Detection of aliphatic hydrocarbons derived by recent “bio-conversion” from fossil fuel oil in North Sea waters

The higher boiling point range of saturated aliphatic hydrocarbon fractions extracted from North Sea water have been re-investigated in detail with improved high resolution glass capillary columns suitable for high temperature gas-chromatography. The resulting chromatograms reveal hydrocarbon patterns, most of which have the same common feature: a smooth distribution of the long-chain n-alkanes combined with a lack of the branched alkanes normally expected for fossil fuel oil. Instead, two homologous series of iso- and anteiso-alkanes could be detected. Since this finding is always associated with traces of present or past fossil fuel oil contamination of the upper water column, these environmental n-, iso and anteisoalkanes are considered to be recently ‘bio-converted’ from fossil fuel oil hydrocarbons. They form a third group beside recent biogenic and fossil petrogenic hydrocarbons in the marine environment. Oil pollution records of the marine environment will have to take into account this group of microbial hydrocarbons.     

Composition and sources of pollutant hydrocarbons in the Severn Estuary

Hydrocarbon distributions in sediment from the Severn Estuary can be explained mainly in terms of a pollutant origin. The aliphatic hydrocarbon distribution is similar to that found in biodegraded crude oils. The distribution of polycyclic aromatic hydrocarbons, including the carcinogen benzo(a)pyrene, is similar to that derived from the pyrolysis of fossil fuels, especially petroleum.     

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.     

Plasmid incidence in marine bacteria isolated from petroleum polluted sites on different petroleum hydrocarbons

Oil-degrading bacteria isolated from oil spills, an industrial bay, and an offshore oil field by liquid enrichment on crude oils and polynuclear aromatic hydrocarbon compounds were screened for extra-chromosomal DNA. Plasmids were detected in 21% of the strains isolated on whole crude oil and in 17% of the strains isolated on polynuclear aromatic hydrocarbons. Multiple plasmids were observed in 50% of the plasmid-containing strains. Pseudomonas was the predominant genus isolated during the study. Plasmids do not appear to be of importance to these strains during degradation of freshly introduced oil at a nonpolluted site such as might be the case in an ocean oil spill. Plasmids do appear to be significant in the adaptation of Pseudomonas species to chronic petroleum pollution.     

Characteristics of remaining oil viscosity in water-and polymer-flooding reservoirs in Daqing Oilfield

The experimental analysis of 21 crude oil samples shows a good correlation between high molecular-weight hydrocarbon components (C 40+) and viscosity.Forty-four remaining oil samples extracted from oil sands of oilfield development coring wells were analyzed by high-temperature gas chromatography (HTGC),for the relative abundance of C 21-,C 21-C 40 and C 40+ hydrocarbons.The relationship between viscosity of crude oil and C 40+ (%) hydrocarbons abundance is used to expect the viscosity of remaining oil.The ...     

The recognition of biodegraded petroleum-derived aromatic hydrocarbons in recent marine sediments

Aromatic hydrocarbon fractions isolated from sediments polluted with crude oil, from sampling stations in and around Sullom Voe, Shetland Islands, were found to exhibit, as the major feature in their gas chromatograms, an unresolved complex mixture or ‘hump’. This feature was absent from the gas chromatograms of the aromatic hydrocarbon fractions isolated from corresponding unpolluted sediments in the region. The observed aromatic hump had little resemblance to the distribution of aromatic hydrocarbons in a typical North Sea crude oil. Incubation studies, however, showed that such a hump was appearing when oil-spiked sediments were aerobically biodegraded. From these incubation studies it was also evident that alkylaromatic hydrocarbons in the crude oil were biodegraded before any change in the normal alkanes was apparent. Therefore, the presence of an unresolved complex mixture in the gas chromatograms of aromatic hydrocarbon fractions from recent sediments can act as a marker to recognize contamination by crude oil.     

