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.     

Levels and spatial distribution of polycyclic aromatic hydrocarbons (PAHs) in sediments from Lenga Estuary, central Chile

The Lenga Estuary is a small brackish wetland located southwest of San Vicente Bay, Region VIII, Chile. Surface sediment from nine sites in the estuary were analysed for PAHs and compared to Sediment Quality Guidelines (SQG). Sediment samples were freeze dried and soxhlet extracted for 16 h using DCM. Identification and quantification was carried out by HPLC. Organic carbon was also determined. Results showed total PAH concentrations ranged from 290 to 6118 (2025 ± 1975) ng g⁻¹ d.w. (2025 ± 1975). Results for organic carbon percentages ranged from 1% to 7%. Statistical analysis showed a significant positive correlation (Pearson test) between organic carbon percentage PAHs. Comparison of contaminant levels and international Sediment Quality Guidelines (SQG) (ERL and ER) suggested that sediment of the Lenga estuary did not show any ecotoxicologial risk for benthic organisms where high levels of PAHs were detected. Monitoring of this and other contaminants is recommended in Chile.     

巢湖表层沉积物中多环芳烃分布特征及来源

于2010年,采用野外采样调查、色谱分析与统计比较的方法,研究巢湖表层沉积物中27个采样点中多环芳烃(PAHs)分布特征及污染来源.结果表明:巢湖表层沉积物中检测出的14种优控PAHs总浓度为116.0~2832.2 ng/g(DW),平均值为898.9±791.0 ng/g(DW).多环芳烃组成主要以5~6环PAHs为主,占总量的32%~58%.沉积物中总有机碳含量与PAHs总量呈现良好相关性.利用蒽/(蒽+菲)与苯并[a]蒽/(苯并[a]蒽+屈)比值法对PAHs来源进行解析得出,巢湖表层沉积物中PAHs主要来源为燃烧源.与国内其它水体PAHs含量对比表明,巢湖沉积物中PAHs污染处于中等水平.生态风险评估得出南淝河表层沉积物中PAHs存在生态风险,其它采样点表层沉积物中PAHs生态风险均较低.     

Biological risk and pollution history of polycyclic aromatic hydrocarbons (PAHs) in Nansha mangrove,South China

Chinese government has taken various measures to alleviate pollution caused by polycyclic aromatic hydrocarbons (PAHs) in the region of Pearl River Delta since the economic reform in 1978, but the effectiveness of these measures remains largely unknown. This study aimed to elucidate the biological risk and pollution history of PAHs by measuring the concentrations of 28 PAHs in the surface and core sediments, respectively, in Nansha mangrove. Results found that the biological risk of PAHs was low without obvious spatial variation. The PAH concentration along the depth gradient indicated that PAH pollution was stabilized since the early 1990s while the source of PAHs has gradually changed from combustion of coal to petroleum products. This implied that the mitigation measures taken by the Chinese government were effective. Compared to marine bottom sediment, we propose that using mangrove sediment can provide a more accurate and precise estimate of pollution history of PAHs.     

Contamination of polycyclic aromatic hydrocarbons (PAHs) in surface sediments and plants of mangrove swamps in Shenzhen,China

The concentrations of 16 individual and total polycyclic aromatic hydrocarbons (∑PAHs) in sediments, roots and leaves of three mangrove swamps in Shenzhen, China, namely Futian, Baguang and Waterlands, were determined. The mean concentration of ∑PAHs in Futian (4480 ng g⁻¹) was significantly higher than that in Baguang (1262 ng g⁻¹) and Waterlands (2711 ng g⁻¹). Among the 16 PAHs, the concentration of naphthalene was the highest. Based on the ratios of phenanthrene/anthracene and fluoranthene/pyrene, PAHs in Futian and Waterlands came from petrogenic and pyrolytic sources, while Baguang was mainly from pyrolytic. More PAHs were accumulated in leaves, as reflected by its higher mean concentration of ∑PAHs (3697 ng g⁻¹) and bioconcentration factor of PAHs (BCF) (>1.5) than that in roots. The BCF values in plants collected from Futian were significantly higher than that from Waterlands. These results indicated that more attention should be paid to the PAH contamination in Futian.     

