Abstract
Compound-specific isotope analysis is increasingly used to demonstrate contaminant degradation in groundwater. The method relies on the frequent occurrence of characteristic shifts in the isotope ratios of contaminants due to the faster degradation of molecules with light isotopes compared to those with heavy isotopes. The goal of the study was to evaluate if the method can also be used to assess biodegradation of petroleum hydrocarbons in the unsaturated zone. The study included laboratory experiments to determine isotopic enrichment for biodegradation of petroleum hydrocarbon compounds under unsaturated conditions and a field experiment. The field experiment consisted of burying an artificial fuel source in the unsaturated zone at a site in Denmark. Concentration and isotope ratios of individual compounds were monitored using a dense network of sampling points. Significant shifts of the isotope ratios of most of the compounds occurred. Initially, a depletion in 13C with distance was observed likely due to the faster diffusion of molecules with 12C only. Later, most of the compounds became in enriched in 13C compared to the source due to biodegradation. To evaluate the relative contribution of diffusion and biodegradation in more detail, the concentration and isotope ratio evolution was simulated using an analytical model. The calculations confirmed that diffusion can lead to significant isotope fractionation at early times. For hydrogen isotopes, the effect of diffusion relative to biodegradation is expected to be smaller due to the large hydrogen isotope fractionation frequently observed during biodegradation of organic compounds. In conclusion, the study demonstrates that especially at early times after spills, the effect of diffusion has to be taken into account in the interpretation of isotope data from the unsaturated zone. Furthermore, it demonstrates that for many compounds, hydrogen isotopes are likely the more sensitive indicator of biodegradation.
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References
Atlas RM (1981) Microbial degradation of petroleum hydrocarbons: an environmental perspective. Microbiological Reviews 45:180–209
Broholm M, Christophersen M, Maier U, Stenby E, Kjeldsen P (2005) Compositional evolution of the emplaced fuel source experiment in the vadose zone field experiment at Airbase Værløse, Denmark. Environ Sci Technol submitted
Cerling TE, Solomon DK, Quade J, Bowman JR (1991) On the isotopic composition of carbon` in soil carbon dioxide. Geochim Cosmochim Acta 55:3403–3405
Christophersen M, Broholm M, Mosbaek H, Karapanagioti H, Kjeldsen P (2005) Emplaced fuel source experiment in the vadose zone at Airbase Vaerlose, Denmark: site characterization and hydrocarbon migration. J Contam Hydrol submitted
Clark I D, Fritz P (1997) Environmental isotopes in hydrogeology Lewis publisher, CRC Press LLC
Elsner M, Zwank L, Hunkeler D, Schwarzenbach RP (2005) A New Concept Linking Observable Stable Isotope Fractionation to Transformation Pathways of Organic Pollutants. Environ Sci Technol. In prep.
Gaganis P, Kjeldsen P, Burganos VN (2004) Modeling Natural Attenuation of Multicomponent Fuel Mixtures in the Vadose Zone: Use of Field Data and Evaluation of Biodegradation Effects. Vadose Zone J 3:1262–1275
Höhener P, Duwig C, Pasteris G, Kaufmann K, Dakhel N, Harms H (2003) Biodegradation of petroleum hydrocarbon vapours: laboratory studies on rates and kinetics in unsaturated alluvial sand. J Contam Hydrol 66:93–115
Hunkeler D, Andersen N, Aravana R, Bernasconi M, Butler BJ (2001) Hydrogen and carbon isotope fractionation during aerobic biodegradation of benzene. Environ Sci Technol 35:3462–3467
Kaufmann K, Christophersen M, Buttler A, Harms H, Höhener P (2004) Microbial community response to petroleum hydrocarbon contamination in the unsaturated zone at the experimental field site Værløse, Denmark. FEMS Microbiology Ecology 48-3:387–399
Kirtland BC, Aelion CM, Stone PA, (2005) Assessing in situ mineralization of recalcitrant organic compounds in vadose zone sediments using δ13C and 14C measurements. J Contam Hydrol 76:1–18
Mancini SA, Ulrich AC, Lacrampe-Couloume G, Sleep B, Edwards EA, Sherwood Lollar B (2003) Carbon and Hydrogen Isotopic Fractionation during Anaerobic Biodegradation of Benzene. Appl Environ Microbiol 69-1:191–198
Meckenstock RU, Morasch B, Griebler C, Richnow HH (2004) Stable isotope fractionation analysis as a tool to monitor biodegradation in contaminated aquifers. J Contam Hydrol 75:215–255
Meckenstock RU, Richnow HH (2002) Quantification of isotope fractionation in experiment with deuterium-labeled substrate. Appl Environ Microbiol 68:5206–5207
Morasch B, Richnow HH, Schink B, Vieth A, Meckenstock RU (2002) Carbon and hydrogen isotope fractionation during aerobic degradation of aromatic hydrocarbons. App Environ Microbiol 68:5191–5194
Pasteris G, Werner D, Kaufmann K, Höhener P (2002) Vapor phase transport and biodegradation of volatile fuel compounds in the non saturated zone: a large scale lysimeter experiement. Environ Sci Technol 36:30–39
Richnow HH, Annweiler E, Michaelis W, Meckenstock RU (2003) Microbial in situ degradation of aromatic hydrocarbons in a contaminated aquifer monitored by carbon isotope fractionation. J Contam Hydrol 65:101–120
Sherwood Lollar B, Slater GF, Ahad J, Sleep B, Spivack J, Brennan M, MacKenzie P (1999) Contrasting carbon isotope fractionation during biodegradation of trichloroethylene and toluene: Implications for intrinsic bioremediation. Org Geochem 30:813–820
Stehmeier LG, Francis M.McD, Jack TR, Diegor E, Winsor L, Abrajano Jr TA (1999) Field and in vitro evidence for in-situ bioremediation using compound specific 13C/12C ratio monitoring. Org Geochem 30:821–833
Steinbach A, Seifert R, Annweiler E, Michaelis W (2004) Hydrogen and carbon isotope fractionation during anaerobic biodegradation of aromatic hydrocarbons — A field study. Environ Sci Technol 38:609–616
Griebler C, Safinowski M, Vieth A, Richnow HH, Meckenstock RU (2004) Combined application of stable carbon isotope analysis and specific metabolites determination for assessing in situ degradation of aromatic hydrocarbons in a tar oil-contaminated aquifer. Environ Sci Technol 38:617–631
Werner D, Broholm M, Höhener P (2004) Simultaneous estimation of nonaqueous phase liquid (NAPL) saturation and diffusive fluxes of volatile organic compounds in the vadose zone. Ground Water Monitoring and Remediation, in press
Werner D, Höhener P (2003) In situ method to measure effective and sorptionaffected gas-phase diffusion coefficients in soils. Environ Sci Technol 37-11:2502–2510
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Bouchard, D., Hunkeler, D., Höhener, P., Aravena, R., Broholm, M., Kjeldsen, P. (2005). Use of stable isotope analysis to assess biodegradation of petroleum hydrocarbons in the unsaturated zone. Laboratory studies, field studies, and mathematical simulations. In: Nützmann, G., Viotti, P., Aagaard, P. (eds) Reactive Transport in Soil and Groundwater. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3-540-26746-8_2
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DOI: https://doi.org/10.1007/3-540-26746-8_2
Publisher Name: Springer, Berlin, Heidelberg
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