Fate of polycyclic aromatic compounds from diluted bitumen spilled into freshwater limnocorrals.

Diluted bitumens (dilbits) are produced by mixing highly viscous bitumen with lighter petroleum products to facilitate transport. The unique physical and chemical properties of dilbit may affect the environmental fate and effects of dilbit-derived chemical compounds when spilled. To further explore this, we monitored experimental spills of Cold Lake Winter Blend (CLWB) dilbit for 70 days in limnocorrals installed in a freshwater boreal lake. A regression design with 2 controls and 7 treatments was used to assess the fate and behaviour of polycyclic aromatic compounds (PACs) as they partitioned from the dilbit into the air, water column and sediments. Treatments ranged from 1.5 to 180 L of CLWB, resulting in oil:water ratios ranging between 1:71000 to 1:500 (v:v). We began to detect elevated concentrations of PACs as early as 6 h post-addition in the air, 12 h post-addition in the water column, and 15-28 d post-addition in the sediments. By the end of the experiment, concentrations of PACs had largely declined in the water column but remained elevated in the sediments. Our results demonstrate that under conditions typical of temperate boreal lakes, only a small proportion of PACs from dilbit enters the aquatic system, but even so, may produce concentrations of ecotoxicological concern, especially in the sediments, which is the ultimate sink for dilbit-derived PACs.

Simulating diluted bitumen spills in boreal lake limnocorrals - part 2: Factors affecting the physical characteristics and submergence of diluted bitumen.

We examined the fate and behaviour of diluted bitumen (dilbit) as it weathered for 70 days in freshwater limnocorrals (10 m diameter × 1.5 m depth) installed in a boreal lake to simulate dilbit spills in a natural aquatic environment. We added seven different dilbit spill 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, %). Volatile hydrocarbons in the dilbit slick decreased rapidly after the dilbit was spilled on the water's surface, and dilbit density and viscosity significantly increased (>1 g mL-1 and >5,000,000 mPa s, respectively). Dilbit sank to the bottom sediments in all treatments, and the time to sinking was positively correlated with spill volume. The lowest dilbit treatment began to sink on day 12, whereas the highest dilbit treatment sank on day 31. Dilbit submerged when its density surpassed the density of freshwater (>0.999 g mL-1), with wind, rain, and other factors contributing to dilbit sinking by promoting the break-up of the surface slick. This experiment improves our ability to predict dilbit's aquatic fate and behaviour, and its tendency to sink in a boreal lake. Our findings should be considered in future pipeline risk assessments to ensure the protection of these important aquatic systems.

Forensic source differentiation of petrogenic, pyrogenic, and biogenic hydrocarbons in Canadian oil sands environmental samples.

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).

Forensic differentiation of biogenic organic compounds from petroleum hydrocarbons in biogenic and petrogenic compounds cross-contaminated soils and sediments.

"Total petroleum hydrocarbons" (TPHs) or "petroleum hydrocarbons" (PHCs) are one of the most widespread soil pollutants in Canada, North America, and worldwide. Clean-up of PHC-contaminated soils and sediments costs the Canadian economy hundreds of million of dollars annually. Much of this activity is driven by the need to meet regulated levels of PHC in soil. These PHC values are legally required to be assessed using standard methods. The method most commonly used in Canada, specified by the Canadian Council of Ministers of the Environment (CCME), measures the total hydrocarbon concentrations in a soil by carbon range (Fraction 1: C(6)-C(10); Fraction 2: C(10)-C(16), Fraction 3: C(16)-C(34): and Fraction 4: C(34)+). Using the CCME method, all of the materials extractible by a mixture of 1:1 hexane:acetone are considered to be petroleum hydrocarbon contaminants. Many hydrocarbon compounds and other extractible materials in soil, however, may originate from non-petroleum sources. Biogenic organic compounds (BOCs) is a general term used to describe a mixture of organic compounds, including alkanes, sterols and sterones, fatty acids and fatty alcohols, and waxes and wax esters, biosynthesized by living organisms. BOCs are also produced during the early stages of diagenesis in recent aquatic sediments. BOC sources could include vascular plants, algae, bacteria and animals. Plants and algae produce BOCs as protective wax coating that are released back into the sediment at the end of their life cycle. BOCs are natural components of thriving plant communities. Many solvent-extraction methods for assessing soil hydrocarbons, however, such as the CCME method, do not differentiate PHCs from BOCs. The naturally occurring organics present in soils and wet sediments can be easily misidentified and quantified as regulated PHCs during analysis using such methods. In some cases, biogenic interferences can exceed regulatory levels, resulting in remediation of petroleum impacts that are not actually present. Consequently, reliance on these methods can trigger unnecessary and costly remediation, while also wasting valuable landfill space. Therefore, it is critically important to develop new protocols to characterize and differentiate PHCs and BOCs in contaminated sediments. In this study, a new reliable gas chromatography-mass spectrometry (GC-MS) method, in combination with a derivatization technique, for characterization of various biogenic compounds (including biogenic alkanes, sterols, fatty acids and fatty alcohols) and PHCs in the same sample has been developed. A multi-criteria approach has been developed to positively identify the presence of biogenic compounds in soil and sediment samples. More than thirty sediment samples were collected from city stormwater management (SWM) ponds and wetlands across Canada. In these wet sediment samples, abundant biogenic n-alkanes, thirteen biogenic sterols, nineteen fatty carboxylic acids, and fourteen fatty alcohols in a wide carbon range have been positively identified. Both PHCs and BOCs in these samples were quantitatively determined. The quantitation data will be used for assessment of the contamination sites and toxicity risks associated with the CCME Fraction 3 hydrocarbons.

Review of behaviour of oil in freezing environments.

The current knowledge of the physical fate and behaviour of crude oil and petroleum products spilled in Arctic situations is reviewed. The fate and final deposition of oil in marine conditions is presented as based on the extant literature. Spreading models were evaluated for oil on ice, under ice, in snow, in brash ice, and between blocks of ice. Models of oil transport under sheet and broken ice were considered, both for sea and river conditions. The ability of ice sheets to trap oil is discussed in relation to oil storage capacity. The effects of oil on a growing ice sheet were examined, both in terms of ice formation and the thermal effects of oil inclusions in ice. The migration of oil through ice was reviewed, focussing primarily on the movement through brine channels. The effects of oil on the surface of ice were considered, with emphasis on the effects of surface pools on ice melt. Similar consideration was given to the effects of oil on snow on the surface of ice. The few quantitative studies of oil in open and dynamic ice conditions are reviewed. Observations of intentional small-scale spills in leads and ice fields are reviewed and compared with observations from real spills. The conditions under which "oil pumping" from leads occurs were quantified. The most common ultimate fate of oil in an ice field is to be released onto the water surface.