Journal of Visualized Experiments
www.jove.com
Video Article
Measuring Carbon-based Contaminant Mineralization Using Combined CO2 Flux and Radiocarbon Analyses 1
1
2
2
Thomas J. Boyd , Michael T. Montgomery , Richard H. Cuenca , Yutaka Hagimoto 1
Marine Biogeochemistry, Code 6114, US Naval Research Laboratory
2
Department of Biological and Ecological Engineering, Oregon State University
Correspondence to: Thomas J. Boyd at [email protected] URL: http://www.jove.com/video/53233 DOI: doi:10.3791/53233 Keywords: Environmental Sciences, Issue 116, mineralization, contaminants, carbon, radiocarbon, CO2, flux, degradation, biodegradation, fossil fuel, petroleum, industrial chemical Date Published: 10/21/2016 Citation: Boyd, T.J., Montgomery, M.T., Cuenca, R.H., Hagimoto, Y. Measuring Carbon-based Contaminant Mineralization Using Combined CO2 Flux and Radiocarbon Analyses. J. Vis. Exp. (116), e53233, doi:10.3791/53233 (2016).
Abstract A method is described which uses the absence of radiocarbon in industrial chemicals and fuels made from petroleum feedstocks which frequently contaminate the environment. This radiocarbon signal — or rather the absence of signal — is evenly distributed throughout a 14 contaminant source pool (unlike an added tracer) and is not impacted by biological, chemical or physical processes (e.g., the C radioactive decay rate is immutable). If the fossil-derived contaminant is fully degraded to CO2, a harmless end-product, that CO2 will contain no radiocarbon. CO2 derived from natural organic matter (NOM) degradation will reflect the NOM radiocarbon content (usually ~4.8) and considerable limestone (CaCO3) may be a poor candidate for applying this technique. Ancient carbonate deposits might dissolve in low pH and bias the analysis. The technique's significance is considerable, as a sole measurement type (natural abundance radiocarbon) can immediately be used to confirm in situ conversion of contaminant to CO2. This analysis is definitive. Radiocarbon cannot become depleted except through radioactive decay - which is constant despite physical, chemical or biological alteration of any starting material. Static radiocarbon measurements (for instance 14 14 DI C) can be made on batch samples and immediately confirm if C-depleted CO2 is prevalent at a site (irrefutably indicating contaminant mineralization to CO2). This information alone is incredibly valuable to site managers as without it, they are required to use numerous indirect lines of evidence to infer that contaminant mineralization is occurring. No other single measurement can provide a concrete connection between carbon-based contaminant and the carbon-containing CO2 produced through complete degradation. Future applications are currently underway in which our group will increase sampling temporal resolution to encompass an entire year. By collecting CO2 and determining the mineralization rate(s) over the spatial extent of the site, we will be able to refine models for contaminant degradation over time. This information is critically needed by site managers in order to most effectively manage contaminated sites. In limited use, regulators at three sites where the technique has been applied have recognized the methods definitive results. This has led to cost savings and helped to guide remedial alternatives.
Disclosures The authors declare that they have no competing financial interests
Acknowledgements Financial support for this research was provided by the Strategic Environmental Research and Development Program (SERDP ER-2338; Andrea Leeson, Program Manager). Michael Pound, Naval Facilities Engineering Command, Southwest provided logistical and site support for the project. Brian White, Erika Thompson and Richard Wong (CBI Federal Services, Inc) provided on-site logistical support, historical site perspective and relevant reports. Todd Wiedemeier (T.H. Wiedemeier & Associates) provided documentation, discussion and historical site perspectives.
