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.     

Distribution and characteristics of PAHs in sediments from the Mediterranean coastal environment of Egypt

To assess the contamination of polycyclic aromatic hydrocarbons (PAHs) in the Mediterranean coastal environment of Egypt, 26 sediment samples from the coastline, harbours, estuaries and coastal lakes were collected and analyzed. The sediment PAH concentrations of thirty-nine 2-6 ring PAHs ranged from 13.5 to 22,600 ng/g. PAH profiles varied according to the nature of the site and its proximity to sources. Industrialized and urbanized region showed high level of PAHs contamination. In general, the contamination levels of PAHs were similar to those observed in contaminated and slightly contaminated sediments of the Mediterranean Sea. Molecular indices based on ratios of selected PAH concentrations were used to differentiate PAHs from pyrogenic and petrogenic and mixed origins. Good correlations were observed between the petrogenic index, MP/P, A-PAHs/P-PAHs and HMW/LMW. Finally, PAH levels in sediments were compared with Sediments Quality Guidelines (ERM-ERL) for evaluation of probable toxic effects on organism.     

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.     

Sources and distribution of aliphatic and polyaromatic hydrocarbons in sediments of Jiaozhou Bay, Qingdao, China

The composition and distribution of aliphatic (n-alkanes) and polyaromatic hydrocarbons (PAHs) were measured for the surface sediments collected at 25 sites from Jiaozhou Bay, Qingdao, China. Total n-alkanes and PAH concentrations ranged from 0.5 to 8.2 microg/gdw and 0.02 to 2.2 microg/gdw, respectively, and the distribution of both n-alkanes and PAHs showed large spatial variations in the bay. The distribution of PAHs in the sediments was predominated by the three or more ring compounds. High hydrocarbon levels were generally found in the areas associated with high anthropogenic impact and port activities in the bay. The calculated hydrocarbon indexes suggest that petroleum contamination was the main source of n-alkanes, while both pyrolytic and petrogenic sources contributed PAHs to the surface sediments of Jiaozhou Bay. In comparison to other polluted coastal sediments, the level of contamination from both aliphatic hydrocarbons and PAHs in Jiaozhou Bay sediments is relatively low at the present time.     

Inputs and sources of hydrocarbons in sediments from Cienfuegos bay, Cuba

The spatial distribution of aliphatic and polycyclic aromatic hydrocarbons (PAHs) was investigated in sediments from the Cienfuegos bay. The highest anthropogenic hydrocarbon inputs were found near the city of Cienfuegos with an unresolved complex mixture (UCM) of aliphatic hydrocarbons and alkylated PAHs, indicative of petrogenic inputs. Parent PAHs, which are typical of high-temperature combustion processes, were evenly distributed in the whole basin and largely prevailing in the southern part of the Cienfuegos city. Biomarker fingerprints assign the sources of pollution to mixes of national and non-national crude oils. The overall levels of anthropogenic hydrocarbons are relatively high compared to relevant areas worldwide and reveal a moderate/high level of hydrocarbon pollution. The Cienfuegos bay sediments received over a period of 5 yr, 50 T/yr of petrogenic unresolved hydrocarbons (UCM) and 2 T/yr of PAHs, being deposited the 80% in the sediments of the north basin.     

Source apportionment of polycyclic aromatic hydrocarbons in surface sediment of mud areas in the East China Sea using diagnostic ratios and factor analysis

Polycyclic aromatic hydrocarbons (PAHs) and aliphatic hydrocarbons (AHs) have been quantified for surface sediments collected from the East China Sea (ECS). Our results showed that relatively high levels of PAHs and AHs occurred in both the inner and outer mud areas, while their concentrations at the control site were much lower. AHs for all samples were dominated by the unresolved complex mixture (UCM). Results from diagnostic ratios revealed that sedimentary PAHs were mainly originated from mixed combustion residues of biomass, coal, and petroleum. Combustion residues of petroleum and oil were responsible for the presence of high AHs concentrations. We also conducted factor analysis (FA) to further characterize the PAH and AH sources. Four factors were identified based on the loading of components and attributed to coal and wood combustion (Factor 1), traffic-related sources (Factor 2), petrogenic source (Factor 3) and natural gas combustion (Factor 4).     

