Polycyclic aromatic hydrocarbon (PAHs) and hopanes in stranded tar-balls on the coasts of Peninsular Malaysia: applications of biomarkers for identifying sources of oil pollution

Malaysian coasts are subjected to various threats of petroleum pollution including routine and accidental oil spill from tankers, spillage of crude oils from inland and offshore oil fields, and run-off from land-based human activities. Due to its strategic location, the Straits of Malacca serves as a major shipping lane. This paper expands the utility of biomarker compounds, hopanes, in identifying the source of tar-balls stranded on Malaysian coasts. 20 tar-ball samples collected from the east and west coast were analyzed for hopanes and polycyclic aromatic hydrocarbons (PAHs). Four of the 13 tar-ball samples collected from the west coast of Peninsular Malaysia were identified as the Middle East crude oil (MECO) based on their biomarker signatures, suggesting tanker-derived sources significantly contributing the petroleum pollution in the Straits of Malacca. The tar-balls found on the east coast seem to originate from the offshore oil platforms in the South China Sea. The presence of South East Asian crude oil (SEACO) tar-balls on the west coast carry several plausible explanations. Some of the tar-balls could have been transported via sea currents from the east coast. The tankers carrying SEACO to other countries could have accidentally spilt the oil as well. Furthermore, discharge of tank washings and ballast water from the tankers were suggested based on the abundance in higher molecular weight n-alkanes and the absence of unresolved complex mixture (UCM) in the tar-ball samples. The other possibilities are that the tar-balls may have been originated from the Sumatran oil fields and spillage of domestic oil from oil refineries in Port Dickson and Malacca. The results of PAHs analysis suggest that all the tar-ball samples have undergone various extent of weathering through evaporation, dissolution and photo-oxidation.     

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).     

Hydrocarbons in surface sediments from the Changjiang (Yangtze River) Estuary, East China Sea

Sedimentary aliphatic (AH) and polycyclic aromatic hydrocarbons (PAHs) were studied in the Changjiang Estuary and the adjacent East China Sea. Total AH ranged from 2.20 to 11.82 μg g⁻¹ and consisted of n-alkanes and a dominant petroleum-related unresolved complex mixture (UCM). Within the n-alkanes, terrestrial plant wax compounds prevailed at nearly all stations. Of the PAHs, biogenic perylene dominated at stations receiving riverine inputs. Anthropogenic PAHs originating from combustion/pyrolysis processes varied from 17 to 157 ng g⁻¹, while fossil PAH concentrations ranged from 42 to 187 ng g⁻¹. Both biogenic and anthropogenic hydrocarbons are primarily derived from riverine discharges and accumulate at shallow-water stations. Distinct phase associations lead, nevertheless, to different sedimentation patterns. Fossil PAHs are enhanced at offshore stations where they are introduced directly by shipping activities. Biomarker fingerprints ascribe their source to Chinese crude oils. The overall levels of anthropogenic hydrocarbons are low compared to relevant areas worldwide and reveal a low/moderate level of hydrocarbon pollution.     

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.     

Echinoderms and oil pollution: A potential stress assay using bacterial symbionts

Oil pollution is a problem in the North Sea. Important sources of oil pollution are spills and drill cutting. Echinoderms are a major component of the macrobenthos in the North Sea (and elsewhere). They tend to be very sensitive to various types of marine pollution. Many species of echinoderms contain symbiotic sub-cuticular bacteria (SCB). The response of Amphiura filiformis, A. chiajei and Ophiothrix fragilis, all of which contain SCB, to oil pollution was studied in laboratory experiments, mesocosms and in the field. Sublethal stress was monitored by examining changes in the tissue loading of SCB. When subjected to hydrocarbon insult, there was a decline in the number of SCB. The potential use of SCB abundance to detect sublethal stress is discussed.     

Measuring ignitability for in situ burning of oil spills weathered under Arctic conditions: from laboratory studies to large-scale field experiments

This paper compares the ignitability of Troll B crude oil weathered under simulated Arctic conditions (0%, 50% and 90% ice cover). The experiments were performed in different scales at SINTEF’s laboratories in Trondheim, field research station on Svalbard and in broken ice (70-90% ice cover) in the Barents Sea. Samples from the weathering experiments were tested for ignitability using the same laboratory burning cell. The measured ignitability from the experiments in these different scales showed a good agreement for samples with similar weathering. The ice conditions clearly affected the weathering process, and 70% ice or more reduces the weathering and allows a longer time window for in situ burning. The results from the Barents Sea revealed that weathering and ignitability can vary within an oil slick. This field use of the burning cell demonstrated that it can be used as an operational tool to monitor the ignitability of oil spills.     