References 1. National Research Council. In situ bioremediation: When does it work?. 1-207 National Academy of Sciences, Washington, DC, (1993). 2. Vangelas, K. M. Summary Document of Workshops for Hanford, Oak Ridge and Savannah River Site as part of the Monitored Natural Attenuation and Enhanced Passive Remediation for Chlorinated Solvents - DOE Alternative Project for Technology Acceleration. 1-89, U.S. Department of Energy, Westinghouse Savannah River Company, Aiken, SC, (2003). 3. Wiedemeier, T. H. et al. Technical Protocol for Evaluating Natural Attenuation of Chlorinated Solvents in Ground Water. 1-248, USEPA Office of Research and Development, Washington, DC, (1998). 4. Wilson, J. T., Kampbell, D. H., Ferrey, M., & Estuestra, P. Evaluation of the Protocol for Natural Attenuation of Chlorinated Solvents: Case Study at the Twin Cities Army Ammunition Plant. 1-49, USEPA Office of Research and Development, Washington, DC, (2001). 5. Elsner, M. et al. Current challenges in compound-specific stable isotope analysis of environmental organic contaminants. Analytical and Bioanalytical Chemistry. 403 9, 2471-2491 (2012). 6. Meckenstock, R. U., Griebler, C., Morasch, B., & Richnow, H. H. Stable isotope fractionation analysis as a tool to monitor biodegradation in contaminated acquifers. Journal of Contaminant Hydrology. 75 3-4, 215-255 (2004). 7. Kirtland, B. C., Aelion, C. M., & Stone, P. A. Assessing in situ mineralization of recalcitrant organic compounds in vadose zone sediments 13 14 using d C and D C measurements. Journal of Contaminant Hydrology. 76 1-2, 1-18 (2005). 8. Kirtland, B. C., Aelion, C. M., Stone, P. A., & Hunkeler, D. Isotopic and Geochemical Assessment of in Situ Biodegradation of Chlorinated Hydrocarbons. Environmental Science and Technology. 37 18, 4205-4212 (2003). 9. Aelion, C. M., Kirtland, B. C., & Stone, P. A. Radiocarbon assessment of aerobic petroleum bioremediation in the vadose zone and groundwater at an AS/SVE site. Environmental Science and Technology. 31 12, 3363-3370 (1997).
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Journal of Visualized Experiments
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10. Boyd, T. J., Pound, M. J., Lohr, D., & Coffin, R. B. Radiocarbon-depleted CO2 evidence for fuel biodegradation at the Naval Air Station North Island (USA) fuel farm site. Environmental Science: Processes & Impacts. 15 5, 912-918 (2013). 11. Coffin, R. B. et al. Radiocarbon and Stable Carbon Isotope Analysis to Confirm Petroleum Natural Attenuation in the Vadose Zone. Environmental Forensics. 9 1, 75-84 (2008). 12. Sihota, N. J., & Ulrich Mayer, K. Characterizing vadose zone hydrocarbon biodegradation using carbon dioxide effluxes, isotopes, and reactive transport modeling. Vadose Zone Journal. 11 4 (2012). 13. Sihota, N. I., Singurindy, O., & Mayer, K. U. CO2-Efflux Measurements for Evaluating Source Zone Natural Attenuation Rates in a Petroleum Hydrocarbon Contaminated Aquifer. Environmental Science & Technology. 45 2, 482-488 (2011). 14. Norman, J. M. et al. A comparison of six methods for measuring soil-surface carbon dioxide fluxes. J. Geophys. Res. 102 D24, 28771-28777 (1997). 15. Amos, R. T., Mayer, K. U., Bekins, B. A., Delin, G. N., & Williams, R. L. Use of dissolved and vapor-phase gases to investigate methanogenic degradation of petroleum hydrocarbon contamination in the subsurface. Water Resources Research. 41 2, 1-15 (2005). 16. Molins, S., Mayer, K. U., Amos, R. T., & Bekins, B. A. Vadose zone attenuation of organic compounds at a crude oil spill site - Interactions between biogeochemical reactions and multicomponent gas transport. Journal of Contaminant Hydrology. 112 1-4, 15-29 (2010). 17. McCoy, K., Zimbron, J., Sale, T., & Lyverse, M. Measurement of Natural Losses of LNAPL Using CO2 Traps. Groundwater. (2014). 18. Boyd, T. J., Montgomery, M. T., Cuenca, R. H., & Hagimoto, Y. Combined radiocarbon and CO2 flux measurements used to determine in situ chlorinated solvent mineralization rate. Environmental Science: Processes & Impacts. (2015). 19. Winslow, S. D., Pepich, B. V., Bassett, M. V., & Wendelken, S. C. Microbial inhibitors for US EPA drinking water methods for the determination of organic compounds. Environmental Science and Technology. 35 20, 4103-4110 (2001). 20. Johnson, K. M., Sieburth, J. M., Williams, P. J. l. B., & Brändström, L. Coulometric total carbon dioxide analysis for marine studies: Automation and Calibration. Mar.Chem. 21 2, 117-133 (1987). 21. Dickson, A. G. Standards for ocean measurements. Oceanography. 