The identification of petroleum acids, also known as ‘naphthenic’ acids (NA), has been an analytical challenge for over 140 years. However, most recent interest in NA has arisen due to concerns over their presence and apparent associated toxic effect in oil platform produced waters and oil sands process waters (OSPW), respectively. Understanding the toxicity, transformations during biodegradation and remediation treatments and predicting the fate of NA in the environment will be aided by the identification of individual NA. However the elucidation of individual acid structures by standard chromatographic techniques, such as GC-MS, has so far been limited by the extreme complexity of the NA mixtures. Recent analysis of NA as the methyl ester derivatives, by multidimensional gas chromatography-mass spectrometry (GC×GC-MS), has resulted in the identification of several tri- to pentacyclic, aromatic and sulphur-containing acids as well as tricyclic diacids. Therefore the current investigation focused on the identification of the abundant bicyclic acids in petroleum and OSPW acid extracts, utilising the unparalleled chromatographic separation and mass spectrometric detection offered by GC×GC-MS. Analysis of fractionated NA as methyl esters, resulted in the first identification of several bicyclic acids in OSPW including several novel bridged bicyclic acids, several fused bicyclic acids, as well as some terpenoid-derived drimane and labdane acids. However, identifications were limited somewhat by a lack of reference mass spectra and lack of availability of reference compounds for co-chromatography. A complementary method, based on an historical approach, involving reduction of NA esters to hydrocarbons, was modified and substantially improved. Analysis of the hydrocarbons resulting from the reduced acids, by GC×GC-MS, and comparison of the hydrocarbon mass spectra with the more abundant reference spectra available for petroleum hydrocarbons, resulted in the identification of over 40 individual bicyclic acids including fused, bridged and terpenoid-derived acids. The study provides the most comprehensive analysis of one of the major classes of NA (the bicyclic acids) to date. The methods developed were applied to the structural elucidation of NA in commercial NA and OSPW NA and resulted in the identification of numerous alicyclic, aromatic and sulphur-containing acids, supporting and extending previous identifications. There is clear potential for this method to be used for the identification of other unknown acids and functionalised biomarkers in complex matrices. The new knowledge of the acid structures in petroleum and OSPW NA can now be used to inform future research into the environmental monitoring and toxicity of NA.
petroleum acids, naphthenic acids, GCxGC-MS, oil sands, structural identification, bicyclics
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