Citation: Piotrowicz-Cie´ slak, A.I.; Maciejczyk, M.; Margas, M.; Rydzy ´ nski, D.; Grajek, H.; Michalczyk, D.J.; Wasilewski, J.; Smyk, B. Studies on the Efficiency of Iron Release from Fe(III)-EDTA and Fe(III)-Cit and the Suitability of These Compounds for Tetracycline Degradation. Molecules 2022, 27, 8498. https://doi.org/10.3390/ molecules27238498 Academic Editor: Caroline Dessent Received: 10 November 2022 Accepted: 25 November 2022 Published: 2 December 2022 Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affil- iations. Copyright: © 2022 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https:// creativecommons.org/licenses/by/ 4.0/). molecules Article Studies on the Efficiency of Iron Release from Fe(III)-EDTA and Fe(III)-Cit and the Suitability of These Compounds for Tetracycline Degradation Agnieszka I. Piotrowicz-Cie´ slak 1, * , Maciej Maciejczyk 2 , Malgorzata Margas 1 , Dariusz Rydzy ´ nski 1 , Hanna Grajek 2 , Dariusz J. Michalczyk 1 , Janusz Wasilewski 3 and Bogdan Smyk 2 1 Department of Plant Physiology, Genetics and Biotechnology, Faculty of Biology and Biotechnology, University of Warmia and Mazury in Olsztyn, Oczapowskiego 1A, 10-718 Olsztyn, Poland 2 Department of Physics and Biophysics, Faculty of Food Science, University of Warmia and Mazury in Olsztyn, Oczapowskiego 4, 10-719 Olsztyn, Poland 3 Department of Biochemistry, Faculty of Biology and Biotechnology, University of Warmia and Mazury in Olsztyn, Oczapowskiego 1A, 10-718 Olsztyn, Poland * Correspondence: acieslak@uwm.edu.pl Abstract: Iron ions can be used to degrade tetracycline dispersed in nature. Studies of absorption and fluorescence spectra and quantum chemistry calculations showed that iron is more readily released from Fe(III)-citrate than from Fe(III)-EDTA, so Fe(III)-citrate (Fe(III)-Cit) is more suitable for tetracycline (TC) degradation. At 30 ◦ C, a severe degradation of TC by Fe(III)-Cit occurred as early as after 3 days of incubation in the light, and after 5 days in the dark. In contrast, the degradation of TC by Fe(III)-EDTA proceeded very slowly in the dark. By the fifth day of incubation of TC with Fe(III)- Cit in darkness, the concentrations of the former compound dropped by 55% and 75%, at 20 ◦ C and 30 ◦ C, respectively. The decrease in tetracycline concentrations caused by Fe(III)-EDTA in darkness at the same temperatures was only 2% and 6%, respectively. Light increased the degradation rates of TC by Fe(III)-EDTA to 20% and 56% at 20 ◦ C and 30 ◦ C, respectively. The key role of the light in the degradation of tetracycline by Fe(III)-EDTA was thus demonstrated. The TC degradation reaction showed a second-order kinetics. The rate constants of Fe(III)-Cit-induced TC degradation at 20 ◦ C and 30 ◦ C in darkness were k = 4238 M −1 day −1 and k = 11,330 M −1 day −1 , respectively, while for Fe(III)- EDTA were 55 M −1 day −1 and 226 M −1 day −1 . In light, these constants were k = 15,440 M −1 day −1 and k = 40,270 M −1 day −1 for Fe(III)-Cit and k = 1012 M −1 day −1 and 2050 M −1 day −1 at 20 ◦ C and 30 ◦ C; respectively. A possible reason for the higher TC degradation rate caused by Fe(III)-Cit can be the result of its lower thermodynamical stability compared with Fe(III)-EDTA, which we confirmed with our quantum chemistry calculations. Two quantum chemistry calculations showed that the iron complex with EDTA is more stable (the free energy of the ensemble is 15.8 kcal/mol lower) than the iron complex with Cit; hence, Fe release from Fe(III)-EDTA is less effective. Keywords: antibiotic elimination; absorption; fluorescence; degradation kinetics; reaction rate 1. Introduction In recent years, antibiotics have been broadly applied in human and veterinary medicine, resulting in their accumulation in the environment. Unlike other more commonly known pollutants, e.g., pesticides and detergents, pharmaceuticals enter the environment in low quantities but continuously [1]. The fact that pharmaceuticals are detected, albeit in trace amounts, in aqueous ecosystems indicates that they have become a very widespread form of pollutants [2]. Most antibiotics remain stable in the environment and may persist long after they have been excreted by animals [3]. Antibiotics are neither very readily absorbed nor metabolised by animal cells, so 30% to 90% of ingested doses are released to the environment in faeces and urine, virtually unmodified or transformed into derivatives Molecules 2022, 27, 8498. https://doi.org/10.3390/molecules27238498 https://www.mdpi.com/journal/molecules