Enhanced degradation of tetracycline by Cu(II) complexation in the FeS/sulfite system

Abstract

This study applied a mineral material of FeS to activate sulfite for efficient degradation of TTC in the presence of Cu(II) based on the identified complexation mechanism through UV-Vis spectra, FTIR spectroscopy and DFT calculation. pH plays an important role in TTC degradation and the initial pH of 6 and 7 were the divide in the contributions of FeS/sulfite oxidation and complex-precipitation. TTC-Cu(II) exhibits a superior promoting effect on the TTC degradation in FeS/sulfite system due to the improvement of TTC electron transfer reactivity and Fe(II) dissolution from FeS. Moreover, the formation of Cu(I) improved the recycling of Fe(II) from Fe(III). Dissolved oxygen-dependent free radicals' generation was confirmed, and TTC degradation was mainly attributed to SO₄^·- and ·OH. The characterization of FeS surface through XPS, XRD, SEM-EDS, Fe(II) deactivation tests, together with the comparison of pseudo-first-order rate constants for TTC degradation by FeS and ferrous ion supported the important role of surface and dissolved Fe(II) in sulfite activation. Furthermore, reasonable degradation pathways of TTC have been proposed according to the detected products by LC-MS. This work highlights the important role of pH, DO and Cu(II) complexation in sulfite activation and TTC degradation, furnishing theoretical support for further relevant studies.

Keywords: Advanced oxidation processes (AOPs); FeS; Organic-metal complexes; Sulfite; Tetracycline.