Abstract
In this work, the activated persulfate oxidation of ciprofloxacin (CIP) using a low-grade titanium ore under sunlight or simulated sunlight were conducted to analyze the CIP degradation efficiency and to identify the transformation products (TPs) generated during oxidation under both types of irradiation sources by using liquid chromatography-quadrupole time-of-flight mass spectrometry (LC-QTOF-MS). All advance oxidation process experiments were performed in a 2700-mL raceway reactor at a pH value of ~ 6.5 and an initial CIP concentration of 1 mg/L, during 90 min of reaction time. The control experiments carried out under simulated sunlight achieved a 97.7 ± 0.6% degradation efficiency, using 385 W/m2 of irradiation with an average temperature increase of 11.7 ± 0.6 °C. While, the experiments under sunlight reached a 91.2 ± 1.3% degradation efficiency, under an average irradiation value of 19.2 ± 0.3 W/m2 in October–November 2019 at hours between 11:00 am and 3:00 pm with an average temperature increase of 1.4 ± 0.8 °C. Mass spectrometry results indicated that 14 of the 108 possible TPs reported in the literature were detected. The calculated exact mass, measured accurate mass, and its characteristic diagnostic fragment ions were listed, and two new TPs were tentative identified. The TP generation analysis showed that some specific compounds were detected in different time intervals with kinetic variations depending on the irradiation used. Consequently, two CIP degradation pathways were proposed, since the type of irradiation determines the CIP degradation mechanism.
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Acknowledgments
Authors gratefully acknowledge the support of the XRD and XRF Laboratory of the Geology Institute at UNAM, a member of the National Laboratory of Mineralogy and Geochemistry of Mexico, in the material characterization, especially to Dr. T. Pi-Puig and Chem. Rufino Lozano, to MSc. Carmén María Morales Álvarez for the HPLC analysis, and to PhD Tania Ariadna García Mejía for the SEM analysis.
Funding
Financial support for this work was provided by Consejo Nacional de Ciencia y Tecnología under PhD grant No. 97840. Financial support of the PAPIIT IV100616 project was provided from the General Direction of Academic Personnel Affairs (DGAPA) and to Instituto de Ingeniería of the Universidad Nacional Autónoma de México. Marina Celia Campos-Mañas acknowledges for personal funding through the Transition Program (University of Almería).
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Conceptualization: J.-A. M.-V., R.-M R.-Z., and A.-A.; methodology: J.-A. M.-V., and M.-C. C.-M.; Formal analysis and investigation: J.-A. M.-V., and M.-C. C.-M.; writing, review, and editing: J.-A. M.-V., M.-C. C.-M., A. A., J.-.A S.-P., and R.-M R.-Z.; funding acquisition: R.-M R.-Z.; resources: R.-M R.-Z., A. A., and J.-.A S.-P.
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Highlights
• The ciprofloxacin (CIP) degradation efficiency and pathway are greatly impacted by the type of irradiation source.
• The system sunlight-persulfate-magnetic fraction can efficiently degrade ciprofloxacin under slights variations of solar irradiation and ambient temperature.
• The type, quantity, and stability of the transformation products (TPs) by using the enhanced persulfate process with a low-grade titanium ore are influenced by the nature of the irradiation source.
• Two never reported CIP TPs have been tentatively identified.
• The system sunlight-persulfate-magnetic fraction has high efficiency into a raceway reactor.
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Macías-Vargas, JA., Campos-Mañas, M.C., Agüera, A. et al. Enhanced activated persulfate oxidation of ciprofloxacin using a low-grade titanium ore under sunlight: influence of the irradiation source on its transformation products. Environ Sci Pollut Res 28, 24008–24022 (2021). https://doi.org/10.1007/s11356-020-11564-8
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DOI: https://doi.org/10.1007/s11356-020-11564-8