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Ozonation of Naphthenic Acids in Water: Kinetic Study

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Abstract

The large amount of oil sands process-affected water (OSPW), produced from the extraction of oil from oil sands in Alberta, Canada, has demonstrated both acute and chronic toxicity to many species due to the presence of naphthenic acids (NAs). The “zero discharge” policy posted by the Alberta government presents a major challenge for the oil sands industries. In this study, ozonation was used to remove model NAs from water. It was found that the removal of NAs increased with the temperature. The kinetics of direct ozonation between molecular ozone and NAs was investigated in the presence of a radical scavenger, sodium bicarbonate. The rate constants of the direct ozonation at 5, 15 and 25 °C were determined to be 0.67, 2.71 and 8.85 M−1 s−1, respectively, and the activation energy of the direct ozonation was found to be 88.85 kJ mol−1. The kinetics of indirect ozonation was also studied. By using pCBA as a hydroxyl radical probe compound to determine the hydroxyl radical concentration and applying the ratio of hydroxyl radical concentration to dissolved ozone concentration, R ct, the rate constants of the indirect ozonation of NAs were found to be 1.12 × 108, 1.78 × 108 and 2.33 × 108 M−1 s−1 at 5, 15 and 25 °C, respectively. In addition, from the Arrhenius plot of the rate constants, the activation energy of the indirect ozonation was found to be 25.41 kJ mole−1.

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References

  • Ahad, J., Pakdel, H., Savard, M., Calderhead, A., Gammon, P., Rivera, A., Peru, K., & Headley, J. V. (2013). Characterization and quantification of mining-related “naphthenic acids” in groundwater near a major oil sands tailings pond. Environmental Science & Technology, 47, 5023–5030.

    Article  CAS  Google Scholar 

  • Al jibouri, A. K. H., & Wu, J. (2015). Model development for naphthenic acids ozonation process. Environmental Science and Pollution Research, 22, 2558–2565.

    Article  CAS  Google Scholar 

  • Alberta Government (2014). Alberta’s oil sands: the facts. http://www.energy.gov.ab.ca/OilSands/pdfs/AlbertasOilSandsFactsJan14.pdf. Accessed 13 may 2015.

  • Anderson, J., Wiseman, S., Wang, N., Moustafa, A., Perez-Estrada, L., Gamal El-Din, M., Martin, J., Liber, K., & Giesy, J. (2012). Effectiveness of ozonation treatment in eliminating toxicity of oil sands process-affected water to Chironomus dilutus. Environmental Science & Technology, 46, 486–493.

    Article  CAS  Google Scholar 

  • APHA. (2005). APHA Method 4500-03, Ozone (residual). indigo colorimetric method. In A. E. Greenberg, L. S. Clesceri, & A. D. Eaton (Eds.), Standard methods for the examination of water and wastewater (21st ed., pp. 4–106). Washington, D.C.: American Public Health Association.

    Google Scholar 

  • Beltrán, F. J. (1997). Theoretical aspects of the kinetics of competitive first reactions of ozone in the O3/H2O2 and O3/UV oxidation processes. Ozone: Science & Engineering, 19, 13–38.

    Article  Google Scholar 

  • Beltrán, F. J., Ovejero, G., Encinar, J. M., & Rivas, J. (1995). Oxidation of polynuclear aromatic hydrocarbons in water. 1. Ozonation. Industrial & Engineering Chemistry Research, 34, 1596–1606.

    Article  Google Scholar 

  • Charpentier, J. C. (1981). Mass transfer rates in gas liquid absorbers and reactors. In J. C. Charpentier (Ed.), Advances in chemical engineering (pp. 3–133). New York: Academic.

    Google Scholar 

  • Clemente, J., MacKinnon, M., & Fedoran, P. (2004). Aerobic biodegradation of two commercial naphthenic acids preparations. Environmental Science & Technology, 38, 1009–1016.

    Article  CAS  Google Scholar 

  • Danckwerts, P. V. (1970). Gas-liquid reactions. New York: McGraw Hill.