The Consequences of the Oder Flood in 1997 on the Distribution of Polycyclic Aromatic Hydrocarbons in the Oder River

Changes in the levels and spatial distribution of PAHs as a consequence of the Oder flood in the summer of 1997 were investigated in post‐flood sediments from the Oder River and the Oder Lagoon. The aim of this study was to identify sources of the PAH pollution and in particular investigate polluted sites (“hot spots”) in the most highly suspected locations of the drainage area. Molecular indices based on isomeric PAH ratios and the ratio of the parent PAHs to methylated PAHs were used to distinguish between the pollution sources. Elevated levels of PAHs were discovered in the post‐flood sediments of the Oder River in comparison to the average regional values. Elevated concentrations of PAHs were also found in fluffy layer samples taken from the Oder Lagoon and the Pomeranian Bight in late August. The highest concentrations of PAHs were observed near power plants or roads with heavy traffic. Most of the contamination originates from high temperature pyrogenic sources with some slight overlays of petrogenic sources. These increased concentrations of pyrogenic origin may be attributable to flooding of municipal and industrial waste disposal areas in the Oder River drainage.     

Fate of polycyclic aromatic hydrocarbon (PAH) contamination in a mangrove swamp in Hong Kong following an oil spill

The fate of polycyclic aromatic hydrocarbon (PAH) contamination in a mangrove swamp (Yi O) in Hong Kong after an oil spill accident was investigated. The concentrations and profiles of PAHs in surface sediments collected from five quadrats (each of 10 m×10 m) covering different degrees of oil contamination and the most contaminated mangrove leaves were examined in December 2000 (30 days after the accident) and March 2001 (126 days later). The concentrations of total PAHs in surface sediments ranged from 138 to 2135 ng g⁻¹, and PAHs concentrations decreased with time. In the most contaminated sediments, total PAHs dropped from 2135 (30 days) to 1196 ng g⁻¹ (120 days), and the decrease was smaller in less contaminated sediments. The percentage reduction in sediment PAHs over three months (44%) was less significant than that in contaminated leaves (85%), indicating PAH in or on leaves disappeared more rapidly. The PAH profiles were very similar in sediments collected from quadrats Q1 and Q2 with benzo[a]anthracene and pyrene being the most abundant PAH compounds, but were different in the other three quadrats. The proportion of the light molecular weight PAHs to total PAHs increased after three months, especially phenanthrene. Results suggest that physical and photo-chemical weathering (tidal washing and photo-oxidation) of crude oil in surface sediments and on plant leaves were important processes in the first few months after the oil spill. The PAH contamination in Yi O swamp came from both petrogenic and pyrolytic sources. The petrogenic characteristic in the most contaminated sediment was confirmed with high values of phenanthrene to anthracene ratio (>10) and low values of fluoranthene to pyrene ratio (0.3–0.4).     

Aliphatic and aromatic hydrocarbons in coastal Caspian Sea sediments

This investigation represents the first extensive study of the spatial distribution and sources of aliphatic (n-alkanes and unresolved complex mixture of fossil hydrocarbons) and polycyclic aromatic hydrocarbons (PAHs) in coastal sediments from the Caspian Sea. PAH concentrations, n-alkanes and biomarker profiles all suggested that there was limited petrogenic contamination in the shallow North Caspian Sea sediments, which are coarse with a low total organic carbon content. In contrast, moderate to high petrogenic contamination was found in the South Caspian Sea, in particular in the offshore oil fields near Baku, Azerbaijan. Contaminant patterns indicated that the PAHs were mainly from fossil sources, with higher contributions of pyrolytic only near industrialized and urban areas. A high contribution of perylene, a geochemically derived PAH, to the total PAHs was found in the west and south at sites influenced by the Kura, Safid Rud, Terek, Sulak and Samur Rivers.     

