Maritime nations around the world proactively engage in preparedness, response, and recovery activities related to marine oil spills. In addition to an individual nation’s capabilities, there are a number of response organizations that are actively engaged in the surveillance, monitoring, and remote sensing of spilled oil. A global survey was conducted of these organizations to better understand surveillance/remote sensing capabilities operationally employed today from four aerial platforms: satellites, fixed-wing aircraft, helicopters, and remotely piloted aircraft systems (RPASs). Satellite remote sensing continues to be used for both routine surveillance of coastal environments and in support of response to oil spills. Additionally, there is a strong continued use of fixed-wing aircraft, and in some cases helicopters, particularly to support operational response to oil spills. Many of these fixed-wing aircraft are outfitted with sensor suites optimized for oil spill detection and documentation. Of particular interest is the recent introduction and widespread use of RPASs for the response of marine oil spills and oiled shorelines. Respondents identified operational gaps in remote sensing capabilities to support oil spill response, including the accurate measurement of oil spill thickness and volume, differentiation between petroleum oil and biogenic materials, and the detection of water-in-oil emulsions. Survey respondents also shared remote sensing capabilities used for oiled shorelines, as well as identifying research and operational gaps in the surveillance of oil spills.

Total petroleum hydrocarbons (TPH), n-alkanes, petroleum biomarkers, and polycyclic aromatic hydrocarbons (PAHs) were analyzed in the sediments collected from the shorelines and bottom of St. Clair River, Ontario, Canada. Most of the sampling sites had low TPH (< 20 μg/g). River bottom sediment usually had higher level of TPHs, total alkanes, total biomarkers, and total PAHs than most of the shoreline ones. Mixed biogenic and petrogenic n-alkanes were present in all the sites. Most sites had trace amounts of petroleum biomarkers. Mixed pyrogenic and petrogenic inputs with the predominant petroleum, have contributed to the detected PAHs at all sampling sites. PAHs detected would not show potential toxicity to benthic organisms in all shoreline sampling sites; however, some light molecular weight PAHs (e.g., phenanthrene, 2-methyl naphthalene, and acenaphthylene) are anticipated to have possible adverse impacts to sediment-dwelling organisms in part of the river bottom sediment.

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.

In June 2016, oil residues and sediment samples were collected from the shoreline of Chedabucto Bay, Nova Scotia, Canada, at sites affected by the 1970 Arrow oil spill. This study aimed to investigate the occurrence, fate, and behaviour of oil components 45 years post-spill by analysing polar naphthenic acid fraction components (NAFCs) through high-performance liquid chromatography–high-resolution mass spectrometry (HPLC–HRMS). In all samples, the most abundant NAFC species were those having only oxygen as the heteroatom ( O o species, o indicating the number of oxygen atoms, from 1 to 8) and a high degree of saturation. NAFC species only containing two oxygen atoms (O 2 ) accounted for 50–70% of all O o species. The abundance of all remaining species was negligible compared with O o species. NAFCs in most Arrow oil residues had higher levels of oxygen species than the oil remaining stored in the sunken tanker. Environmental sediment samples collected from near a marina away from the spill site contained a dominant biological, whereas all Arrow oil residues were mainly composed of NAFCs that are characteristic of petroleum. The abundance of NAFCs in the Arrow oil residues varied between sites, confirming that site-specific environmental conditions play a major role in controlling the fate and behaviour of oil components, including NAFCs.

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.

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-C-34 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.

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.

Observations made for the analysis of the oil spill dispersant tracer dioctyl sulfosuccinate (DOSS) during LC50 toxicity testing, highlighted a stability issue for this tracer compound in seawater. A liquid chromatography high-resolution quadrupole time-of-flight mass spectrometry (LC/QToF) was used to confirm monooctyl sulfosuccinate (MOSS) as the only significant DOSS breakdown product, and not the related isomer, 4-(2-ethylhexyl) 2-sulfobutanedioate. Combined analysis of DOSS and MOSS was shown to be applicable to monitoring of spill dispersants Corexit (R) EC9500A, Finasol OSR52, Slickgone NS, and Slickgone EW. The unassisted conversion of DOSS to MOSS occurred in all four oil spill dispersants solubilized in seawater, although differences were noted in the rate of MOSS formation. A marine microcosm study of Corexit EC9500A, the formulation most rapid to form MOSS, provided further evidence of the stoichiometric conversion of DOSS to MOSS under conditions relevant to real world dilbit spill. Results supported combined DOSS and MOSS analysis for the monitoring of spill dispersant in a marine environment, with a significant extension of sample collection time by 10 days or longer in cooler conditions. Implications of the unassisted formation of MOSS and combined DOSS:MOSS analysis are discussed in relation to improving dispersant LC50 toxicity studies.

