Hydrocarbons in bivalve mollusks of Port Valdez, Alaska: Consequences of five years' permitted discharge

Petroleum hydrocarbons were investigated in Mytilus edulis and Macoma balthica at six intertidal sites in Port Valdez, Alaska after three to five years of oil terminal operation. Information about the concentrations of total hydrocarbons, unresolved complex mixture, normal alkanes, isoprenoids, olefins, hopanes and polycyclic aromatic hyrocarbons shows that petroleum accumulation in these bivalve mollusks is greatest at the Valdez municipal boat harbor and a crude oil terminal which has been permitted to discharge 170 kg oil day⁻¹. Accumulation two- to ten-fold less were observed at 3 km from the terminal and boat harbor. The temporal trends in petroleum hydrocarbon concentrations in M. edulis and M. balthica reflect the effects of selective retention and depuration of different hydrocarbon classes as well as variation in hydrocarbon sources. It is not clear whether the petroleum concentrations in Port Valdez bivalves had reached steady state by 1982, the final sampling time reported here.     

Petroleum hydrocarbons in sediments of Southampton water estuary

The sediments of Southampton Water were analysed for petroleum hydrocarbons to determine the fate of petrochemical refinery waste in the estuary. Much of the petroleum hydrocarbons appears to be removed by adsorption onto estuarine sediments close to source. Surface sediment concentrations range from 3·1mg/g dry weight near a refinery to 0·5 mg/g dry weight at locations distant from the refinery.The absence of any change with depth in total hydrocarbon concentrations from some sediment cores and the presence of distinct ‘oil’ horizons in others suggests that mixing of sediments in the area is very random. Sedimentation rates in areas where a distinct oil horizon was observed ranged from 1 to 3cm a year.     

The effects of oil exploration and production in the northern North Sea: Part 2—microbial biodegradation of hydrocarbons in water and sediments, 1978–1981

The potential of heterotrophs to degrade aromatic hydrocarbons derived from oil in water and sediments in the northern North Sea around the Brent, Beryl, Forties and Murchison oilfields and at a number of stations, from the Forties field to the Firth of Forth, was estimated using 1-¹⁴C naphthalene and 7, 10-¹⁴C benzo(a)pyrene. The degradation of uniformly labelled ¹⁴C mixed 1-amino acids was used as a measure of total heterotrophic activity. Results showed that microorganisms have the potential to degrade the smaller aromatic hydrocarbon molecules rapidly in the water column and in surface sediments. Close to the Beryl platform, where diesel-washed drill cuttings have been continuously dumped, the rate of input of hydrocarbons to the sediment has exceeded the rate of degradation. Mineralization of benzo(a)pyrene, estimated in the sediments only, was minimal. Close to production platforms the biodegradation rate of mixed 1-amino acids showed no increase comparable with that found for naphthalene, suggesting that existing microbial populations had not increased but adapted to degrade oil in water and sediments.     

Persistence of oiling in mussel beds after the Exxon Valdez oil spill

Persistence and weathering of Exxon Valdez oil in intertidal mussel (Mytilus trossulus) beds in Prince William Sound (PWS) and along the Gulf of Alaska was monitored from 1992 to 1995. Beds with significant contamination included most previously oiled areas in PWS, particularly within the Knight Island group and the Kenai Peninsula. In sediments, yearly mean concentrations of total petroleum hydrocarbons ranged from < 60 micrograms/g in reference beds to 62,258 micrograms/g wet wt., or approximately 0 to 523 micrograms/g dry wt. total polynuclear aromatic hydrocarbons (TPAHs). In mussels, mean TPAH concentrations ranged up to 8.1 micrograms/g dry wt. Hydrocarbon concentrations declined significantly with time in some, but not all mussels and sediments, and should reach background levels within three decades of the spill in most beds. In 1995, mean hydrocarbon concentration was greater than twice background concentration in sediments from 27 of 34 sites, and in mussels from 18 of 31 sites.     

