Behavior and toxicological impact of spilled diluted bitumen and conventional heavy crude oil in the unsaturated zone

Demand for unconventional crude oils continues to drive the production of diluted bitumen (dilbit) within Western Canada, promoting increased transport volumes across the extensive 700,000 km pipeline system of Canada and the USA. Despite this vast extent of terrestrial transport, the current understanding of the behavior and fate of spilled dilbit within shallow groundwater systems is limited. To this end, oil spill experiments with a dilbit (Cold Lake Blend) and a physicochemically similar conventional heavy crude oil (Conventional Heavy Blend) were conducted for 104 days in large soil columns (1 m height × 0.6 m diameter) engineered to model contaminant transport in the unsaturated (vadose) zone. Around two-fold greater concentrations and 6-41 % faster rates of vadose zone transport of benzene, toluene, ethylbenzene and xylenes (BTEX) and polycyclic aromatic compounds (PACs) were observed in the dilbit- compared to conventional heavy crude-contaminated columns. As determined by Orbitrap mass spectrometry, the O_xS_x species abundances in the acid extractable organics (AEOs) fraction of column leachate from both oil types increased over time, ostensibly due to microbial degradation of petroleum. Bioaccumulation of petroleum constituents in fathead minnow (Pimephales promelas) larvae exposed to contaminated leachate was confirmed through the induction of developmental malformations lasting up to 34 days and increased abundance of cyp1a mRNA observed throughout the experiment. Toxicity was comparable between the two oils but could not be fully attributed to metals, BTEX, PACs or AEOs, implying the presence of uncharacterized teratogens capable of being transported within the vadose zone following terrestrial dilbit and conventional heavy crude oil surface spills.