Chemical Weathering Patterns of Diluted Bitumen Spilled into Freshwater Limnocorrals.

Due to the sudden nature of oil spills, few controlled studies have documented how oil weathers immediately following accidental release into a natural lake environment. Here, we evaluated the weathering patterns of Cold Lake Winter Blend, a diluted bitumen (dilbit) product, by performing a series of controlled spills into limnocorrals installed in a freshwater lake in Northern Ontario, Canada. Using a regression-based design, we added seven different dilbit volumes, ranging from 1.5 to 180 L, resulting in oil-to-water ratios between 1:71,000 (v/v) and 1:500 (v/v). We monitored changes in the composition of various petroleum hydrocarbons (PHCs), including n-alkanes, polycyclic aromatic hydrocarbons (PAHs), and oil biomarkers in dilbit over time, as it naturally weathered for 70 days. Depletion rate constants (kD) of n-alkanes and PAHs ranged from 0.0009 to 0.41 d-1 and 0.0008 to 0.38 d-1, respectively. There was no significant relationship between kD and spill volume, suggesting that spill size did not influence the depletion of petroleum hydrocarbons from the slick. Diagnostic ratios calculated from concentrations of n-alkanes, isoprenoids, and PAHs indicated that evaporation and photooxidation were major processes contributing to dilbit weathering, whereas dissolution and biodegradation were less important. These results demonstrate the usefulness of large scale field studies carried out under realistic environmental conditions to elucidate the role of different weathering processes following a dilbit spill.

The fate and behavior of petroleum biomarkers in diluted bitumen and conventional crude oil exposed to natural sunlight in simulated seawater.

Given that the physicochemical properties of diluted bitumen (dilbit) can differ from those of conventional crude oil, understanding the fate and behavior of this petroleum product in the environment becomes vital. This study involves the analysis of the photolytic behavior of some representative petroleum biomarkers, bicyclic sesquiterpanes (BSs), admantanes (ADs), diamantanes (DAs), and mono- and triaromatic steranes (MASs and TASs), by exposing Cold Lake Blend (CLB) and Alberta Sweet Mixed Blend (MSW) to winter and summer insolation after being spilled onto artificial brines. Aromatic steranes in all control samples remained relatively stable, whereas the biomarkers of BSs, ADs, and DAs were less stable. Similar to the exhaustive loss of the C10-C17 alkanes, 91%-99% of BSs, ADs, and DAs were lost after five days of insolation, especially in summer. Both MASs and TASs were lost gradually in most scenarios, although both of them were lost faster in MSW than observed for CLB. The removal of MASs and TASs did not differ significantly from each other, although their loss was less than observed for PAHs having similar number of rings and greater than for the C21-C33n-alkanes. Therefore, photooxidation, not evaporation or biodegradation, was the main factor responsible for oxidizing these aromatic steranes. However, biomarkers of BSs, ADs and DAs were mostly lost through evaporation. Therefore, aromatic steranes have the potential to be utilized to evaluate the photolytic behavior of petroleum hydrocarbons, while BSs, ADs, and DAs should not be used for this purpose.

Effects of asphaltenes on the photolytic and toxic behavior of bitumen and conventional oil products on saltwater.

The effects of asphaltenes on the photolytic and toxic behavior of petroleum oil on seawater was investigated by exposing five original oils and their maltenes to solar irradiation for seven days. Polycyclic aromatic hydrocarbons (PAHs) experienced the fastest photo-oxidation, but negligible photolytic loss was observed for most normal alkanes and all the petroleum biomarkers from tri-cyclic to pentyl-cyclic terpanes in the test total oil and maltenes. The removal of most PAHs from some maltenes was greater than the corresponding total oils. Deasphalting process did not affect the characteristics of naphthenic acid fraction components (NAFCs) in all control samples. In all test oils, solar irradiation formed abundant NAFCs, in particular those only containing oxygen as the heteroatoms (Oo species). The formed Oo species were abundant in congeners having highly saturated congeners, and shifted to a lighter carbon number after exposed. Deasphalting process significantly enhanced the formation of Oo species (o from 2 to 4) for all test oils, in particular for the Cold Lake Blend and Bunker C. The toxicity of exposed maltenes was generally higher than the exposed total oil for most oils, suggesting the aqueous toxicity level was positively related to the formed NAFC intermediates.

Occurrence, characterization, source, and risk assessment of petroleum-related hydrocarbons in sediments along St. Clair River, Ontario, Canada.

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.

Occurrence, characterization, and ecological assessment of petroleum-related hydrocarbons on the shoreline of Fraser River Delta, British Columbia, Canada.

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.

Simulating diluted bitumen spills in boreal lake limnocorrals - Part 1: Experimental design and responses of hydrocarbons, metals, and water quality parameters.

