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.     

Effect of non-petroleum oil spills on wintering birds near Vancouver

Within the period of our records, spills of vegetable oils at Vancouver harbour have caused greater losses of birds than spills of petroleum oils. Vegetable oils affect birds by feather wetting but do not exhibit odour and slick characteristics of petroleum oils. Because most vegetable oils are edible their potential danger to aquatic birds may go unnoticed; sites of storage and transhipment of vegetable oils may be overlooked in oil spill contingency planning.     

Pyrolysis of spill oils adsorbed on zeolites with product oils recycling

Experimentally, a feasibility study for adsorption and catalytic pyrolysis of spill oils on Cu/ZSM-5 for recycling of light oils has been conducted in the present work. The adsorption and pyrolysis of model compounds such as heptane, toluene, and diesel (to stimulate the spill oils) on Cu/ZSM-5 have been investigated on a continuous fixed-bed reactor. By component fitted X-ray absorption near edge structural (XANES) spectroscopy, catalytic active species such as metallic copper (Cu) (77-84%) and Cu(2)O (6-7%) are found in the channels of ZSM-5 during pyrolysis of heptane or toluene. Pyrolysis of diesel effected by Cu/ZSM-5 yields gas (C(1)-C(5)) (32%) and light oil (68%) that can be used as auxiliary fuels.     

Pyrolysis of spill oils adsorbed on zeolites with product oils recycling

Experimentally, a feasibility study for adsorption and catalytic pyrolysis of spill oils on Cu/ZSM-5 for recycling of light oils has been conducted in the present work. The adsorption and pyrolysis of model compounds such as heptane, toluene, and diesel (to stimulate the spill oils) on Cu/ZSM-5 have been investigated on a continuous fixed-bed reactor. By component fitted X-ray absorption near edge structural (XANES) spectroscopy, catalytic active species such as metallic copper (Cu) (77–84%) and Cu₂O (6–7%) are found in the channels of ZSM-5 during pyrolysis of heptane or toluene. Pyrolysis of diesel effected by Cu/ZSM-5 yields gas (C₁–C₅) (32%) and light oil (68%) that can be used as auxiliary fuels.     

Application of the luciferase cell culture bioassay for the detection of refined petroleum products

A luciferase cell culture-based bioassay, developed to detect 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)-like activity of halo-genated and polycyclic aromatic hydrocarbons, was optimized to detect refined petroleum products and to determine their relative inducing potency. Quality control standards from 32 refined products (gasolines and diesels, jet fuels, lubricating oils, fuel oils and weathered products) and three commercial products were evaluated. Induction equivalents (I-EQs) were determined by direct comparison of the EC50 and EC20 values (based on the median and 20% TCDD maximal response, respectively) from dose-response curves for each product to those obtained with TCDD. Most petroleum products were active in the luciferase bioassay, with those products composed of fractions produced later in the distillation process (i.e. fuel oils) inducing higher levels. Additionally, weathering of products reduced their induction potency. Based on the high I-EQ estimates of many products, biological effects associated with exposure may have been previously underestimated using other diagnostic methods.     

Compound-specific stable carbon isotopic composition of petroleum hydrocarbons as a tool for tracing the source of oil spills

With the increasing demand for and consumption of crude oils, oil spill accidents happen frequently during the transportation of crude oils and oil products, and the environmental hazard they pose has become increasingly serious in China. The exact identification of the source of spilled oil can act as forensic evidence in the investigation and handling of oil spill accidents. In this study, a weathering simulation experiment demonstrates that the mass loss of crude oils caused by short-term weathering mainly occurs within the first 24h after a spill, and is dominated by the depletion of low-molecular weight hydrocarbons (相似文献   

Photocatalytic degradation of spill oils on TiO(2) nanotube thin films

The nitrogen-doped TiO(2) nanotube (N-TNT) thin films were synthesized using ZnO nanorods as the template and doped with urea at 623K. Under ultraviolet (UV) and visible light irradiation, the efficiencies for photocatalytic degradation of methylene blue is as high as 30%. About 10% of toluene (representing aromatics in the spill oils) in sea water can be photocatalytically degraded under visible light radiation for 120 min. The aliphatic model compound (1-hexadecene) has, on the contrary, a less efficiency (8%) on the N-TNT photocatalyst. On the average, under visible light radiation, the effectnesses of the N-TNT for photocatalytic degradation of model compounds in the spill oils in sea water are 0.38 mg toluene/gN-TNTh and 0.25 mg 1-hexadecene/gN-TNTh. It is expected that spill oils in the harbors or seashores can be adsorbed and photocatalytically degraded on the N-TNT thin films that are coated onto levee at the sea water surface level.     