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 (PAHs) in a large South American industrial coastal area (Santos Estuary, Southeastern Brazil): sources and depositional history

Located in southeastern Brazil, the Santos Estuary has the most important industrial and urban population area of South America. Since the 1950's, increased urbanization and industrialization near the estuary margins has caused the degradation of mangroves and has increased the discharge of sewage and industrial effluents. The main objectives of this work were to determine the concentrations and sources of polycyclic aromatic hydrocarbons (PAHs) in sediment cores in order to investigate the input of these substances in the last 50 years. The PAHs analyses indicated multiple sources of these compounds (oil and pyrolitic origin), basically anthropogenic contributions from biomass, coal and fossil fuels combustion. The distribution of PAHs in the cores was associated with the formation and development of Cubat?o industrial complex and the Santos harbour, waste disposal, world oil crisis and the pollution control program, which results in the decrease of organic pollutants input in this area.     

Composition of in situ burn residue as a function of weathering conditions

Troll B crude oil was weathered under Arctic conditions with different ice coverage: open water, 50% ice and 90% ice. Samples (100 mL) were taken during the experiment and tested for ignitability in a burning cell. From each burning a residue sample was taken for analysis. The burning process removed the light compounds eluting before C13. No effect from the prior weathering time or the different ice coverage was seen in the burn residue composition. The content of selected Poly Aromatic Hydrocarbons (PAHs) was determined and it was noted that the concentration of PAHs with more than 4 rings were increased. The source origin of the PAHs was investigated by use of relative ratios of PAH isomers and indicated that some formation of PAHs was additionally taking place during burning.     

Identification and quantification of mixed sources of oil spills based on distributions and isotope profiles of long-chain n-alkanes

Combined with quantitative determination of concentration and isotopic composition of petroleum hydrocarbons, weathering simulation experiments on artificially mixed oils and their two end-member oils are performed for identification and quantification of mixed sources. The >C₁₈n-alkanes show no appreciable losses during a short-term weathering process. An approach based on distribution of long-chain n-alkanes (>C₁₈) is suggested for estimating the contribution proportion of each source in mixed oils. Stable carbon isotope profile of individual n-alkanes is a powerful tool to differentiate sources of oil spills, but unavailable to accurately allocate each contribution due to a relatively large analytical error.     

Chemical characterization of naturally weathered oil residues in the sediment from Yellow River Delta, China

With its close proximity to Shengli Oilfield, China’s second largest oilfield, the Yellow River Delta is at high risk for crude oil contamination. The massive oil discharge in oilfield may offer a chance for a natural experiment to investigate compositional changes of oil residues and study the stability of source- and weathering-dependent molecular parameters in oil residues after spills. The results demonstrate that the conventional diagnostic ratios, such as C₂₉20S/(20S + 20R), C₂₉/C₃₀H, C₃₀βα/αβ, C₃₁22S/(22S + 22R), C₂-DBTs/C₂-PHENs, C₃-DBTs/C₃-PHENs, DBT/MCHRY, CHRY/PHENs, are also valid for oil source identification even after extensive weathering of spilled oils in terrestrial environment, although some exceptions were encountered for extensively weathered sample. Moreover, the ratios of selected specific biomarkers (the oleanane index, the gammacerane index) have been developed and assessed as source indicators. Finally, we find that some maturity parameters based on alkyl naphthalenes and methyl phenanthrenes in petroleum geochemistry, such as the methylnaphthalene ratios (TMNr, TeMNr, PMNr), the methylphenanthrene ratios (MPI-1, MPDF), can be applied for the source identification and correlation at their lightly to moderately weathered stage.     

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.     

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.     

Effects of an oil spill in the northern Baltic

Oil pollution from the tanker Palva which ran aground in Finnish waters in 1969 provides an example of the hazards of oil spills in cold waters. The Palva incident and its aftermath were studied by Finnish biologists and some of their findings are reported here. The chief casualties were eider ducks, but fortunately long-term effects appear to have been small.     

