Degradation pathway of the naphthalene azo dye intermediate 1-diazo-2- naphthol-4-sulfonic acid using Fenton's reagent

Degradation of naphthalene dye intermediate 1-diazo-2- naphthol-4-sulfonic acid (1,2,4-Acid) by Fenton process has been studied in depth for the purpose of learning more about the reactions involved in the oxidation of 1,2,4-Acid. During 1,2,4-Acid oxidation, the solution color initially takes on a dark red, then to dark black associated with the formation of quinodial-type structures, and then goes to dark brown and gradually disappears, indicating a fast degradation of azo group. The observed color changes of the solution are a result of main reaction intermediates, which can be an indicator of the level of oxidization reached. Nevertheless, complete TOC removal is not accomplished, in accordance with the presence of resistant carboxylic acids at the end of the reaction. The intermediates generated along the reaction time have been identified and quantified. UPLC–(ESI)–TOF–HRMS analysis allows the detection of 19 aromatic compounds of different size and complexity. Some of them share the same accurate mass but appear at different retention time, evidencing their different molecular structures. Heteroatom oxidation products like SO42- have also been quantified and explanations of their release are proposed. Short-chain carboxylic acids are detected at long reaction time, as a previous step to complete the process of dye mineralization. Finally, considering all the findings of the present study and previous related works, the evolution from the original 1,2,4-Acid to the final products is proposed in a general reaction scheme.

Graphical abstractFigure optionsDownload full-size imageDownload high-quality image (71 K)Download as PowerPoint slideHighlights► This work assessed the Fenton's degradation of 1-diazo-2- naphthol-4-sulfonic in aqueous solutions. ► The solution color went from dark red to dark black, then to light brown. ► Up to 19 main intermediates were identified by UPLC-(ESI)-TOF-MS. ► Monitoring the by-products generated becomes fundamental for subsequent bio-treatment.