23 3, 34-47 (2010). 14 22. Stuiver, M., & Polach, H. A. Discussion: Reporting of C Data. Radiocarbon. 19 3, 355-363 (1977). 23. Zheng, C., & Wang, P. P. MT3DMS: A modular three-dimensional multispecies transport model for simulation of advection, dispersion, and chemical reactions of contaminants in groundwater systems; documentation and user's guide. DTIC Document, (1999). 24. Harbaugh, A. W. MODFLOW-2005, the US Geological Survey modular ground-water model: The ground-water flow process. US Department of the Interior, US Geological Survey, (2005). 25. Winston, R. B. in Ground Water - Book 6. Vol. Techniques and Methods 6-A29 Ch. 29, U.S. Geological Survey, (2009). 26. Accord Engineering Inc. Semi-Annual Post-Closure Maintenance Report for Calendar Year 2011 Installation Restoration (IR) Program Site 2 (Old Spanish Bight Landfill), Site 4 (Public Works Salvage Yard), and Site 5, Unit 1 (Golf Course Landfill). San Diego, CA, (2011). 27. Geosyntec Consultants. Annual Progress Report October 2010 to December 2011, Operable Unit 24. Columbia, MD, (2012).
Copyright © 2016 Creative Commons Attribution-NonCommercial-NoDerivs 3.0 Unported License
October 2016 | 116 | e53233 | Page 12 of 12
www.jove.com
Video Article
Measuring Carbon-based Contaminant Mineralization Using Combined CO2 Flux and Radiocarbon Analyses 1
1
2
2
Thomas J. Boyd , Michael T. Montgomery , Richard H. Cuenca , Yutaka Hagimoto 1
Marine Biogeochemistry, Code 6114, US Naval Research Laboratory
2
Department of Biological and Ecological Engineering, Oregon State University
Correspondence to: Thomas J. Boyd at [email protected] URL: http://www.jove.com/video/53233 DOI: doi:10.3791/53233 Keywords: Environmental Sciences, Issue 116, mineralization, contaminants, carbon, radiocarbon, CO2, flux, degradation, biodegradation, fossil fuel, petroleum, industrial chemical Date Published: 10/21/2016 Citation: Boyd, T.J., Montgomery, M.T., Cuenca, R.H., Hagimoto, Y. Measuring Carbon-based Contaminant Mineralization Using Combined CO2 Flux and Radiocarbon Analyses. J. Vis. Exp. (116), e53233, doi:10.3791/53233 (2016).
Abstract A method is described which uses the absence of radiocarbon in industrial chemicals and fuels made from petroleum feedstocks which frequently contaminate the environment. This radiocarbon signal — or rather the absence of signal — is evenly distributed throughout a 14 contaminant source pool (unlike an added tracer) and is not impacted by biological, chemical or physical processes (e.g., the C radioactive decay rate is immutable). If the fossil-derived contaminant is fully degraded to CO2, a harmless end-product, that CO2 will contain no radiocarbon. CO2 derived from natural organic matter (NOM) degradation will reflect the NOM radiocarbon content (usually ~4.8) and considerable limestone (CaCO3) may be a poor candidate for applying this technique. Ancient carbonate deposits might dissolve in low pH and bias the analysis. The technique's significance is considerable, as a sole measurement type (natural abundance radiocarbon) can immediately be used to confirm in situ conversion of contaminant to CO2. This analysis is definitive. Radiocarbon cannot become depleted except through radioactive decay - which is constant despite physical, chemical or biological alteration of any starting material. Static radiocarbon measurements (for instance 14 14 DI C) can be made on batch samples and immediately confirm if C-depleted CO2 is prevalent at a site (irrefutably indicating contaminant mineralization to CO2). This information alone is incredibly valuable to site managers as without it, they are required to use numerous indirect lines of evidence to infer that contaminant mineralization is occurring. No other single measurement can provide a concrete connection between carbon-based contaminant and the carbon-containing CO2 produced through complete degradation. Future applications are currently underway in which our group will increase sampling temporal resolution to encompass an entire year. By collecting CO2 and determining the mineralization rate(s) over the spatial extent of the site, we will be able to refine models for contaminant degradation over time. This information is critically needed by site managers in order to most effectively manage contaminated sites. In limited use, regulators at three sites where the technique has been applied have recognized the methods definitive results. This has led to cost savings and helped to guide remedial alternatives.
