PLUME OF OIL METABOLITES IN GROUNDWATER:
FORMATION, EVOLUTION, AND TOXICITY

V. S. Putilina^1*, I. V. Galitskaya^1**, T. I. Yuganova^1***
Sergeev Institute of Environmental Geoscience, Russian Academy of Sciences
Ulanskii per. 13, str. 2, Moscow, 101000 Russia.
*E-mail: vputilina@yandex.ru,
**E-mail: galgeoenv@mail.ru,
***E-mail: tigryu@gmail.com

The transformation of oil hydrocarbons in groundwater is mainly related to the processes of biodegra­dation. At sites where residual crude oil or petroleum hydrocarbon fuel contaminants are present in the environment, biodegradation reactions result in the formation of partial oxidation products, i.e., me­tabolites. These transformation products are more soluble than the parent petroleum hydrocarbons, due to their greater polarity and corresponding low volatility. Transformation products from residual source zones are distributed in aqueous phase to form a plume of contamination in groundwater. The content of metabolites depends on the redox conditions and the presence of the terminal electron acceptors, as well as on the structure of the original hydrocarbon compounds. The article considers the conditions for formation of metabolites, their degradation, migration to groundwater and plume formation, toxicity of metabolites. Examples of modeling the migration of metabolites in the saturated zone are given.

Keywords: oil hydrocarbons, metabolites, transformation, electron acceptors, aerobic processes, anaerobic processes, migration, toxicity.

DOI: https://doi.org/10.31857/S0869-78092019138-45

REFERENCES

1. Baedecker, M.J., Cozzarelli, I.M., Eganhouse, R.P. Crude oil in a shallow sand and gravel aquifer - III. Biogeochemical reactions and mass balance modeling in anoxic groundwater. Applied Geochemistry, 1993, vol. 8, no. 6, pp. 569-586.

2. Bekins, B.A., Cozzarelli, I.M., Erickson, M.L., Steenson, R.A., Thorn, K.A. Crude oil metabolites in groundwater at two spill sites. Groundwater, 2016, vol. 54, no. 5, pp. 681-691.

3. Chaplin, B.P., Delin, G.N., Lahvis, M.A., Baker, R. Long term evolution of biodegradation and volatilization rates in a crude-oil-contaminated aquifer. Bioremediation Journal, 2002, vol. 6, no. 3, pp. 237-255.

4. Cozzarelli, I.M., Baedecker, M.J., Eganhouse, R.P., Goerlitz, D.F. The geochemical evolution of low-molecular-weight organic acids derived from the degradation of petroleum contaminants in groundwater. Geochimica et Cosmochimica Acta, 1994, vol. 58, no. 2, pp. 863-877.

5. Cozzarelli, I.M., Bekins, B.A., Baedecker, M.J., Aiken, G.R., Eganhouse, R.P., Tuccillo, M.E. Progression of natural attenuation processes at a crudeoil spill site: I. Geochemical evolution of the plume. Journal of Contaminant Hydrology, 2001, vol. 53, no. 3-4, pp. 369-385.

6. Delin, G.N., Essaid, H.I., Cozzarelli, I.M., Lahvis, M.H., Bekins, B.A. Ground water contamination by crude oil near Bemidji, Minnesota: U.S. Geological Survey Fact Sheet 084-98, USGS, 1998. http://pstrust. org/docs/usgs_doc1.pdf. (accessed 9.07.2018)

7. Essaid, H.I, Bekins, B.A., Herkelrath, W.N., Delin, G.N. Crude oil at the Bemidji site: 25 years of monitoring, modeling, and understanding. Ground Water, 2011, vol. 49, no. 5, pp. 706-726.

8. Lewan, M.D., Warden, A., Dias, R.F., Lowry, Z.K., Hannah, T.L., Lillis, P.G., Kokaly, R.F., Hoefen, T.M., Swayze, G.A., Mills, C.T., Harris, S.H., Plumlee, G.S. Asphaltene content and composition as a measure of Deepwater Horizon oil spill losses within the first 80 days. Organic Geochemistry, 2014, vol. 75, pp. 54-60.