    Google Scholar 

  • Del Rio, L., Hadwin, A., Pinto, L., MacKinnon, M., & Moore, M. M. (2006). Degradation of naphthenic acids by sediment micro-organisms. Journal of Applied Microbiology, 101, 1049–1061.

    Article  Google Scholar 

  • Elovitz, M. S., & von Gunten, U. (1999). Hydroxyl radical/ozone ratios during ozonation processes. I. The Rct concept. Ozone Science & Engineering, 21, 239–260.

    Article  CAS  Google Scholar 

  • Elovitz, M. S., von Gunten, U., & Kaiser, H. (2000). Hydroxyl radical/ozone ratios during ozonation processes. II. The effect of temperature, pH, alkalinity, and DOM properties. Ozone Science & Engineering, 22, 123–150.

    Article  CAS  Google Scholar 

  • Energy Resources Conservation Board (ERCB) (2013). ST98–2013: Alberta’s energy reserve 2012 and supply/demand outlook 2013-2022. (pp. 3-2). Calgary, AB, Canada.: Government of Alberta. http://www.aer.ca/documents/sts/ST98/ST98-2013.pdf. Accessed 13 may 2015.

  • Gamal El-Din, M., Fu, H., Wang, N., Chelme-Ayala, P., Pérez-Estrada, L., Drzewicz, P., Martin, J., Zubot, W., & Smith, W. (2011). Naphthenic acids speciation and removal during petroleum-coke adsorption and ozonation of oil sands process-affected water. Science of the Total Environment, 409, 5119–5125.

    Article  CAS  Google Scholar 

  • Government of Alberta (2010). Facts about water in Alberta. http://environment.gov.ab.ca/info/library/6364.pdf. Accessed 13 may 2015.

  • Han, X., MacKinnon, M., & Martin, J. (2009). Estimating the in situ biodegradation of naphthenic acids in oil sands process waters by HPLC/HRMS. Chemosphere, 76, 63–70.

    Article  CAS  Google Scholar 

  • He, Y., Patterson, S., Wang, N., Hecker, M., Martin, J., Gamal El-Din, M., Giesy, J., & Wiseman, S. (2012). Toxicity of untreated and ozone-treated oil sands process-affected water (OSPW) to early life stages of the fathead minnow (Pimephales promelas). Water Research, 46, 6359–6368.

    Article  CAS  Google Scholar 

  • Hoigne, J., & Bader, H. (1976). The role of hydroxyl radical reactions in ozonation processes in aqueous solutions. Water Research, 10, 377–386.

    Article  CAS  Google Scholar 

  • Hoigné, J., & Bader, H. (1983a). Rate constants of direct reactions of ozone with organic and inorganic compounds in water. I. Non-dissociating organic compounds. Water Research, 17, 173–183.

    Article  Google Scholar 

  • Hoigné, J., & Bader, H. (1983b). Rate constants of reactions of ozone with organic and inorganic compounds in water. II. Dissociating organic compounds. Water Research, 17, 185–194.

    Article  Google Scholar 

  • Holowenko, F. M., MacKinnon, M. D., & Fedorak, P. M. (2001). Naphthenic acids and surrogate naphthenic acids in methanogenic microcosms. Water Research, 35, 2595–2606.

    Article  CAS  Google Scholar 

  • Hwang, G., Dong, T., Islam, M., Sheng, Z., Pérez-Estrada, L., Liu, Y., & Gamal El-Din, M. (2013). The impacts of ozonation on oil sands process-affected water biodegradability and biofilm formation characteristics in bioreactors. Bioresource Technology, 130, 269–277.

    Article  CAS  Google Scholar 

  • Kannel, P., & Gan, T. (2012). Naphthenic acids degradation and toxicity mitigation in tailings wastewater systems and aquatic environments: a review. Journal of Environmental Science and Health Part A, 47, 1–21.

    Article  CAS  Google Scholar 

  • Lester, Y., Avisar, D., & Mamane, H. (2010). Photodegradation of the antibiotic sulphamethoxazole in water with UV/H2O2 advanced oxidation process. Environmental Technology, 31(2), 175–183.

    Article  CAS  Google Scholar 

  • Levenspiel, O. (1999). Chemical reaction engineering (1st ed.). New York: Wiley.