Disclosures The authors declare that they have no competing financial interests
Acknowledgements Financial support for this research was provided by the Strategic Environmental Research and Development Program (SERDP ER-2338; Andrea Leeson, Program Manager). Michael Pound, Naval Facilities Engineering Command, Southwest provided logistical and site support for the project. Brian White, Erika Thompson and Richard Wong (CBI Federal Services, Inc) provided on-site logistical support, historical site perspective and relevant reports. Todd Wiedemeier (T.H. Wiedemeier & Associates) provided documentation, discussion and historical site perspectives.
References 1. National Research Council. In situ bioremediation: When does it work?. 1-207 National Academy of Sciences, Washington, DC, (1993). 2. Vangelas, K. M. Summary Document of Workshops for Hanford, Oak Ridge and Savannah River Site as part of the Monitored Natural Attenuation and Enhanced Passive Remediation for Chlorinated Solvents - DOE Alternative Project for Technology Acceleration. 1-89, U.S. Department of Energy, Westinghouse Savannah River Company, Aiken, SC, (2003). 3. Wiedemeier, T. H. et al. Technical Protocol for Evaluating Natural Attenuation of Chlorinated Solvents in Ground Water. 1-248, USEPA Office of Research and Development, Washington, DC, (1998). 4. Wilson, J. T., Kampbell, D. H., Ferrey, M., & Estuestra, P. Evaluation of the Protocol for Natural Attenuation of Chlorinated Solvents: Case Study at the Twin Cities Army Ammunition Plant. 1-49, USEPA Office of Research and Development, Washington, DC, (2001). 5. Elsner, M. et al. Current challenges in compound-specific stable isotope analysis of environmental organic contaminants. Analytical and Bioanalytical Chemistry. 403 9, 2471-2491 (2012). 6. Meckenstock, R. U., Griebler, C., Morasch, B., & Richnow, H. H. Stable isotope fractionation analysis as a tool to monitor biodegradation in contaminated acquifers. Journal of Contaminant Hydrology. 75 3-4, 215-255 (2004). 7. Kirtland, B. C., Aelion, C. M., & Stone, P. A. Assessing in situ mineralization of recalcitrant organic compounds in vadose zone sediments 13 14 using d C and D C measurements. Journal of Contaminant Hydrology. 76 1-2, 1-18 (2005). 8. Kirtland, B. C., Aelion, C. M., Stone, P. A., & Hunkeler, D. Isotopic and Geochemical Assessment of in Situ Biodegradation of Chlorinated Hydrocarbons. Environmental Science and Technology. 37 18, 4205-4212 (2003). 9. Aelion, C. M., Kirtland, B. C., & Stone, P. A. Radiocarbon assessment of aerobic petroleum bioremediation in the vadose zone and groundwater at an AS/SVE site. Environmental Science and Technology. 31 12, 3363-3370 (1997).
