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A high resolution mass spectrometry method was developed for the environmental impact monitoring of oil spill dispersants. Previously reported instability of dioctyl sulfosuccinate (DOSS) dispersant tracer was addressed by the new procedure. The method monitors both DOSS and its degradation product, monooctyl sulfosuccinate (MOSS), by liquid chromatography time-of-flight mass spectrometry. The related isomer, 4-(2-ethylhexyl) 2-sulfobutanedioate, was chromatographically resolved from MOSS but was not a product of DOSS degradation. Using this direct injection method (10 μL), the practical lower limit of quantitation was 0.5 nM for each analyte, a concentration equivalent to 0.22 ng mL−1, or 0.30 ng mL−1 including initial dilution factor with acetonitrile. The method was shown applicable to analysis of the dispersants Corexit® EC9500 A, Finasol OSR 52, Slickgone NS, and Slickgone EW for which DOSS is an active ingredient. A marine microcosm study of Corexit EC9500A, together with diluted bitumen (dilbit), at 15 ± 1 °C, provided evidence of the stoichiometric conversion of DOSS to MOSS under conditions reflecting a western Canadian marine environment. The advantage of the developed method is in its ability to extend environmental seawater sample collection time from 4 days for DOSS alone, to 14 days when both DOSS and MOSS are simultaneously analysed and results combined. The collection time is likely extended beyond the 14 day period with cooler temperatures. Preservation of collected seawater samples using sodium hydroxide, converting DOSS into MOSS in situ, was rejected due to stability issues. Addition of disodium ethylenediaminetetraacetic acid did not improve hold times, thus eliminating the theory of cation induced micelle effects causing DOSS loss.

The characterization of spilled petroleum products in an oil spill is necessary for identifying the spill source, selection of clean-up strategies, and evaluating potential environmental and ecological impacts. Existing standard methods for the chemical characterization of spilled oils are time-consuming due to the lengthy sample preparation for analysis. The main objective of this study is the development of a rapid screening method for the fingerprinting of spilled petroleum products using excitation/emission matrix (EEM) fluorescence spectroscopy, thereby delivering a preliminary evaluation of the petroleum products within hours after a spill. In addition, the developed model can be used for monitoring the changes of aromatic compositions of known spilled oils over time. This study involves establishing a fingerprinting model based on the composition of polycyclic and heterocyclic aromatic hydrocarbons (PAH and HAHs, respectively) of 130 petroleum products at different states of evaporative weathering. The screening model was developed using parallel factor analysis (PARAFAC) of a large EEM dataset. The significant fluorescing components for each sample class were determined. After which, through principal component analysis (PCA), the variation of scores of their modeled factors was discriminated based on the different classes of petroleum products. This model was then validated using gas chromatography-mass spectrometry (GC-MS) analysis. The rapid fingerprinting and the identification of unknown and new spilled oils occurs through matching the spilled product with the products of the developed model. Finally, it was shown that HAH compounds in asphaltene and resins contribute to ≥4-ring PAHs compounds in petroleum products.

The occurrence, spatial distribution and source of petroleum-related hydrocarbons, and the degree of weathering of Arrow oil residues persisting on the shoreline of Chedabucto Bay, Nova Scotia, were assessed. The hydrocarbons assessed included total petroleum hydrocarbons (TPH), n-alkanes from n-C9 to n-C40, petroleum biomarkers like terpanes, hopanes and steranes, non-alkylated polycyclic aromatic hydrocarbons (PAHs) and their alkylated homologues (APAHs). Trapped Arrow oil in the sunken tanker has not experienced any marked weathering. The collected environmental samples could be classified into three groups. Group 1 samples were oil free identified by low TPH, highly resolved fractions, a predominantly biogenic source of n-alkanes, and trace amounts of petroleum biomarkers probably from the historical (1970) oil spill. Group 2 samples had higher TPH and the other targets than Group 1 samples. The mixed petrogenic and terrestrial plant inputs were the source of n-alkanes, while the pattern of APAHs indicated that their source varied from site to site, being either recently released petroleum or Arrow oil residues. Group 3 samples mainly contained oil residues from Arrow oil spill, having very high levels of TPH, APAHs and biomarkers; however, most samples were free of n-alkanes. Group 3 samples were mostly found on the southern shoreline of Chedabucto Bay, especially in the upper to middle intertidal zone of the shorelines characterized by mixed pebble/cobble/boulders. The extent of weathering of n-alkanes and APAHs showed no relation to each other, although n-alkanes were depleted more fully than APAHs for most of the oil residues. Thus, various natural attenuation processes, especially for microbial degradation, have contributed to the aging of these oil residues. The degree of weathering varied with different environmental conditions.

The present study investigated oil dispersant toxicity to fish species typical of the cooler regions of Canada, together with less well-documented issues pertaining to oil dispersant monitoring. The oil dispersant toxicity of Corexit EC9500A was assessed for the freshwater fish species rainbow trout and the seawater species coho, chinook, and chum, with a final median lethal concentration (LC50) acute lethality range between 35.3 and 59.8 mg/L. The LC50 range was calculated using confirmed 0-h dispersant concentrations that were justified by fish mortality within the first 24 h of exposure and by variability of the dispersant indicator dioctyl sulfosuccinate (DOSS) used to monitor concentrations at later time points. To investigate DOSS as an oil dispersant indicator in the environment, microcosm systems were prepared containing Corexit EC9500A, Finasol OSR52, Slickgone NS, and Slickgone EW dispersants together with diluted bitumen. The DOSS indicator recovery was found to be stable for up to 13 d at 5 °C, 8 d at 10 °C, but significantly less than 8 d at ≥15 °C. After 3 d at temperatures ≥15 °C, the DOSS indicator recovery became less accurate and was dependent on multiple environmental factors including temperature, microbial activity, and aeration, with potential for loss of solvents and stabilizers. A final assessment determined DOSS to be a discrepant indicator for long-term monitoring of oil dispersant in seawater. Environ Toxicol Chem 2018;37:1309-1319. © 2018 SETAC.