Exposure to hydrocarbons 10 years after the Exxon Valdez oil spill: evidence from cytochrome P4501A expression and biliary FACs in nearshore demersal fishes

Three biomarkers of hydrocarbon exposure, CYP1A in liver vascular endothelium, liver ethoxyresorufin O-deethylase (EROD), and biliary fluorescent aromatic compounds (FACs), were examined in the nearshore fishes, masked greenling (Hexagrammos octogrammus) and crescent gunnel (Pholis laeta), collected in Prince William Sound, Alaska, 7-10 years after the Exxon Valdez oil spill (EVOS). All biomarkers were elevated in fish collected from sites originally oiled, in comparison to fish from unoiled sites. In 1998, endothelial CYP1A in masked greenling from sites that were heavily oiled in 1989 was significantly higher than in fish collected outside the spill trajectory. In 1999, fishes collected from sites adjacent to intertidal mussel beds containing lingering Exxon Valdez oil had elevated endothelial CYP1A and EROD, and high concentrations of biliary FACs. Fishes from sites near unoiled mussel beds, but within the original spill trajectory, also showed evidence of hydrocarbon exposure, although there were no correlations between sediment petroleum hydrocarbon and any of the biomarkers. Our data show that 10 years after the spill, nearshore fishes within the original spill zone were still exposed to residual EVOS hydrocarbons.     

Incorporation,distribution and fate of saturated petroleum hydrocarbons in sediments from a controlled marine ecosystem

A simulation of a chronic input of petroleum into an estuarine environment was investigated using the facilities at the Marine Ecosystems Research Laboratory at the University of Rhode Island. An oil-water dispersion of No. 2 fuel oil was added to the system (twice weekly for 24 weeks) and the saturated hydrocarbons from this oil were measured in suspended material and sediments. After the initial chronic oil addition, trace amounts of hydrocarbons were detected in the sediments within two weeks, but substantial accumulation was not detected for approximately 135 days. The oil appeared to enter the sediment via the suspended material, with most of the saturated hydrocarbons associated with smaller size sediment particles (< 45 μm to > 0·3 μm). With time, the fuel oil saturated hydrocarbons in the sediments were mixed to a depth of 3 to 4 cm. Although only 12% of the total saturated hydrocarbons added to the system were found in the sediments, these hydrocarbons appear to be relatively stable and were still detectable in these sediments for at least six months after the last oil addition.     

潮间带沉积物厌氧烃降解细菌的多样性及Desulfovibrio subterraneus ND17的分离鉴定

潮间带作为海陆交界处,易受到来自海洋的石油污染,且各类石油烃进入沉积物后的降解过程尚不清楚。前人在各类生境中对好氧微生物烃降解方面已有较多研究,但对近海潮间带环境中的厌氧烃降解鲜有报道。本研究对青岛女岛湾潮间带沉积物深层样品以混合烃（中长链烷烃、多环芳烃）为碳源,硫酸盐作为电子受体进行厌氧富集培养。富集菌群的细菌多样性表明在混合烃作为碳源的作用下,优势菌群转变为脱硫叠球菌科（Desulfosarcinaceae）、脱硫杆菌科（Desulfobacteraceae）等具有石油烃降解潜力的硫酸盐还原菌。经分离纯化得到一株厌氧烃降解菌ND17,与地下脱硫弧菌属模式种Desulfovibrio subterraneus HN2T 16S rRNA基因序列的相似度为99.93%。进一步实验表明,菌株ND17在厌氧条件下对二十四烷和菲的降解率可分别达到53.9%和35.7%。这也是首次对脱硫弧菌属单菌在厌氧条件下进行石油烃降解的研究。脱硫弧菌作为一种广泛分布在厌氧环境的细菌,本研究为进一步认识其在海洋石油污染环境中的修复潜力提供了支撑。     

The effects of oil exploration and production in the northern north sea: Part 1–The levels of hydrocarbons in water and sediments in selected areas, 1978–1981

In the light of increasing oil exploration and production in the northern North Sea, the Brent, Beryl and Forties oil fields, representing three different types of operation, and a number of stations between the Forties field and the Firth of Forth, were sampled to determine the levels of total (by fluorescence), alkane (by glass capillary gas chromatography) and aromatic (by gas chromatography-mass spectrometry) hydrocarbons in water and sediments. Close to the Beryl platform, where diesel-washed drill cuttings have been dumped, there was an accumulation of petrogenic hydrocarbons in the sediment, resulting in a build up of certain aryl hydrocarbons, notably the dibenzthiophenes and 3- and 4-ring aromatic compounds. In all the sediment samples analysed for aromatic hydrocarbons, relatively large amounts of 5- and 6-ring compounds were found in areas expected to be free of pollution, as well as from areas around oil platforms and from the Firth of Forth. Their source is likely to be windborne combustion products.     

