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

Abstract

● 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.

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

References

[1] Badr E S A, Achterberg E P, Tappin A D, Hill S J, Braungardt C B. (2003). Determination of dissolved organic nitrogen in natural waters using high-temperature catalytic oxidation. Trends in Analytical Chemistry, 22(11): 819–827

[2] Bhojani G, Jani S, Saha N K. (2022). Facile biodegradation of N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone by source-derived Bacillus strain APS1 for water reclamation and reuse. Journal of Cleaner Production, 334: 130098

[3] Camargo J A, Alonso Á. (2006). Ecological and toxicological effects of inorganic nitrogen pollution in aquatic ecosystems: a global assessment. Environment International, 32(6): 831–849

[4] Doane T A. (2017). The abiotic nitrogen cycle. ACS Earth & Space Chemistry, 1(7): 411–421

[5] Fortune W B, Mellon M G. (1938). Determination of iron with o-phenanthroline: a spectrophotometric study. Industrial & Engineering Chemistry. Analytical Edition, 10(2): 60–64

[6] Funkey C P, Latour R J, Bronk D A. (2015). Abiotic effects on effluent dissolved organic nitrogen along an estuarine transect. Water Environment Research, 87(3): 258–265

[7] Hosomi M, Sudo R. (1986). Simultaneous determination of total nitrogen and total phosphorus in freshwater samples using persulfate digestion. International Journal of Environmental Studies, 27(3–4): 267–275

[8] Huang J, Kankanamge N R, Chow C, Welsh D T, Li T, Teasdale P R. (2018). Removing ammonium from water and wastewater using cost-effective adsorbents: a review. Journal of Environmental Sciences, 63: 174–197

[9] Kitidis V, Uher G, Woodward E M S, Owens N J P, Upstill-Goddard R C. (2008). Photochemical production and consumption of ammonium in a temperate river–sea system. Marine Chemistry, 112(1–2): 118–127

[10] Leng L, Xu S, Liu R, Yu T, Zhuo X, Leng S, Xiong Q, Huang H. (2020). Nitrogen containing functional groups of biochar: an overview. Bioresource Technology, 298: 122286

[11] Li D, Xu X, Li Z, Wang T, Wang C. (2020). Detection methods of ammonia nitrogen in water: A review. Trends in Analytical Chemistry, 127: 115890

[12] Li M, Qiang Z, Hou P, Bolton J R, Qu J, Li P, Wang C. (2016). VUV/UV/chlorine as an enhanced advanced oxidation process for organic pollutant removal from water: assessment with a novel mini-fluidic VUV/UV photoreaction system (MVPS). Environmental Science & Technology, 50(11): 5849–5856

[13] Liu S, Han J, Ding Y, Gao X, Cheng H, Wang H, Liu C, Wang A. (2022). Advanced reduction process to achieve efficient degradation of pyridine. Chemosphere, 287: 132240

[14] Long L, Yang Y, You S, Wei L, Chen B. (2022). Using formaldehyde as a novel chemical actinometer for 185 nm vacuum ultraviolet photon flux quantification in water. Journal of Photochemistry and Photobiology A: Chemistry, 432: 114080

[15] Man Q, Zhang P, Huang W, Zhu Q, He X, Wei D. (2022). A heterotrophic nitrification-aerobic denitrification bacterium Halomonas venusta TJPU05 suitable for nitrogen removal from high-salinity wastewater. Frontiers of Environmental Science & Engineering, 16(6): 69

[16] Palys M J, Wang H, Zhang Q, Daoutidis P. (2021). Renewable ammonia for sustainable energy and agriculture: vision and systems engineering opportunities. Current Opinion in Chemical Engineering, 31: 100667

[17] Pang D, Qiu L, Wang Y, Zhu R, Ouyang F. (2015). Photocatalytic decomposition of acrylonitrile with N–F codoped TiO₂/SiO₂ under simulant solar light irradiation. Journal of Environmental Sciences-China, 33: 169–178

[18] Rain-Franco A, Muñoz C, Fernandez C. (2014). Ammonium production off central Chile (36 S) by photodegradation of phytoplankton-derived and marine dissolved organic matter. PLoS One, 9(6): e100224

[19] Sutton M A, Erisman J W, Dentener F, Möller D. (2008). Ammonia in the environment: from ancient times to the present. Environmental Pollution, 156(3): 583–604

[20] Vähätalo A V, Järvinen M. (2007). Photochemically produced bioavailable nitrogen from biologically recalcitrant dissolved organic matter stimulates production of a nitrogen-limited microbial food web in the Baltic Sea. Limnology and Oceanography, 52(1): 132–143

[21] Wang Y, Zhang Y, Zhu X, Liu Y, Wu Z. (2022). Fluorine-induced oxygen vacancies on TiO₂ nanosheets for photocatalytic indoor VOCs degradation. Applied Catalysis B: Environmental, 316: 121610

[22] Worsfold P J, Monbet P, Tappin A D, Fitzsimons M F, Stiles D A, McKelvie I D. (2008). Characterisation and quantification of organic phosphorus and organic nitrogen components in aquatic systems: a review. Analytica Chimica Acta, 624(1): 37–58

[23] Xing X, Li N, Liu D, Cheng J, Hao Z. (2022). Effect of Cu-ZSM-5 catalysts with different CuO particle size on selective catalytic oxidation of N,N-Dimethylformamide. Frontiers of Environmental Science & Engineering, 16(10): 125

[24] Yang G, Xu H, Luo Y, Hei S, Song G, Huang X. (2023). Novel electro-assisted micro-aerobic cathode biological technology induces oxidative demethylation of N,N-dimethylformamide for efficient ammonification of refractory membrane-making wastewater. Journal of Hazardous Materials, 442: 130001

[25] Yang Y, Sun P, Padhye L P, Zhang R. (2021). Photo-ammonification in surface water samples: mechanism and influencing factors. Science of the Total Environment, 759: 143547

[26] Zhang Y, Chang L, Yan N, Tang Y, Liu R, Rittmann B E. (2014). UV photolysis for accelerating pyridine biodegradation. Environmental Science & Technology, 48(1): 649–655

[27] Zhang Y, Zhang R, Li S L, Mostofa K M G, Fu X, Ji H, Liu W, Sun P. (2021). Photo-ammonification of low molecular weight dissolved organic nitrogen by direct and indirect photolysis. Science of the Total Environment, 764: 142930

[28] Zhang Y, Zhang H, Dong X, Yue D, Zhou L. (2022). Effects of oxidizing environment on digestate humification and identification of substances governing the dissolved organic matter (DOM) transformation process. Frontiers of Environmental Science & Engineering, 16(8): 99

RIGHTS & PERMISSIONS

Higher Education Press 2024