Kinetic and Pathway Modeling of Reductive 2,4,6-Trinitrotoluene Biodegradation with Different Electron Donors
Publication: Journal of Environmental Engineering
Volume 141, Issue 8
Abstract
A comprehensive model was applied to simulate a laboratory microcosm study of biodegradation rates and the branched production and loss of daughter products. The aim of the investigation was to evaluate the effect of electron donors (lactate, ethanol, and natural organic matter) on 2,4,6-trinitrotoluene (TNT) biodegradation rate and pathway in historically contaminated sediments undergoing biostimulation. Simulation results show overall TNT degradation rates for lactate-amended microcosms were greater than ethanol-amended microcosms by a factor of 1.7 and 3.0 times compared with natural organic matter amended microcosms. Differences in observed biomass concentrations () were thought to be a contributing factor. TNT degradation pathway modeling included determination of branching coefficients representing whether the first nitro group reduction occurred in the ortho or para position. Branching coefficients were greater for the initial reduction of para (17–27% initial TNT concentration) over ortho (3–9% initial TNT concentration) for all test conditions. However, greater degradate recovery and a different (lower para:ortho) ratio was observed for ethanol compared with lactate and unamended conditions. Given the variation in sorption parameters among degradate isomers, these results suggest that differences in pathway branching stimulated by different electron donors are potentially relevant to the long-term persistence of TNT degradation products and the ultimate success of bioremediation-based remedial strategies.
Get full access to this article
View all available purchase options and get full access to this article.
Acknowledgments
Funding for this work was provided by Versar, Inc., Chantilly, Virginia. The authors thank H. Clarkson Meredith (Versar Atlantic Regional Operations), Jeffrey Zoeckler (HANA Engineers & Consultants), Ankit Gupta (AECOM Environment), Jody Smiley (Virginia Tech), and Rachel Thomas (Virginia Tech) for technical and laboratory assistance.
References
Admassu, W., Sethuraman, A. V., Crawford, R., and Korus, R. A. (1998). “Growth kinetics of Clostridium bifermentans and its ability to degrade TNT using an inexpensive alternative medium.” Biorem. J., 2(1), 17–28.
Adrian, N., and Arnett, C. (2007). “Anaerobic biotransformation of explosives in aquifer slurries amended with ethanol and propylene glycol.” Chemosphere, 66(10), 1849–1856.
Adrian, N., Arnett, C., and Hickey, R. (2003). “Stimulating the anaerobic biodegradation of explosives by the addition of hydrogen or electron donors that produce hydrogen.” Water Res., 37(14), 3499–3507.
Alavi, G., Chung, M., Lichwa, J., D’Alessio, M., and Ray, C. (2011). “The fate and transport of RDX, HMX, TNT and DNT in the volcanic soils of Hawaii: A laboratory and modeling study.” J. Hazard. Mater., 185(2–3), 1600–1604.
Breitung, J., Bruns-Nagel, D., Steinbach, K., Kaminski, L., Gemsa, D., and von Löw, E. (1996). “Bioremediation of 2,4,6-trinitrotoluene-contaminated soils by two different aerated compost systems.” Appl. Microbiol. Biotechnol., 44(6), 795–800.
Cole, J. R., et al. (2009). “The ribosomal database project: Improved alignments and new tools for rRNA analysis.” Nucleic Acids Res., 37(D), 141–145.
Daun, G., Lenke, H., Knackmuss, H.-J., and Reuss, M. (1999). “Experimental investigations and kinetic models for the cometabolic biological reduction of trinitrotoluene.” Chem. Eng. Technol., 22(4), 308–313.
Daun, G., Lenke, H., Reuss, M., and Knackmuss, H.-J. (1998). “Biological treatment of TNT-contaminated soil. 1. Anaerobic cometabolic reduction and interaction of TNT and metabolites with soil components.” Environ. Sci. Technol., 32(13), 1956–1963.
Drzyzga, O., Bruns-Nagel, D., Gorontzy, T., Blotevogel, K.-H., Gemsa, D., and von Low, E. (1998). “Incorporation of 14 C-labeled 2,4,6-trinitrotoluene metabolites into different soil fractions after anaerobic and aerobic treatment of soil/molasses mixtures.” Environ. Sci. Technol., 32(22), 3529–3535.
