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.
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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 (R = 1.25) and biodegradation (37% and 44% of initial toluene at the two sampling ports). Sorption and biodegradation were found to directly affect toluene (13)C/(12)C 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 (equ)(sorption) = -0.31 , (kin)(transverse-dispersion) = -0.82 , and (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.