Tracing anthropogenic contamination in the Pearl River estuarine and marine environment of South China Sea using sterols and other organic molecular markers

5beta-Coprostanol together with eight other sterols and unresolved complex mixtures (UCMs) were quantitatively investigated for surficial sediments and surface waters to assess the impacts of anthropogenic activities on the Pearl River estuarine and marine environment of South China Sea. The studied area extends from the Pearl River Estuary southward to the open sea. 5beta-Coprostanol concentrations ranged from trace amounts to 53 microgg(-1) TOC in surficial sediments. The highest levels and highest percentages of coprostanol were found in the Pearl River estuary, especially in the inner estuary and those sites close to the submarine outfalls of Hong Kong. For waters, only in estuarine samples was coprostanol quantitatively detected, ranging from 11 to 299 ngL(-1). Bimodal UCM "humps" were observed for most sediment samples, with concentrations ranging from 215 to 10,491 microg g(-1) TOC in sediments and from 2 to 26 mcirogL(-1) in waters, respectively. Progressive seaward declines in concentrations were found for both 5beta-coprostanol and UCM in surficial sediments. Trace or no 5beta-coprostanol was found in open-sea samples. Concentrations of coprostanol and UCM in surficial sediments are correlated. These results imply that there are obvious anthropogenic contaminations in the Pearl River estuary. The submarine outfalls in Hong Kong represent important sources of the sewage pollution to the Pearl River estuarine sediments evidenced by a combination of coprostanol concentration, diagnostic indices, sterol profiles and UCM. No obvious dispersion or transport of the sewage contamination occurred from the Pearl River estuary to the open South China Sea indicated by fecal sterol biomarkers.     

Enrichment and partitioning of polycyclic aromatic hydrocarbons in the sea surface microlayer and subsurface water along the coast of Xiamen Island,China

Sea microlayer (SML) and subsurface water (SSW) samples were collected around Xiamen Island to study the enrichment and partitioning of polycyclic aromatic hydrocarbons (PAHs). Total PAH concentrations ranged from 93.43 to 411.05 ng L⁻¹ in the SML and 49.29–279.42 ng L⁻¹ in the SSW. Compared with the results of previous studies before pollution control measurements, PAHs levels decreased significantly. The enrichment factors (EFs) of dissolved and particulate PAHs varied from 0.68 to 2.71 and 0.43–3.56. EFs showed the consistent enrichment trends with sites and exhibited different enrichment characteristics between 2 and 3 ring PAHs and 4 ring PAHs. Furthermore, the much higher concentrations of BaP (strong carcinogenicity) were accompanied by higher EFs in the SML samples from the Western Xiamen Harbour, which together indicated the risk of impacts to the fish eggs that usually float on the SML water after exposure to oil spills and combustion, contributed directly by the port and shipping activities.     

Survival and movements of Magellanic penguins rehabilitated from oil fouling along the coast of South America, 2000-2010

Oil pollution is a significant conservation concern. We examined data from six institutions along the coast of South America: Emergency Relief Team of the International Fund for Animal Welfare, Fundación Mundo Marino, Centro de Recupera??o de Animais Marinhos, Natura Patagonia, Associa??o R3 Animal, and Mar del Plata Aquarium and data from resightings in Argentina, Brazil, Chile and Falkland/Malvinas Islands. From 2000 to 2010, 2183 oiled Magellanic penguins were rehabilitated as part of the routine activities of these institutions or during emergency responses to eight oil spills in which they were involved; all rehabilitated penguins were flipper banded and released. Since their release, 41 penguins were resighted until 31 December 2011. The results demonstrate that, when combined with other prevention strategies, the rehabilitation of Magellanic penguins is a strategy that contributes to the mitigation of adverse effects of oil spills and chronic pollution to the species.     

Use of aliphatic hydrocarbons to infer terrestrial organic matter in coastal marine sediments off China

Sediment samples from the marine systems along the coast of China, covering Yellow Sea, inner shelf of the East China Sea (ECS) and the South China Sea (SCS), were analyzed for n-alkanes and organic carbon. The concentrations of Σn-C(15-35) were 120-1680ngg(-1) dry weight with an average of 560ngg(-1). Short-chain n-alkanes (C(21)) were mainly derived from terrestrial higher plants. Organic carbon deposited into Yellow Sea and Southeast Hainan within the SCS was mainly of terrestrial (13-110%; mean: 58%) and marine (48-110%; mean: 86%) sources, respectively. On the other hand, organic carbon accumulated in the SCS adjacent to the Pearl River Estuary was derived from both terrestrial and marine sources.     

