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Back-diffusion of chlorinated ethenes (CEs) from low-permeability layers (LPLs) causes contaminant persistence long after the primary spill zones have disappeared. Naturally occurring degradation in LPLs lowers remediation time frames, but its assessment through sediment sampling is prohibitive in conventional remediation projects. Scenario simulations were performed with a reactive transport model (PHT3D in FloPy) accounting for isotope effects associated with degradation, sorption, and diffusion, to evaluate the potential of CSIA data from aquifers in assessing degradation in aquitards. The model simulated a trichloroethylene (TCE) DNAPL and its pollution plume within an aquifer-aquitard-aquifer system. Sequential reductive dechlorination to ethene and sorption were uniform in the aquitard and did not occur in the aquifer. After 10 years of loading the aquitard through diffusion from the plume, subsequent source removal triggered release of TCE by back-diffusion. In the upper aquifer, during the loading phase, δ13C-TCE was slightly enriched (up to 2‰) due to diffusion effects stimulated by degradation in the aquitard. In the upper aquifer, during the release phase, (i) source removal triggered a huge δ13C increase especially for higher CEs, (ii) moreover, downstream decreasing isotope ratios (caused by downgradient later onset of the release phase) with temporal increasing isotope ratios reflect aquitard degradation (as opposed to downstream increasing and temporally constant isotope ratios in reactive aquifers), and (iii) the carbon isotope mass balance (CIMB) enriched up to 4‰ as lower CEs (more depleted, less sorbing) have been transported deeper into the aquitard. Thus, enriched CIMB does not indicate oxidative transformation in this system. The CIMB enrichment enhanced with more sorption and lower aquitard thickness. Thin aquitards are quicker flushed from lower CEs leading to faster CIMB enrichment over time. CIMB enrichment is smaller or nearly absent when daughter products accumulate. Aquifer CSIA patterns indicative of aquitard degradation were similar in case of linear decreasing rate constants but contrasted with previous simulations assuming a thin bioactive zone. The Rayleigh equation systematically underestimates the extent of TCE degradation in aquifer samples especially during the loading phase and for conditions leading to long remediation time frames (low groundwater flow velocity, thicker aquitards, strong sorption in the aquitard). The Rayleigh equation provides a good and useful picture on aquitard degradation during the release phase throughout the sensitivity analysis. This modelling study provides a framework on how aquifer CSIA data can inform on the occurrence of aquitard degradation and its pitfalls.

The tri-halogenated phenols, 2,4,6-trichlorophenol (TCP) and 2,4,6-tribromophenol (TBP), are known as groundwater contaminants. Indigenous bacteria may degrade these compounds aerobically or anaerobically, with the aerobic process initiated by ring hydroxylation at the para position. Stable isotope analysis can be proposed as a tool for determining biodegradation process of these compounds in the environment. However, to date isotope fractionation in microbial oxidation of trihalogenated phenols has not been reported. This work aimed to investigate carbon and halogen (chlorine or bromine) isotope effects associated with the process by two microbial strains: Achromobacter piechaudii strain TBPZ which is capable of degrading both TCP and TBP, and Ralstonia eutropha strain JMP 134 which was extensively studied in the past to characterize the TCP oxidation mechanism. Low carbon isotope effects were observed in all degradation experiments. Opposite fractionation trends were detected for TCP and TBP by strain TBPZ (eC = −0.51 ± 0.28‰ and eC = +0.68 ± 0.26‰, respectively). Strain JMP presented a low inverse carbon isotope effect for TCP oxidation (eC = +0.26 ± 0.13‰), contrary to that of strain TBPZ. For the halogen atoms, low yet significant normal halogen isotope effects were detected in all cases (−0.49 to −1.43‰ for chlorine, and −0.42‰ for bromine). The results suggest that the observed isotope effects do not reflect the ring hydroxylation. Instead, they likely represent rate-limiting steps preceding the catalysis of hydroxylation. Dual-element isotope effects observed in this study did not enable distinguishing between oxidation and reduction of TCP. The oxidation and reduction dual-element trends were distinct for TBP. However, it is uncertain if this difference can be extrapolated from the laboratory to the field, since the isotope effects in TBP degradation are strongly influenced by slow steps prior to hydroxylation.

