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Photocatalysis of a Commercial Naphthenic Acid in Water Using Fixed-Film TiO2

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Abstract

Photolysis or photocatalysis may provide a process for mitigating ecological risks of naphthenic acids (NAs) contained in energy-derived waters such as refinery effluents and process waters. If effective, fixed-film TiO2 photocatalysis of NAs could decrease operational expenses as well as capital costs for water treatment. The overall objective of this study was to measure rates and extents of photolysis and photocatalytic degradation of commercial NAs using bench-scale fixed-film TiO2 and confirm changes in NA concentrations using sensitive vertebrate (fish = Pimephales promelas) and invertebrate (Daphnia magna) species. Specific objectives were to (1) measure rates and extents of degradation of commercial (Fluka) NAs throughout an 8-h duration of natural sunlight (“photolysis”) and natural sunlight in the presence of fixed-film TiO2 (“photocatalysis”) and (2) measure changes in toxicity in terms of mortality with sentinel fish and microinvertebrate species. Bench-scale chambers using thin-film TiO2 irradiated with natural sunlight were used to measure photocatalysis, and HPLC was used to quantify NAs. After 4 h in photocatalysis treatments, >92 % decline was observed with an average removal rate of 15.5 mg/L/h and half-life of 2 h. After 5 h of photocatalysis, there was no measurable NA toxicity for fish (P. promelas) or microinvertebrates (D. magna). Photocatalytic degradation achieved efficacious rates and extents of removal of Fluka NAs and eliminated acute toxicity to sentinel aquatic organisms, indicating the potential for application of this technology for mitigating ecological risks. Coupled with existing treatment processes (i.e., aerobic biodegradation), photocatalysis can augment rates and extents of NA removal from impacted waters.

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Acknowledgments

Funding support for this research was provided by Shell Canada Ltd. and Suncor Energy. The authors are also grateful to Dr. Wayne Chao of Clemson University for providing analytical support.

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Authors and Affiliations

  1. Department of Forestry and Environmental Conservation, Clemson University, 261 Lehotsky Hall, Clemson, SC, 29634, USA

    Andrew D. McQueen, Ciera M. Kinley, Alyssa J. Calomeni & John H. Rodgers Jr.

  2. Department of Environmental Engineering and Earth Sciences, 300 Brackett Hall, Clemson, SC, 29634, USA

    Rebecca L. Kiekhaefer & James W. Castle

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  1. Andrew D. McQueen
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  2. Ciera M. Kinley
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  3. Rebecca L. Kiekhaefer
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  4. Alyssa J. Calomeni
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  5. John H. Rodgers Jr.
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  6. James W. Castle
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Correspondence to Andrew D. McQueen.

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McQueen, A.D., Kinley, C.M., Kiekhaefer, R.L. et al. Photocatalysis of a Commercial Naphthenic Acid in Water Using Fixed-Film TiO2 . Water Air Soil Pollut 227, 132 (2016). https://doi.org/10.1007/s11270-016-2835-x

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