Synergistic effects of fluorinated substituents and Fe(Ⅱ) on ferrihydrite transformation and antibiotic degradation

Ferrihydrite is commonly associated with antibiotics in natural environments due to its strong sorption capabilities and high specific surface area. Under reducing conditions, Fe(II) acts as a catalyst for the transformation of ferrihydrite into more crystalline minerals. However, the influence of a...

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Main Authors: Liting Wang, Shikun Wei, Liwen Zhang, Zhiyong Guo, Yan Lei, Deming Dong
Format: Article
Language:English
Published: Elsevier 2025-06-01
Series:Ecotoxicology and Environmental Safety
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Online Access:http://www.sciencedirect.com/science/article/pii/S0147651325006499
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author Liting Wang
Shikun Wei
Liwen Zhang
Zhiyong Guo
Yan Lei
Deming Dong
author_facet Liting Wang
Shikun Wei
Liwen Zhang
Zhiyong Guo
Yan Lei
Deming Dong
author_sort Liting Wang
collection DOAJ
description Ferrihydrite is commonly associated with antibiotics in natural environments due to its strong sorption capabilities and high specific surface area. Under reducing conditions, Fe(II) acts as a catalyst for the transformation of ferrihydrite into more crystalline minerals. However, the influence of antibiotic molecular structure on the Fe(II)-catalyzed transformation of ferrihydrite and the associated degradation mechanisms of antibiotics have remained unclear. This study employed enoxacin (ENO), a representative fluorinated pharmaceutical, and pipemidic acid (PPA), a structural analog of ENO, to investigate the effect of fluorinated substituents on Fe(II)-facilitated ferrihydrite transformation. The results revealed that the transformation of ferrihydrite in the ENO system was 2.8 times greater than in the PPA system. ENO degradation reached 74.3 %, which was 1.13 times higher than that of PPA. ENO degradation products were more prone to hydroxylation, decarboxylation, and piperazine ring oxidation, whereas PPA degradation primarily involved oxidation of the piperazine ring. The fluorinated substituent in ENO facilitated ferrihydrite transformation by influencing the concentration of adsorbed Fe(II) and the distribution of antibiotics within the mineral inside. Furthermore, the fluorinated substituent in ENO enhanced degradation by increasing electron transfer between ENO and Fe(III), raising the content of adsorbed Fe(II) and promoting the formation of goethite. Collectively, these findings provide new insights into the environmental behavior of ferrihydrite and the fate of structurally different antibiotics in natural systems.
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spelling doaj-art-47c3e4ee48ad4398a0c7dae52b79a7d72025-08-20T03:13:30ZengElsevierEcotoxicology and Environmental Safety0147-65132025-06-0129811831310.1016/j.ecoenv.2025.118313Synergistic effects of fluorinated substituents and Fe(Ⅱ) on ferrihydrite transformation and antibiotic degradationLiting Wang0Shikun Wei1Liwen Zhang2Zhiyong Guo3Yan Lei4Deming Dong5Key Laboratory of Groundwater Resources and Environment, Ministry of Education, Jilin Provincial Key Laboratory of Water Resources and Environment, College of New Energy and Environment, Jilin University, Changchun 130012, China; School of Materials and Environmental Engineering, Chengdu Technological University, Chengdu, Sichuan 610031, ChinaKey Laboratory of Groundwater Resources and Environment, Ministry of Education, Jilin Provincial Key Laboratory of Water Resources and Environment, College of New Energy and Environment, Jilin University, Changchun 130012, ChinaKey Laboratory of Groundwater Resources and Environment, Ministry of Education, Jilin Provincial Key Laboratory of Water Resources and Environment, College of New Energy and Environment, Jilin University, Changchun 130012, ChinaKey Laboratory of Groundwater Resources and Environment, Ministry of Education, Jilin Provincial Key Laboratory of Water Resources and Environment, College of New Energy