Characteristic of oil pollution of the Sea of Azov and regularities in its dynamics

Oil pollution of water and bottom sediments (BS) of the Sea of Azov is characterized by using the results of studies carried out in different seasons of 1985–2005. Regularities in the dynamics of oil pollution are discussed and correlated with the stages in changes in the country’s economy.     

Carbon pools and fluxes in the China Seas and adjacent oceans

The China Seas include the South China Sea, East China Sea, Yellow Sea, and Bohai Sea. Located off the Northwestern Pacific margin, covering 4700000 km~2 from tropical to northern temperate zones, and including a variety of continental margins/basins and depths, the China Seas provide typical cases for carbon budget studies. The South China Sea being a deep basin and part of the Western Pacific Warm Pool is characterized by oceanic features; the East China Sea with a wide continental shelf, enormous terrestrial discharges and open margins to the West Pacific, is featured by strong cross-shelf materials transport; the Yellow Sea is featured by the confluence of cold and warm waters; and the Bohai Sea is a shallow semiclosed gulf with strong impacts of human activities. Three large rivers, the Yangtze River, Yellow River, and Pearl River, flow into the East China Sea, the Bohai Sea, and the South China Sea, respectively. The Kuroshio Current at the outer margin of the Chinese continental shelf is one of the two major western boundary currents of the world oceans and its strength and position directly affect the regional climate of China. These characteristics make the China Seas a typical case of marginal seas to study carbon storage and fluxes. This paper systematically analyzes the literature data on the carbon pools and fluxes of the Bohai Sea,Yellow Sea, East China Sea, and South China Sea, including different interfaces(land-sea, sea-air, sediment-water, and marginal sea-open ocean) and different ecosystems(mangroves, wetland, seagrass beds, macroalgae mariculture, coral reefs, euphotic zones, and water column). Among the four seas, the Bohai Sea and South China Sea are acting as CO_2 sources, releasing about0.22 and 13.86–33.60 Tg C yr~(-1) into the atmosphere, respectively, whereas the Yellow Sea and East China Sea are acting as carbon sinks, absorbing about 1.15 and 6.92–23.30 Tg C yr~(-1) of atmospheric CO_2, respectively. Overall, if only the CO_2 exchange at the sea-air interface is considered, the Chinese marginal seas appear to be a source of atmospheric CO_2, with a net release of 6.01–9.33 Tg C yr~(-1), mainly from the inputs of rivers and adjacent oceans. The riverine dissolved inorganic carbon (DIC) input into the Bohai Sea and Yellow Sea, East China Sea, and South China Sea are 5.04, 14.60, and 40.14 Tg C yr~(-1),respectively. The DIC input from adjacent oceans is as high as 144.81 Tg C yr~(-1), significantly exceeding the carbon released from the seas to the atmosphere. In terms of output, the depositional fluxes of organic carbon in the Bohai Sea, Yellow Sea, East China Sea, and South China Sea are 2.00, 3.60, 7.40, and 5.92 Tg C yr~(-1), respectively. The fluxes of organic carbon from the East China Sea and South China Sea to the adjacent oceans are 15.25–36.70 and 43.93 Tg C yr~(-1), respectively. The annual carbon storage of mangroves, wetlands, and seagrass in Chinese coastal waters is 0.36–1.75 Tg C yr~(-1), with a dissolved organic carbon(DOC) output from seagrass beds of up to 0.59 Tg C yr~(-1). Removable organic carbon flux by Chinese macroalgae mariculture account for 0.68 Tg C yr~(-1) and the associated POC depositional and DOC releasing fluxes are 0.14 and 0.82 Tg C yr~(-1), respectively. Thus, in total, the annual output of organic carbon, which is mainly DOC, in the China Seas is 81.72–104.56 Tg C yr~(-1). The DOC efflux from the East China Sea to the adjacent oceans is 15.00–35.00 Tg C yr~(-1). The DOC efflux from the South China Sea is 31.39 Tg C yr~(-1). Although the marginal China Seas seem to be a source of atmospheric CO_2 based on the CO_2 flux at the sea-air interface, the combined effects of the riverine input in the area, oceanic input, depositional export,and microbial carbon pump(DOC conversion and output) indicate that the China Seas represent an important carbon storage area.