Diamonds in the rough: identification of individual naphthenic acids in oil sands process water

Expansion of the oil sands industry of Canada has seen a concomitant increase in the amount of process water produced and stored in large lagoons known as tailings ponds. Concerns have been raised, particularly about the toxic complex mixtures of water-soluble naphthenic acids (NA) in the process water. To date, no individual NA have been identified, despite numerous attempts, and while the toxicity of broad classes of acids is of interest, toxicity is often structure-specific, so identification of individual acids may also be very important. Here we describe the chromatographic resolution and mass spectral identification of some individual NA from oil sands process water. We conclude that the presence of tricyclic diamondoid acids, never before even considered as NA, suggests an unprecedented degree of biodegradation of some of the oil in the oil sands. The identifications reported should now be followed by quantitative studies, and these used to direct toxicity assays of relevant NA and the method used to identify further NA to establish which, or whether all NA, are toxic. The two-dimensional comprehensive gas chromatography-mass spectrometry method described may also be important for helping to better focus reclamation/remediation strategies for NA as well as in facilitating the identification of the sources of NA in contaminated surface waters.