乌兹别克斯坦阿姆河流域水体中多环芳烃的分布、来源及风险评估

为研究乌兹别克斯坦境内阿姆河地区水体中多环芳烃（PAHs）污染特征、来源并进行风险评估,采用高效液相色谱二极管阵列检测器串联荧光检测器法,对研究区域50个采样点中16种优先控制的多环芳烃进行了检测分析.结果表明,阿姆河地区水体中多环芳烃总浓度范围为3.19~779 ng/L,平均值为98.4 ng/L,中位值为40.1 ng/L,单体浓度范围为0~333 ng/L,检出浓度最高的单体为苊烯,5种单体芴、蒽、荧蒽、芘和的检出率为100%,单体苯并[b]荧蒽的检出总量最高,水样中总浓度为786 ng/L,平均值为15.7 ng/L,中值为2.79 ng/L.不同水体含中低环多环芳烃（2~4环）与高环多环芳烃（5~6环）总浓度相近,但不同采样点间浓度差异较大.浓度较高的采样点主要集中在阿姆河三角洲的城市、农业灌溉区及近咸海区域.与世界不同研究区域相比,阿姆河流域多环芳烃浓度处于中等水平.采用相对丰度法、同分异构体比值法及正定矩阵分解法相结合进行源解析,表明研究区域水体中多环芳烃多为混合来源,其中阿姆河下游河段水体多环芳烃主要来源于生物质燃烧,而阿姆河三角洲区域主要来源于生物质燃烧、石油、天燃气燃烧及汽车尾气排放.生态风险评估结果显示,研究区水体单体多环芳烃中萘、苊、菲和蒽的生态风险较低,其余单体处于中等风险等级,其中苯并[b]荧蒽的污染程度较为严重;总体上阿姆河流域ΣPAHs风险等级相对较低,但仍有12和8个点位分别处于中等风险2和高风险等级,且主要集中在阿姆河三角洲地区,需采取相应措施加以控制.     

Levels and spatial distribution of polycyclic aromatic hydrocarbons (PAHs) in superficial sediment from 15 Italian marine protected areas (MPA)

Surface sediment from 15 Italian marine protected areas (MPA) were analysed for polycyclic aromatic hydrocarbons (PAHs). The organic carbon percentage was also determined. Total PAH concentrations (ng g⁻¹ d.w.) ranged from 0.71 (Penisola del Sinis) to 1550 (Miramare). Individual PAH analysis showed that three and four rings PAHs were the most frequently detected isomers and accounted for 60-70% of the PAH total concentrations. PAH ratio analysis showed a prevalence of pyrolytic PAH origin at most of the MPAs with exception of Porto Cesareo and Ustica where a petrogenic origin was detected. Results for organic carbon percentages ranged from 0.3% (Capo Rizzuto) to 2% (Punta Campanella). These results are comparable to other Mediterranean marine environments. However, our results shows that some MPAs, such as Miramare, Porto Cesareo, Isola Capo Rizzuto and Punta Campanella, are subject to strong pressure from urban and industrial activities where high PAH levels were detected.     

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.     

Occurrence of polycyclic aromatic hydrocarbons (PAHs) in seawater from the Western Taiwan Strait,China

Seawater samples (including surface water and bottom water) were collected from the Western Taiwan Strait (WTS) during June 24–25, 2009; polycyclic aromatic hydrocarbons (PAHs) in dissolved phase and particulate phase were analyzed, respectively. The results showed that the total concentrations of PAHs in the dissolved phase and particulate phase were ranged from 12.3 to 58.0 ng L⁻¹, and 10.3–45.5 ng L⁻¹, which showed a low-middle contamination level in the China Seas. The spatial variability of PAHs may be related to the complicated currents of WTS, especially the Min-Zhe coastal current. PAHs diagnostic ratios suggested that PAHs mainly originated from the inputs of pyrolytic (combustion) sources, which might be contributed to land-based atmospheric deposition. The particle-water partition coefficients of individual PAH showed that partitions were not correlated with suspended particulate matter content, dissolved organic carbon or salinity, similar to the Yangtze coastal area.     

Occurrence of polycyclic aromatic hydrocarbons (PAHs) in seawater from the Western Taiwan Strait, China

Seawater samples (including surface water and bottom water) were collected from the Western Taiwan Strait (WTS) during June 24-25, 2009; polycyclic aromatic hydrocarbons (PAHs) in dissolved phase and particulate phase were analyzed, respectively. The results showed that the total concentrations of PAHs in the dissolved phase and particulate phase were ranged from 12.3 to 58.0 ng L(-1), and 10.3-45.5 ng L(-1), which showed a low-middle contamination level in the China Seas. The spatial variability of PAHs may be related to the complicated currents of WTS, especially the Min-Zhe coastal current. PAHs diagnostic ratios suggested that PAHs mainly originated from the inputs of pyrolytic (combustion) sources, which might be contributed to land-based atmospheric deposition. The particle-water partition coefficients of individual PAH showed that partitions were not correlated with suspended particulate matter content, dissolved organic carbon or salinity, similar to the Yangtze coastal area.     

