Model Complexity Needed for Quantitative Analysis of High Resolution Isotope and Concentration Data from a Toluene-Pulse Experiment

Separating microbial- and physical-induced effects on the isotope signals of contaminants has been identified as a challenge in interpreting compound-specific isotope data. In contrast to simple analytical tools, such as the Rayleigh equation, reactive-transport models can account for complex interactions of different fractionating processes. The question arises how complex such models must be to reproduce the data while the model parameters remain identifiable. In this study, we reanalyze the high-resolution data set of toluene concentration and toluene-specific δ¹³C from the toluene-pulse experiment performed by Qiu et al. (this issue). We apply five reactive-transport models, differing in their degree of complexity. We uniquely quantify degradation and sorption properties of the system for each model, estimate the contributions of biodegradation-induced, sorption-induced, and transverse-dispersion-induced isotope fractionation to the overall isotope signal, and investigate the error introduced in the interpretation of the data when individual processes are neglected. Our results show that highly resolved data of both concentration and isotope ratios are needed for unique process identification facilitating reliable model calibration. Combined analysis of these highly resolved data demands reactive transport models accounting for nonlinear degradation kinetics and isotope fractionation by both reactive and physical processes such as sorption and transverse dispersion

Direct Experimental Evidence of Non-first Order Degradation Kinetics and Sorption-Induced Isotopic Fractionation in a Mesoscale Aquifer: ¹³C/¹²C Analysis of a Transient Toluene Pulse

The injection of a mixed toluene and D₂O (conservative tracer) pulse into a pristine mesoscale aquifer enabled a first direct experimental comparison of contaminant-specific isotopic fractionation from sorption versus biodegradation and transverse dispersion on a relevant scale. Water samples were taken from two vertically resolved sampling ports at 4.2 m distance. Analysis of deuterium and toluene concentrations allowed quantifying the extent of sorption (<i>R</i> = 1.25) and biodegradation (37% and 44% of initial toluene at the two sampling ports). Sorption and biodegradation were found to directly affect toluene ¹³C/¹²C breakthrough curves. In particular, isotope trends demonstrated that biodegradation underwent Michaelis–Menten kinetics rather than first-order kinetics. Carbon isotope enrichment factors obtained from an optimized reactive transport model (Eckert et al., this issue) including a possible isotope fractionation of transverse dispersion were ε^equ_sorption = −0.31 ‰, ε^kin_{transverse‑dispersion} = −0.82 ‰, and ε^kin_{biodegradation} = −2.15 ‰. Extrapolation of our results to the scenario of a continuous injection predicted that (i) the bias in isotope fractionation from sorption, but not transverse dispersion, may be avoided when the plume reaches steady-state; and (ii) the relevance from both processes is expected to decrease at longer flow distances when isotope fractionation of degradation increasingly dominates