The composition and distribution of saturated and aromatic hydrocarbons in nearshore sediments, river sediments, and coastal peat of the Alaskan Beaufort Sea: Implications for detecting anthropogenic hydrocarbon inputs

A 3-year program, to determine spatial and temporal trends in sediment concentrations of hydrocarbons and metals from oil and gas exploration and development activities, was conducted in the US Beaufort Sea. Concentrations of saturated and aromatic hydrocarbons in sediments from the Beaufort Sea were elevated in comparison to non-polluted shelf-sediments from other regions of the US coast. Potential natural sources for hydrocarbons that were examined included riverine sediments and coastal peat. Significant quantities of fossil hydrocarbons characterize the surface sediments from the entire region. Sediment inputs from river discharges appear to account for this observation. The use of source-diagnostic ratios has allowed the differentiation of various sources in an area with high naturally-occurring hydrocarbon concentrations where effects due to oil and gas exploration and development activities may be obscured.     

Retrospective analysis: bile hydrocarbons and histopathology of demersal rockfish in Prince William Sound,Alaska, after the Exxon Valdez oil spill

Demersal rockfish are the only fish species that have been found dead in significant numbers after major oil spills, but the link between oil exposure and effect has not been well established. After the 1989 Exxon Valdez oil spill in Prince William Sound, Alaska, several species of rockfish (Sebastes spp.) from oiled and reference sites were analyzed for hydrocarbon metabolites in bile (1989-1991) and for microscopic lesions (1990 and 1991). Biliary hydrocarbons consistent with exposure to Exxon Valdez oil were elevated in 1989, but not in 1990 or 1991. Significant microscopic findings included pigmented macrophage aggregates and hepatic megalocytosis, fibrosis, and lipid accumulation. Site differences in microscopic findings were significant with respect to previous oil exposure in 1991 (P=0.038), but not in 1990. However, differences in microscopic findings were highly significant with respect to age and species in both years (P<0.001). We conclude that demersal rockfish were exposed to Exxon Valdez oil in 1989, but differences in microscopic changes in 1990 and 1991 were related more to age and species differences than to previous oil exposure.     

渤海石油污染:来自表层沉积物中生物标志物的证据

通过对渤海表层沉积物中饱和烃的分布、来源和分子组成特征的系统分析,探讨了沉积物中生物标志物对石油污染的指示意义。研究表明,沉积物中色谱不可分辨的混合物(UCM)和正构烷烃的分布及组成特征显示出沉积物不同程度地受到了石油烃输入和细菌微生物作用的影响,其中以渤海湾沿岸区域最为明显。渤海湾近岸区和黄河口附近沉积物中正构烷烃平均碳链长度(ACL)低于其他地区,姥鲛烷/植烷(Pr/Ph)也普遍低于1.0,表明可能受到来自于石油平台开采活动、船舶航行、河流输入的石油烃的影响。C₂₇-18α(H)-三降藿烷(Ts)与C₂₇-17α(H)-三降藿烷(Tm)的比值(Ts/Tm)、C₃₁升藿烷22S/(22S+22R)和αααC₂₉甾烷20S/(20S+20R)的比值表明该区域沉积物中有机质成熟度较高,可能受到外来石油烃输入及其衍生物的影响。通过与周边环境中生物标志物分子组成特征的对比发现,沉积物中甾烷和萜类化合物主要来源于石油及其衍生物。将饱和烃各参数进行归一化处理,得到了石油污染的综合替代性指标,并初步圈定了石油污染相对较重的区域。     

Assessment of Aliphatic and Polycyclic Aromatic Hydrocarbons and Trace Elements in Coastal Sediments of the Saronikos Gulf,Greece (Eastern Mediterranean)