Polycyclic aromatic hydrocarbons in coastal sediments of southwest Taiwan: An appraisal of diagnostic ratios in source recognition

Fifty-seven surface sediment samples were collected from the coast of southwest Taiwan and analyzed for polycyclic aromatic hydrocarbons (PAHs). Concentrations of total PAHs (28 PAH compounds) ranged from 15 to 907 ng g⁻¹ dry weight. Diagnostic ratios showed that PAHs in the sediments of the Gaoping estuary were predominantly of petroleum origin, whereas sediments from the Kaohsiung coast contained principally combustion-derived PAHs. Principal component analysis indicated that emissions from automobiles and coal burning were the main sources of combustion-derived PAHs. The relatively high ratios of perylene/penta-aromatic PAH isomers in sediments from the Tainan coast and some off-shore stations on the Kaohsiung coast suggest a significant diagenetic PAH contribution. The study shows that certain diagnostic ratios are useful and sensitive in delineating the distribution of PAHs from specific sources in southwest Taiwan. The phenanthrene/anthracene ratio is a better indicator than the methylphenanthrenes/phenanthrene ratio for tracing petrogenic PAHs, and the benzo(a)anthracene/chrysene and indeno(1,2,3-c,d)pyrene/benzo(g,h,i)perylene ratios are more specific than the benzo(a)pyrene/benzo(e)pyrene and benzo(b)fluoranthcene/benzo(k)fluoranthcene ratios in distinguishing PAHs from various pyrogenic sources.     

Distribution and source recognition of polycyclic aromatic hydrocarbons in the sediments of Hsin-ta Harbour and adjacent coastal areas,Taiwan

Thirty-three sediment samples from Hsin-ta Harbour and neighboring coastal areas were analyzed by GC-MS for polycyclic aromatic hydrocarbons (PAHs). Total concentrations of 30 analyzed parental and alkylated PAHs ( summation operator PAH) varied from 98.1 to 3382 ng/g dry weight. MP/P (methylphenanthrenes/phenanthrene) values larger than 2 coincided with very low P/A (phenanthrene/anthracene) values at inner harbour stations, revealing that a significant portion of low molecular weight PAHs are probably from petrogenic pollution sources, specifically, illegal disposal of used motor oil. The 4,6-dimethyldibenzothiophene/3,6-dimethylphenanthrene (4,6-C(2)D/3,6-C(2)P) ratio is found to be more useful than the MP/P ratio in tracing petrogenic PAHs from the inner harbour area to the adjacent coastal environment. In addition, according to hierarchical cluster analysis, collected sediments cluster in three major groups, Off-shore Group, Near-shore Group and Inner Harbour Group. Three diagnostic ratios, 4,6-C(2)D/3,6-C(2)P, PER/ summation operator PAH (perylene to summation operator PAH) and BaA/CHR (benzo(a)anthracene/chrysene), representing petrogenic, biogenic and pyrogenic origins, are found to be effective in differentiating and characterizing sediments among the groups in this study. Enrichment of pyrogenic and petrogenic PAHs in sediments collected exhibits mixing or dilution, spatially, by biogenic (or natural) PAHs.     

Hydrocarbons in sediments of a chronically contaminated bay: the challenge of source assignment

Aliphatic hydrocarbons and 39 PAH (parental and alkylated homologs) determined in ca. 100 sediment samples from the Guanabara Bay, Rio de Janeiro, were evaluated for source discrimination using new approaches. Concentrations of total PAH were in the range of 96-135,000 μg kg(-1) similar to other coastal urbanized embayment. Traditional diagnostic ratios were not as efficient PAH source indicators, e.g. biomass combustion was assigned as the major source of the pyrolytic PAH although the hydrographic basin is highly industrialized and urbanized. It is proved petrogenic imprint cannot be detected if only the 16 USEPA PAH are determined. The high production in the eutrophic system is not apparent in the aliphatic fraction dominated by land derived n-alkanes due to the effectiveness of microbial degradation. The present work demonstrates the complexity of hydrocarbon forensics when applied to chronically contaminated environments.     

