; however, three orders of magnitude higher concentrations of PAHs, with a petrogenic signature, were detected at a small city (Sines). Hopanes were detected in the pellets at all locations. This study demonstrated that multiple sample locations, including locations in both urban and remote areas, are necessary for country-scale pellet watch.

Sedimentary PBDEs in urban areas of tropical Asian countries

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.

Historical occurrences of polybrominated diphenyl ethers and polychlorinated biphenyls in Manila Bay, Philippines, and in the upper Gulf of Thailand

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.

Biomagnification and debromination of polybrominated diphenyl ethers in a coastal ecosystem in Tokyo Bay

By field sampling and laboratory experiments we compared the mechanisms by which polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) are biomagnified. We measured PBDEs and PCBs, together with stable carbon and nitrogen isotopes as an index of trophic level, in low-trophic-level organisms collected from a coastal area in Tokyo Bay. PBDEs were biomagnified to a lesser degree than PCBs. The more hydrophobic congeners of each were biomagnified more. However, the depletion of BDE congeners BDE99 and BDE153 from fish was suggested. To study congener-specific biotransformation of halogenated compounds, we conducted an in vitro experiment using hepatic microsomes of two species of fish and five BDE congeners (BDE47, 99, 100, 153, and 154) and five CB congeners with the same substitution positions as the PBDEs. BDE99 and 153 were partially debrominated, but BDE47 and 154 were not debrominated. This congener-specific debromination is consistent with the field results. Both in vitro and field results suggested selective debromination at the meta position. The CB congeners were not transformed in vitro. This result is also consistent with the field results, that PCBs were more biomagnified than PBDEs. We conclude that metabolizability is an important factor in the biomagnification of chemicals, but other factors must be responsible for the lower biomagnification of PBDEs in natural ecosystems.