In this study, the water accommodated and particle-laden hydrocarbon species, and the toxicity of the aqueous phase after oil-sediment interactions by varying the weathering states of diluted bitumen (Cold Lake blend (CLB)), oil type from light to heavy, and sediment type. Compared to the original oils, the sediment-laden total petroleum hydrocarbons (TPH) contained fewer hydrocarbons in the carbon range C34 range. Sediment-laden oil amounts generally decreased with an increased viscosity and asphaltene content of the test oils, as well as with increased sediment particle size. The presence of sediments significantly decreased the oil accommodated in water due to the formation of oil particulate aggregates (OPA) after mixing and settling. Less water accommodated TPH and polycyclic aromatic hydrocarbons (PAHs) were observed for weathered CLB products. However, oil and sediment types did not clearly affect the water accommodated TPH and PAHs. Light molecular PAHs and their alkylated congeners accounted for most of the water accommodated PAH congeners. A microtoxicity test demonstrated that with or without sediment, and regardless of sediment type, the toxicity of the water phase did not change significantly. Light oil of Alberta sweet mixed blend (ASMB) had the highest toxicity, followed by fresh CLB, and then all other oils, suggesting that ASMB and fresh CLB had relatively higher levels of light toxic components dissolved in the water phase compared with the other tested oils.

The Fraser River Delta is a unique and dynamic region supporting the diverse ecosystems and habitats in the Canadian West Coast. Total petroleum hydrocarbons (TPH), n-alkanes, petroleum biomarkers, and polycyclic aromatic hydrocarbons (PAHs) were analyzed for the intertidal sediments taken from the shorelines of the Delta area, British Columbia, Canada, to establish the baseline background data. Most of the sampling sites had low TPH (< 40 μg/g); only two samples had TPH from 100 to 150 μg/g. Mainly biogenic n-alkanes were present in all sites. Non-detectable to trace amounts of petroleum biomarkers were found at most sites. Mixed pyrogenic and petrogenic inputs contributed to the presence of PAHs at most sites. PAHs are not present in amounts anticipated negative effects to benthic organisms in all sampling sites, except that benzo (a) pyrene (BaP) from the upper intertidal zone (UIZ) of Burnaby Fraser Foreshore Park may have possible adverse biological effects.

The ability to characterize the composition of emerging unconventional Bakken tight oil is essential to better prepare for potential spills and to assess associated environmental concerns. The present work measured and compared the physical and chemical properties of Bakken crudes with conventional crude oils from various regions and different types of refined petroleum products. The physicochemical properties of Bakken crude are overall similar to those of conventional light crudes. The Bakken crude consists of high concentrations of monoaromatic hydrocarbons and alkylated PAHs with a clear dominance of the alkylated naphthalene homologues followed by the phenanthrene series. Its pyrogenic index (PI) values are considerably lower than typical conventional crude oils. The Bakken crude oils in this study exhibit a low abundance of petroleum biomarker such as terpanes, steranes and diamondoids and bicyclic sesquiterpanes. Since tight oil from the Bakken region is produced from low-permeability formations, variations in abundance and diagnostic ratios of common target petroleum hydrocarbons were found among these oils.

2017-336:Diluted bitumen (dilbit), an oil sands product, may present new response challenges differing from conventional crude oil in terms of its potential environmental impacts. Simple naphthenic acids (NAs), a complex group of monocarboxylic acids, with a general formula CnH2n+zO2, may be present in the source bitumen or may be created by photolytic weathering. Knowing the composition and concentrations of NAs created during the photo-degradation process of dilbit will help understand the fate, behavior and toxicity of dilbit.In the present study, two diluted bitumen products, Cold Lake Blend (CLB) and Access Western Blend (AWB), were mixed with saltwater and irradiated with natural solar light (Ottawa, Canada, 45.4°N) over winter and summer seasons, to assess the impact of sunlight on the chemical fate of the dilbit. For comparison, a light, sweet crude oil was exposed under similar conditions. The samples were analyzed by high performance liquid chromatography-high resolution mass spectrometry to examine the molecular transformation of diluted bitumen by solar irradiation. The abundances of NAs in all three test oils increased significantly after 90 days of solar irradiation, strongly suggesting that polar NAs were formed by photolysis. Further, greater increases in NAs in the light crude were found than in the two dilbits. Similarly, the lighter oil had higher photolytic removal rates of petroleum hydrocarbons than the two dilbits.The concentrations of NAs in oils exposed during the summer were generally higher than those exposed in winter. During summer exposure, the abundance of total NAs increased up to the 30-day’s solar exposure, then fell again, indicating the transient nature of these compounds. However, net increases in polar NA compounds were observed for all the winter exposed samples. Greater increases were observed in the smaller NA compounds (average C-number decreased), also accompanied by an increase in saturation (average z-number decreased).These chemical changes strongly indicate the effect of sunlight on the potential behaviour, fate and effects of spilled oil, with creation of new resin group compounds and reduction of aromatics and saturates. These changes may affect the viscosity of the oil and its ability to uptake water. These chemical compositions also imply significant changes to the ecological effects of the oil following a spill when aged in sunlight.

2017-217 One of the major unknowns with respect to the fate and behavior of spilled dilbit is its state of buoyancy, particularly when mixed with sediments. What form do diluted bitumen and sediment mixtures take, and will they float or sink in water column? In this study, we evaluated the fate and behavior of Cold Lake Blend-Winter at three different weathering states (i.e., fresh, medium, and heavily weathered) in high-energy mixing marine conditions, with (and without) sufficient concentrations of sediments to ensure formation of oil-particulate aggregates (OPA). Conventional light crude oil and intermediate and heavy fuel oils were also included to serve as references for behavior of other types of oils. Two mineral sediments including kaolin (fine) and sand (coarse) as well as natural sediment from the Douglas Channel (DC) in northern British Columbia, (medium) were used for this evaluation. The resulting OPAs were characterized in terms of buoyancy, OPA density, particle size distribution, and morphology to better understand the oil-sediment interaction. In the absence of sediment, mixing of the oils with water resulted in meso/entrained–water-in-oil mixtures; these mixtures remained floating on the water surface. However, in presence of kaolin or the DC sediments, a significant portion of the OPA sank to the bottom of the water column for all oils, with the exception of the light crude oil and the highly weathered Cold Lake Blend-Winter. The later did not uptake as much sediment and instead formed discrete free-floating tarballs. In experiments with the larger sand sediment, no OPAs formed. The density and particle size analysis revealed that the OPAs of the oils with higher viscosity tended to have larger densities and particle sizes. Microscopic examination of the OPAs showed that all consisted of oil droplets surrounded by sediment particles and were present in single droplet or multiple-droplet clusters.

