Carbon and Chlorine Isotope Fractionation Patterns Associated with Different Engineered Chloroform Transformation Reactions

To use compound-specific isotope analysis for confidently assessing organic contaminant attenuation in the environment, isotope fractionation patterns associated with different transformation mechanisms must first be explored in laboratory experiments. To deliver this information for the common groundwater contaminant chloroform (CF), this study investigated for the first time both carbon and chlorine isotope fractionation for three different engineered reactions: oxidative C–H bond cleavage using heat-activated persulfate, transformation under alkaline conditions (pH ∼ 12) and reductive C–Cl bond cleavage by cast zerovalent iron, Fe(0). Carbon and chlorine isotope fractionation values were −8 ± 1‰ and −0.44 ± 0.06‰ for oxidation, −57 ± 5‰ and −4.4 ± 0.4‰ for alkaline hydrolysis (pH 11.84 ± 0.03), and −33 ± 11‰ and −3 ± 1‰ for dechlorination, respectively. Carbon and chlorine apparent kinetic isotope effects (AKIEs) were in general agreement with expected mechanisms (C–H bond cleavage in oxidation by persulfate, C–Cl bond cleavage in Fe(0)-mediated reductive dechlorination and E1_CB elimination mechanism during alkaline hydrolysis) where a secondary AKIE_Cl (1.00045 ± 0.00004) was observed for oxidation. The different dual carbon-chlorine (Δδ¹³C vs Δδ³⁷Cl) isotope patterns for oxidation by thermally activated persulfate and alkaline hydrolysis (17 ± 2 and 13.0 ± 0.8, respectively) vs reductive dechlorination by Fe(0) (8 ± 2) establish a base to identify and quantify these CF degradation mechanisms in the field.