Combined effects of land reclamation,channel dredging upon the bioavailable concentration of polycyclic aromatic hydrocarbons (PAHs) in Victoria Harbour sediment,Hong Kong

The up-to-date concentration of polycyclic aromatic hydrocarbons (PAHs) in sediment materials of Victoria Harbour was investigated so as to evaluate the pollution potential associated with the reclamation projects in Hong Kong. A total of 100 sediment samples were collected at 20 locations. Except the control point in reservoir, the PAHs concentrations were detectable levels all sites (131–628.3 ng/g, dw) and such values were higher than Dutch Target and Intervention Values (the New Dutch standard in 2016). The PAHs concentration indicating that construction waste and wastewater discharges were the main pollutant sources. Results of correlation in single cell gel electrophoresis assay (comet assay) studies also revealed that the PAHs concentration was highly correlated (< 0.01) with DNA migration (i.e. the length of tail moment of fish cells) in 5 mg/ml of PAHs. The above observation indicates that the PAHs present in the sediment may substantially effect the marine ecosystem. Although the dredged sediment can be a useful sea-filling material for land reclamation; however, the continuing leaching of PAHs and its impact on the aquatic environment need to be studied further.     

Concentrations of PAHs (polycyclic aromatic hydrocarbons) in various marine organisms in relation to those in sediments and to trophic level

Sediments and marine organisms such as mussels (Mytilus galloprovincialis), fish (Mullus barbatus, Serranus scriba), crabs (Polybius henslowi) and shrimp-like crustaceans (mysids, euphausiids) were sampled on European coasts, France, Spain) and analysed for their PAH content by gas chromatography/mass spectrometry (GC-MS). The PAH concentrations determined in the organisms were significantly negatively correlated with logK_ow values, but to different extents according to the species. This was explained by the greater exposure of the organisms to the lower molecular weight compounds with differences resulting from different feeding habits, habitat, and biotransformation capacities of the organisms in relation to trophic levels. The influence of these observations on the use of different sentinel species in biomonitoring programmes is discussed.     

Temporal changes in Sphingomonas and Mycobacterium populations in mangrove sediments contaminated with different concentrations of polycyclic aromatic hydrocarbons (PAHs)

The change in community diversity and structure of the indigenous, dominant, polycyclic aromatic hydrocarbon (PAH)-degrading bacterial genera, Sphingomonas and Mycobacterium, due to contamination in the environment is not very well known. A combination of PCR-DGGE with specific primers and a cultivation-dependent microbiological method was used to detect different populations of Sphingomonas and Mycobacterium in mangrove sediments. The structure of the entire bacterial community (including Sphingomonas) did not show a shift due to environmental contamination, whereas the diversity of Mycobacterium populations in mangrove sediments with higher PAH contamination increased from exposure between Day 0 and Day 30. The isolated Mycobacterium strains migrated to the same position as the major bands of the bacterial communities in Mycobacterium-specific DGGE. A dioxygenase gene system, nidA, which is commonly found in PAH-degrading Mycobacterium strains, was also detected in the more highly contaminated sediment slurries. The present study revealed that Mycobacterium species were the dominant PAH-degraders and played an important role in degrading PAHs in contaminated mangrove sediments.     

Human health risk of polycyclic aromatic hydrocarbons from consumption of blood cockle and exposure to contaminated sediments and water along the Klang Strait,Malaysia

The concentration of carcinogenic poly aromatic hydrocarbons (c-PAHs) present in water and sediment of Klang Strait as well as in the edible tissue of blood cockle (Anadara granosa) was investigated.The human health risk of c-PAHs was assessed in accordance with the standards of the United States Environmental Protection Agency (US EPA). The cancer risks of c-PAHs to human are expected to occur through the consumption of blood cockles or via gastrointestinal exposure to polluted sediments and water in Kalng Strait. The non-carcinogenic risks that are associated with multiple pathways based on ingestion rate and contact rates with water were higher than the US EPA safe level at almost all stations, but the non-carcinogenic risks for eating blood cockle was below the level of US EPA concern. A high correlation between concentrations of c-PAHs in different matrices showed that the bioaccumulation of c-PAHs by blood cockles could be regarded as a potential health hazard for the consumers.     