2017-182 The dispersal and weathering processes of crude and fuel oils have been studied for decades and significant scientific information has been published. However, the fate and behaviour of spilled nonconventional crude oil such as diluted bitumen products are less well understood. There is concern that a spill of the oil sands diluted bitumen may come into contact with marine shorelines as it is transported throughout Canada. There is uncertainty related to the fate of spilled diluted bitumen and potential interactions with shorelines. A Shoreline Oil Spill Research and Development Program was undertaken by Environment and Climate Change Canada (ECCC). In 2013, a 3-year study was initiated and focused on the marine shorelines of northern British Columbia (BC). Four field campaigns were conducted along the entire length of coast throughout the Douglas and Granville channels as well as Banks and Haida Gwaii islands. The field campaigns were used as an opportunity to develop and employ a new approach to collect and compile an extensive pre-spill baseline dataset. Data included an aerial survey with high definition video and a ground survey of representative shorelines where samples were collected and analyzed for petroleum hydrocarbons, carboxylic acid, pesticides, heavy metals, calcium carbonate and sediment grain size. Baseline levels of hydrocarbons in the sediment of the study areas were estimated based on the analysis of total petroleum hydrocarbons (TPH), n-alkanes ranging from n-C9 to n-C40, petroleum related biomarkers such as terpanes and steranes, polycyclic aromatic hydrocarbons (PAHs) and their alkylated homologues (APAHs).

Two diluted bitumen, Cold Lake Blend (CLB), Accessed Western Blend (AWB), and Alberta Sweet Mixed Blend #5 crude oil (ASMB#5), were spiked into 3.3% NaCl aqueous solution, then exposed to natural sunlight for 90 days in the winter and summer in the Northern Hemisphere (Ottawa, Canada). The effects of temperature and solar intensity on the photolytic behavior of diluted bitumen were evaluated. Simultaneously, the photolytic similarities and differences between diluted bitumen and crude oil were compared. It was found that, in all test oils, the decrease of all total petroleum hydrocarbons followed a pseudo-first-order reaction kinetic with the exposure time regardless of seasons. Aromatic fractions had the highest apparent rate constants. Similarly, the chemical fingerprinting analysis of test oils demonstrated that polycyclic aromatic hydrocarbons (PAHs) and their alkylated homologues (APAHs) were the most photosensitive compounds among the identified targets, followed by n-alkanes, then terpanes, and steranes. The photolytic efficiencies of the target petroleum hydrocarbons in ASMB#5 were generally higher than the two diluted bitumen. Photolysis of APAHs occurred faster in summer than in winter; however, APAHs with different number of rings and degree of alkylation did not have obvious photolytic differences. These phenomena suggest that the photolytic similarities between dilbits and conventional crude oil depend on their similar chemical structure of petroleum hydrocarbons; their differences depend on the specific oil properties. The accumulated solar irradiation intensity and temperature are the main factors contributing to their photolytic differences for winter and summer exposed oils.

Fluorescence spectroscopy analysis of oil and environmental samples collected from four oil spill incidents in Canada—a 2016 pipeline spill into the North Saskatchewan River (NSR), Saskatchewan; a 2015 train derailment in Gogama, Ontario; the 1970 sinking of the SS Arrow ship in Chedabucto Bay, Nova Scotia; and the 1970 sinking of the Irving Whale barge in the Gulf of St. Lawrence—permitted assessment of the PAH content of environmentally weathered samples. A recently developed fluorescence fingerprinting model based on excitation–emission matrix-parallel factor analysis-principal component analysis (EEM-PARAFAC-PCA) was applied to (i) evaluate the intensity of the abundant PAH groups in the samples, (ii) investigate changes in the PAH composition of environmental samples over time due to weathering, and (iii) classify the original spilled oil and environmental samples within the already established classes of the fingerprinting PCA model. The environmental sediment samples collected from the Husky Energy spill site show loss of PAHs occurring over the course of 15 months post-spill. However, the extent of weathering depends on several environmental factors rather than solely the time of weathering, the PAH loss was maximum at 15 months. There was a decrease in the PAH content of the environmental samples of Gogama spill collected 20 months post-spill. Almost all of Gogama environmental sediment samples underwent substantial weathering, making PCA classification impractical. The SS Arrow and Irving Whale samples fell within adjacent PCA groups, as they both had a similar type of spilled oil (Bunker C) with similarity in chemical composition.

The characterization, occurrence, fate and behaviour of spilled oil in the affected boreal freshwater ecosystem were investigated in this study following a spill in March 2015, in Gogama, Ontario, Canada. A physicochemical property analysis of the source oil showed that the spilled oil was consistent with a conventional light oil. Oil samples collected immediately following the spill had lost their relatively light molecular alkanes and polycyclic aromatic hydrocarbons (PAHs) due to evaporation or dissolution. Twenty months post-spill, oil contamination levels decreased at sites located furthest from the accident site. Most of the sampling sites close to the incident site contained lightly weathered source oil, while some sediment contained heavily weathered source oil. Biogenic and pyrogenic inputs were also present in all the oil-contaminated sediments, where light molecular weight hydrocarbons had higher loss rates than heavy ones. Branched alkanes were more resistant to loss than corresponding straight isomers. Water samples usually had a lower loss of both alkylated PAHs and alkanes than in the underlying sediments. This difference can be ascribed to the fractionation of petroleum hydrocarbons between being deposited in sediment, and being released into water phases, especially when oils were freshly released into the water phase by disturbing bottom sediment. Aside from the rapid loss through evaporation and dissolution, microbial degradation was the major weathering process causing the loss of hydrocarbons 20 months after the spill.

Lubricating oil plays a critical role to reduce friction and to ensure the machines are more energy efficient in terms of fuel consumption and power output. The use of unqualified lube oil can result in malfunctions and damage to engines and machinery. Since petroleum-based lube oils are among the most valuable refined products, in some regions, fake, used, or waste lube oils have occasionally been deliberately adulterated into lube oil to extend the volume sold. On the other hand, used or waste lube oil is hazardous material, containing contaminants such as metals and polycyclic aromatic hydrocarbons produced by the engine during use. It becomes an environmental problem when it is purposely disposed of or accidentally spilled into the environment. Some jurisdictions now have relevant regulations to prohibit these illegal activities; therefore, forensic analysis of lube oils is essential to differentiate fake and used lube products from virgin oils, to identify and to track the adulteration source, and to identify the source of spilled oil. This work involved a fingerprinting analysis of a suite of oil samples including a virgin lube oil, used motor oils, a waste lube oil from a motor workshop, a regular diesel oil and a biodiesel blend, etc. The chemical fingerprints such as the abundance and distribution profiles of total petroleum hydrocarbon, polycyclic aromatic hydrocarbons (PAHs), particularly the higher molecular pyrogenic PAHs, and biomarkers indicate that the used and the waste lube oils are mixtures of mainly lube oil and a small amount of diesel type fuel. The presence of C16 to C20 fatty acid methyl esters (FAME) with the dominance of C16:0 and C18:1 isomers suggests that the used and the waste lube oils both contain residual palm oil-based biodiesel.

