Isomer-specific monitoring of naphthenic acids at an oil sands pit lake by comprehensive two-dimensional gas chromatography–mass spectrometry

Naphthenic acids (NAs) are persistent, toxic contaminants that are found to accumulate in oil sands process-affected water (OSPW) and tailings after bitumen extraction. A number of strategies for the reclamation of oil sands tailings are currently being tested, including the development of the first demonstration pit lake by Syncrude Canada, Base Mine Lake (BML). An important component of reclamation activities is understanding the source and cycling of NAs in such reclamation systems. However, NAs exist as a highly complex mixture of thousands of compounds which makes their analysis an ongoing challenge. Herein, comprehensive two-dimensional gas chromatography coupled to time of flight mass spectrometry (GC × GC/TOFMS) was used to analyze the methylated extracts of water samples from the water cap and fluid fine tailings (FFT) deposit of BML to characterize the variations in NA distributions between geochemical zones. A collection of (alkylated) monocyclic-, bicyclic-, adamantane-, and thiophene-type carboxylic acids were identified. Total relative abundances were calculated for each NA class (by summation of peak areas of all detected isomers) and minimal variability was detected in the water cap. Total relative abundances for each NA class were either similar or higher in the FFT, relative to the water cap. Examination of isomer distributions indicated that differences in abundance values were generally driven by variations in only one or two isomers of a given NA class. Furthermore, GC × GC revealed distinct isomer profiles were observed between two FFT samples and between the FFT and water cap. While it is not yet clear whether these differences are due to differences in sources of NAs or in their environmental processing, these results illustrate the capability of GC × GC to investigate these questions and thus contribute to the management of these compounds within reclamation or environmental systems.