9. Lundegard, P.D., Sweeney, R.E. Total petroleum hydrocarbons in groundwater - Evaluation of nondissolved and nonhydrocarbon fractions. Environmental Forensics, 2004, vol. 5, no. 2, pp. 85-95.

10. Mao, D., Lookman, R., van de Weghe, H., Weltens, R. Vanermen, G., de Brucker, N., Diels, L. Combining HPLC-GCXGC, GCXGC/ToF-MS, and selected ecotoxicity assays for detailed monitoring of petroleum hydrocarbon degradation in soil and leaching water. Environmental Science & Technology, 2009, vol. 43, no. 20, pp. 7651-7657.

11. Melbye, A.G., Brakstad, O.G., Hokstad, J.N., Gregersen, I.K., Hansen, B.H., Booth, A.M., Rowland, S.J., Tollefsen, K.E. Chemical and toxicological characterization of an unresolved complex mixture-rich biodegraded crude oil. Environmental Toxicology & Chemistry, 2009, vol. 28, no. 9, pp. 1815-1824.

12.Ng, G.-H.C., Bekins, B.A., Cozzarelli, I.M., Baedecker, M.J., Bennett, P.C., Amos, R.T. A mass balance approach to investigating geochemical controls on secondary water quality impacts at a crude oil spill site near Bemidji, MN. Journal of Contaminant Hydrology, 2014, vol. 164, pp. 1-15.

13.Rojo, F. Degradation of alkanes by bacteria. Environ-mental Microbiology, 2009, vol. 11, no. 10, pp. 24772490.

14. Scott, A.C., Mackinnon, M.D., Fedorak, P.M. Naph-thenic acids in Athabasca oil sands tailings waters are less biodegradable than commercial naphthenic acids. Environmental Science & Technology, 2005, vol. 39, no. 21, pp. 8388-8394.

15. Steenson, R., Hellmann-Blumberg, U., Elias, D., Brown, K., Fry, N., Naugle, A., Meillier, L., Prowell, C. Petroleum Metabolites. Literature Review and Assessment Framework: Technical Resource Document. San Francisco Bay Regional Water Quality Control Board, 2016, 56 p. http://www.waterboards.ca.gov/sanfrancis- cobay/publications_forms/documents/SF_WB_Pe- troleum_Metabolites.pdf. (accessed 9.07.2018)

16. Thorn, K.A., Aiken, G.R. Biodegradation of crude oil into nonvolatile organic acids in a contaminated aquifer near Bemidji, Minnesota. Organic Geochemistry, 1998, vol. 29, no. 4, pp. 909-931.

17. Watson, J.S., Jones, D.M., Swannell, R.P.J., van Duin, A.C.T. Formation of carboxylic acids during aerobic biodegradation of crude oil and evidence of microbial oxidation of hopanes. Organic Geochemistry, 2002, vol. 33, no. 10, pp. 1153-1169.

18. Zemo, D.A., O'Reilly, K.T., Mohler, R.E., Tiwary, A.K., Magaw, R.I., Synowiec, K.A. Nature and estimated human toxicity of polar metabolite mixtures in groundwater quantified as TPHd/DRO at biodegrading fuel release sites. Groundwater Monitoring & Remediation, 2013, vol. 33, no. 4, pp. 44-56.

19. Zemo, D.A., O'Reilly, K.T., Mohler, R.E., Magaw R.I. Devine C.E., Ahn S., Tiwary A.K. Life cycle of petroleum biodegradation metabolite plumes, and implications for risk management at fuel release sites. Integrated Environmental Assessment & Management, 2017, Volume 9999, Number 9999, pp. 1-14. http://onlinelibrary.wiley. com/doi/10.1002/ieam.1848/epdf. (accessed 9.07.2018)