Oil sands process-affected water composition effect on Henry's law constants for polycyclic aromatic compounds: Theory and experiment.

Oil sands process-affected water (OSPW) is a source of atmospheric emission for polycyclic aromatic compounds (PACs), compounds known to have toxic effects on humans. Estimating emissions and assessing the chemical fate of PACs requires measured or predicted physical-chemical properties such as Henry's law constants (H), that can be used to predict chemical transfer into the atmosphere. OSPW is a complex water-based mixture that is highly variable in composition and nature and contains both organic and inorganic ions. This study uses COSMO-RS solvation theory to estimate and compare Henry's law constants for a set of PACs in both water and theoretically modelled OSPW, to assess the expected deviation that occurs from pure water H values due to the ionic content within OSPW. Experimental measurements of Henry's law constants for PACs in pure water and OSPW using EVA-coated passive dosing and sampler beads were also made in support of our theoretical predictions. For the theory work, OSPW composition data for the Athabasca oil sands in Alberta were used to model a simulated OSPW environment with realistic sodium, chloride, fluoride, sulfate, potassium, bicarbonate, and naphthenic acid concentrations. Theory results indicate that the combined presence of these ions at OSPW concentrations has a negligible effect on H values, causing on average a 3% or 0.014 log unit deviation. By comparison, temperature has a much larger influence on H values, with estimations showing an average 0.20 log unit increase for a 5 °C increase in temperature. The experimental results demonstrate that Henry's law constants can be accurately and precisely measured with this technique in pure water but with less precision in OSPW. Nevertheless, the experimental results support the conclusion that Henry's law constants for OSPW can be accurately estimated assuming a pure water phase.