Weathering of Oil in a Surficial Aquifer

The composition of crude oil in a surficial aquifer was determined in two locations at the Bemidji, MN, spill site. The abundances of 71 individual hydrocarbons varied within 16 locations sampled. Little depletion of these hydrocarbons (relative to the pipeline oil) occurred in the first 10 years after the spill, whereas losses of 25% to 85% of the total measured hydrocarbons occurred after 30 years. The C_6‐30 n‐alkanes, toluene, and o‐xylene were the most depleted hydrocarbons. Some hydrocarbons, such as the n‐C_10–24 cyclohexanes, tri‐ and tetra‐ methylbenzenes, acyclic isoprenoids, and naphthalenes were the least depleted. Benzene was detected at every sampling location 30 years after the spill. Degradation of the oil led to increases in the percent organic carbon and in the δ ¹³C of the oil. Another method of determining hydrocarbon loss was by normalizing the total measured hydrocarbon concentrations to that of the most conservative analytes. This method indicated that the total measured hydrocarbons were depleted by 47% to 77% and loss of the oil mass over 30 years was 18% to 31%. Differences in hydrocarbon depletion were related to the depth of the oil in the aquifer, local topography, amount of recharge reaching the oil, availability of electron acceptors, and the presence of less permeable soils above the oil. The results from this study indicate that once crude oil has been in the subsurface for a number of years there is no longer a “starting oil concentration” that can be used to understand processes that affect its fate and the transport of hydrocarbons in groundwater.     

Isolation and characterization of two crude oil-degrading yeast strains, Yarrowia lipolytica PG-20 and PG-32, from the Persian Gulf

Among six crude oil-degrading yeasts that were isolated from an oil-polluted area in the Persian Gulf, two yeast strains showed high degradation activity of aliphatic hydrocarbons. From an analysis of 18S rRNA sequences and biochemical characteristics, these strains were identified as Yarrowia lipolytica strains PG-20 and PG-32. Gas Chromatography (GC) analysis of the crude oil remaining in the culture medium after 1 week at 30°C showed that the strains PG-20 and PG-32 degraded 68% and 58% of crude oil, respectively. The optimal growth condition and biodegradation of hydrocarbons was in ONR medium with an acidic pH (pH5). These two strains may degrade aliphatic hydrocarbons more efficiently than aromatic hydrocarbons, although strain PG-20 had better degradation than strain PG-32. The two Y. lipolytica strains reduce surface tension when cultured on hydrocarbon substrates (1% v/v). These strains showed a cell surface hydrophobicity higher than 70%. These results suggested that Y. lipolytica strains PG-20 and PG-32 have high crude oil degrading activity due to their high emulsifying activity and cell hydrophobicity. In conclusion, these yeast strains can be useful for the bioremediation process in the Persian Gulf and decreasing oil pollution in this marine ecosystem.     

Crude-oil hydrocarbon composition characteristics and oil viscosity prediction in the northern Songliao Basin

Crude oil hydrocarbon composition characteristics and oil viscosity prediction are important bases in petroleum exploration.A total of 54 oil/heavy-oil samples and 17 oil sands were analyzed and quantified using both comprehensive 2D gas chromatography(GC×GC)and comprehensive 2D gas chromatography/time-of-flight mass spectrometry(GC×GC/TOFMS).The results show that crude oil in the West slope is mainly heavy oil and its hydrocarbon composition is characterized overall by paraffinsmono-aromaticsnaphthenesnon-hydrocarbonsdi-aromaticstri-aromaticstetra-aromatics.Aromatics are most abundant and non-hydrocarbons are least abundant,whilst content differences among paraffins,naphthenes,aromatics,and non-hydrocarbons are less than 15%.There are two types of heavy oil,secondary type and mixing type.Biodegradation is the main formation mechanism of heavy oil.Biodegradation levels cover light biodegradation,moderate biodegradation,and severe biodegradation.With increasing biodegradation,paraffin content decreases while contents of aromatics and nonhydrocarbons increase.In contrast,naphthene content increases first and then decreases with increasing biodegradation.In severe biodegradation stage,naphthenes decrease more quickly than aromatics and non-hydrocarbons.This provides a new method for studying oil/heavy-oil biodegradation mechanism and biodegradation resistance of different hydrocarbons at different biodegradation stages.In the Longhupao-Daan terrace and Qijia-Gulong depression,most crude oil is conventional oil.Its composition is dominated by paraffins with the lowest content of aromatics.In some casual oil wells from the Longhupao-Daan terrace,crude oil from Saertu oil reservoirs is moderately biodegraded whereas crude oil from Putaohua oil reservoir is lightly biodegraded.Chemical parameters using saturate hydrocarbons and aromatics are usually not suitable for determining organic type and thermal maturity of biodegraded oil,especially of moderately or severely biodegraded oil,whilst Ts/(Ts+Tm)ratio can be used to determine thermal maturity of both conventional crude oil and heavy oil.     