Photocatalytic degradation of spill oils on TiO2 nanotube thin films

The nitrogen-doped TiO₂ nanotube (N-TNT) thin films were synthesized using ZnO nanorods as the template and doped with urea at 623 K. Under ultraviolet (UV) and visible light irradiation, the efficiencies for photocatalytic degradation of methylene blue is as high as 30%. About 10% of toluene (representing aromatics in the spill oils) in sea water can be photocatalytically degraded under visible light radiation for 120 min. The aliphatic model compound (1-hexadecene) has, on the contrary, a less efficiency (8%) on the N-TNT photocatalyst. On the average, under visible light radiation, the effectnesses of the N-TNT for photocatalytic degradation of model compounds in the spill oils in sea water are 0.38 mg toluene/gN-TNT h and 0.25 mg 1-hexadecene/gN-TNT h. It is expected that spill oils in the harbors or seashores can be adsorbed and photocatalytically degraded on the N-TNT thin films that are coated onto levee at the sea water surface level.     

Underground Storage Tank Monitoring: Observation Well Based Systems

A growing number of state and local governments and petroleum-related companies require the use of release detection systems for underground petroleum storage tanks. This has resulted in a confusing array of commercially available petroleum product detection devices, many of which have not been extensively field-tested. These systems, which are installed in ground water observation wells, vapor wells or U-tubes, include hydrocarbon-detecting paste, bailers, interface probes, electrical resistivity sensors, thermal-conductivity sensors, hydrocarbon-soluble devices, hydrocarbon-permeable materials and vapor detectors. This paper describes the available state-of-the-art technology for leak detection and the application for which each system is best suited.     

Formation mechanism of condensates,waxy and heavy oils in the southern margin of Junggar Basin,NW China

It is a challenge to determine the source and genetic relationship of condensate, waxy and heavy oils in one given complicated petroliferous area, where developed multiple sets of source rocks with different maturity and various chemical features.The central part of southern margin of Junggar Basin, NW China is such an example where there are condensates, light oils, normal density oils, heavy crude oils and natural gases. The formation mechanism of condensates has been seriously debated for long time;however, no study has integrated it with genetic types of waxy and heavy oils. Taking the central part of southern margin of Junggar Basin as a case, this study employs geological and geochemical methods to determine the formation mechanism of condensates,waxy and heavy oils in a complicated petroliferous area, and reveals the causes and geochemical processes of the co-occurrence of different types of crude oils in this region. Based on detailed geochemical analyses of more than 40 normal crude oils, light oils,condensates and heavy oils, it is found that the condensates are dominated by low carbon number n-alkanes and enriched in light naphthenics and aromatic hydrocarbons. Heptane values of these condensates range from 19% to 21%, isoheptane values from1.9 to 2.1, and toluene/n-heptane ratios from 1.5 to 2.0. The distribution of n-alkanes in the condensates presents a mirror image with high density waxy crude oils and heavy oils. Combined with the oil and gas-source correlations of the crude oils, condensates and natural gas, it is found that the condensates are product of evaporative fractionation and/or phase-controlled fractionation of reservoir crude oils which were derived from mature Cretaceous lacustrine source rocks in the relatively early stage. The waxy oils are the intermediate products of evaporative fractionation and/or phase-controlled fractionation of reservoir crude oils, while the heavy oils are in-situ residuals. Therefore, evaporative fractionation and/or phase-controlled fractionation would account for the formation of the condensate, light oil, waxy oil and heavy oil in the central part of southern margin of Junggar Basin, resulting in a great change of the content in terms of light alkanes, naphthenics and aromatics in condensates, followed by great uncertainties of toluene/n-heptane ratios due to migration and re-accumulation. The results suggest that the origin of the condensate cannot be simply concluded by its ratios of toluene/n-heptane and n-heptane/methylcyclohexane on the Thompson's cross-plot, it should be comprehensively determined by the aspects of geological background, thermal history of source rocks and petroleum generation,physical and chemical features of various crude oils and natural gas, vertical and lateral distribution of various crude oils in the study area.     

Petroleum hydrocarbons in the arctic ocean surface water

The concentration of petroleum hydrocarbons in Arctic surface water under the ice north of Svalbard has been determined by fluorescence spectrofluorometry using three different excitation/emission wavelength combinations. With Kuwait crude oil as a reference, the concentration range is 0.1–0.6 μg l^?1 crude oil equivalents with respect to light molecular weight components and 0.05–0.2 μg l^?1 heavy molecular weight components.     

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.     