Esteve-Nunez, A., Caballero, A., and Ramos, J. L. (2001). “Biological degradation of 2,4,6-trinitrotoluene.” Microbiol. Mol. Biol. Rev., 65(3), 335–352.
Fahrenfeld, N., Zoeckler, J., Widdowson, M., and Pruden, A. (2013). “Effect of biostimulants on 2,4,6-trinitrotoluene (TNT) degradation and bacterial community composition in contaminated aquifer sediment enrichments.” Biodegradation, 24(2), 179–190.
Fuller, M., Hatzinger, P., Rungmakol, D., Schuster, R., and Steffan, R. (2004). “Enhancing the attenuation of explosives in surface soils at military facilities: Combined sorption and biodegradation.” Environ. Toxicol. Chem., 23(2), 313–324.
Fuller, M., and Manning, J. (2004). “Microbiological changes during bioremediation of explosives-contaminated soils in laboratory and pilot-scale bioslurry reactors.” Bioresour. Technol., 91(2), 123–133.
Gallagher, E. M., Young, L. Y., McGuinness, L. M., and Kerkhof, L. J. (2010). “Detection of 2,4,6-trinitrotoluene-utilizing anaerobic bacteria by 15 N and 13 C incorporation.” Appl. Environ. Microbiol., 76(5), 1695–1698.
Gerlach, R., Steiof, M., Zhang, C., and Hughes, J. B. (1999). “Low aqueous solubility electron donors for the reduction of nitroaromatics in anaerobic sediments.” J. Contam. Hydrol., 36(1–2), 91–104.
Haderlein, S. B., Weissmahr, K. W., and Schwarzenbach, R. P. (1996). “Specific adsorption of nitroaromatic explosives and pesticides to clay minerals.” Environ. Sci. Technol., 30(2), 612–622.
Hofstetter, T. B., Heijman, C. G., Haderlein, S. B., Holliger, C., and Schwarzenbach, R. P. (1999). “Complete reduction of TNT and other (poly)nitroaromatic compounds under iron-reducing subsurface conditions.” Environ. Sci. Technol., 33(9), 1479–1487.
Hwang, P., Chow, T., and Adrian, N. R. (1998). “Transformation of TNT to triaminotoluene by mixed cultures incubated under methanogenic conditions.” USACERL Technical Rep. 98/116.
Hwang, P., Chow, T., and Adrian, N. R. (2000). “Transformation of trinitrotoluene to triaminotoluene by mixed cultures incubated under methanogenic conditions.” Environ. Toxicol. Chem., 19(4), 836–841.
In, B. H., Park, J. S., Namkoong, W., Hwang, E. Y., and Kim, J. D. (2008). “Effect of co-substrate on anaerobic slurry phase bioremediation of TNT-contaminated soil.” Korean J. Chem. Eng., 25(1), 102–107.
Lenke, H., et al. (1998). “Biological treatment of TNT-contaminated soil. 2. Biologically induced immobilization of the contaminants and full-scale application.” Environ. Sci. Technol., 32(13), 1964–1971.
Li, A., Marx, K., Walker, J., and Kaplan, D. (1997). “Trinitrotoluene and metabolites binding to humic acid.” Environ. Sci. Technol., 31(2), 584–589.
Martel, R., Robertson, T., Doan, M., Thiboutot, S., Ampleman, G., Provatas, A., and Jenkins, T. (2008). “2,4,6-Trinitrotoluene in soil and groundwater under a waste lagoon at the former Explosives Factory Maribyrnong (EFM), Victoria, Australia.” Environ. Geol., 53(6), 1249–1259.
Michalsen, M. M., Weiss, R., King, A., Gent, D., Medina, V. F., and Istok, J. D. (2013). “Push-pull tests for estimating RDX and TNT degradation rates in groundwater.” Ground Water Monit. Rem., 33(3), 61–68.
Neidhardt, F. C. (1996). “Escherichia coli and Salmonella.” Cellular and molecular biology, Vol. 1, American Society for Microbiology Press, 14.
