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).

Field fluorometers as dispersed oil-in-water monitors.

A laboratory study of the Turner Instrument flow-through models 10AU and 10 fluorometers was conducted to review their ability to measure real-time oil-in-water concentrations, to compare the results to other total petroleum hydrocarbon (TPH) procedures and to improve the understanding of the relationship of the fluorescence to the chemical composition of the oils. Comparison of the fluorometer results to standard infrared and gas chromatography laboratory procedures showed all methods capable of detecting and differentiating between small changes in oil concentration. The infrared and gas chromatography generated similar values while the fluorometer values were of the same order of magnitude but typically 20-80% higher. The chemical composition of the oils was determined by gas chromatographic techniques and compared to the signal outputs of the fluorometers. It was found that the fluorometer data could not be directly linked to the concentration of any specific aromatic hydrocarbon such as naphthalene or to the sum of the polycyclic aromatic hydrocarbon (PAH) compounds. Evidence suggests that the fluorescence signal is generated by a combination of PAH compounds. Also, the response of the fluorometers may also be influenced by the presence of volatile aromatic compounds such as benzene, toluene, ethyl benzene and xylene (BTEX) and C3-benzenes (BTEX + C3B) in combination with the PAH compounds.