Aerial application of dispersants in Bantry Bay following the Betelgeuse incident

For the first time during a significant oil spill, aircraft were used in preference to surface vessels to apply chemical dispersants, following the tragic accident to the French registered tanker in Bantry Bay, south-west Eire. In this particular case, with an ideally situated landing strip, close to the source of the spill of fresh crude oil, the response proved to be highly effective and prevented the vast majority of the oil lost after the 6th day from reaching the nearby shorelines. The ability of the pilot of the spray aircraft to rapidly locate and to select for treatment only those slicks or parts of slicks posing a significant threat also resulted in the minimum amount of dispersant being used to maximum effect.     

Tar ball frequency data and analytical results from a long-term beach monitoring program

Following the spill of fuel oils from the New Carissa in February 1999, approximately 300 km of beaches on the Pacific coast of North America were surveyed. A long-term observation program focused on the documentation of stranded tar balls in the vicinity of the spill site. Systematic beach surveys which were conducted over the period March 1999 to April 2001 and semi-logarithmic scale, time-series plots proved the most useful format for identifying trends. Beach monitoring continued through to August 2001. by which time 212 tar balls had been analyzed by GC/MS for their chemical characteristics. The samples of tar balls collected between February 1999 and August 2001 were qualitatively compared with New Carissa source oils (NCSO) and 101 (48%) were not consistent with NSCO. The presence of tar balls that are not related to an incident can confound attempts to define cleanup or endpoint criteria and to assess possible injury to natural resources.     

Hebei Spirit oil spill monitored on site by fluorometric detection of residual oil in coastal waters off Taean, Korea

The spatiotemporal distributions of dissolved and/or dispersed oil in seawater and pore water were monitored on site by fluorometric detection method after the Hebei Spirit oil spill. The oil concentrations in intertidal seawater, 15 days after the spill, were as high as 16,600 μg/L and appeared to decrease below the Korean marine water quality standard of 10 μg/L at most sites 10 months after the spill. Fluorometric detection of oil in pore water was introduced to eliminate the effects of grain size for the quantification of oil in sediments and to better explain spatial and temporal distribution of oil pollution at sandy beaches. The fluorescence detection method was compared with the conventional laboratory technique of total petroleum hydrocarbon analysis using gas chromatography. The method of fluorescence detection of oil was capable of generating results much faster and more cost-effectively than the traditional GC technique.     

Intrinsic bioremediation of a petroleum-impacted wetland

Following the 1994 San Jacinto River flood and oil spill in southeast Texas, a petroleum-contaminated wetland was reserved for a long-term research program to evaluate bioremediation as a viable spill response tool. The first phase of this program, presented in this paper, evaluated the intrinsic biodegradation of petroleum in the contaminated wetland. Sediment samples from six test plots were collected 11 times over an 11-month period to assess the temporal and spatial petroleum concentrations. Petroleum concentrations were evaluated using gas chromatography-mass spectrometer analyses of specific target compounds normalized to the conservative biological marker, C(30)17alpha,21beta(H)-hopane. The analyses of specific target compounds were able to characterize that significant petroleum biodegradation had occurred at the site over the one-year period. Total resolved saturate and total resolved aromatic hydrocarbon data indicated the petroleum was degraded more than 95%. In addition, first-order biodegradation rate constants were calculated for the hopane-normalized target compounds and supported expected biodegradation patterns. The rapid degradation rates of the petroleum hydrocarbons are attributed to conditions favorable to biodegradation. Elevated nutrient levels from the flood deposition and the unconsolidated nature of the freshly deposited sediment possibly provided a nutrient rich, oxic environment. Additionally, it is suggested that an active and capable microbial community was present due to prior exposure to petroleum. These factors provided an environment conducive for the rapid bioremediation of the petroleum in the contaminated wetland.     

Petroleum source rock identification of United Kingdom Atlantic Margin oil fields and the Western Canadian Oil Sands using Platinum,Palladium, Osmium and Rhenium: Implications for global petroleum systems