Copyright © 2016 Creative Commons Attribution-NonCommercial-NoDerivs 3.0 Unported License
October 2016 | 116 | e53233 | Page 11 of 12
Journal of Visualized Experiments
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10. Boyd, T. J., Pound, M. J., Lohr, D., & Coffin, R. B. Radiocarbon-depleted CO2 evidence for fuel biodegradation at the Naval Air Station North Island (USA) fuel farm site. Environmental Science: Processes & Impacts. 15 5, 912-918 (2013). 11. Coffin, R. B. et al. Radiocarbon and Stable Carbon Isotope Analysis to Confirm Petroleum Natural Attenuation in the Vadose Zone. Environmental Forensics. 9 1, 75-84 (2008). 12. Sihota, N. J., & Ulrich Mayer, K. Characterizing vadose zone hydrocarbon biodegradation using carbon dioxide effluxes, isotopes, and reactive transport modeling. Vadose Zone Journal. 11 4 (2012). 13. Sihota, N. I., Singurindy, O., & Mayer, K. U. CO2-Efflux Measurements for Evaluating Source Zone Natural Attenuation Rates in a Petroleum Hydrocarbon Contaminated Aquifer. Environmental Science & Technology. 45 2, 482-488 (2011). 14. Norman, J. M. et al. A comparison of six methods for measuring soil-surface carbon dioxide fluxes. J. Geophys. Res. 102 D24, 28771-28777 (1997). 15. Amos, R. T., Mayer, K. U., Bekins, B. A., Delin, G. N., & Williams, R. L. Use of dissolved and vapor-phase gases to investigate methanogenic degradation of petroleum hydrocarbon contamination in the subsurface. Water Resources Research. 41 2, 1-15 (2005). 16. Molins, S., Mayer, K. U., Amos, R. T., & Bekins, B. A. Vadose zone attenuation of organic compounds at a crude oil spill site - Interactions between biogeochemical reactions and multicomponent gas transport. Journal of Contaminant Hydrology. 112 1-4, 15-29 (2010). 17. McCoy, K., Zimbron, J., Sale, T., & Lyverse, M. Measurement of Natural Losses of LNAPL Using CO2 Traps. Groundwater. (2014). 18. Boyd, T. J., Montgomery, M. T., Cuenca, R. H., & Hagimoto, Y. Combined radiocarbon and CO2 flux measurements used to determine in situ chlorinated solvent mineralization rate. Environmental Science: Processes & Impacts. (2015). 19. Winslow, S. D., Pepich, B. V., Bassett, M. V., & Wendelken, S. C. Microbial inhibitors for US EPA drinking water methods for the determination of organic compounds. Environmental Science and Technology. 35 20, 4103-4110 (2001). 20. Johnson, K. M., Sieburth, J. M., Williams, P. J. l. B., & Brändström, L. Coulometric total carbon dioxide analysis for marine studies: Automation and Calibration. Mar.Chem. 21 2, 117-133 (1987). 21. Dickson, A. G. Standards for ocean measurements. Oceanography. 23 3, 34-47 (2010). 14 22. Stuiver, M., & Polach, H. A. Discussion: Reporting of C Data. Radiocarbon. 19 3, 355-363 (1977). 23. Zheng, C., & Wang, P. P. MT3DMS: A modular three-dimensional multispecies transport model for simulation of advection, dispersion, and chemical reactions of contaminants in groundwater systems; documentation and user's guide. DTIC Document, (1999). 24. Harbaugh, A. W. MODFLOW-2005, the US Geological Survey modular ground-water model: The ground-water flow process. US Department of the Interior, US Geological Survey, (2005). 25. Winston, R. B. in Ground Water - Book 6. Vol. Techniques and Methods 6-A29 Ch. 29, U.S. Geological Survey, (2009). 26. Accord Engineering Inc. Semi-Annual Post-Closure Maintenance Report for Calendar Year 2011 Installation Restoration (IR) Program Site 2 (Old Spanish Bight Landfill), Site 4 (Public Works Salvage Yard), and Site 5, Unit 1 (Golf Course Landfill). San Diego, CA, (2011). 27. Geosyntec Consultants. Annual Progress Report October 2010 to December 2011, Operable Unit 24. Columbia, MD, (2012).
Copyright © 2016 Creative Commons Attribution-NonCommercial-NoDerivs 3.0 Unported License
October 2016 | 116 | e53233 | Page 12 of 12