Polycyclic aromatic sulfur heterocycles (PASHs), as a group of major sulfur-containing compounds, widely occur in crude oil and its refined products. Accurate analyses of these petrochemical components play an important role in monitoring oil quality, forensic source identification, and assessment of environmental impact of an oil spill. PASHs occur at relatively lower abundances in most crude oils and refined petroleum products than their corresponding aromatic hydrocarbons and are co-eluted together with some petroleum hydrocarbons in chromatographic analysis, resulting in high uncertainty for their quantitation. Capillary gas chromatography coupled with a quadrupole time-of-flight mass spectrometry (GC-QTOF-MS) provides high resolution and high mass accuracy, which facilitates discrimination of the delicate mass defects of isobaric compounds with the same nominal mass and external matrix material. In this work, GC-QTOF-MS was applied to analyze bicyclic to pentacyclic PASHs including benzothiophenes, dibenzothiophenes, benzonaphthothiophenes, dinaphthothiophenes and their C1- to C4- alkylated homologues in a number of crude oils, refined petroleum products, and environmental samples. GC-QTOF-MS analysis substantially improved the identification confidence and reduced quantitation uncertainty of PASHs and polycyclic aromatic hydrocarbons (PAHs) by eliminating the interferences presented in nominal mass chromatograms.

Total petroleum hydrocarbons (TPH), n-alkanes, petroleum biomarkers, and polycyclic aromatic hydrocarbons (PAHs) were analyzed in the intertidal sediments of Burrard Inlet, Vancouver, British Columbia, Canada. Most of the sampling sites had low TPH (40 μg/g). Only 10% of sampling sites, located nearby a harbour and densely populated areas, had relatively high TPH (260 μg/g). Main biogenic n-alkanes were present in all the sites, except for the main petrogenic input in the sample from the upper intertidal zone (UIZ) of the Maplewood Mudflats. Most sites had trace amounts of petroleum biomarkers. Mixed pyrogenic and petrogenic inputs contributed to PAHs at most sites. PAHs did not show potential toxicity to benthic organisms at most sites; however, possible negative effects from some of the detected PAHs were found for the samples from the UIZs of the Maplewood Mudflats and Labour View Park, and from the lower intertidal zone (LIZ) of Gates Park.

In 1985, the MV Manolis L ran aground and sank on Blow Hard Rock near the Change Islands in Notre Dame Bay, Newfoundland and Labrador. From 2013 to 2016, the Canadian Coast Guard (CCG) conducted several operations to trap and recover oil leaking from the sunken tanker. Seventeen samples were collected between 2013 and 2016 from the sunken vessel to identify the oil source and evaluate the evolution of the physicochemical properties of the oil trapped in the sunken vessel. Most of the oils collected in 2016 and all the oils collected from 2013 to 2015 were heavy fuel oils that had not undergone significant weathering (Group 1). Two oils collected in 2016 were identified as diesel oil in terms of their hydrocarbon composition (Group 2). Other two oils collected in 2016 (Group 3) had similar hydrocarbon properties as Group 1 heavy fuel oils; however, they had greater quantities of biomarkers and GC-detectable total petroleum hydrocarbons (TPH) in the >n-C34 fraction and a lower quantity of resolved components, such as n-alkanes and PAHs. Detailed chemical fingerprinting pointed to these samples as being heavy fractions of Group 1 oils that had settled into a residual layer or had weathered through evaporation loss. Neither the heavy fuel oil nor diesel oil experienced significant loss through photo-oxidation and biodegradation, even 31 years post-sinking. Physical deposition, evaporation, and/or dissolution, especially deposition, were the main factors altering the physicochemical properties of the heavy fuel oil trapped in the sunken vessel.

Following the 16TAN Husky oil spill along the North Saskatchewan River (NSR), the occurrence and natural attenuation of the petroleum hydrocarbons were assessed by analyzing the littoral zone sediments/oil debris collected from July 2016 to October 2017. Husky oil-free, mixed sediment-Husky oil, and Husky oil debris samples were identified for all the collected samples. Shoreline sediments were contaminated by mixed biogenic, pyrogenic and petrogenic inputs prior to the spill. Oil stranded on the shoreline of NSR was moved or buried due to the very dynamic conditions of the shoreline, or cleaned through a series of cleanup activities after the spill. Most normal alkanes were naturally weathered, whereas most of the branched alkanes and all of the saturated petroleum biomarkers remained. Some lighter molecular weight (e.g., 2 to 3-ring) polycyclic aromatic hydrocarbons (PAHs) were lost rapidly after the spill, whereas sulfur containing components, e.g., dibenzothiophenes and benzonaphthothiiophenes, and those having a heavier molecular weight did not change markedly even 15 months post-spill. Similarly, some light hydrocarbons (e.g.

A large amount of polycyclic aromatic hydrocarbons (PAHs) and their heterocyclic analogues (N, S, O) are released to the marine environment from natural oil seeps, oil spills, bilge discharges and input of land-based sources. Many of these compounds are toxic and have a deleterious effect on marine biota. Nitrogen-containing compounds in crude oils are typically present as cyclic compounds such as polycyclic aromatic nitrogen heterocycles (PANHs) and are generally classified into the two categories of nonbasic (N-PANHs) and basic compounds (B-PANHs). Chromatographic analyses of PANHs are easily to be interfered by other oil components without proper sample preparation prior to instrumental analysis. In this work, dual solid phase extraction columns of 3-(isocyanato)propyl-functionalized silica gel (Si-NCO) and silica gel were employed to efficiently separate both N-PANHs and B-PANHs from saturated and aromatic petroleum hydrocarbons, which enable simultaneous accurate analyses of these groups with single sample preparation. Crude oils studied contain various concentrations of N-PANHs including carbazole, benzocarbazole and B-PANHs including quinolone, acridine and benzoacridine as well as their alkylated homologues. These compounds in light fuel and lubricating oil are generally not detected or are only in trace concentration, but have considerable abundance in heavy fuel oils. Crude oils from different sources and various petroleum products have their unique absolute concentrations and relative distribution patterns of PANHs. Chemical fingerprints of PANHs can provide valuable information for forensic oil spill identification and improve the understanding of the fate, behaviour and chemical degradation of spilled crude oil.