and Environment, Jilin University, Changchun 130012, China; Corresponding authors.School of Materials and Environmental Engineering, Chengdu Technological University, Chengdu, Sichuan 610031, China; Corresponding authors.Key Laboratory of Groundwater Resources and Environment, Ministry of Education, Jilin Provincial Key Laboratory of Water Resources and Environment, College of New Energy and Environment, Jilin University, Changchun 130012, ChinaFerrihydrite is commonly associated with antibiotics in natural environments due to its strong sorption capabilities and high specific surface area. Under reducing conditions, Fe(II) acts as a catalyst for the transformation of ferrihydrite into more crystalline minerals. However, the influence of antibiotic molecular structure on the Fe(II)-catalyzed transformation of ferrihydrite and the associated degradation mechanisms of antibiotics have remained unclear. This study employed enoxacin (ENO), a representative fluorinated pharmaceutical, and pipemidic acid (PPA), a structural analog of ENO, to investigate the effect of fluorinated substituents on Fe(II)-facilitated ferrihydrite transformation. The results revealed that the transformation of ferrihydrite in the ENO system was 2.8 times greater than in the PPA system. ENO degradation reached 74.3 %, which was 1.13 times higher than that of PPA. ENO degradation products were more prone to hydroxylation, decarboxylation, and piperazine ring oxidation, whereas PPA degradation primarily involved oxidation of the piperazine ring. The fluorinated substituent in ENO facilitated ferrihydrite transformation by influencing the concentration of adsorbed Fe(II) and the distribution of antibiotics within the mineral inside. Furthermore, the fluorinated substituent in ENO enhanced degradation by increasing electron transfer between ENO and Fe(III), raising the content of adsorbed Fe(II) and promoting the formation of goethite. Collectively, these findings provide new insights into the environmental behavior of ferrihydrite and the fate of structurally different antibiotics in natural systems.http://www.sciencedirect.com/science/article/pii/S0147651325006499Fluorinated substituentAntibioticTransformationFerrihydriteGoethite
spellingShingle Liting Wang
Shikun Wei
Liwen Zhang
Zhiyong Guo
Yan Lei
Deming Dong
Synergistic effects of fluorinated substituents and Fe(Ⅱ) on ferrihydrite transformation and antibiotic degradation
Ecotoxicology and Environmental Safety
Fluorinated substituent
Antibiotic
Transformation
Ferrihydrite
Goethite
title Synergistic effects of fluorinated substituents and Fe(Ⅱ) on ferrihydrite transformation and antibiotic degradation
title_full Synergistic effects of fluorinated substituents and Fe(Ⅱ) on ferrihydrite transformation and antibiotic degradation
title_fullStr Synergistic effects of fluorinated substituents and Fe(Ⅱ) on ferrihydrite transformation and antibiotic degradation
title_full_unstemmed Synergistic effects of fluorinated substituents and Fe(Ⅱ) on ferrihydrite transformation and antibiotic degradation
title_short Synergistic effects of fluorinated substituents and Fe(Ⅱ) on ferrihydrite transformation and antibiotic degradation
title_sort synergistic effects of fluorinated substituents and fe ii on ferrihydrite transformation and antibiotic degradation
topic Fluorinated substituent
Antibiotic
Transformation
Ferrihydrite
Goethite
url http://www.sciencedirect.com/science/article/pii/S0147651325006499
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AT shikunwei synergisticeffectsoffluorinatedsubstituentsandfeiionferrihydritetransformationandantibioticdegradation
AT liwenzhang synergisticeffectsoffluorinatedsubstituentsandfeiionferrihydritetransformationandantibioticdegradation
AT zhiyongguo synergisticeffectsoffluorinatedsubstituentsandfeiionferrihydritetransformationandantibioticdegradation
AT yanlei synergisticeffectsoffluorinatedsubstituentsandfeiionferrihydritetransformationandantibioticdegradation
AT demingdong synergisticeffectsoffluorinatedsubstituentsandfeiionferrihydritetransformationandantibioticdegradation