Large-scale, in-lake enclosures (limnocorrals) were used to simulate spills of diluted bitumen (dilbit) in a boreal lake. In this study we use these simulated spills, which covered a range of sizes (oil:water ratio) representative of the upper 25% of onshore crude oil spills in North America (2008-2019), to assess the fate of dilbit-derived hydrocarbons and metals as well as the impacts of the spills on standard water quality parameters. The systems were monitored over 70 days following the application of dilbit amounts ranging between 1.5 and 179.8 L into 10-m diameter, ~100 m3 limnocorrals. The concentration of total petroleum hydrocarbons (TPH) in the water column increased rapidly over the first two weeks reaching a plateau that ranged between 200 µg/L and 2200 µg/L for the lowest and highest treatment respectively. The concentration of total polycyclic aromatic compounds (PACs) also increased over the first two weeks, prior to a slow decrease until day 70. The maximum measured concentrations in the highest treatment were 2858 ng/L for the sum of all 46 quantified PACs, 2716 ng/L for alkylated PACs and 154 ng/L for the 16 EPA priority PAHs. The concentrations of PACs in the sediment increased continuously over the study in the three highest treatments with maximum observed concentrations of 189 ng/g for ΣPAC46, 169 ng/g for ΣPACalk. No significant treatment-related changes in the 16 EPA priority PAHs were observed in the sediment. Of the 25 metals quantified in the water column, only manganese, molybdenum, and vanadium displayed a significant treatment effect with increases of 280, 76 and 25% respectively in the total fraction. These results can help us understand and predict the fate of oil-derived contaminants following a spill and characterize the exposure of freshwater organisms living within them. These results should help inform the risk assessment of future dilbit transportation projects.

Occurrence, characterization, and ecological assessment of petroleum-related hydrocarbons in intertidal marine sediments of Burrard Inlet, Vancouver, British Columbia, Canada.

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.

Biodegradation potential assessment by using autochthonous microorganisms from the sediments from Lac Mégantic (Quebec, Canada) contaminated with light residual oil.

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.

Simulating a Spill of Diluted Bitumen: Environmental Weathering and Submergence in a Model Freshwater System.

The main petroleum product transported through pipelines in Canada is diluted bitumen (dilbit), a semiliquid form of heavy crude oil mixed with natural gas condensates to facilitate transport. The weathering, fate, behavior, and environmental effects of dilbit are crucial to consider when responding to a spill; however, few environmental studies on dilbit have been completed. We report on 11-d-long experimental spills of dilbit (Cold Lake Winter Blend) in outdoor microcosms meant to simulate a low-energy aquatic system containing natural lake water and sediments treated with low (1:8000 oil:water) and high (1:800 oil:water) volumes of dilbit. In the first 24 h of the experiment, volatile hydrocarbons quickly evaporated from the dilbit, resulting in increased dilbit density and viscosity. These changes in dilbit's physical and chemical properties ultimately led to its submergence after 8 d. We also detected rapid accumulation of polycyclic aromatic compounds in the water column of the treated microcosms following the spills. The present study provides new information on the environmental fate and behavior of dilbit in a freshwater environment that will be critical to environmental risk assessments of proposed pipeline projects. In particular, the study demonstrates the propensity for dilbit to sink under ambient environmental conditions in freshwaters typical of many boreal lakes. Environ Toxicol Chem 2019;38:2621-2628. © 2019 SETAC.

Occurrence, source and ecological assessment of petroleum related hydrocarbons in intertidal marine sediments of the Bay of Fundy, New Brunswick, Canada.

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.

Effect of evaporative weathering and oil-sediment interaction on the fate and behavior of diluted bitumen in marine environments. Part 2. The water accommodated and particle-laden hydrocarbon species and toxicity of the aqueous phase.

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.

Fate of oxygenated intermediates in solar irradiated diluted bitumen mixed with saltwater.

Two types of diluted bitumen (dilbit) and a light crude oil spiked onto the surface of saltwater were irradiated with natural solar light in Ottawa to assess the impact of sunlight to the fate of oxygenated intermediates. Oxygenated components, including carbonyl polycyclic aromatic hydrocarbons (PAHs) and acidic polar fractions (naphthenic acid fraction compounds, NAFCs), were identified after periods of solar exposure under both winter and summer conditions. Carbonyl PAHs and NAFCs were formed in both seasons; however, light crude and summer irradiation produced higher abundance of them than dilbits and winter exposure. The formed NAFCs were abundant with the congeners containing a heteroatom of oxygen only (Oo species), accompanied by the minor amounts of sulfur- and nitrogen-containing acids. The produced Oo species were predominant with the congeners with light molecular weight, high degree of saturation and heavy oxygen numbers. For both carbonyl PAHs and NAFCs, their abundance continually increased throughout the period of winter exposure. In the summer, some carbonyl PAHs and all Oo species increased during the early exposure period; then they decreased with continued exposure for most oils, illustrating their transitional nature. Oxygenated intermediates thus appear to have been created through the photo-oxidation of non-to medium-polar petroleum hydrocarbons or the intermediates of aldehydes or ketones (O1). Oil properties, the duration of exposure, exposure season and the chemical structure of these intermediates are critical factors controlling their fate through photo-oxidation. The observed chemical changes highlight the effects of sunlight on the potential behavior, fate and impact of spilled oil, with the creation of new resin group compounds and the reduction of aromatics and saturates. These results also imply that the ecological effects of spilled oil, after ageing in sunlight, depend on the specific oil involved and the environmental conditions.

Occurrence, source and ecological assessment of baseline hydrocarbons in the intertidal marine sediments along the shoreline of Douglas Channel to Hecate Strait in British Columbia.

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.