Park, C., Kim, T.-H., Kim, S., Lee, J., and Kim, S.-W. (2002). “Biokinetic parameter estimation for degradation of 2,4,6-trinitrotoluene (TNT) with Pseudomonas putida KP-T201.” J. Biosci. Bioeng., 94(1), 57–61.
Pavlostathis, S. G., and Jackson, G. H. (1999). “Biotransformation of 2,4,6–trinitrotoluene in Anabaena sp. cultures.” Environ. Toxicol. Chem., 18(3), 412–419.
Pennington, J. C., et al. (1995). “Fate of 2,4,6-trinitrotoluene in a simulated compost system.” Chemosphere, 30(3), 429–438.
R Core Team. (2013). R: A language and environment for statistical computing, R Foundation for Statistical Computing, Vienna, Austria.
Rectanus, H., Widdowson, M., Chapelle, F., Kelly, C., and Novak, J. (2007). “Investigation of reductive dechlorination supported by natural organic carbon.” Ground Water Monit. Rem., 27(4), 53–62.
Rectanus, H. V. (2006). “Sustainability of reductive dechlorination at chlorinated solvent contaminated sites: Methods to evaluate biodegradable natural organic carbon.” Ph.D. thesis, Virginia Polytechnic Institute and State Univ., Blacksburg, VA.
Riefler, R. G., and Smets, B. F. (2002). “NAD(P)H:Flavin mononucleotide oxidoreductase inactivation during 2,4,6-trinitrotoluene reduction.” Appl. Environ. Microbiol., 68(4), 1690–1696.
Robertson, T. J., et al. (2007). “Fate and transport of 2,4,6-trinitrotoluene in loams at a former explosives factory.” Soil Sediment Contam., 16(2), 159–179.
Schwarzenbach, R. P., Gschwend, P. M., and Imboden, D. M. (2003). “Activity coefficient and solubility in water.” Environmental organic chemistry, 2nd Ed., Wiley, Hoboken, NJ, 166.
Smets, B., Yin, H., and Esteve-Nuñez, A. (2007). “TNT biotransformation: When chemistry confronts mineralization.” Appl. Microbiol. Biotechnol., 76(2), 267–277.
Suzuki, M. T., Taylor, L. T., and DeLong, E. F. (2000). “Quantitative analysis of small-subunit rRNA genes in mixed microbial populations via 5′-nuclease assays.” Appl. Environ. Microbiol., 66(11), 4605–4614.
Tharakan, J., and Gordon, J. (1999). “Cometabolic biotransformation of trinitrotoluene (TNT) supported by aromatic and non-aromatic cosubstrates.” Chemosphere, 38(6), 1323–1330.
Thorn, K. A., Pennington, J. C., Kennedy, K. R., Cox, L. G., Hayes, C. A., and Porter, B. E. (2008). “N-15 NMR study of the immobilization of 2,4- and 2,6-dinitrotoluene in aerobic compost.” Environ. Sci. Technol., 42(7), 2542–2550.
Upson, R. T., and Burns, S. E. (2006). “Sorption of nitroaromatic compounds to synthesized organoclays.” J. Colloid Interface Sci., 297(1), 70–76.
Wilke, B., Gattinger, A., Fröhlich, E., Zelles, L., and Gong, P. (2004). “Phospholipid fatty acid composition of a 2,4,6-trinitrotoluene contaminated soil and an uncontaminated soil as affected by a humification remediation process.” Soil Biol. Biochem., 36(4), 725–729.
Yin, H., Wood, T. K., and Smets, B. F. (2005). “Reductive transformation of TNT by Escherichia coli: Pathway description.” Appl. Microbiol. Biotechnol., 67(3), 397–404.
Information & Authors
Information
Published In
Journal of Environmental Engineering
Volume 141 • Issue 8 • August 2015
Copyright
© 2015 American Society of Civil Engineers.
History
Received: Jul 28, 2014
Accepted: Dec 18, 2014
Published online: Feb 17, 2015
Discussion open until: Jul 17, 2015
Published in print: Aug 1, 2015
Authors
Metrics & Citations
Metrics
Citations
Download citation
If you have the appropriate software installed, you can download article citation data to the citation manager of your choice. Simply select your manager software from the list below and click Download.