The total oxidizable precursor (TOP) assay can be useful for integrating precursors to perfluoroalkyl acids (pre-PFAAs) into the assessment of sites contaminated by per- and polyfluoroalkyl substances (PFAS). Current research gaps include risks of instrumental matrix effects due to the complexity of post-oxidation extracts, potential reproducibility issues during TOP itself, and limited information for zwitterionic and cationic pre-PFAAs. We first investigated a suitable method for the analysis of groundwater samples, using liquid chromatography high-resolution mass spectrometry (UHPLC-HRMS). Initial sample pre-treatment through filtration could affect the dissolved PFAS concentrations and was therefore avoided. Amending the postoxidation samples with methanol allowed for improved precision and low instrumental matrix effects. We also documented the oxidation yields of 23 anionic, neutral, zwitterionic, and cationic precursor compounds of PFAAs. These precursor compounds were amenable to TOP conversion. The total oxidative yield of 6:2 fluorotelomer sulfonamidoalkyl betaine (6:2 FTAB), for instance, was 80 mol%, with C3-C5 PFCAs as major oxidation products (minor: C6-C7 PFCAs). The method was applied to determine a wide range of PFAS (n = 41) without oxidation as well as ΔPFCA via persulfate oxidation in AFFF-impacted groundwater samples from fire-equipment testing sites in Ontario and Newfoundland, Canada. Summed PFAS concentrations as high as 5 mg L−1 were reported before oxidation, and post-oxidation increases of PFCAs up to + 2300% were observed. A significant contribution of increases in individual PFCAs was attributed to precursors such as 6:2 FTAB, fluorotelomer sulfonates (6:2 FtS, 8:2 FtS), perfluorooctane sulfonamidoalkyl amine (PFOSAm), and perfluorohexane sulfonamide (FHxSA) at the active firefighting training site.

The world of per- and polyfluoroalkyl substances (PFAS) is full of many useful and unique industrial and consumer products. Groundwater treatment for contaminated soil leachate is generally a reactionary measure that has been proven effective for preventing PFAS release to sources of drinking water. P. J. Lasier studied the transfer of PFAS from soil to an aquatic worm, Lumbriculus variegatus, and calculated bioaccumulation factors. The two main paths of PFAS entry into soil are industrial waste sites and the application of aqueous film-forming foams at military bases, airports, and municipal firefighting training areas. All remediation of PFAS methods can be divided into two categories: destructive and nondestructive. Destructive methods involve chemical transformations of PFAS leading to a change in their toxicological characteristics. The plan also included excavation of all soils on site that exceeded the Minnesota industrial soil reference values for perfluorooctanesulfonate and perfluorooctanoic acid, followed by backfilling of the site with uncontaminated soil.

This paper summarizes the results of the decontamination of the infrastructure materials concrete, limestone, brick and asphalt contaminated with 60Co, 85Sr, 137Cs and 241Am. The paper focuses on the effect of differences in substrate properties and of the pH of the radionuclide solution used for surface contamination on adsorption or ion exchange of the radionuclides and how these factors affect the decontamination effectiveness. A six-component chemical formulation was used and a process effectiveness of up to 76% was obtained depending on the substrate and radionuclide. Asphalt was the easiest material to decontaminate because of its more hydrophobic nature. Concrete and limestone (and to some extent brick) were less effectively decontaminated as their porous surfaces allowed penetration of radionuclides into water-filled pores in the substrate facilitating adsorption or ion exchange and making them difficult to remove. Brick was the most difficult material to decontaminate because the major component of brick is clay which retains most mono- and divalent ions. The removal of 60Co, 85Sr and 137Cs from the surfaces of concrete, limestone and brick increased when the pH of the radionuclide solutions was moderately acidic to neutral compared to when they were highly acidic. The variability in the test results was similar to that observed in other studies using other decontamination methods, attributed to the inhomogeneity of the substrates used and considered representative of real infrastructure materials.

Total petroleum hydrocarbons (TPH), n-alkanes, petroleum-related biomarkers of terpanes and steranes, and polycyclic aromatic hydrocarbons (PAHs) were analyzed in the intertidal sediments in the Bay of Fundy, Nova Scotia/New Brunswick, Canada. Sites close to the harbour and more densely populated areas had higher TPH levels than other pristine areas. n-Alkanes presented a typical single bell-shape in n-C16 to n-C35 range and an obvious odd to even carbon preference. Most sites had trace amounts of petroleum biomarkers. Abundant non-alkylated PAHs and lower amounts of alkylated PAHs represented the major input of the incomplete combustion of solid (e.g., coal, coke, biomass, and coal tar) and liquid fuels. The toxicity estimation for PAHs indicates that they did not have potential toxicity to benthic organisms at most sampling sites. However, possible to probable negative effects from the measured PAH concentrations were found for the two samples from Courtenay Bay and Saint Andrews.

This chapter presents specific cases to describe how to apply forensic chemical fingerprinting to characterize and differentiate biogenic and pyrogenic hydrocarbons from petrogenic hydrocarbons in various petroleum-contaminated environmental samples. The most important criteria from quantitative chromatographic analyses are concentrations, distribution profiles and diagnostic ratios of source-specific petroleum compounds such as normal alkanes and isoprenoids, unsubstituted PAHs (polycyclic aromatic hydrocarbons) and their alkylated series, biomarker terpanes and steranes, bicyclic sesquiterpanes and diamondoids. Chromatographic profiles of gas chromatography–flame ionization detection detectable component and distribution of normal alkanes provide primary diagnostic information for the identification and differentiation of petrogenic and biogenic sources. PAH distributions and associated diagnostic ratios, such as pyrogenic index and perylene index, are very useful tools in distinguishing petrogenic hydrocarbons from both pyrogenic and biogenic hydrocarbons. As petroleum-characteristic alkylated PAH homologues and biomarkers are rarely recognized in biogenic and pyrogenic sources, their co-occurrence can be used as an unambiguous indicator of petrogenic contamination, whereas the absence of petroleum-characteristic component and presence of abundant biogenic compounds such as dominant odd-numbered n-alkanes, sterols, fatty acids and alcohols could serve as strong evidences of a predominance of natural organic compounds in samples.

A large amount of polycyclic aromatic hydrocarbons (PAHs) and their heterocyclic analogues (N, S, O) are released to the marine environment from natural oil seeps, oil spills, bilge discharges and input of land-based sources. Many of these compounds are toxic and have a deleterious effect on marine biota. Nitrogen-containing compounds in crude oils are typically present as cyclic compounds such as polycyclic aromatic nitrogen heterocycles (PANHs) and are generally classified into the two categories of nonbasic (N-PANHs) and basic compounds (B-PANHs). Chromatographic analyses of PANHs are easily to be interfered by other oil components without proper sample preparation prior to instrumental analysis. In this work, dual solid phase extraction columns of 3-(isocyanato)propyl-functionalized silica gel (Si-NCO) and silica gel were employed to efficiently separate both N-PANHs and B-PANHs from saturated and aromatic petroleum hydrocarbons, which enable simultaneous accurate analyses of these groups with single sample preparation. Crude oils studied contain various concentrations of N-PANHs including carbazole, benzocarbazole and B-PANHs including quinolone, acridine and benzoacridine as well as their alkylated homologues. These compounds in light fuel and lubricating oil are generally not detected or are only in trace concentration, but have considerable abundance in heavy fuel oils. Crude oils from different sources and various petroleum products have their unique absolute concentrations and relative distribution patterns of PANHs. Chemical fingerprints of PANHs can provide valuable information for forensic oil spill identification and improve the understanding of the fate, behaviour and chemical degradation of spilled crude oil.

