The removal performance and mechanisms of tetracycline over Mn-rich limonite

Naturally occurring Mn-rich limonite mainly composed of goethite and manganese oxides was used to remove tetracycline (TC) from the aqueous solution. The effects of dosage, initial solution pH, temperature, and coexisting anions on TC removal were investigated. Results showed that 95% of TC (30.0 mg·L^-1) was removed in a wide pH range of 3.0-9.0 by limonite with high specific surface area (145.0 m²·g^-1) and mesoporous structure. The presence of Cl^-, NO₃^-, and SO₄^2- in the studied concentration range did not influence TC removal efficiency significantly, while PO₄^3- inhibited the adsorption of TC over limonite due to the competition with TC for active sites. Integrated with the FT-IR analysis, electrostatic interaction and complexation were proved to be the adsorption mechanisms of TC by limonite. The quenching experiments and ESR analysis revealed that singlet oxygen (¹O₂) also was involved in TC degradation. In addition, limonite displayed an efficient recycling performance and stability after four cycles. This study revealed that the Mn-rich limonite was a promising adsorbent for TC removal from aqueous solutions and promoted the application of natural mineral material in the environmental field.