Lay summary
Compound-specific stable isotope analysis (CSIA) offers new avenues for assessing transformation pathways of organic micropollutants. Fractionation of stable isotopes in individual compounds is usually indicative for an ongoing (bio)chemical reaction and thus allows one to identify such processes in complex environments as well as studying the mechanisms of degradation. However, a more comprehensive exploitation of stable isotope analysis in contaminant studies is currently hampered as both isotope effects and reaction pathways of many organic pollutants, especially those with N-containing functional groups, are not understood adequately on a mechanistic level. In fact, reactions at N-containing structural moieties (e.g., nitro-, amino-, and azo-compounds, amides, ureas) are often the initial site of attack for transformation processes of contaminants such as pesticides, pharmaceuticals, or explosives.
In this project, we will develop approaches to study isotope effects during the oxidation of substituted anilines. Our principal goal is to investigate the multielement isotope fractionation of aromatic N-alkyl amines for a comprehensive application of CSIA to enzyme- and mineral-catalyzed oxidations and addition reactions of this compound class.From the combined evaluation of carbon, hydrogen, and nitrogen isotope fractionation and the corresponding apparent kinetic isotope effects, we will be able to identify the typical bonding changes at the reactive atoms in a set of probe compounds covering substituted aromatic N-methyl and N,N-dimethyl amines as well as N,N-dimethyl di- and triazines. On the basis of the interpretation of multielement isotope effects we will be able to delinate the different, sometimes competing transformation processes of micropollutants containing reactive N-alkyl amine moieties.