Natural attenuation, biostimulation and bioaugmentation on biodegradation of polycyclic aromatic hydrocarbons (PAHs) in mangrove sediments

The biodegradability of a mixture of PAHs, namely fluorene (Fl), phenanthrene (Phe) and pyrene (Pyr), in mangrove sediment slurry was investigated. At the end of week 4, natural attenuation based on the presence of autochthonous microorganisms degraded more than 99% Fl and Phe but only around 30% of Pyr were degraded. Biostimulation with addition of mineral salt medium degraded over 97% of all three PAHs, showing that nutrient amendment could enhance Pyr degradation. Bioaugmentation with inoculation of a PAH-degrading bacterial consortium enriched from mangrove sediments did not show any promotion effect and the degradation percentages of three PAHs were similar to that by natural attenuation. Some inhibitory effect was observed in bioaugmentation treatment in week 1 with only 50% Fl and 70% Phe degraded. These results indicate that autochthonous microbes may interact and even compete with the enriched consortium during PAH biodegradation. Natural attenuation appeared to be the most appropriate way to remedy Fl- and Phe-contaminated mangrove sediments while biostimulation was more capable to degrade Pyr-contaminated sediments. The study also shows that although a large portion of the added PAHs (more than 95%) was adsorbed onto the sediments at the beginning of the experiment, most PAHs were degraded in 4 weeks, suggesting that the degraders could utilize the adsorbed PAHs efficiently.     

Distribution and sources of polycyclic aromatic hydrocarbons (PAHs) in sediments from Zhanjiang Bay and Leizhou Bay, South China

The concentrations and spatial distribution of polycyclic aromatic hydrocarbons have been investigated in two adjacent bays of Zhanjiang and Leizhou, China. The total concentrations of the 16 USEPA priority PAHs were ranged from 41.96 to 933.90ng/g dry weight with an average concentration of 315.98ng/g and ranged from 21.72 to 319.61ng/g with an average concentration of 103.91ng/g in Zhanjiang and Leizhou Bays, respectively. The spatial distribution of PAHs was site-specific and appeared to be somewhat positively correlated with TOC and negatively correlated with sediment grain size in the two bays. The values of Phe/Ant, BaA/228 and InP/276 were higher than 10, less than 0.2, and from 0.2 to 0.5, respectively, indicating that the sources of PAHs in the two bays were mainly from petroleum and its combustion, which predominantly originated from those ships and boats coming and going in the two bays.     

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.     

Atmospheric concentrations of polycyclic aromatic hydrocarbons (PAHs) in an urban traffic site in Erzurum,Turkey

This study presents daily and seasonal variations of PAH concentrations in Erzurum atmosphere in summer season of 2008 and in winter seasons of 2008 and 2009. Sampling location at Erzurum urban center was selected to represent the effects of traffic (University junction). 18 PAH compounds were analyzed by GC–MS. Average total PAH concentration (gas + particulate) of 18 PAH compounds were measured during 2008 winter (431 ngm^?3) and summer (103 ngm^?3) seasons at the University junction. Daily and seasonal variations of PAH compounds were investigated and compared with other urban centers in the literature. Multiple linear regression and artificial neural network (ANN) models were constructed to determine the impacts of meteorological parameters on measured individual PAH concentrations. Results of the multiple linear regression and ANN models indicated that wind speed, wind direction and intensity of total solar radiation were the most significant factors for the measured concentrations of PAH compounds.     

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).     

Nature, distribution and origin of polycyclic aromatic hydrocarbons (PAHs) in the sediments of Olbia harbor (Northern Sardinia, Italy)

The nature, origin and distribution of US EPA polycyclic aromatic hydrocarbons (PAHs) in the sediments of Olbia harbor (North Sardinia, Italy) were investigated by gas-chromatography/mass spectrometry (GCMS). PAH concentrations in the sediments (SigmaPAHs) ranged from 0.16 to 0.77 microg g(-1), indicating a homogeneously low level of pollution. A rather exceptional prevalence of low molecular weight PAHs was substantiated: nearly 80% of SigmaPAHs include naphthalene (15.19%) and phenanthrene (64.47%). Carcinogenic compounds were present in very low (BaP, BkF, BaA and DBA) or negligible (BbF and Inp) concentrations. As indicated by the Phen/Ant molar ratio, the main source of PAHs is petrogenic, probably due to oil spills from shipping. The low/high molecular weight ratio (ranging between 1.2 and 26) distinguishes the sediments of the tourist harbor from those of the commercial/industrial harbor. Moreover, a slight but meaningful pyrolytic contribution to pollution was found in the tourist harbor, which has the most polluted sediments in the whole harbor. Finally, good linear correlations were found between a selected PAH (Phen and Naph) and selected sums of PAHs (i.e. the total amount of the other 15 US EPA and the sum of low molecular weight PAHs).