Naphthenic acids quantification in organic solvents using fluorescence spectroscopy

Abstract

Quantification of naphthenic acids in water has been traditionally performed after extraction with organic solvents followed by analytic methods that are complex and costly for preliminary research or for continuous monitoring purposes. This study examines the application of fluorescence in organic solvents as an effective alternative, and the role of organic solvents on quantification results. Nine organic solvents were used: three polar protic alcohols (methanol, ethanol, and propanol), three polar aprotic (dichloromethane, acetone, and acetonitrile) and three non-polar (hexane, toluene, and diethyl ether). The calibration curves of the polar protic solvents performed the best; they had lower light scattering and higher method sensitivity than polar aprotic and non-polar. Methanol was selected for further experiments having a strong linearity for concentrations lower than 250 mg/L (R² > 0.99), and a low relative standard deviation (< 10%). The method sensitivity was improved by 70% using a methanol-deionized water mixture (50:50) as a solvent. The synchronous fluorescence mode with a reduced offset value of Δλ = 10 nm demonstrated potential for fingerprinting. The fluorescence technique for quantifying total naphthenic acids directly in organic solvents is a cost-effective analytical method compatible with the solid phase extraction of the sample.

Keywords:

• Naphthenic acids
• fluorescence
• oil sands
• methanol
• Athabasca River

Acknowledgments

The authors would like to thank Jela Burkus for providing technical support in the lab experiments. The authors also acknowledge the financial support from the Mexican National Council of Science and Technology (CONACYT), the Natural Sciences and Engineering Research Council of Canada (NSERC), and Alberta Environment and Sustainable Resource Development.