The Canadian oil sands industry stores toxic oil sands process-affected water (OSPW) in large tailings ponds adjacent to the Athabasca River or its tributaries, raising concerns over potential seepage. Naphthenic acids (NAs; C(n)H(2n-Z)O(2)) are toxic components of OSPW, but are also natural components of bitumen and regional groundwaters, and may enter surface waters through anthropogenic or natural sources. This study used a selective high-resolution mass spectrometry method to examine total NA concentrations and NA profiles in OSPW (n = 2), Athabasca River pore water (n = 6, representing groundwater contributions) and surface waters (n = 58) from the Lower Athabasca Region. NA concentrations in surface water (< 2-80.8 μg/L) were 100-fold lower than previously estimated. Principal components analysis (PCA) distinguished sample types based on NA profile, and correlations to water quality variables identified two sources of NAs: natural fatty acids, and bitumen-derived NAs. Analysis of NA data with water quality variables highlighted two tributaries to the Athabasca River-Beaver River and McLean Creek-as possibly receiving OSPW seepage. This study is the first comprehensive analysis of NA profiles in surface waters of the region, and demonstrates the need for highly selective analytical methods for source identification and in monitoring for potential effects of development on ambient water quality.

This paper summarizes various lines of evidence, including new geophysical and geochemical surveys indicating the discharge of naturally occurring saline formation water from Cretaceous and Devonian formations to the Athabasca River downstream of Fort McMurray — an active oil sands extraction area. The following features are indicative of saline water discharge: (i) the hydrogeological setting of the reach which is situated near the western, up-dip, and subcropping, edge of the Western Canada Sedimentary Basin; (ii) springs and seepage along area rivers and tributaries that have been observed and reported in previous studies; and (iii) a significant increase in dissolved solids in the river, particularly chloride, occurring in a downstream direction from Fort McMurray. Further evidence of the saline groundwater discharge was obtained from electromagnetic surveys conducted along a 125 km reach from the Clearwater River to the Firebag River. This technique was used to map the distribution of saline water in the riverbed hyporheic zone, and revealed broad zones of generally high terrain electrical conductivity values in deeply incised Cretaceous- and Devonian-aged subcrop areas, but with numerous point-source and lineal anomalies attributed to occurrence of saline water discharge in less incised areas. Porewater sampling using drive-point piezometers was then used to confirm the presence of saline water in selected zones. Depth-wise gradients in chemical parameters observed in the riverbed porewaters in these zones are interpreted as evidence of upward movement of saline formation water mixing with the Athabasca River. Geochemical properties of the porewater are consistent with natural sources of groundwater flow from the Cretaceous- and Devonian-aged formations discharging along various reaches of the river.

With growth of the Canadian oil sands industry, concerns have been raised about possible seepage of toxic oil sands process-affected water (OSPW) into the Athabasca River (AR). A sampling campaign in fall 2015 was undertaken to monitor for anthropogenic seepage while also considering natural sources. Naphthenic acids (NAs) and thousands of bitumen-derived organics were characterized in surface water, groundwater, and OSPW using a highly sensitive online solid phase extraction-HPLC-Orbitrap method. Elevated NA concentrations and bitumen-derived organics were detected in McLean Creek (30.1 μg/L) and Beaver Creek (190 μg/L), two tributaries that are physically impacted by tailings structures. This was suggestive of OSPW seepage, but conclusive differentiation of anthropogenic and natural sources remained difficult. High NA concentrations and bitumen-derived organics were also observed in natural water located far north of the industry, including exceedingly high concentrations in AR groundwater (A5w-GW, 2000 μg/L) and elevated concentration in a tributary river (Pierre River, 34.7 μg/L). Despite these evidence for both natural and anthropogenic seepage, no evidence of any bitumen-derived organics was detected at any location in AR mainstem surface water. The chemical significance of any bitumen-derived seepage to the AR was therefore minimal, and focused monitoring in tributaries will be valuable in the future.

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