Mahua Saha

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.

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.

Ubiquitous occurrence of sulfonamides in tropical Asian waters.

Seven sulfonamides, trimethoprim, five macrolides, lincomycin and three tetracyclines were measured in 150 water samples of sewage, livestock and aquaculture wastewater, and river and coastal waters, in five tropical Asian countries. The sum of the concentrations of the target antibiotics in sewage and heavily sewage-impacted waters were at sub- to low-ppb levels. The most abundant antibiotic was sulfamethoxazole (SMX), followed by lincomycin and sulfathiazole. The average concentration of SMX in sewage or heavily sewage-impacted waters was 1720 ng/L in Vietnam (Hanoi, Ho Chi Minh, Can Tho; n=15), 802ng/L in the Philippines (Manila; n=4), 538 ng/L in India (Kolkata; n=4), 282 ng/L in Indonesia (Jakarta; n=10), and 76 ng/L in Malaysia (Kuala Lumpur; n=6). These concentrations were higher than those in Japan, China, Europe, the US and Canada. A predominance of sulfonamides, especially SMX, is notable in these tropical countries. The higher average concentrations, and the predominance of SMX, can be ascribed to the lower cost of the antibiotics. Both the concentration and composition of antibiotics in livestock and aquaculture wastewater varied widely. In many cases, sulfamethazine (SMT), oxytetracycline (OTC), lincomycin, and SMX were predominant in livestock and aquaculture wastewater. Both human and animal antibiotics were widely distributed in the respective receiving waters (i.e., the Mekong River and Manila Bay). SMT/SMX ratios indicate a significant contribution from livestock wastewater to the Mekong River and nearby canals, with an estimated ~10% of river water SMX derived from such wastewater. Mass flow calculations estimate that 12 tons of SMX is discharged annually from the Mekong River into the South China Sea. Riverine inputs of antibiotics may significantly increase the concentration of such antibiotics in the coastal waters.

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.

Spatial variability in persistent organic pollutants and polycyclic aromatic hydrocarbons found in beach-stranded pellets along the coast of the state of São Paulo, southeastern Brazil

High spatial variability in polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), organochlorine pesticides, such as DDTs, and polybrominated diphenylethers was observed in plastic pellets collected randomly from 41 beaches (15 cities) in 2010 from the coast of state of São Paulo, southeastern Brazil. The highest concentrations ranged, in ng g(-1), from 192 to 13,708, 3.41 to 7554 and <0.11 to 840 for PAHs, PCBs and DDTs, respectively. Similar distribution pattern was presented, with lower concentrations on the relatively less urbanized and industrialized southern coast, and the highest values in the central portion of the coastline, which is affected by both waste disposal and large port and industrial complex. Additional samples were collected in this central area and PCB concentrations, in ngg(-)(1), were much higher in 2012 (1569 to 10,504) than in 2009/2010 (173 to 309) and 2014 (411), which is likely related to leakages of the PCB commercial mixture.

Establishing Criteria of Relative Abundance of Alkyl Polycyclic Aromatic Hydrocarbons (PAHs) for Differentiation of Pyrogenic and Petrogenic PAHs: An Application to Indian Sediment

Various source materials such as crude oil, automobile exhaust, coal, and wood combustion products were analyzed for polycyclic aromatic hydrocarbons (PAHs) and hopanes. Hopanes were detected in coal combustion-derived soot, along with petrogenic sources. Based on the correlation between the alkylated PAHs/parental PAHs ratio with their respective C30 hopane/PAHs ratio in these source materials, the criteria for differentiating the petrogenic and pyrogenic sources of PAHs were established. This study concluded that sediments contained exclusively pyrogenic PAHs when the following conditions were met: MP/P (methylphenanthrenes to phenanthrene) = 0.5, MPy/Py [(methylpyrenes + methylfluoranthenes) to (pyrene + fluoranthene)] = 0.15, and MC/C [(methylchrysenes + methylbenz[a]anthracenes) to (chrysene + benz[a]anthracene)] = 0.2. By contrast, the sediments contained exclusively petrogenic PAHs when the ratios of MP/P, MPy/Py, MC/C, and methyl PAHs (MPAHs)/PAHs exceeded 3.5, 1.5, 2.0, and 2.2, respectively. Based on these criteria, an intensive source apportionment of PAHs to sediments from three Indian metro cities, Chennai (n = 6), Mumbai (n = 6) and Kolkata (n = 12) (2003–2007), was determined. This investigation found that sedimentary PAHs from India were depleted in alkylated PAHs with low MP/P ≈ 0.7, MPy/Py ≈ 0.14, and MC/C ≈ 0.3, which contrasted with other tropical Asian countries, where elevated values of these ratios were detected. Among the three cities, Kolkata waters were more strongly influenced by pyrogenic sources of PAHs with very low alkylated PAHs ratios than Chennai and Mumbai sediments. The compositional differences were attributed to the dominant coal and biomass in Kolkata compared to the dominant usage of petrogenic cooking fuel (e.g., kerosene) and automobile-derived sources in Chennai and Mumbai.

Source analysis of radiocesium in river waters using road dust tracers

Following the Fukushima Dai-ichi Nuclear Power Station accident, regional road dust, heavily contaminated with radiocesium, now represents a potential source of radiocesium pollution in river water. To promote effective countermeasures for reducing the risk from radiocesium pollution, it is important to understand its sources. This study evaluated the utility of metals, including Al, Fe, and Zn as road dust tracers, and applied them to analyze sources of 137Cs in rivers around Fukushima during wet weather. Concentrations of Zn in road dust were higher than agricultural and forest soils, whereas concentrations of Fe and Al were the opposite. Concentrations of Zn were weakly but significantly correlated with benzothiazole, a molecular marker of tires, indicating Zn represents an effective tracer of road dust. Al, Fe, and Zn were frequently detected in suspended solids in river water during wet weather. Distribution coefficients of these metals and 137Cs exceeded 104, suggesting sorptive behavior in water. Although concentrations of Al, Fe, Zn, and 137Cs were higher in fine fractions of road dust and soils than in coarse fractions, use of ratios of 137Cs to Al, Fe, or Zn showed smaller differences among size fractions. The results demonstrate that combinations of these metals and 137Cs are useful for analyzing sources of radiocesium in water. These ratios in river water during wet weather were found to be comparable with or lower than during dry weather and were closer to soils than road dust, suggesting a limited contribution from road dust to radiocesium pollution in river water.