Elsevier

Chemosphere

Volume 303, Part 1, September 2022, 134963
Chemosphere

Sunlit expeditious visible light-mediated photo-fenton degradation of ciprofloxacin by exfoliation of NiCo2O4 and Zn0·3Fe2·7O4 over g-C3N4 matrix: A brief insight on degradation mechanism, degraded product toxicity, and genotoxic evaluation in Allium cepa

https://doi.org/10.1016/j.chemosphere.2022.134963Get rights and content

Highlights

  • A dual Z – scheme based visible-light driven ternary g–C3N4–NiCo2O4–Zn0.3Fe2·7O4 nanomaterial was successfully synthesized.

  • The effect of operating parameters on ciprofloxacin degradation was investigated.

  • A possible degradation pathway of ciprofloxacin has been proposed based on GC-MS/MS analysis.

  • The degraded intermediates have been screened for chronic and acute toxicity effects by QSAR method.

  • g–C3N4–NiCo2O4–Zn0.3Fe2·7O4 explicated non-toxic nature upon treatment with Allium cepa.

Abstract

Pharmaceutical pollutant in the environmental water bodies has become a major concern, which causes adverse effect to aquatic entities. This study provides an incisive insight on the photocatalytic degradation of ciprofloxacin (CIP) and the development of rationally engineered g–C3N4–NiCo2O4–Zn0.3Fe2·7O4 nanocomposite for boosted photocatalytic performance under visible light irradiation. The g–C3N4–NiCo2O4–Zn0.3Fe2·7O4 nanocomposite was synthesized via ultrasonication-assisted hydrothermal method. The characterization of the as-prepared material was evaluated by XPS, SEM, HR-TEM, PL, FT-IR, EIS, ESR, XRD, BET, and UV–Vis DRS techniques. Furthermore, the effect of catalytic dosage, drug dosage, and pH changes was explored, where g–C3N4–NiCo2O4–Zn0.3Fe2·7O4-10% unveiled excellent visible light photo-Fenton degradation of 92% for CIP at 140 min. The hydroxyl radicals (OH.) served as the predominant radical species on the photodegradation of CIP, which was confirmed by performing a radical scavenging test. Furthermore, the degradation efficiency was determined by six consecutive cycle tests, where the nanomaterial exhibited excellent stability with 98.5% reusable efficiency. The degradation of CIP was further scrutinized by GC-MS analysis, where the degraded intermediate products and the possible pathway were elucidated. The degraded product toxicity was determined by ECOSAR program, where the degraded products haven't exhibited any considerable toxic effects. In addition, the genotoxicity of the nanomaterial was determined by treating them with root tips of A. cepa, where it was found to be non-toxic. Here, the prepared g–C3N4–NiCo2O4–Zn0.3Fe2·7O4 nanocomposite (CNZ NCs) shows eco-friendly and excellent photo-Fenton activity for environmental applications.

Section snippets

Credit author statement

G. Harini Methodology, Writing - original draft, Investigation, Formal analysis. Mohammad K. Okla Writing - review & editing, Funding acquisition. Ibrahim A. Alaraidh – Investigation and Formal analysis. Asmaa Mohebaldin – Formal analysis, Writing – review & editing. Abdullah A. AL-ghamdiInvestigation, Formal analysis. Mostafa A. Abdel-Maksoud – Investigation, Formal analysis. Ramadan F. Abdelaziz – Investigation, Formal analysis. Lija L. Raju – Investigation, Formal analysis. Ajith M. Thomas

Materials

Nickel sulphate (NiSO4), cobaltous sulphate (CoSO4), liquor ammonia and ferric nitrate (FeNO3) were obtained from Sisco Research Laboratory, Mumbai. Zinc sulphate (ZnSO4) and urea was obtained from HI media Pvt Ltd, India. All the obtained chemicals were directly used as they were of analytical grade.

Characterization of CNZ NCs

The morphological features of the prepared NCs and their counterparts were inspected via scanning electron microscope (SEM, Zessis Sigma, Germany) and high-resolution transmission electron microscope (HR-TEM, JEOL JEM 2100, Tokyo, Japan). Energy dispersive X-Ray spectroscopy (EDAX, JOEL 2100, Japan) was used to validate the elemental composition of the prepared sample. Crystallinity and its associated characteristics were determined by X-Ray diffraction (XRD), using Bruker D8 Advances, which

Possible degradation intermediates and pathway

The degraded products of CIP were estimated by using gas chromatography-mass spectroscopy (GC-MS/MS). As per the previous reports, the most probable radical attack on CIP might occur on the F atom, cyclopropyl group, piperazine ring, and carboxyl group (Li et al., 2020). Concerning these major vulnerable sites (either highly electrophilic or nucleophilic) and the obtained intermediate products, their corresponding radical attack sites has been represented in Fig. 6. Combining the obtained

Toxicity assessment of intermediates

The ECOSAR program was used to predict the toxicity of CIP and its intermediates in three different aquatic entities (Green algae, fish and daphnid), where the results are depicted in supplementary material Fig. S5. It has been noted that the degraded intermediates (P2 – P12) showed lower toxicity than its parent compound. Hence, it's evident that the prepared photocatalyst significantly reduces aquatic toxicity and doesn't introduce any secondary toxic effects.

Genotoxic evaluation of CNZ-10

Allium cepa is one of the widely used model systems to evaluate the genotoxicity of engineered nanomaterials. The cytotoxic and chromosomal aberrations in root tips of Allium cepa treated with various CNZ – 10 NCs concentration has been represented in supplementary material Table. S3. The cell cycle analysis shows that there was no significant change in the percentage of dividing cells (prophase, metaphase, anaphase, and telophase) with increasing CNZ NCs concentration when compared to the

Conclusion

g–C3N4–NiCo2O4–Zn0.3Fe2·7O4 NCs exhibited enhanced photo-Fenton catalytic activity under visible light towards CIP. A series of characterizations have indicated that the prepared NCs have high optical absorption, suppressed recombination rate, and enhanced charge carrier longevity. Moreover, CNZ-10 NCs exhibited expeditious photo-Fenton performance with 92% degradation efficiency within 140 min. Meanwhile, the role of catalytic dosage, drug dosage, and pH have been explored and elucidated,

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

The authors extend their appreciation to the Researchers Supporting Project number (RSP-2021/176) King Saud University, Riyadh, Saudi Arabia. Authors sincerely thank the management of Bannari Amman Institute of Technology, Tamil Nadu for providing necessary facilities for carrying out this work.

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