With the increasing use of biodiesel and its blends with petroleum fuel, the corresponding environmental issues also occur during its production, application and transportation. The photolysis behavior for biodiesel and the impacts of biodiesel on the photo-oxidation of petroleum hydrocarbons in simulated freshwater was studied by irradiated with ultra violet (UV) and simulated sunlight in the present study. The results indicated that the photolysis rates of fatty acid methyl esters (FAMEs) were mainly depended on their degree of saturation, slightly on water matrices and the initial concentration of biodiesel, regardless of biodiesel sources. Similar results were observed for total organic carbon (TOC) removal rates; however, TOC removal rates were slightly dependent on the initial concentration of biodiesel. The presence of humic acid and pyrogallic acid or lake water matrices slightly inhibited the removal rates of TOC. The photolysis rates of individual petroleum hydrocarbons with and without the presence of biodiesel followed similar rules. In brief, alkanes with light molecular weights were transformed faster than those with heavy molecules, the removal of polycyclic aromatic hydrocarbons (PAHs) were more significantly than alkanes, and the removal of alkylated PAHs (APAHs) increased concurrently with the alkylation level in each family. The presence of biodiesel only inhibited the photolysis of some heavy alkanes and PAHs, not for all other petroleum hydrocarbons. Biodiesel, as a surfactant-like material, could stabilize small oil droplets initially formed by agitation, therefore, these droplets experience longer lifetimes in the water phase before re-aggregating into larger globules and rising to the surface. The apparent solubility of petroleum hydrocarbons, especially for those with heavier molecular weights, has been enhanced in the presence of FAMEs. In this scenario, light needs to penetrate water phase to degrade these targets compared with diesel alone. The direct contacting opportunities between UV light and targets, and radicals produced to attack targets were reduced, which finally resulted in the inhibited photolysis rates of some heavy molecular weight hydrocarbons.

The present study investigated oil dispersant toxicity to fish species typical of the cooler regions of Canada, together with less well-documented issues pertaining to oil dispersant monitoring. The oil dispersant toxicity of Corexit EC9500A was assessed for the freshwater fish species rainbow trout and the seawater species coho, chinook, and chum, with a final median lethal concentration (LC50) acute lethality range between 35.3 and 59.8 mg/L. The LC50 range was calculated using confirmed 0-h dispersant concentrations that were justified by fish mortality within the first 24 h of exposure and by variability of the dispersant indicator dioctyl sulfosuccinate (DOSS) used to monitor concentrations at later time points. To investigate DOSS as an oil dispersant indicator in the environment, microcosm systems were prepared containing Corexit EC9500A, Finasol OSR52, Slickgone NS, and Slickgone EW dispersants together with diluted bitumen. The DOSS indicator recovery was found to be stable for up to 13 d at 5 °C, 8 d at 10 °C, but significantly less than 8 d at ≥15 °C. After 3 d at temperatures ≥15 °C, the DOSS indicator recovery became less accurate and was dependent on multiple environmental factors including temperature, microbial activity, and aeration, with potential for loss of solvents and stabilizers. A final assessment determined DOSS to be a discrepant indicator for long-term monitoring of oil dispersant in seawater. Environ Toxicol Chem 2018;37:1309-1319. © 2018 SETAC.

The fate and behavior of diluted bitumen spilled in marine conditions has recently become a topic of much interest, yet, only limited knowledge is available. One of the major issues of a diluted bitumen spill on water is whether the product will sink, especially when suspended sediment is present in the water column. This study demonstrated how weathering processes influenced the key spill-related properties of a diluted bitumen product (Cold Lake Blend-Winter), and how interaction of diluted bitumen with sediment affected its tendency to float or sink in water. This study showed that the weathering states of the oils as well as the size of sediment are important factors influencing oil-sediment interactions and the tendency of the formed oil-particulate aggregates for buoyancy. When mixing with fine- and medium-sized sediments, the fresh to moderately weathered oils formed oil-particulate aggregates and sank in saltwater, while the very heavily-weathered oil formed discrete free-floating tarballs.

The occurrence, source and ecological assessment of baseline hydrocarbons in the intertidal zone along the northern British shoreline were evaluated based on analyzing total petroleum hydrocarbons (TPH), n-alkanes, petroleum related biomarkers such as terpanes and steranes, and polycyclic aromatic hydrocarbons (PAHs) including non-alkylated and alkylated homologues (APAHs). The TPH levels, n-alkanes, petroleum biomarkers and PAHs in all the sampling sites, except for Masset Harbor/York Point at Gil Island were low, without obvious unresolved complex mixture (UCM) and petroleum contamination input. Specifically, n-alkanes showed a major terrestrial plants input; PAHs with abundant non-alkylated PAHs but minor APAHs showed a major pyrogenic input. However, obvious petroleum-derived hydrocarbons have impacted Masset Harbor. A historical petroleum input was found in York Point at Gil Island, due to the presence of the low level of petroleum biomarkers. Ecological assessment of 13 non-alkylated PAHs in Masset Harbor indicated no potential toxicity to the benthic organisms.

The characterization, identification, and correlation of oils are comprehensive and challenging tasks due to the wide variability in petroleum products. Forensic oil fingerprinting analysis becomes even more complicated once oil is released into the environment and subjected to various weatherings. It is extremely important to collect reliable evidence for each specific case. The most important criteria from quantitative chromatographic analyses are concentrations, distribution profiles, and diagnostic ratios of source-specific petroleum compounds. The selection of diagnostic ratios should be based upon a particular spill case including the oil type, weathering condition, and the abundance and distribution of target compounds. Oil fingerprinting analysis has advanced greatly in recent decades due to the rapid development of analytical and statistical techniques. Although automatic analysis using computerized techniques and database inputs could be a trend in the future, defensible source identification still heavily relies on systematic analysis, meticulous examination, and scientific interpretation of all available information by experienced environmental forensic scientists. This chapter provides an overview of analytical methodologies for separation and analysis of selected petroleum hydrocarbons and detailed chromatographic and quantitative chemical fingerprints of various crudes and refined petroleum products. This chapter also discussed the weathering effect on the chemical properties of oils under evaporation, biodegradation, and photodegradation.