Biodegradation of petroleum hydrocarbons at low temperature in the presence of the dispersant Corexit 9500

Our study examined the effects of Corexit 9500 and sediment on microbial mineralization of specific aliphatic and aromatic hydrocarbons found in crude oil. We also measured gross mineralization of crude oil, dispersed crude oil and dispersant by a marine microbial consortium in the absence of sediment. When provided as carbon sources, our consortium mineralized Corexit 9500 the most rapidly, followed by fresh oil, and finally weathered oil or dispersed oil. However, mineralization in short term assays favored particular components of crude oil (2-methyl-naphthalene > dodecane > phenanthrene > hexadecane > pyrene) and was not affected by addition of nutrients or sediment (high sand, low organic carbon). Adding dispersant inhibited hexadecane and phenanthrene mineralization but did not affect dodecane and 2-methyl-naphthalene mineralization. Thus, the effect of dispersant on biodegradation of a specific hydrocarbon was not predictable by class. The results were consistent for both high and low oiling experiments and for both fresh and weathered oil. Overall, our results indicate that environmental use of Corexit 9500 could result in either increases or decreases in the toxicity of residual oil through selective microbial mineralization of hydrocarbons.     

The effect of volatile components in oil on evolutionary characteristics of diamondoids during oil thermal pyrolysis

On the basis of the results of simulation experiments, now we better understand the contribution of high carbon number hydrocarbons to diamondoid generation during thermal pyrolysis of crude oil and its sub-fractions(saturated, aromatic, resin, and asphalene fractions). However, little is known about the effect of volatile components in oil on diamondoid generation and diamondoid indices due to the lack of attention to these components in experiments. In this study, the effect of volatile components in oil on diamondoid generation and maturity indices was investigated by the pyrolysis simulation experiments on a normal crude oil from the HD23 well of the Tarim Basin and its residual oil after artificial volatilization, combined with quantitative analysis of diamondoids. The results indicate that the volatile components(≤n C12) in oil have an obvious contribution to the generation of adamantanes, which occurs mainly in the early stage of oil cracking(Easy Ro1.0%), and influences the variations in maturity indices of adamantanes; but they have no obvious effect on the generation and maturity indices of diamantanes. Therefore, some secondary alterations e.g., migration, gas washing, and biodegradation, which may result in the loss of light hydrocarbons in oil under actual geological conditions, could affect the identification of adamantanes generated during the late-stage cracking of crude oil, and further influence the practical application of adamantane indices.     