This study demonstrates that petroleum and source rocks are enriched in Pt and Pd to the ppb level, and that the ¹⁸⁷Os/¹⁸⁸Os composition coupled with the Pt/Pd value permits the fingerprinting of petroleum to its source. Oils from the United Kingdom Atlantic Margin (sourced from the Upper Jurassic Kimmeridge Clay Fm.) as well as source rock samples have been analysed for Pt and Pd. When the Pt/Pd value is compared with ¹⁸⁷Os/¹⁸⁸Os (calculated at the time of oil generation; Os_g) the values from both the known source and the oils are similar, demonstrating that they can be used as an oil to source fingerprinting tool. This inorganic petroleum fingerprinting tool is particularly important in heavily biodegraded petroleum systems where traditional fingerprinting techniques (e.g. biomarkers) are severely hampered, e.g. the world's largest oil sand deposit, the West Canadian Oil Sands (WCOS). This has caused the source of the WCOS to be hotly debated, with no present day consensus between inputs from potential source units e.g. Exshaw and Gordondale Fms. ¹⁸⁷Os/¹⁸⁸Os and Pt/Pd fingerprinting of the oil sands shows that the majority of the petroleum have similar ¹⁸⁷Os/¹⁸⁸Os and Pt/Pd values, supporting the hypothesis of one principal source. Analysis of the potential source rocks establishes that the principal source of the oil sands to be from the Jurassic Gordondale Fm., with a minor Exshaw Fm. input. Thus, the combination of previously pioneered Re–Os petroleum geochronology with ¹⁸⁷Os/¹⁸⁸Os and Pt/Pd values of petroleum permits both a temporal and spatial understanding of petroleum systems.     

“REMOTE SENSING”— AN EVALUATION OF ITS IMPACT ON EARTH SCIENCE—*

“Remote sensing” techniques have been used for many years as an exploration tool; broadly speaking, any method using sensors not directly connected to the earth's surface falls into this group. It is preferable, however, to use the term solely with reference to a number of new sensors which have recently become available to earth scientists for the detection of various radiations of the electromagnetic spectrum in the wave length range from 0.1 micron (UV) to some centimeters including the visible and infrared regions. Radiations artificially induced in the earth (active sensing) or spontaneous radiations (passive sensing) can be detected. Some of the bands investigated seem promising for application to geological surveys, especially using sensors on aircraft and satellites, which allow synoptic and large scale investigations. A brief account is given of the results already achieved and of future developments such as the ERTS and manned satellite (post Apollo) “earth observation” programmes. The potential role of Europe in the field is discussed. Details are given of some applications of thermal I.R. imagery to geological and vulcanological problems, with special emphasis on the research carried out in Italy.     

Geochemical characteristics of crude oils from the Sagara oil field, Shizuoka Prefecture, Japan

Abstract   Six oil samples collected from the Sagara oil field, Shizuoka Prefecture, were geochemically analyzed. Unlike the Niigata oils, the Sagara oils: (i) are low-sulphur light oils dominated by gasoline and kerosene fractions; (ii) have low values of environment index in light hydrocarbon compositions; (iii) have high Pr/ n -C₁₇ and low Ph/ n -C₁₈ ratios and high oleanane/hopane ratios; (iv) have high relative abundance of C₂₉ and low relative abundance of C₂₈ regular steranes; and (v) have 'light' stable carbon isotope compositions. These characteristics show that the source rocks of the Sagara oils contain mainly marine organic matter, but with more input of terrigenous organic matter deposited under more oxic conditions compared to those of the Niigata oils. The light carbon isotope compositions and the low relative abundance of C₂₈ regular steranes of the Sagara oils suggest that their source rock is not Miocene, but probably Paleogene in age. The Sagara oils probably migrated along faults from deeper parts of the basin.     

Overpressure development and oil charging in the central Junggar Basin,Northwest China: Implication for petroleum exploration

The Junggar Basin is one of the largest and most petroliferous superimposed petroleum basins in China. The central depression area has become the frontier field for petroleum exploration. The characteristics of potential source rocks and reservoir sandstones, and the pressure regime in the central Junggar Basin were studied. Permian shales are dominated by hydrogen-rich, oil-prone algal organic matter, and Jurassic mudstones are dominated by hydrogen-poor, higher-plant derived organic matter. These source rocks are widespread and have been mature for hydrocarbon generation, suggesting good to excellent exploration potential, both for crude oils and for natural gases. The deeply buried Jurassic sandstones usually have low porosity and permeability. However, sandstones beneath the Jurassic/Cretaceous unconformity display relatively high porosity and permeability, suggesting that meteoric water leaching had improved the quality of the sandstones. Overpressure developed over much of the central Junggar Basin. The overpressured rocks are characterized by slightly increased interval transit time, low sandstone permeability, increased organic matter maturity, and high relative hydrocarbon-gas contents. Mudstones in the overpressured system have quite the same clay mineral compositions as mudstones in the lower part of the normally pressured system. Overpressure generation in the central Junggar Basin is best to be explained as the result of hydrocarbon generation and fluid retention in low-permeability rocks. Petroleum generated from Permian and Jurassic source rocks could migrate laterally through preferential petroleum migration pathways and accumulated in structural traps or lithological traps in the overpressured system, or migrate vertically through faults/hydraulic fractures into the overlying, normally pressured system and accumulate in structural or lithological traps. Therefore, commercial petroleum reservoirs could be potentially found in both the overpressured system, and in the normally pressured system.