The benefits of global pesticide use come at the cost of their widespread occurrence in the environment. An array of abiotic and biotic transformations effectively removes pesticides from the environment, but may give rise to potentially hazardous transformation products. Despite a large body of pesticide degradation data from regulatory testing and decades of pesticide research, it remains difficult to anticipate the extent and pathways of pesticide degradation under specific field conditions. Here, we review the major scientific challenges in doing so and discuss emerging opportunities to identify pesticide degradation processes in the field.

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.