@article{PAR00019786, title = {{R}elevance of {N}-nitrosation reactions for secondary amines in nitrate-rich wastewater under {UV}-{C} treatment}, author = {{B}rienza, {M}. and {M}anasfi, {R}. and {C}hiron, {S}erge}, editor = {}, language = {{ENG}}, abstract = {{T}his study investigated the transformation of secondary amine pharmaceuticals in {UV}-{C}/{NO}3- and in nitrate-rich wastewater at 254 nm by taking diclofenac, diphenylamine, mefenamic acid and furosemide as probe compounds. {T}he degradation of targeted compounds were positively related to nitrate concentration and mainly caused by the formation of peroxynitrite and related reactive nitrogen species (e.g., nitrogen oxide and nitrogen dioxide radicals). {M}ajor transformation products were identified to provide fundamental understanding of the selective oxidation of secondary amine with reactive nitrogen species. {UV} photolysis, hydroxyl radical oxidation, nitration and nitrosation processes were found to be the most significant transformation pathways. {I}n case of diphenylamine, for which most of the identified intermediates were available as standard, the relative significance of each transformation route could be established, highlighting for the first time the important role of {N}-nitrosation processes in {UV}/{NO}3- treatment followed by the decomposition of the resulting {N}-nitroso compounds by an alpha hydroxylation mechanism. {T}his specific transformation pathway was of concern because it constitutes the molecular basis of {N}-nitrosamine carcinogenicity and may contribute to the increase in effluent genotoxicity under {UV}-{C} treatment in addition to the formation of nitrophenols. {H}ydrogenocarbonate ions at concentration values higher than 300 mg/{L} appeared to be a protective specie against nitrosation processes due to the formation of carbamate adducts but {H}2{O}2 in {UV}-{C}/{H}2{O}2 could be responsible for an exacerbation of the {N}-nitrosation pathway due to an addition source of hydroxyl radical in the system. {T}he occurrence of major transformation products of diclofenac was confirmed in nitrate-rich wastewater under {UV}-{C} treatment at pilot-scale operation.}, keywords = {{S}econdary amine ; {UV}-{C} phototransformation ; {N}itrate ; {G}enotoxicity ; {T}ransformation pathway}, booktitle = {}, journal = {{W}ater {R}esearch}, volume = {162}, numero = {}, pages = {22--29}, ISSN = {0043-1354}, year = {2019}, DOI = {10.1016/j.watres.2019.06.055}, URL = {https://www.documentation.ird.fr/hor/{PAR}00019786}, }