Ultra Performance Liquid Chromatography Ion Mobility Time-of-Flight Mass Spectrometry Characterization of Naphthenic Acids Species from Oil Sands Process-Affected Water

Ultraperformance liquid chromatography ion mobility time-of-flight mass spectrometry (UPLC-IM-TOFMS), integrating traveling wave ion mobility spectrometry (TWIMS) with negative electrospray ionization (ESI) mode, was used to achieve two-dimensional (2D) separation (drift vs retention times) of naphthenic acids (NAs). Unprocessed and ozonated commercial NAs were used for method development. Only O₂–NAs were found in unprocessed NAs with ozonation creating O₃–NAs and O₄–NAs. Unprocessed and ozonated oil sands process-affected waters (OSPW) were examined to validate the method for complex matrix NAs. Ozonation increased the <i>x</i> number for O_<i>x</i>–NAs (2 ≤ <i>x</i> ≤ 5) and also impacted the −<i>Z</i> number distribution. OSPW extracted using dichloromethane removed the potential for sample matrix impacts and was used for MS/MS NAs characterization. The O_<i>x</i>–NAs (2 ≤ <i>x</i> ≤ 6) were identified with O₂–NAs separated into three clusters indicating isobaric and isomeric species. MS/MS was used to verify compounds, while also indicating the presence of CH₃CH₂S– NAs groups. This result may be useful for future studies of sulfur-NAs fate, toxicity, and treatment. Overall, the value-added information provided by UPLC-IM-TOFMS makes it a promising analytical technique for analysis of NAs in complex OSPW samples. Moreover, this methodology can be used for other matrices to investigate relative molecular sizes and to separate complex species (e.g., fatty acids, lipids), making it beneficial for environmental and bioanalytical applications.