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 (∑PAHs: ∼1000 to ∼100 000 ng/g-dry) than in rural areas (∼10 to ∼100 g-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 ≈ 0.5, MPy/Py ≈ 0.1, and MC/C ≈ 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 ≈ 1-4, MPy/Py ≈ 0.3-1, and MC/C ≈ 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.     

Reconstruction of pollution history of organic contaminants in the upper Gulf of Thailand by using sediment cores: first report from Tropical Asia Core (TACO) project

This paper reports the first reconstruction of a pollution history in tropical Asia from sediment cores. Four sediment core samples were collected from an offshore transect in the upper Gulf of Thailand and were analyzed for organic micropollutants. The cores were dated by measurement of (137)Cs and geochronometric molecular markers (linear alkylbenzenes, LABs; and tetrapropylene-type alkylbenzenes, TABs). Polychlorinated biphenyl (PCB) concentrations showed a subsurface maximum in layers corresponding to the 1970s, indicating the effectiveness of regulation of PCBs in Thailand. LAB concentrations increased over time, indicating the increase in input of sewage into the Gulf during the last 30 years. Hopanes, biomarkers of petroleum pollution, also increased over time, indicating that the inputs of automobile-derived hydrocarbons to the coastal zone has been increasing owing to the increased number of cars in Thailand since the 1950s. Polycyclic aromatic hydrocarbons (PAHs) increased in the layers corresponding to the 1950s and 1960s, probably because of the increased inputs of automobile-derived PAHs. PAH concentrations in the upper layers corresponding to the 1970s and later remained constant or increased. The absence of a subsurface maximum of PAHs contrasts with results observed in industrialized countries. This can be explained by the facts that the Thai economy did not depend on coal as an energy source in the 1960s and that economic growth has continued since the 1970s to the present. The deposition flux of PAHs and hopanes showed a dramatic offshore decrease, whereas that of LABs was uniform.     

Distribution and origins of polycyclic aromatic hydrocarbons (PAHs) in riverine, estuarine, and marine sediments in Thailand

To assess the status of polycyclic aromatic hydrocarbon (PAH) contamination in coastal and riverine environments in Thailand, we collected 42 surface sediment samples from canals, a river, an estuary, and coastal areas in Thailand in 2003 and analyzed them for PAHs with 3-7 benzene rings by gas chromatography-mass spectrometry (GC-MS). The total concentration of PAHs ranged from 6 to 8399 ng/g dry weight. The average total PAH concentrations were 2290+/-2556 ng/g dry weight (n=8) in canals, 263+/-174 (n=11) in the river, 179+/-222 (n=9) in the estuary, and 50+/-56 (n=14) in coastal areas. Comparison of the concentration range with a worldwide survey of sedimentary PAH concentrations ranked PAH contamination in Thai sediments as low to moderate. The ratio of the sum of methylphenanthrenes to phenanthrene (MP/P ratio) allows discrimination of PAH sources between petrogenic (>2) and pyrogenic (<0.5) origins. Sediments from urban canals in Bangkok showed the highest PAH concentrations and petrogenic signatures (MP/P=1.84+/-0.98 [n=6] in canal sediments) with abundant alkylated PAHs, indicating major sources of petrogenic PAHs in the city. To identify the sources of the petrogenic inputs in Thailand, we analyzed triterpanes, biomarkers of petroleum pollution, in the sediment samples and in potential source materials. Hopane profiles were remarkably uniform throughout the nation, suggesting a diffuse single source (e.g. automobiles). Molecular profiles of hopanes and PAHs in sediments from the urban canals were similar to those in street dust, indicating that street dust is one of the major sources of petrogenic PAHs in the urban area. On the other hand, low levels of PAHs (approximately 50 ng/g) with a pyrogenic signature (MP/P ratio approximately 0.5) were widely recorded in remote areas of the coast and the Chao Phraya River. These pyrogenic PAHs may be atmospherically transported throughout the nation. Middle and lower reaches of the Chao Phraya River, the river mouth, and the upper Gulf of Thailand showed intermediate concentrations and profiles of PAHs, indicating mixtures of petrogenic and pyrogenic origins. Perylene was abundant in sediments, representing up to approximately 60% of total identified PAHs. High inputs of soil due to frequent heavy rains could contribute to the high perylene abundance in the sediments. Sedimentary PAH concentrations decreased offshore with a half distance of approximately 10 km in the upper Gulf off the mouth of the Chao Phraya River. This is probably due to active deposition of laterally transported riverborne particles.     

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.