Improved approaches to ecotoxicity testing of petroleum products

Crude oils produced in the North West shelf of Western Australia are highly volatile, a characteristic not shared by most of the Northern Hemisphere crude oils on which internationally accepted toxicity test protocols were developed. Because of this volatility and some other factors, the LC50 and EC50 values obtained from acute toxicity tests will be significantly affected by the changes of toxicant concentration in test solutions during the period of exposure. To address these issues all steps of a standard protocol for crude oil toxicity testing have been revised. A systematic study has been performed on factors which affect petroleum hydrocarbon solubilisation in aqueous systems during test solution preparations. The influence of mixing time, agitation energy and volume/interface ratio on a hydrocarbon concentration in a water-soluble fraction (WSF) was studied for heavy, medium and light crude oils. A study of the sensitivity of marine unicellular algae to WSF of crude oils was conducted with Isochrysis sp., Nannochloropsis-like sp. and Nitzchia closterium. Total concentrations of hydrocarbons dissolved in test solutions were estimated by UV-spectrometry and GC/FID chemical analyses. When the toxicant concentration decreased during the exposure period, the EC50 values derived from initial or final concentrations either underestimate or overestimate toxicity, respectively. Therefore, weighted average concentrations (WAC) calculated for the whole test period were recommended for expressing hydrocarbon concentrations in test solutions of crude oils. Toxicity indices calculated from WAC of total hydrocarbons for different crude oils can be compared regardless of the rates of hydrocarbon loss.     

Aliphatic and aromatic hydrocarbons in sediments of Santos and Cananéia, SP, Brazil.

Sediment samples from Santos and Cananéia, S?o Paulo Brazil were analysed by GC-FID and GC-MS for aliphatic and aromatic hydrocarbons in order to gather information on the degree of contamination by oil and other biogenic contributions. Concentrations of total n-alkanes in Santos varied from 1.05 to 4.29 microg g(-1) and aromatic hydrocarbons from 0.08 to 42.39 microg g(-1). In Cananéia total n-alkanes varied from 4.37 to 157.90 microg g(-1). However, aromatic hydrocarbons were not detected. In Cananéia n-alkanes of terrestrial plants with high molecular weight predominate (n-C25, n-C27, n-C29, n-C31 and n-C33). In Santos, a more uniform distribution of the n-alkanes and aromatic hydrocarbons was found at all the sediment stations. The hydrocarbon data from stations close to the Saboó Wharf, at Alemoa and in the COSIPA Channel revealed alarming levels of acenaphthylene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene and chrysene.     

Effects of sheens associated with offshore oil and gas development on the feather microstructure of pelagic seabirds

Operational discharges of hydrocarbons from maritime activities can have major cumulative impacts on marine ecosystems. Small quantities of oil (i.e., 10 ml) results in often lethally reduced thermoregulation in seabirds. Thin sheens of oil and drilling fluids form around offshore petroleum production structures from currently permissible operational discharges of hydrocarbons. Methodology was developed to measure feather microstructure impacts (amalgamation index or AI) associated with sheen exposure. We collected feather samples from two common North Atlantic species of seabirds; Common Murres (Uria aalge) and Dovekies (Alle alle). Impacts were compared after feather exposure to crude oil and synthetic lubricant sheens of varying thicknesses. Feather weight and microstructure changed significantly for both species after exposure to thin sheens of crude oil and synthetic drilling fluids. Thus, seabirds may be impacted by thin sheens forming around offshore petroleum production facilities from discharged produced water containing currently admissible concentrations of hydrocarbons.     

Bioconcentration factors for petroleum hydrocarbons, PAHs, LABs and biogenic hydrocarbons in the blue mussel

Bioconcentration factors (K_bc) for petroleum hydrocarbons, PAHs, LABs and biogenic hydrocarbons in Mytilus edulis were measured in field experiments using time-integrating water samplers. Seven deployments at five sites gave lipid weight K_bcs for total hydrocarbons ranging from 0.99 × 10⁶ to 3.1 × 10⁶ (mean 1.6 × 10⁶)—a narrower range than has been obtained previously. Bioconcentration factors for the PAHs were similar to those for total hydrocarbons where the major hydrocarbon source was oil. However, at other sites the factors for PAHs were an order of magnitude lower than those for petroleum and for hydrocarbons originating from algae. Compositional profiles for the linear alkyl benzenes (LABs) suggested that these compounds were assimilated primarily from the dissolved phase, despite their greater abundance on particles.     

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.     