Reactive transport modeling of multi-element, compound-specific isotope analysis (CSIA) data has great potential to quantify sequential microbial reductive dechlorination (SRD) and alternative pathways such as oxidation, in support of remediation of chlorinated solvents in groundwater. As a key step towards this goal, a model was developed that simulates simultaneous carbon, chlorine, and hydrogen isotope fractionation during SRD of trichloroethene, via cis-1,2-dichloroethene (and trans-DCE as minor pathway), and vinyl chloride to ethene, following Monod kinetics. A simple correction term for individual isotope/isotopologue rates avoided multi-element isotopologue modeling. The model was successfully validated with data from a mixed culture Dehalococcoides microcosm. Simulation of Cl-CSIA required incorporation of secondary kinetic isotope effects (SKIEs). Assuming a limited degree of intramolecular heterogeneity of δ37Cl in TCE decreased the magnitudes of SKIEs required at the non-reacting Cl positions, without compromising the goodness of model fit, whereas a good fit of a model involving intramolecular CCl bond competition required an unlikely degree of intramolecular heterogeneity. Simulation of H-CSIA required SKIEs in H atoms originally present in the reacting compounds, especially for TCE, together with imprints of strongly depleted δ2H during protonation in the products. Scenario modeling illustrates the potential of H-CSIA for source apportionment.

The macromolecular compositions of subfossil plants from boreal Sphagnum bogs and restiad bogs (New Zealand) have been studied by pyrolysis-gas chromatography/mass spectrometry to evaluate the extent of degradation in the anoxic zone (catotelm) of a peat bog. Degradation of vascular plant polysaccharides was apparent only into the upper catotelm. Sphagnum was degraded more slowly than vascular plants, but no cessation of degradation was observed. The inferred rate of degradation varied depending on type of plant, extent of aerobic, precatotelmic degradation, and mode of litter deposition (rooting versus at the surface). Environmental forcing on anaerobic carbon dynamics would potentially be largest if the hydrology was disturbed at a wet and vascular plant-rich site. Peat deposited under a dry regime would be relatively inert in anaerobic conditions. Although catotelmic degradation is usually not extensive, in some cases, if labile organic matter is retained in the aerobic phase (e.g., restiad bogs) a major fraction of peat is degraded in catotelm, potentially resulting in a delayed major export of 14 C-old methane.

Field evidence from underground storage tank sites where leaded gasoline leaked indicates the lead scavengers 1,2-dibromoethane (ethylene dibromide, or EDB) and 1,2-dichloroethane (1,2-DCA) may be present in groundwater at levels that pose unacceptable risk. These compounds are seldom tested for at UST sites. Although dehalogenation of EDB and 1,2-DCA is well established, the effect of fuel hydrocarbons on their biodegradability under anaerobic conditions is poorly understood. Microcosms (2 L glass bottles) were prepared with soil and groundwater from a UST site in Clemson, South Carolina, using samples collected from the source (containing residual fuel) and less contaminated downgradient areas. Anaerobic biodegradation of EDB occurred in microcosms simulating natural attenuation, but was more extensive and predictable in treatments biostimulated with lactate. In the downgradient biostimulated microcosms, EDB decreased below its maximum contaminant level (MCL) (0.05 microg/L) at a first order rate of 9.4 +/- 0.2 yr(-1). The pathway for EDB dehalogenation proceeded mainly by dihaloelimination to ethene in the source microcosms, while sequential hydrogenolysis to bromoethane and ethane was predominant in the downgradient treatments. Biodegradation of EDB in the source microcosms was confirmed by carbon specific isotope analysis, with a delta13C enrichment factor of -5.6 per thousand. The highest levels of EDB removal occurred in microcosms that produced the highest amounts of methane. Extensive biodegradation of benzene, ethylbenzene, toluene and ortho-xylene was also observed in the source and downgradient area microcosms. In contrast, biodegradation of 1,2-DCA proceeded at a considerably slower rate than EDB, with no response to lactate additions. The slower biodegradation rates for 1,2-DCA agree with field observations and indicate that even if EDB is removed to below its MCL, 1,2-DCA may persist.