Isotope Fractionation Associated with the Indirect Photolysis of Substituted Anilines in Aqueous Solution

摘要

Organic micropollutants containing aniline substructures are susceptible to different light-induced transformation processes in aquatic environments and water treatment operations. Here, we investigated the magnitude and variability of C and N isotope fractionation during the indirect phototransformation of four para-substituted anilines in aerated aqueous solutions. The model photosensitizes, namely 9,10-anthraquinone-1,5'disulfonate and methylene blue, were used as surrogates for dissolved organic matter chromophores generating excited triplet states in sunlit surface waters. The transformation of aniline, 4-CH_3-, 4-OCH_3-, and 4-Cl-aniline by excited triplet states of the photosensitizers was associated with inverse and normal N isotope fractionation, whereas C isotope fractionation was negligible. The apparent ~(15)N kinetic isotope effects (AKIE) were almost identical for both photosensitizers, increased from 0.9958 ± 0.0013 for 4-OCH_3-aniline to 1.0035 ± 0.0006 for 4-Cl-aniline, and correlated well with the electron donating properties of the substituent. N isotope fractionation is pH-dependent in that H~+ exchange reactions dominate below and N atom oxidation processes above the pK_a value of the substituted aniline's conjugate acid. Correlations of C and N isotope fractionation for indirect phototransformation were different from those determined previously for the direct photolysis of chloroanilines and offer new opportunities to distinguish between abiotic degradation pathways.