Gas chromatography–isotope ratio mass spectrometry (GC-IRMS) has made it possible to analyze natural stable isotope ratios (e.g., 13C/12C, 15N/14N, 2H/1H) of individual organic contaminants in environmental samples. They may be used as fingerprints to infer contamination sources, and may demonstrate, and even quantify, the occurrence of natural contaminant transformation by the enrichment of heavy isotopes that arises from degradation-induced isotope fractionation. This review highlights an additional powerful feature of stable isotope fractionation: the study of environmental transformation mechanisms. Isotope effects reflect the energy difference of isotopologues (i.e., molecules carrying a light versus a heavy isotope in a particular molecular position) when moving from reactant to transition state. Measuring isotope fractionation, therefore, essentially allows a glimpse at transition states! It is shown how such position-specific isotope effects are “diluted out” in the compound average measured by GC-IRMS, and how a careful evaluation in mechanistic scenarios and by dual isotope plots can recover the underlying mechanistic information. The mathematical framework for multistep isotope fractionation in environmental transformations is reviewed. Case studies demonstrate how isotope fractionation changes in the presence of mass transfer, enzymatic commitment to catalysis, multiple chemical reaction steps or limited bioavailability, and how this gives information about the individual process steps. Finally, it is discussed how isotope ratios of individual products evolve in sequential or parallel transformations, and what mechanistic insight they contain. A concluding session gives an outlook on current developments, future research directions and the potential for bridging the gap between laboratory and real world systems.

Stable isotope fractionation to investigate natural transformation mechanisms of organic contaminants: principles, prospects and limitations.

Quantification of organic pollutant degradation in contaminated aquifers using compound specific stable isotope analysis – Review of recent developments

Carbon isotope fractionation is of great interest in assessing chlorinated ethene transformation by nanoscale zero-valent iron at contaminated sites, particularly in distinguishing the effectiveness of an implemented abiotic degradation remediation scheme from intrinsic biotic degradation. Transformation of trichloroethylene (TCE), cis-dichloroethylene (cis-DCE), and vinyl chloride (VC) with two types of nanoscale iron materials showed different reactivity trends, but relatively consistent carbon isotope enrichment factors (e) of −19.4‰ ± 1.8‰ (VC), −21.7‰ ± 1.8‰ (cis-DCE), and −23.5‰ ± 2.8‰ (TCE) with one type of iron (FeBH), and from −20.9‰ ± 1.1‰ to −26.5‰ ± 1.5‰ (TCE) with the other (FeH2). Products of the dichloroelimination pathway (ethene, ethane, and acetylene) were consistently 10‰ more isotopically depleted than those of the hydrogenolysis pathway (cis-DCE from TCE, VC from cis-DCE), displaying a characteristic pattern that may serve as an indicator of abiotic dehalogenation reactions and as a d...

Identifying Abiotic Chlorinated Ethene Degradation: Characteristic Isotope Patterns in Reaction Products with Nanoscale Zero-Valent Iron

The microbial degradation of organic substrates often exhibits a fractionation of stable isotopes which leads to an enrichment of the heavier isotope in the remaining substrate. The use of this effect to quantify the amount of biodegraded substrate in contaminated aquifers requires that the isotope fractionation factor is constant in time and space. In many natural and engineered systems the bioavailable concentration at the location of the enzymes differs from the average bulk concentration of the substrate. When enzymatically driven substrate degradation is coupled to a preceding transport step controlling the bioavailability of the substrate, the observed isotope fractionation becomes a function of the bulk substrate concentration. The sensitivity of the observed isotope fractionation factor toward such substrate concentration changes depends on the ratio of bulk substrate concentration and Michaelis-Menten constant and on the ratio between the specific affinity of the microorganisms toward the substrate and the first order rate constant of the bioavailability limiting transport process. Highest sensitivities toward substrate concentration were found for combinations of high substrate concentration with low substrate bioavailability (i.e., high ratios of substrate concentration and Michaelis-Menten constant, and high ratios of specific affinity and transport rate constant). As a consequence, changes in concentration and isotopic composition of a bioavailability limited substrate in batch experiments should not exhibit a linear relation in a Rayleigh plot, and the slope of the Rayleigh plot should show a decreasing trend with concentration decrease. When using isotope fractionation to quantify biodegradation along groundwater flow paths, changes in observed isotope fractionation might occur while contaminant concentration decreases along a flow path.

Impact of Bioavailability Restrictions on Microbially Induced Stable Isotope Fractionation. 1. Theoretical Calculation

Carbon (C), chlorine (Cl), and hydrogen (H) isotope effects were determined during dechlorination of TCE to ethene by a mixed Dehalococcoides (Dhc) culture. The C isotope effects for the dechlorination steps were consistent with data published in the past for reductive dechlorination (RD) by Dhc. The Cl effects (combined with an inverse H effect in TCE) suggested that dechlorination proceeded through nucleophilic reactions with cobalamin rather than by an electron transfer mechanism. Depletions of 37Cl in daughter compounds, resulting from fractionation at positions away from the dechlorination center (secondary isotope effects), further support the nucleophilic dechlorination mechanism. Determination of C and Cl isotope ratios of the reactants and products in the reductive dechlorination chain offers a potential tool for differentiation of Dhc activity from alternative transformation mechanisms (e.g., aerobic degradation and reductive dechlorination proceeding via outer sphere mechanisms), in studies of ...

3D-CSIA: carbon, chlorine, and hydrogen isotope fractionation in transformation of TCE to ethene by a Dehalococcoides culture.

Factors controlling the carbon isotope fractionation of tetra- and trichloroethene during reductive dechlorination by Sulfurospirillum ssp. and Desulfitobacterium sp. strain PCE-S

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Factors controlling the carbon isotope fractionation of tetra- and trichloroethene during reductive dechlorination by Sulfurospirillum ssp. and Desulfitobacterium sp. strain PCE-S