Distribution,sources and potential toxicological significance of polycyclic aromatic hydrocarbons (PAHs) in surface soils of the Yellow River Delta,China

PAH concentrations of 61 surface soil samples collected from the Yellow River Delta (YRD), China were measured to determine occurrence levels, sources, and potential toxicological significance of PAHs. The total concentrations of ∑PAHs ranged from 27 to 753 ng/g d.w., with a mean of 118 ± 132 ng/g. The highest concentrations was found in the mid-southern part of the YRD (753 ng/g), which was associated with the oil exploration. The ratios indicated that the PAHs throughout the YRD were mostly of pyrogenic origin; while various sites in mid-southern part in the region were derived mainly from the petrogenic sources. Multivariate statistical analyses supported that the PAHs in surface soils of the YRD were principally from the coal and biomass combustion, petroleum spills, and/or vehicular emissions. The toxic assessment suggested that the PAHs in soils were at low potential of ecotoxicological contamination level for the YRD.     

Distribution and sources of polynuclear aromatic hydrocarbons in Mangrove surficial sediments of Deep Bay, China

Twelve sediment samples collected from three transects of mangrove swamp of Deep Bay, Shenzhen, China, were determined for polynuclear aromatic hydrocarbons (PAHs). The total PAHs concentrations ranged from 237 to 726 ng g(-1) dry weight, and showed strong correlation with total organic carbon (TOC), clay content and Pb concentrations. The highest PAHs concentrations were found in the samples from mangrove sediments. Overall, PAHs in Deep Bay sediment were lower than those in other developed areas. The biological effect due to PAHs alone in Deep Bay is expected to be low, based on the comparisons of individual and total PAHs concentrations determined in the sediment with those in USEPA sediment quality guidelines. Four and five-ring compounds dominated the PAHs composition pattern profiles. Principal component analysis (PCA) was applied to further investigate the source of PAHs. The PAH sources of Deep Bay mangrove swamp were suggested to be primarily combustion of fossil fuel, especially leaded-gasoline exhaust.     

Spatio-temporal distribution and characteristics of PAHs in sediments from Masan Bay, Korea

The distribution of polycyclic aromatic hydrocarbons (PAHs) has been investigated in the surface and core sediments from Masan Bay, Korea. Total PAHs in the surface sediments ranged from 207 to 2670 ng/g dry weight with a mean value of 680 ng/g. Qualitative similarity and quantitative difference between inner and outer bay indicate that the main sources of PAHs are located in the inner bay and outer bay is also affected by the same sources. Vertical distribution of PAHs revealed that three distinctive stages could be differentiated with the help of PCA analysis. The highest concentration (industrialization stage) appeared between late 1950s and 1980, which was 10 years later than other developed countries. A strong pyrolytic source fingerprint has been detected with slight influence of petrogenic sources, and diagenetic PAH, perylene also contributed. Total organic carbon normalized PAHs (sum of 13 PAHs, 8.85-88.0 microg/g OC) were under the threshold effects concentration (TEC, 290 microg/g OC).     

Distribution,sources, and ecological risk assessment of polycyclic aromatic hydrocarbons in surface sediments from the Nantong Coast,China

The distribution, sources, and ecological risk assessment of 16 polycyclic aromatic hydrocarbons (PAHs) in surface sediments from the Nantong coast in China were investigated. The results indicated that the total concentrations of the 16 PAHs in the surface sediments from the study area ranged from 1.4 to 87.1 ng g^? 1 dw (mean value 19.9 ng g^? 1 dw), which were generally low compared to the adjacent offshore area and other coastal zones around the world. The selected PAH ratios and the principal components analysis for each site showed that petroleum combustion and petrogenic pollution (mainly caused by petroleum spills) were the dominant PAHs sources in the surface sediments of the coast. The ecological risk assessment indicated that most of the individual PAHs had few negative effects in this area.     

Dynamic behaviour of polycyclic aromatic hydrocarbons in Brighton marina, UK

The distribution of polycyclic aromatic hydrocarbons (PAHs) between various phases is fundamental in the control of their movement and impact in the marine environment. In this study samples of water and sediments were regularly collected from Brighton marina, UK, to quantify the intensity, spatial and temporal variations of PAH contamination. The results show clearly that PAH behaviour in marine systems is highly complex, and controlled by the interplay of PAH sources, compound physicochemical properties, water and sediment movement, and field conditions. Levels of total PAHs (16 compounds) in the dissolved phase were found to vary between <2 and 11,400 ng/l, with higher values observed in the winter months. Total PAH concentration in sediment samples varied between 24 and 4710 ng/g dry weight. PAHs in water were dominated by low molecular mass compounds (2-ring), while PAHs in sediments were mainly derived from 2-4 ring compounds. In addition, dissolved concentrations were increased during sediment dredging and after a period of severe rainfall. PAHs in Brighton marina are likely to be from both pyrolytic and petrogenic sources; as a result, field-derived distribution coefficients for individual PAHs between sediment and water tend to follow the equilibrium partition models, although slight exceedance is apparent. The extended partition model incorporating soot carbon has achieved limited success in better predicting PAH behaviour.     