Surface sediments from the Saronikos Gulf were analyzed for their aliphatic hydrocarbon (AHC) and polycyclic aromatic hydrocarbon (PAH) content by gas chromatography – mass spectrometry (GC/MS). The concentrations of Fe, Cr, As, Sb, Co and Sc were also determined by neutron activation analysis (NAA). The survey was performed at the beginning of the operation of Athens’ sewage primary treatment unit and the results can be used to monitor the unit's long-term effects in the area. The composition of aliphatic hydrocarbons indicated a chronic oil-pollution in the Saronikos Gulf sediments. The industrially impacted Elefsis Bay sediments suffered from heavy petroleum pollution, while the sediments near the sewage outfall had a moderate degree of pollution. Mixed source patterns of polycyclic aromatic hydrocarbons with dominant pyrolytic inputs have been identified in the sediments. Total concentrations of Fe, As and Sb along with their Sc normalized values presented elevated values in Elefsis Bay sediments. Chromium was found enriched in the sediments near the Athens sewage outfall. Factor analysis results showed that a part of As and Sb in Elefsis Bay sediments could be associated with organic or sulphidic phases. In addition, the lithogenic fraction of the sediments and the Fe oxides/hydroxides were important trace element carriers. Chromium and PAH inputs from the sewage outfall were also detected. Comparison of PAH and trace element concentrations with internationally-used sediment quality guidelines (SQG) revealed that Elefsis Bay sediments had the greatest potential of causing adverse effects in benthic organisms.     

Comparison between petroleum hydrocarbon concentrations and magnetic properties in Chennai coastal sediments,Bay of Bengal,INDIA

Petroleum hydrocarbon concentrations (PHC) of surface sediments along the Chennai coast, India, were measured by UV-Fluorescence (UVF) Spectroscopy and the results are expressed in terms of Chrysene equivalents. The concentration of PHC in sediment varies widely (from 1.88 ppm to 39.76 ppm) as compared to the baseline (1.88 ppm) with higher values obtained in the northern part of the study area. The highest magnetic susceptibility (96.8 × 10⁻⁸ m³kg⁻¹) value was determined from the Chennai harbour area. The magnetic parameters show that the Chennai coastal sediments are dominated by ferrimagnetic minerals. The positive correlation (r² = 0.86; p < 0.05) between petroleum hydrocarbon concentrations and magnetic susceptibility suggests that the magnetic minerals and petroleum hydrocarbons along the Chennai coast are derived from the same sources. Factor analysis shows that the magnetic concentration dependent parameters (χ, χ_ARM and SIRM) covary with the petroleum hydrocarbon concentration, suggesting that large amounts of magnetic minerals originate from anthropogenic activities. It is evident that using magnetic measurements may be considered a simple, rapid, cheap and non-destructive method to determine petroleum hydrocarbon concentrations in coastal sediments. Furthermore, this technique may be applied to petroleum exploration studies. Magnetic susceptibility measurements in sediments have been proposed as complementary or alternative means of exploration and assessment of hydrocarbon reservoirs.     

Petroleum-related hydrocarbons in deep and subsurface sediments from South-Western Barents Sea

Subsurface sediments from a pockmark area in South-Western Barents Sea have been earlier found to contain elevated levels of petroleum-related polycyclic aromatic hydrocarbons. This work describes a comprehensive analysis of various biomarkers, including the highly source-specific hopanes, in a 4.5?m long gravity core from the same area, together with subsurface sediment samples from other areas in the region without pockmarks present ("background samples"). A clear difference between the pockmark gravity core and the background sediment cores was found, both with regard to genesis and the level of transformation of organic matter. A number of indicator parameters, such as methylphenanthrene index (MPI-1), point towards a significantly higher maturity of hydrocarbons in the pockmark core throughout its length as compared to the other sampled locations. Higher contents of microbial hopanoids (hopenes) may indicate the former presence of petroleum. These findings confirm the hypothesis of a natural hydrocarbon source in the deeper strata present in the studied location with pockmarks.     

