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Electrochemical treatment of penicillin, cephalosporin, and fluoroquinolone antibiotics via active chlorine: evaluation of antimicrobial activity, toxicity, matrix, and their correlation with the degradation pathways

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Abstract

Antibiotics are pharmaceuticals widely consumed and frequently detected in environmental water, where they can induce toxic effects and development of resistant bacteria. Their structural variety makes the problem of antibiotics in natural water more complex. In this work, six highly used antibiotics (at 40 μmol L−1) belonging to three different classes (penicillins, cephalosporins, and fluoroquinolones) were treated using an electrochemical system with a Ti/IrO2 anode and a Zr cathode in the presence of NaCl (0.05 μmol L−1). The attack of electrogenerated active chlorine was found to be the main degradation route. After only 20 min of treatment, the process decreased more than 90% of the initial concentration of antibiotics, following the degradation order: fluoroquinolones > penicillins > cephalosporins. The primary interactions of the degrading agent with fluoroquinolones occurred at the cyclic amine (i.e., piperazyl ring) and the benzene ring. Meanwhile, the cephalosporins and penicillins were initially attacked on the β-lactam and sulfide groups. However, the tested penicillins presented an additional reaction on the central amide. In all cases, the transformations of antibiotics led to the antimicrobial activity decreasing. On the contrary, the toxicity level showed diverse results: increasing, decreasing, and no change, depending on the antibiotic type. In fact, due to the conservation of quinolone nucleus in the fluoroquinolone by-products, the toxicity of the treated solutions remained unchanged. With penicillins, the production of chloro-phenyl-isoxazole fragments increased the toxicity level of the resultant solution. However, the opening of β-lactam ring of cephalosporin antibiotics decreased the toxicity level of the treated solutions. Finally, the application of the treatment to synthetic hospital wastewater and seawater containing a representative antibiotic showed that the high amount of chloride ions in seawater accelerates the pollutant degradation. In contrast, the urea and ammonium presence in the hospital wastewater retarded the removal of this pharmaceutical.

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Acknowledgements

The authors thank COLCIENCIAS (Departamento Administrativo de Ciencia, Tecnología e Innovación, Colombia) and Swiss National Foundation for the financial support through the projects “Desarrollo y evaluación de un sistema electroquímico asistido con luz solar para la eliminación de contaminantes emergentes en agua (No. 111565842980)” and “Treatment of the hospital wastewaters in Cote d’Ivoire and in Colombia by advanced oxidation processes (IZ01Z0_ 146919)”, respectively. The authors also thank the biology student Martha Verbel-Olarte for her useful collaboration in the toxicity test development. E.Serna-Galvis thanks COLCIENCIAS for his Ph.D. scholarship (Convocatoria 647 de 2014).

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  1. Grupo de Investigación en Remediación Ambiental y Biocatálisis (GIRAB), Instituto de Química, Facultad de Ciencias Exactas y Naturales, Universidad de Antioquia UdeA, Calle 70 No. 52-21, Medellín, Colombia

    Efraím A. Serna-Galvis, Karen E. Berrio-Perlaza & Ricardo A. Torres-Palma

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  1. Efraím A. Serna-Galvis
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  2. Karen E. Berrio-Perlaza
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  3. Ricardo A. Torres-Palma
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Correspondence to Ricardo A. Torres-Palma.

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Serna-Galvis, E.A., Berrio-Perlaza, K.E. & Torres-Palma, R.A. Electrochemical treatment of penicillin, cephalosporin, and fluoroquinolone antibiotics via active chlorine: evaluation of antimicrobial activity, toxicity, matrix, and their correlation with the degradation pathways. Environ Sci Pollut Res 24, 23771–23782 (2017). https://doi.org/10.1007/s11356-017-9985-2

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