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Mark E. Fuller

Publications and source records attributed to Mark E. Fuller.

2 recordsLinked to original sources

Validation of stable isotope ratio analysis to document the biodegradation and natural attenuation of RDX, ESTCP Project ER-201208

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is a common soil contaminant at current and former military facilities, including many training and testing ranges. Because RDX is readily transported through soils to the subsurface, this nitramine explosive now also impacts groundwater and drinking water at numerous locations across the country. A significant issue with RDX contamination on ranges and at other military installations is that it often occurs over expansive areas, where in situ or ex situ treatment technologies are difficult to implement. One potential alternative for military ranges and other facilities is monitored natural attenuation (MNA), in which contaminant degradation by natural processes, including biodegradation, are evaluated. However, one limitation of this approach for RDX is the inability to accurately evaluate whether the nitramine is biodegrading under field conditions, as rates may be relatively slow. One potential technique to overcome this limitation is the use of compound-specific stable isotope analysis (CSIA), where biological contaminant destruction can be documented as changes in the ratio of stable isotopes of specific elements in a molecule; for RDX, ratios of 15 N/ 14 N and 13 C/ 12 C are relevant. The objective of this project is to validate a CSIA method to confirm and constrain rates of aerobic and anaerobic biodegradation of RDX at field sites. This technique can be utilized by DoD to provide critical data to support MNA as a remedy for treating this energetic in groundwater, and confirm the effectiveness of in situ enhanced bioremediation remedies. The stable isotopic composition of NO 3 - and NO 2 - was also measured when these anions co-occurred with RDX to evaluate whether these potential degradation products from RDX could be used to further demonstrate MNA in the field.

Report

Relating carbon and nitrogen isotope effects to reaction mechanisms during aerobic or anaerobic degradation of RDX (Hexahydro-1,3,5-Trinitro-1,3,5-Triazine) by pure bacterial cultures

Kinetic isotopic fractionation of carbon and nitrogen during RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) biodegradation was investigated with pure bacterial cultures under aerobic and anaerobic conditions. Relatively large bulk enrichments in 15 N were observed during biodegradation of RDX via anaerobic ring cleavage (ε 15 N = −12.7‰ ± 0.8‰) and anaerobic nitro reduction (ε 15 N = −9.9‰ ± 0.7‰), in comparison to smaller effects during biodegradation via aerobic denitration (ε 15 N = −2.4‰ ± 0.2‰). 13 C enrichment was negligible during aerobic RDX biodegradation (ε 13 C = −0.8‰ ± 0.5‰) but larger during anaerobic degradation (ε 13 C = −4.0‰ ± 0.8‰), with modest variability among genera. Dual-isotope ε 13 C/ε 15 N analyses indicated that the three biodegradation pathways could be distinguished isotopically from each other and from abiotic degradation mechanisms. Compared to the initial RDX bulk δ 15 N value of +9‰, δ 15 N values of the NO 2 − released from RDX ranged from −7‰ to +2‰ during aerobic biodegradation and from −42‰ to −24‰ during anaerobic biodegradation. Numerical reaction models indicated that N isotope effects of NO 2 − production were much larger than, but systematically related to, the bulk RDX N isotope effects with different bacteria. Apparent intrinsic ε 15 N-NO 2 − values were consistent with an initial denitration pathway in the aerobic experiments and more complex processes of NO 2 − formation associated with anaerobic ring cleavage. These results indicate the potential for isotopic analysis of residual RDX for the differentiation of degradation pathways and indicate that further efforts to examine the isotopic composition of potential RDX degradation products (e.g., NO x ) in the environment are warranted.

Applied and Environmental Microbiology