In situ microbial degradation of Prudhoe Bay crude oil in Beaufort Sea sediments

This study examined the fate of Prudhoe Bay crude oil in nearshore sediments of the Beaufort Sea, in situ, with emphasis on the rôle of microorganisms in the weathering process. The results indicate that oil is degraded in Arctic sediments very slowly; only after 1 year's exposure was biodegradation evident. Several factors probably contributed to the slow rate of microbial weathering, including: limited populations of hydrocarbon utilising microorganisms; localised high oil concentrations; low temperatures; limiting nutrient concentrations (unfavourable C:N and C:P ratios); low oxygen tensions and limited circulation of interstitial waters in fine-grained sediments. Abiotic weathering of the oil was also slow, with limited loss of low molecular weight aliphatic and aromatic hydrocarbons during 2 years' exposure. Significant features of the overall weathering process were: lack of initial loss of low molecular weight compounds; aliphatic compounds were not preferentially degraded over aromatic compounds and C₁₇, and lower molecular weight normal alkanes were preferentially degraded over higher molecular weight alkanes. The results of this study indicate that hydrocarbons will persist relatively unaltered for several years if Beaufort Sea sediments are contaminated with petroleum.     

Characterization of hydrocarbons in a subsurface oil-rich layer in the Sargasso Sea

The hydrocarbon composition of seawater samples collected within a subsurface oil-rich layer in the southwest North Atlantic Ocean (Sargasso Sea) during February–March, 1978, has been examined in detail. Chromatograms generated through gas chromatographs/mass spectrometry (GC/MS) analyses of saturated and aromatic hydrocarbons are characterized by a narrow unresolved envelope (UCM or unresolved complex mixture) containing isoprenoids as major resolved peaks, suggesting a petroleum source which has undergone moderate biodegradative weathering. Distributions of terpanes, steranes and polycyclic aromatic hydrocarbons corroborate the inferred fossil origin. Stable carbon isotopic compositions (δ¹³C) suggest that the source of these hydrocarbons is enriched in ¹³C in comparison with most petroleums. The results support the previous suggestions (Harvey et al., 1979) that this layer is part of a massive submarine oil seep originating somewhere on the Venezuelan shelf, although its origin cannot be attributed to seepage of a specific oil formation.     

Natural background and anthropogenic inputs of polycyclic aromatic hydrocarbons (PAH) in sediments of South-Western Barents Sea

Polycyclic aromatic hydrocarbons (PAH) were measured in sediment cores from 13 locations in South-Western Barents Sea as part of a detailed study of the Norwegian seabed under the MAREANO program. The generally low PAH levels found, an average around 200 ng g⁻¹ dry weight for sum PAH, indicate low inputs of petroleum hydrocarbons to the marine environment in the area. Differences in PAH composition and various PAH ratios indicate a natural, mostly petrogenic origin of PAH in sediments from the open sea locations, while the fjord locations show higher pyrogenic PAH contents with an increase towards upper sediment layers, indicating low inputs from human activities. Petrogenic PAH levels increase in deeper sediments at open sea locations, also when normalised to total organic carbon (TOC) contents, suggesting natural leakages of oil-related hydrocarbons in the area.     

Biota: sediment partitioning of aluminium smelter related PAHs and pulp mill related diterpenes by intertidal clams at Kitimat, British Columbia

