Elucidation of the last steps of photo-ammonification: analytical method development and mechanism elucidation

Highlights

● A new method was developed for simultaneous quantification of multiple NOCs.

● The final steps in the photo-ammonification of NOCs were elucidated.

● This method is less susceptible to organic interference.

Abstract

The mechanisms underlying the photo-ammonification of nitrogenous organic compounds (NOCs) remain unclear, partly due to the analytical challenges of small NOC intermediates. This study introduced a simple methodology for accurately and simultaneously quantifying multiple small NOCs during ammonification processes. The developed method employed phenyl isothiocyanate as derivatization reagents, followed by high-performance liquid chromatography analysis to measure primary and secondary amines, amides, as well as NH₄⁺ over variable photo-ammonification conditions. In our experimental setup, vacuum ultraviolet (VUV) irradiation serves as the controlled reaction environment to simulate harsh photo-ammonification environment. Representative NOCs, including pyridine, N,N-dimethylformamide, and acrylonitrile, were chosen due to their structural diversity and environmental relevance as model NOCs. This method was able to achieve excellent nitrogen mass balance, and revealed that the last steps of photo-ammonification involved oxidation of nitrogen-adjacent carbon to amide followed by the cleavage of N–C bond. This novel method may also help quantitative investigation of nitrogen transformations in different environmental contexts.

Graphical abstract

Keywords

Ammonification / NOCs / Amines / Nitrogen mass balance

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Acknowledgements

This work was supported by the project from the National Natural Science Foundation of China (Nos. 52100110 and 42177197) and the Natural Science Foundation of Tianjin (China) (No. 22JCYBJC00270).

Conflict of Interest

The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11783-024-1860-z and is accessible for authorized users.

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