Perfluorinated compounds (PFCs) are emerging environmental pollutants. Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) are the two primary PFC contaminants that are widely found in water, particularly in groundwater. This study compared the adsorption behaviors of PFOS and PFOA on several commercially available adsorbents in water. The tested adsorbents include granular activated carbon (GAC: Filtrasorb 400), powdered activated carbon, multi-walled carbon nanotube (MCN), double-walled carbon nanotube, anion-exchange resin (AER: IRA67), non-ion-exchange polymer, alumina, and silica. The study demonstrated that adsorption is an effective technique for the removal of PFOS/PFOA from aqueous solutions. The kinetic tests showed that the adsorption onto AER reaches equilibrium rapidly (2 h), while it takes approximately 4 and 24 h to reach equilibrium for MCN and GAC, respectively. In terms of adsorption capacity, AER and GAC were identified as the most effective adsorbents to remove PFOS/PFOA from water. Furthermore, MCN, AER, and GAC proved to have high PFOS/PFOA removal efficiencies (≥98%). AER (IRA67) and GAC (Filtrasorb 400) were thus identified as the most promising adsorbents for treating PFOS/PFOA-contaminated groundwater at mg L−1 level based on their equilibrium times, adsorption capacities, removal efficiencies, and associated costs.

Sensitive equipment materials were decontaminated from organophosphorus compounds paraoxon or parathion by immersion into a catalytic reactive solution and by spraying with the same solution. Immersion of contaminated material samples into methanol-based catalytic solutions resulted in an effective decontamination. Greater than 99% decontamination was observed for paraoxon on high-impact polystyrene (HI-PS) over 15 min of reaction time. Under the same process conditions, the decontamination from parathion did not exceed 95%. The catalytic decompositions of paraoxon and parathion followed first-order reaction kinetics with rate constants of 5.4 × 10–3 and 1.3 × 10–3 s–1, respectively. These values were by an order of a magnitude lower than the respective rate constants reported for homogeneous reactions in a methanol solution. Decontamination by spraying the catalyst on the contaminated surface revealed that multiple applications would be required to overcome a rapid evaporation of methanol from the surfac...

Polycyclic aromatic hydrocarbons (PAHs) are compounds of concern because most of these compounds are toxic, carcinogenic, or mutagenic and are relatively persistent in the environment. Reliable quantitative information of PAHs is important to evaluate the acute and chronic harmful effects of PAHs on the ecosystem. Crude oils and refined petroleum products contain many highly abundant PAHs and heterocyclic PAHs, in particular the alkylated homologues of naphthalene, phenanthrene, dibenzothiophene, fluorene and chrysene (APAH). The alkylated PAH homologues usually occur in significantly higher concentrations than their corresponding unsubstituted parent PAHs. Petrogenic alkylated PAHs generally consist of large numbers of isomers. Unlike those individual unsusbstituted PAHs, most of the APAH isomers are not commercially available. Therefore, historically, the target APAHs are generally quantified using the relative response factors (RRFs) obtained from their respective unsubstituted parent PAH compounds, this inevitably results in the quantitative results of APAH being significantly underestimated. In order to improve the accuracy of the measurement of PAHs and their alkylated homologues in oil and oil related samples, this study measured and compared the response factors of a large number of alkylated PAHs relative to the internal standards in gas chromatography-mass spectrometry (GC-MS) analysis, with the goal of developing a more accurate quantitative methodology for the determination of oil APAHs, and eventually leading to a standardized methodology of quantitative APAH analysis. The PAHs in different oils and related environmental samples collected from oil impacted areas were determined using this GC-MS methodology. Furthermore, the influence of the measurement methodology on the diagnostic ratios of target PAHs was also assessed in this work.

Remote-sensing for oil spills is reviewed. The use of visible techniques is ubiquitous, however it gives only the same results as visual monitoring. Oil has no particular spectral features that would allow for identification among the many possible background interferences. Cameras are only useful to provide documentation. In daytime oil absorbs light and remits this as thermal energy at temperatures 3-8K above ambient, this is detectable by infrared (IR) cameras. Laser fluorosensors are useful instruments because of their unique capability to identify oil on backgrounds that include water, soil, weeds, ice and snow. They are the only sensor that can positively discriminate oil on most backgrounds. Radar detects oil on water by the fact that oil will dampen water-surface capillary waves under low to moderate wave/wind conditions. Radar offers the only potential for large area searches, day/night and foul weather remote sensing.

To facilitate monitoring efforts, a forensic chemical fingerprinting methodology has been applied to characterize and differentiate pyrogenic (combustion derived) and biogenic (organism derived) hydrocarbons from petrogenic (petroleum derived) hydrocarbons in environmental samples from the Canadian oil sands region. Between 2009 and 2012, hundreds of oil sands environmental samples including water (snowmelt water, river water, and tailings pond water) and sediments (from river beds and tailings ponds) have been analyzed. These samples were taken from sites where assessments of wild fish health, invertebrate communities, toxicology and detailed chemistry are being conducted as part of the Canada-Alberta Joint Oil Sands Monitoring Plan (JOSMP). This study describes the distribution patterns and potential sources of PAHs from these integrated JOSMP study sites, and findings will be linked to responses in laboratory bioassays and in wild organisms collected from these same sites. It was determined that hydrocarbons in Athabasca River sediments and waters were most likely from four sources: (1) petrogenic heavy oil sands bitumen; (2) biogenic compounds; (3) petrogenic hydrocarbons of other lighter fuel oils; and (4) pyrogenic PAHs. PAHs and biomarkers detected in snowmelt water samples collected near mining operations imply that these materials are derived from oil sands particulates (from open pit mines, stacks and coke piles).

The present study investigated the storage stability of two commercially available biodiesels and their blends with diesel spiked with different impurities, which were stored at two different temperatures (15 and 40 °C) with air tight and light screen. These samples were periodically monitored during the whole storage period by measuring a number of properties, such as acid value (AV), induction time (IT) and composition of fatty acid methyl esters (FAMEs). It was found that (1) acid values increased but induction time decreased with the extension of storage for all samples without copper; however, both IT and AV values kept nearly constant for all samples with copper; (2) the presence of water did not contribute significantly to the degradation of all tested samples over time; and (3) higher temperature (40 °C) was favorable to the degradation of unsaturated FAMEs, accompanying with the altered acid values and induction time in comparison with the same samples stored at 15 °C. Faster degradation of FAMEs in blended samples than those in pure biodiesels may be partially due to the diluting effects of antioxidants in biodiesel. However, the presence of any impurities did not affect the degradation rates of FAMEs, which was not in agreement with the above mentioned AV and IT time series. This suggested that the addition of copper affected the measurement of AV and IT. Therefore, for samples with copper, FAME profiles can represent their quality more appropriately than IT or AV.