The question of polycyclic aromatic hydrocarbon (PAH) bioavailability and its relationship to specific PAH sources with different PAH binding characteristics is an important one, because bioavailability drives PAH accumulation in biota and ultimately the biochemical responses to the PAH contaminants. The industrial harbour at Kitimat (British Columbia, Canada) provides an ideal location to study the bioavailability and bioaccumulation of sediment hydrocarbons to low trophic level biota. Samples of soft shell clams (Mya arenaria) and intertidal sediment collected from multiple sites over six years at various distances from an aluminium smelter and a pulp and paper mill were analysed for 106 PAHs, plant diterpenes and other aromatic fraction hydrocarbons. Interpretation using PAH source ratios and multivariate data analysis reveals six principal hydrocarbon sources: PAHs in coke, pitch and emissions from anode combustion from the aluminium smelter, vascular plant terpenes and aromatised terpenes from the pulp and paper mill, petroleum PAHs from shipping and other anthropogenic activities and PAHs from natural plant detritus. Harbour sediments predominantly contain either pitch or pyrogenic PAHs from the smelter, while clams predominantly contain plant derived PAHs and diterpenes from the adjacent pulp mill. PAHs from the smelter have low bioavailability to clams (Biota-Sediment Accumulation Factors; BSAFs <1 for pitch and coke; <10 for anode combustion, decreasing to ∼0.1 for the mass 300 and 302 PAHs), possibly due to binding to pitch or soot carbon matrices. Decreases in PAH isomer ratios between sediments and clams likely reflect a combination of variation in uptake kinetics of petroleum PAHs and compound specific metabolism, with the importance of petroleum PAHs decreasing with increasing molecular weight. Plant derived compounds exhibit little natural bioaccumulation at reference sites, but unsaturated and aromatised diterpenes released from resins by industrial pulping processes are readily accumulated by the clams (BSAFs >500). Thus while most of the smelter associated PAHs in sediments may not be bioavailable to benthic organisms, the plant terpenes (including retene, totarol, ferruginol, manool, dehydroabietane and other plant terpenes that form the chemical defence mechanism of conifers) released by pulp mills are bioavailable and possess demonstrated toxic properties. The large scale release of plant terpenes by some of the many pulp mills located in British Columbia and elsewhere represents a largely undocumented risk to aquatic biota.     

Geochemical overview and undiscovered gas resources generated from Hamitabat petroleum system in the Thrace Basin,Turkey

Since the first drill in 1957, three oil, 19 gas and condensate fields have been discovered in the Thrace Basin. However, any petroleum system with its essential elements and processes has not been assigned yet. This study consists of two parts, (1) geochemical overview of the previous work in order to get a necessary help to construct a petroleum system and (2) calculation of quantitative undiscovered hydrocarbon resources generated from this system. An extensive overview study showed that the primary reservoir and source rocks in the Thrace Basin are the Middle Eocene Hamitabat sandstones and shales, respectively, hence it appears that the most effective petroleum system of the Thrace Basin becomes the Hamitabat (!) petroleum system. Currently, 18.5 billion m³ of in-place gas, 2.0 million m³ (12.7 million bbl) in-place waxy oil as well as minor amount of associated condensate were discovered from this system. This study showed that the regional distribution of the oil and gas fields almost overlapped with the previously constructed pod of active Hamitabat shales implying that short and up-dip vertical migration pathway of hydrocarbons from the source to trapping side was available. Thermal model demonstrated that hydrocarbon generation from the Hamitabat shales commenced in the Early Miocene. The amount of quantitative gas generation based on the mean-original TOC = 0.94 wt%, mean-original HI = 217 HC/g TOC and the volume of the pod of active source rock = 49 km³ is approximately 110 billion m³ of gaseous hydrocarbons that results in a high generation–accumulation efficiency of 17% when 18.5 billion m³ of already discovered hydrocarbons are considered.     

大连湾石油污染沉积物中细菌群落结构分析

大连新港"7.16"输油管道爆炸溢油事故发生后,为探究石油污染与细菌群落结构变化之间的关系及在石油生物降解过程中起重要作用的细菌菌群,本研究对大连湾表层沉积物中石油烃含量和细菌宏基因组16SrDNA V3区进行分析。结果表明:溢油初期2010年8月DLW01站位表层沉积物石油烃含量高达1 492mg/kg,符合第三类沉积物质量标准,随着时间推移,2011年4月、2011年7月、2011年12月航次各站位沉积物中石油烃含量基本呈下降趋势,且均符合第一类沉积物质量标准;16S rDNA PCR-DGGE方法分析表明,石油烃含量高的区域优势细菌种类少,反之则较丰富;海洋环境中同一地点的细菌群落能保持一定稳定性;大连湾石油污染沉积物中变形菌门γ-变形菌纲和拟杆菌门一直保持较高的优势度,是在石油生物降解过程中起重要作用的细菌菌群,而厚壁菌门只在石油烃含量低的区域出现;此外,出现的对污染物敏感的嗜冷杆菌可作为石油污染指示生物进行深入研究。