    Google Scholar 

  • Martin, J., Barri, T., Han, X., Fedorak, P., Gamal El-Din, M., Perez, L., Scott, A., & Jiang, J. (2010). Ozonation of oil sands process water accelerates microbial bioremediation. Environmental Science and Technology, 44, 8350–8356.

    Article  CAS  Google Scholar 

  • Natural Resources Canada (2011). Canadian crude oil, natural gas and petroleum products: review of 2009 & outlook to 2030. http://www.nrcan.gc.ca/sites/www.nrcan.gc.ca/files/energy/pdf/eneene/sources/crubru/revrev/pdf/revrev-09-eng.pdf. Accessed 13 may 2015.

  • Neta, P., & Dorfman, L. M. (1968). Pulse radiolysis studies. XIII: rate constants for the reaction of hydroxyl radicals with aromatic compounds in aqueous solutions. Advances in Chemistry Series, 81, 222–230.

    Article  Google Scholar 

  • Perez-Estrada, L., Han, X., Drzewicz, P., Gamal El-Din, M., Fedorak, P., & Martin, J. (2011). Structure-reactivity of naphthenic acids in the ozonation process. Environmental Science & Technology, 45, 7431–7437.

    Article  CAS  Google Scholar 

  • Scott, A., Zubot, W., MacKinnon, M., Smith, D., & Fedorak, P. (2008). Ozonation of oil sands process water removes naphthenic acids and toxicity. Chemosphere, 71, 156–160.

    Article  CAS  Google Scholar 

  • Sotelo, J., Beltrán, F. J., Benitez, J., & Beltran-Heredia, J. (1989). Henry’s law constant for the ozone-water system. Water Research, 23, 1239–1246.

    Article  CAS  Google Scholar 

  • Staehelin, J., & Hoigné, J. (1982). Decomposition of ozone in water: rate of initiation by hydroxide ions and hydrogen peroxide. Environmental Science & Technology, 16, 676–681.

    Article  CAS  Google Scholar 

  • Staehelin, J., & Hoigné, J. (1985). Decomposition of ozone in water in the presence of organic solutes acting as promoters and inhibitors of radical chain reactions. Environmental Science & Technology, 19, 1206–1213.

    Article  CAS  Google Scholar 

  • Suncor Energy (2010). Summary report on sustainability. http://sustainability.suncor.com/2010/default.aspx. Accessed 13 may 2015.

  • Wang, N., Chelme-Ayala, P., Perez-Estrada, L., Garcia-Garcia, E., Pun, J., Martin, J., Belosevic, M., & Gamal El-Din, M. (2013). Impact of ozonation on naphthenic acids speciation and toxicity of oil sands process-affected water to Vibrio fischeri and mammalian immune system. Environmental Science & Technology, 47, 6518–6526.

    CAS  Google Scholar 

  • Wu, J. (2005). Ozone treatment. In S. Lee (Ed.), Encyclopedia of chemical processing (pp. 1993–2001). New York: Marcel Dekker.

    Google Scholar 

  • Wu, J., Doan, H., & Upreti, S. (2008). Decolorization of aqueous textile reactive dye by ozone. Chemical Engineering Journal, 142, 156–160.

    Article  CAS  Google Scholar 

  • Yao, C., & Haag, W. (1991). Rate constants for direct reactions of ozone with several drinking water contaminants. Water Research, 25, 761–773.

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors wish to thank the Natural Sciences and Engineering Research Council of Canada (NSERC) for the financial support. The Queen Elizabeth II Graduate Scholarship in Science and Technology (QEII—GSST) and Ontario Graduate Scholarship (OGS) offered to A. Al jibouri by Ontario government and Ryerson University and financial aid from Ryerson University to A. Al jibouri are also acknowledged.

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Al-jibouri, A.K.H., Wu, J. & Upreti, S.R. Ozonation of Naphthenic Acids in Water: Kinetic Study. Water Air Soil Pollut 226, 338 (2015). https://doi.org/10.1007/s11270-015-2600-6

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  • DOI: https://doi.org/10.1007/s11270-015-2600-6

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