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 July 2013, a fatal train derailment led to an explosion and fire in the town of Lac-Mégantic (LM), Quebec, and the crude oil contamination of regional surface water, soil, and sediment in the adjacent Lake Mégantic. This study investigated the degradation potential of the spilled crude oil by using the sediments from the incident site as the source of microorganisms. Two light crude oils (LM source oil and Alberta Sweet Mixed Blend (ASMB)) were tested at 22 °C for 4 weeks and 4 °C for 8 weeks, respectively. The post-incubation biological and chemical information of the samples were analysed. There was no marked difference in degradation efficacy and biological activities for both the LM and ASMB oils, although the biodegradation potential differed between the two incubations. Higher temperature favoured the growth of microorganisms, thus for the degradation of all petroleum hydrocarbons, except for some conservative biomarkers. The degradation of both oils followed the order of resolved components > total saturated hydrocarbons (TSH) > unresolved complex mixture (UCM) >total aromatic hydrocarbons (TAH). Normal alkanes were generally degraded more significantly than branched ones, and polycyclic aromatic hydrocarbons (PAHs). Degradation of polycyclic aromatic hydrocarbons (PAHs) and their alkylated congeners (APAHs) for both incubations generally decreased as the number of aromatic rings, and the degree of alkylation increased. This study showed that the LM sediments can biodegrade the petroleum hydrocarbons efficaciously if appropriate ambient temperatures are generated to favour the growth of autochthonous microorganisms.

Naphthenic acids (NAs) or naphthenic acid fraction compounds (NAFCs) are generally recognized as a family of cycloaliphatic carboxylic acids naturally occurring in petroleum. These acid extractable organics (AEOs) from petroleum industry activities including oil sands produced waters (OSPW) have led to increasing environmental concern in recent years due to their potential release into the environment. This study presents a characterization of naphthenic acids in a number of crude oils and refined petroleum products from various sources. NAs with unsaturated degree of z - 2 to z - 24 and carbon number ranging from 6 to 60 were determined by liquid chromatography-high resolution Orbitrap mass spectrometry (LC-HRMS). NA profiles generally vary from oil to oil. Conventional light crude oils generally contain low concentrations of NAs, while heavier crudes and oil sands bitumen contain significant levels of NAs. NAs in Federated and Alaska North Slope crude oils are relatively low with O-2-NA concentrations of 139 mu g/g and 419 mu g/g, respectively, while their abundances are as high as 7994 mu g/g in Venezuelan Orinoco bitumen. The ratio of even to odd (E/O) carbon number NAs in all petroleum oils studied is close to 1.0 for z - 2 to z - 24 NAs. NA series z 0 to z - 12 in bitumen account for about 90% of the total determined NAs, and z - 14 to z - 24 NAs make up the remaining similar to 10%. Moreover, z - 2 similar to - 6 (1- to 3-ring) NAs are the most predominant in all oil samples. In terms of distribution according to carbon number, C-6 to C-21 NAs (alpha-group) make up about 44.2% of the total NAs in an Alberta oil sands bitumen. Caustic extraction of oil sands bitumen mostly transports the more toxic low-molecular weight portion of NAs into OSPW, in which alpha-group NAs constitute about 90% of the total NAs. Evaporation (up to 23.6% by weight) weathering slightly enriched the NAs but likely did not affect the distribution profile of NAs in a diluted bitumen (dilbit).

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., <C10) were lost over the first kilometers from the point of entry (POE), while heavier hydrocarbons did not show any major differences away from the POE. Very large inter-site and inter-survey discrepancies were found for samples. Evaporation into the air and dissolution into water, combined with biodegradation, were together or independently the main contributors to the loss of the light molecular hydrocarbons.

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.

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 (101,11), 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 (R) 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 degrees 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. (C) 2019 Published by Elsevier B.V.

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.

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 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 59.8mg/L. The LC50 range was calculated using confirmed 0-h dispersant concentrations that were justified by fish mortality within the first 24h 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 degrees C, 8 d at 10 degrees C, but significantly less than 8 d at 15 degrees C. After 3 d at temperatures 15 degrees 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. (C) 2018 SETAC