Investigating the different transformations of tetracycline using birnessite under different reaction conditions and various humic acids

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.