Sources and distribution of polycyclic aromatic hydrocarbons in the sediments of Kaoping River and submarine canyon system, Taiwan

In this study, we measured and analyzed polycyclic aromatic hydrocarbons (PAHs) in surface sediment samples collected from the Kaoping river and submarine canyon (KPSC) system to determine the compositional patterns and characteristic distributions of PAH and to elucidate the transport and fate of these land-derived particles. Concentrations of total PAH (sum of 28 PAH compounds) ranged from 22.6 to 45,100 ngg(-1) dry weight (dw) and the highest concentrations were found in the sediments of Donggang Harbor. The ratio of perylene to sum of penta-aromatic PAH isomers (47-55%) was higher in off-shore stations, suggesting a diagenetic PAH source. Various isomeric ratios also indicated that combustion was a significant source of PAH to the sediment at stations located along the Kaoping river and the north-western shelf of the Kaoping estuary. However, in the south-eastern shelf and some canyon sites, petroleum-derived PAHs were a more significant source of these compounds. Principal component analysis and hierarchical cluster analysis suggest PAHs in the sediments from the north-western shelf, and river and canyon sediments might be a pyrogenic product of coal and diesel-burning vehicles, while those of the south-eastern shelf may be petrogenic. PAH concentrations and compositional patterns are effective tracers of particulate transport in KPSC system. The seaward transport of riverine particulates was found to be mostly directed to NW-shelf and/or canyon.     

Aliphatic and aromatic hydrocarbons in marine biota and coastal sediments from the Gulf and the Gulf of Oman

The composition and spatial distribution of aliphatic and polycyclic aromatic hydrocarbons (PAHs) were investigated in biota and coastal sediments from four countries surrounding the Gulf (Bahrain, Qatar, United Arab Emirates and Oman). The levels of total petroleum hydrocarbons (TPH), aliphatic unresolved mixture and PAHs in sediments and biota were relatively low compared to world-wide locations reported to be chronically contaminated by oil. Only in the case of the sediments collected near the BAPCO oil refinery in Bahrain, having concentrations of 779 μg g⁻¹ total petroleum hydrocarbon equivalents and 6.6 μg g⁻¹ ∑PAHs, can they be categorized as chronically contaminated. Some evidence of oil contamination was also apparent in sediments and bivalves around Akkah Head and Abu Dhabi in the UAE, and near Mirbat in Oman. Contaminant patterns in sediments and biota indicated that the PAHs were mainly from fossil sources, with the exception of the high PAH concentrations in sediments near the BAPCO refinery that contained substantial concentrations of carcinogenic PAH combustion products.     

‘Fingerprinting’ petroleum hydrocarbons in bottom sediment,plankton, and sediment trap collected seston

Water carried particulate matter (seston) collected in sediment traps has been used for fingerprinting petrogenic hydrocarbons (PHC) along an urban influenced transect in the Stockholm archipelago. Gas-chromatography (GC) and gas chromatography-mass spectrometry (GC-MS) have been used for identification and quantification of n-alkanes, the isoprenoids pristane and phytane, pentacyclic triterpanes, the unresolved complex mixture (UCM) and total hydrocarbon content (THC). Preserved seston has been compared with anoxic seston and anoxic bottom surface sediments to establish the effects of degradation processes, and with spring bloom plankton as a reference of biological material. The results show that samples of seston, collected and preserved in sediment traps, are very suitable for carrying out fingerprint analyses of petrogenic hydrocarbons. A gradient of increasing PHC downflux towards the urban area was found and petrogenic contamination of the waters was detected along the whole transect.