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Investigating the different transformations of tetracycline using birnessite under different reaction conditions and
Hang Vo-Minh Nguyen1, Doo-Hee Lee2, Han-Saem Lee3
1Department of Environment Energy Engineering, Seoul National University of Science & Technology, 232 Gongneung-ro, Seoul, 01811, South Korea.
Abstract:
Prior studies have successfully used manganese oxides to facilitate the transformation of tetracycline in aqueous solution. To further understand the kinetic and the transformation pathway of tetracycline via birnessite (δ-MnO2) under different conditions, experiments were conducted at pH levels of 3, 6, and 9 in the presence or absence of Aldrich humic acid (ADHA). Tetracycline removal followed the pseudo-second-order reaction model in all investigated cases, and the removal efficiency (g mg-1 h -1) followed the following trend: pH 3 (0.45/0.27) > pH 6 (0.036/0.087) > pH 9 (0.036/0.103) in the absence/presence of ADHA. Liquid chromatography-mass spectrometry/mass spectrometry results identified five main transformation products at m/z 495, 477, 493, 459, and 415, produced by the transformation reactions, including hydration, oxidation, desaturation, and oxy reduction. Notably, in the presence of ADHA at pH 3, products with higher toxicity secondary (m/z 477 and 495) were reduced, while less toxicity products (m/z 459 and 415) were enhanced. The experiments utilizing tetracycline and δ-MnO2 with varied humic acids (HA) revealed that HA with high polar organic carbon groups, such as O-alkyl, exhibited higher removal efficiency at pH 6. This research offers the first comprehensive insights into the pathway transformations of tetracycline via δ-MnO2 under different pH conditions and HA types. For further understanding, future work should investigate the binding of HA, TTC, and/or Mn2+ and the oxidation capacity of MnO2 after the reaction to clarify Mn2+ elution mechanisms.
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