Development of oil hydrocarbon fingerprinting and identification techniques

Oil, refined product, and pyrogenic hydrocarbons are the most frequently discovered contaminants in the environment. To effectively determine the fate of spilled oil in the environment and to successfully identify source(s) of spilled oil and petroleum products is, therefore, extremely important in many oil-related environmental studies and liability cases. This article briefly reviews the recent development of chemical analysis methodologies which are most frequently used in oil spill characterization and identification studies and environmental forensic investigations. The fingerprinting and data interpretation techniques discussed include oil spill identification protocol, tiered analytical approach, generic features and chemical composition of oils, effects of weathering on hydrocarbon fingerprinting, recognition of distribution patterns of petroleum hydrocarbons, oil type screening and differentiation, analysis of “source-specific marker” compounds, determination of diagnostic ratios of specific oil constituents, stable isotopic analysis, application of various statistical and numerical analysis tools, and application of other analytical techniques. The issue of how biogenic and pyrogenic hydrocarbons are distinguished from petrogenic hydrocarbons is also addressed.     

Geochemical characteristics of light hydrocarbons in cracking gases from chloroform bitumen A,crude oil and its fractions

The composition characteristics of light hydrocarbons from crude oil, chloroform bitumen A, saturated hydrocarbon fraction, aromatic hydrocarbon fraction, and asphaltene fraction during cracking have been studied systematically. The results revealed that the content of n-alkanes, branched alkanes and cycloalkanes in light hydrocarbons from the samples gradually decreased as the simulation temperature increased, and finally almost depleted completely, while the abundance of methane, benzene and its homologues increased obviously and became the main products. The ratios of benzene/ n-hexane and toluene/n-heptane can be used as measures for oil cracking levels. Variation characteristics of maturity parameters of light hydrocarbons, for example, iC₄/nC₄, iC₅/nC₅, isoheptane value, 2,2-DMC₄/nC₆, and 2-MC₆+3-MC₆/nC₇ for different samples with increasing pyrolysis temperature, are consistent with those in petroleum reservoirs, indicating that these parameters may be efficient maturity index.     

Isolation and characterization of a novel hydrocarbon-degrading bacterium Achromobacter sp. HZ01 from the crude oil-contaminated seawater at the Daya Bay,southern China

Microorganisms play an important role in the biodegradation of petroleum contaminants, which have attracted great concern due to their persistent toxicity and difficult biodegradation. In this paper, a novel hydrocarbon-degrading bacterium HZ01 was isolated from the crude oil-contaminated seawater at the Daya Bay, South China Sea, and identified as Achromobacter sp. Under the conditions of pH 7.0, NaCl 3% (w/v), temperature 28 °C and rotary speed 150 rpm, its degradability of the total n-alkanes reached up to 96.6% after 10 days of incubation for the evaporated diesel oil. Furthermore, Achromobacter sp. HZ01 could effectively utilize polycyclic aromatic hydrocarbons (PAHs) as its sole carbon source, and could remove anthracene, phenanthrene and pyrence about 29.8%, 50.6% and 38.4% respectively after 30 days of incubation. Therefore, Achromobacter sp. HZ01 may employed as an excellent degrader to develop one cost-effective and eco-friendly method for the bioremediation of marine environments polluted by crude oil.     

Phase distribution of hydrocarbons in the water column after a pelagic deep ocean oil spill

Spills from wrecks are a potential major source of pollution in the deep ocean. However, not much is known about the fate of a spill at several kilometers depth, beyond the oceans continental shelves. Here, we report the phase distribution of hydrocarbons released from the wrecks of the Prestige tanker, several years after it sank in November 2002 to depths between 3500 and 3800 m. The released oil reached the surface waters above the wrecks without any signs of weathering and leaving an homogenous signature throughout the water column. At depths of several kilometers below the sea surface, the occurrence and spread of the deep sea oil spill could be evaluated better by quantifying and characterizing the dissolved hydrocarbon signature, rather than just the investigation of hydrocarbons in the suspended particulate matter.