Naphthenic acids in oil sands process waters: Identification by conversion of the acids or esters to hydrocarbons

Abstract Concerns over the toxicity associated with ‘naphthenic’ acids (NA) within oil produced waters and oil sands process waters (OSPW), whether justified or not, have increased the need for the structural elucidation of NA. Certainly, oil sands mining operations, such as those in Alberta, Canada, result in the production of large volumes of OSPW contaminated with NA. Monitoring NA, predicting the toxicities and accounting for the toxicity of residual NA after clean-up treatments, have all been hindered by the lack of NA identifications. Recently, a method involving the conversion of the esters of petroleum NA to the corresponding hydrocarbons before analysis by comprehensive two-dimensional gas chromatography-mass spectrometry (GC × GC–MS), resulted in the most comprehensive study of bicyclic NA from petroleum to date. Here, we present results of the analysis by GC × GC–MS of NA extracted from OSPW after conversion of the acids or ester derivatives to the corresponding hydrocarbons. The identifications presented include novel alicyclic, aromatic and sulfur-containing hydrocarbons and thus, by inference, of the corresponding acids. This supports and significantly extends, previous identifications of OSPW NA as their methyl esters and can now be used to better inform environmental monitoring programs and toxicity studies.