Aromatic steroids including monoaromatic (MAS) and triaromatic steroids (TAS) are a series of naphthenoaromatic hydrocarbons, which consist of mixed structures of aromatic and saturated 6-carbon or 5-carbon rings. Although these aromatic steroids are in relatively low concentration in oils, their specific fingerprints and high weathering resistance make them desirable biomarkers for the characterization, correlation, differentiation, and source identification in environmental forensic investigations of oil spills. This study presents a quantitative GC/MS analysis of these aromatic hydrocarbons in a number of crude oils and refined petroleum products including light and mid-range distillate fuels, heavy fuels, and lubricating oils collected from various sources. TAS-cholestanes (C26), TAS-ergostanes (C27), and TAS-stigmastanes (C28) are the most distinguishable triaromatic steroids in most oil samples. C26 TAS-cholestane (20R) and C27 TAS-ergostane (20S) are coeluted and often present as the highest peak i...

The most commonly used total petroleum hydrocarbons (TPH) analysis method measures petroleum hydrocarbon concentrations in soil by carbon range that can be detected by gas chromatography/flame ionization detection (GC/FID). Different cleanup procedures have been performed for removing some naturally occurring organics from petrogenic hydrocarbons prior to GC/FID analysis. To evaluate the different pre-treatment methods, more than 60 samples (including background soil and plant samples, as well as oil contaminated soil samples) were sampled from 2008 to 2010 in Canada. TPH values without cleanup (TPH-T), with column cleanup (TPH-F 3) and with in-situ cleanup (TPH-F) were compared to evaluate the effects of different pre-treatment methods on the TPH analysis values. Different total solvent extractable materials (TSEM) loading amounts were applied for in-situ silica gel cleanup method to evaluate the effect of the TSEM loading amount on the measured TPH-F values. The column cleanup method was evaluated by co...

A case study is presented for the forensic identification of several spilled biodiesels and its blends with petroleum oil using integrated forensic oil fingerprinting techniques. The integrated fingerprinting techniques combined SPE with GC/MS for obtaining individual petroleum hydrocarbons (aliphatic hydrocarbons, polyaromatic hydrocarbons and their alkylated derivatives and biomarkers), and biodiesel hydrocarbons (fatty acid methyl esters, free fatty acids, glycerol, monoacylglycerides, and free sterols). HPLC equipped with evaporative scattering laser detector was also used for identifying the compounds that conventional GC/MS could not finish. The three environmental samples (E1, E2, and E3) and one suspected source sample (S2) were dominant with vegetable oil with high acid values and low concentration of fatty acid methyl ester. The suspected source sample S2 was responsible for the three spilled samples although E1 was slightly contaminated by petroleum oil with light hydrocarbons. The suspected source sample S1 exhibited with the high content of glycerol, low content of glycerides, and high polarity, indicating its difference from the other samples. These samples may be the separated byproducts in producing biodiesel. Canola oil source is the most possible feedstock for the three environmental samples and the suspected source sample S2.

Decontamination of sensitive equipment materials contaminated by organophosphorus (OP) compounds by a two-stage process was evaluated. The process involved extraction of OP from contaminated materials with methanol (first stage), followed by decomposition of OP by heterogeneous catalytic methanolysis (second stage). In a series of tests diazinon, malathion, paraoxon, parathion, and other organophosphorus pesticides were spiked onto sensitive equipment materials and extracted with methanol after a presented contact time. After extraction, the lowest quantity of residue was found for diazinon, while parathion was the most persistent. High-impact polystyrene (HI-PS) retained 10-fold or more mass of OP than other tested materials. The surface of the HI-PS was deteriorated after contacting with OP due to a plasticizing effect. A longer contact time with HI-PS and lower polarity factor of OP resulted in higher residual amounts of OP after extraction. In the second stage of the process, diazinon and paraoxon wer...

Even though the design and electronics of sensors are becoming increasingly sophisticated and sensors are becoming much less expensive, the operational use of remote sensing equipment lags behind the development of the technology. The most common forms of oil spill surveillance and mapping is done with simple still or video photography, which provide little, if any, forensic data. Remote sensing from aircraft is still the most common form of oil spill tracking. Attempts to use satellite remote sensing for oil spills, although successful, are not necessarily as claimed and are generally limited to identifying features at sites of known oil spills. The laser fluorosensor is a most useful instrument to forensics because of its unique capability to positively identify oil against most backgrounds, including water, soil, weeds, ice, and snow. Radar offers the only potential for searching in large areas and carrying out remote sensing during foul weather conditions, but offers very poor positive detection characteristics and thus low forensic capability. The usefulness of the visible spectrum for oil detection is limited. It is, however, an economical way to document oil spills and provide baseline data on shorelines or relative positions.

With the increasing use of biodiesel and its blends with conventional petroleum diesel, the corresponding environmental issues arise during their manufacturing, application, and transportation. Chemical fingerprinting methodology is extremely important for characterizing spilled biodiesel, monitoring the affected ecosystem, and determining the fate and behavior of biodiesel or its blends with diesel in the environment. This chapter describes the chemical composition of biodiesel and provides an overview of the analytical methodologies used in the chemical fingerprinting analysis of biodiesel and biodiesel blends. The identification of biodiesels derived from different feedstocks is based on the composition of fatty acid methyl esters, free sterols, free fatty acids, glycerides and glycerol, the diagnostic ratios of several target analytes, and the cross-plots of representative diagnostic ratios. The weathering effects on biodiesel and the application of biodiesel and the blends of biodiesel/petroleum oil fingerprints in forensic oil spill identification are also discussed.

The fingerprinting of oil spills can be a challenge to analytical chemists due to the complex nature of crude oils and the low concentrations of many constituents of interest. Oils spilled into the environment are immediately subject to various natural weathering processes, subsequently altering the chemical fingerprints and composition of spilled oils. In addition, background materials could severely interfere with the accurate determination of petroleum compounds when applying currently established analytical techniques, for example, single quadrupole GC–MS. Gas chromatography coupled with quadrupole time-of-flight mass spectrometer (GC–QTOF) greatly enhances the resolution of individual series of compounds and, owing to GC–QTOF’s accurate mass measurements, subsequently reduces interferences from the sample matrix and thereby provides more accurate identification and quantitation of targeted spilled oil components. This chapter provides an introduction and overview of the application of GC–QTOF in the chemical fingerprinting analysis of petroleum oils and petroleum-contaminated environmental samples.