Profiling low molecular weight organic compounds from naphthenic acids, acid extractable organic mixtures, and oil sands process-affected water by SPME-GC-EIMS

Abstract

Naphthenic acids (NAs) are complex mixtures of carboxylic acids from petroleum that have industrial applications and that may be released to the environment after oil spills. There is significant research on the chemical composition and toxicity of water-soluble NAs derived from oil sands mining in Alberta, Canada. Yet, little is known about low molecular weight organic compounds (LMWOC) from these sources. Headspace solid-phase microextraction coupled to gas chromatography-electron impact mass spectrometry was used for LMWOC profiling of commercial NA blends, and an acid-extractable organics (AEOs) mixture from a tailings pond. From Sigma 1, Sigma 2, Merichem NAs and the AEO extract, 54, 56, 40 and 4 compounds were identified, respectively. These include aliphatic and cyclic hydrocarbons, carboxylic acids, alkylbenzenes, phenols, naphthalene and alkyl-naphthalene, and decalin compounds. A sample of oil sands process-affected water (OSPW) and aqueous solutions of the NA blends were evaluated for matrix effects on LMWOC profiles. Principal component and clustering analyses revealed that LMWOC profiles of commercial extracts were closely related but distinct from the AEO and OSPW samples. Some of the identified LMWOC are reported to be genotoxic or carcinogenic, and therefore the NA mixtures and AEOs should be considered hazardous materials and further evaluated.

Keywords: Acid-extractable organics; Canadian oil sands; Low molecular weight organic compounds; Naphthenic acids; Oil sands process-affected water; SPME–GC–MS.