Photocatalytic mechanisms of 2,4-dinitroanisole degradation in water deciphered by C and N dual-element isotope fractionation

APTIM Authors/Contributors

Background/Objectives

In surface water environments, photodegradation may be an important process for the natural attenuation of 2,4-dinitroanisole (DNAN). Understanding the photolysis and photocatalysis mechanisms of DNAN is difficult because the photosensitivity of nitro groups and the behavior of DNAN as a potential photosensitizer are unclear in aqueous solutions. Here, we investigate the degradation mechanisms of DNAN under UV-A (λ ~ 350 nm) and UV-C (λ ~ 254 nm) irradiation in a photolysis reactor where aqueous solution was continuously recycled through a UV-irradiated volume from a non-irradiated external reservoir. By tracking C and N isotopic fractionation in DNAN and its reaction products, we observed normal ¹³C fractionation (ε_C = -3.34‰) and inverse ¹⁵N fractionation (ε_N = +12.30‰) under UV-A (λ ~ 350 nm) irradiation, in contrast to inverse ¹³C fractionation (ε_C = +1.45‰) and normal ¹⁵N fractionation (ε_N = -3.79‰) under UV-C (λ ~ 254 nm) irradiation. These results indicate that DNAN can act as a photosensitizer and may follow a product-to-parent reversion mechanism in surface water environments. The data also indicate that photocatalytic degradation of DNAN in aqueous systems can be monitored via C and N stable isotope analysis.

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