Highly efficient adsorption of tetracycline using chitosan-based magnetic adsorbent

Herein, tetracycline adsorption employing magnetic chitosan (CS·Fe3O4) as the adsorbent is reported. The magnetic adsorbent was synthesized by the co-precipitation method and characterized through FTIR, XRD, SEM, and VSM analyses. The experimental data showed that the highest maximum adsorption capa...

Full description

Autores:
Bruckmann, Franciele
Schnorr, Carlos Eduardo
da Rosa Salles, Theodoro
Batista Nunes, Franciane
Baumann, Luiza
Irineu Müller, Edson
Silva Oliveira, Luis Felipe
Dotto, Guilherme Luiz
Bohn Rhoden, Cristiano Rodrigo
Tipo de recurso:
Article of investigation
Fecha de publicación:
2022
Institución:
Corporación Universidad de la Costa
Repositorio:
REDICUC - Repositorio CUC
Idioma:
eng
OAI Identifier:
oai:repositorio.cuc.edu.co:11323/10936
Acceso en línea:
https://hdl.handle.net/11323/10936
https://repositorio.cuc.edu.co/
Palabra clave:
Antibiotics
Emerging pollutants
Iron oxide nanoparticles
Magnetic nanocomposites
Rights
openAccess
License
Atribución 4.0 Internacional (CC BY 4.0)
id RCUC2_1d274cc5c74a4eed6c771286fb990e30
oai_identifier_str oai:repositorio.cuc.edu.co:11323/10936
network_acronym_str RCUC2
network_name_str REDICUC - Repositorio CUC
repository_id_str
dc.title.eng.fl_str_mv Highly efficient adsorption of tetracycline using chitosan-based magnetic adsorbent
title Highly efficient adsorption of tetracycline using chitosan-based magnetic adsorbent
spellingShingle Highly efficient adsorption of tetracycline using chitosan-based magnetic adsorbent
Antibiotics
Emerging pollutants
Iron oxide nanoparticles
Magnetic nanocomposites
title_short Highly efficient adsorption of tetracycline using chitosan-based magnetic adsorbent
title_full Highly efficient adsorption of tetracycline using chitosan-based magnetic adsorbent
title_fullStr Highly efficient adsorption of tetracycline using chitosan-based magnetic adsorbent
title_full_unstemmed Highly efficient adsorption of tetracycline using chitosan-based magnetic adsorbent
title_sort Highly efficient adsorption of tetracycline using chitosan-based magnetic adsorbent
dc.creator.fl_str_mv Bruckmann, Franciele
Schnorr, Carlos Eduardo
da Rosa Salles, Theodoro
Batista Nunes, Franciane
Baumann, Luiza
Irineu Müller, Edson
Silva Oliveira, Luis Felipe
Dotto, Guilherme Luiz
Bohn Rhoden, Cristiano Rodrigo
dc.contributor.author.none.fl_str_mv Bruckmann, Franciele
Schnorr, Carlos Eduardo
da Rosa Salles, Theodoro
Batista Nunes, Franciane
Baumann, Luiza
Irineu Müller, Edson
Silva Oliveira, Luis Felipe
Dotto, Guilherme Luiz
Bohn Rhoden, Cristiano Rodrigo
dc.subject.proposal.eng.fl_str_mv Antibiotics
Emerging pollutants
Iron oxide nanoparticles
Magnetic nanocomposites
topic Antibiotics
Emerging pollutants
Iron oxide nanoparticles
Magnetic nanocomposites
description Herein, tetracycline adsorption employing magnetic chitosan (CS·Fe3O4) as the adsorbent is reported. The magnetic adsorbent was synthesized by the co-precipitation method and characterized through FTIR, XRD, SEM, and VSM analyses. The experimental data showed that the highest maximum adsorption capacity was reached at pH 7.0 (211.21 mg g−1). The efficiency of the magnetic adsorbent in tetracycline removal was dependent on the pH, initial concentration of adsorbate, and the adsorbent dosage. Additionally, the ionic strength showed a significant effect on the process. The equilibrium and kinetics studies demonstrate that Sips and Elovich models showed the best adjustment for experimental data, suggesting that the adsorption occurs in a heterogeneous surface and predominantly by chemical mechanisms. The experimental results suggest that tetracycline adsorption is mainly governed by the hydrogen bonds and cation–π interactions due to its pH dependence as well as the enhancement in the removal efficiency with the magnetite incorporation on the chitosan surface, respectively. Thermodynamic parameters indicate a spontaneous and exothermic process. Finally, magnetic chitosan proves to be efficient in TC removal even after several adsorption/desorption cycles.
publishDate 2022
dc.date.issued.none.fl_str_mv 2022-11-11
dc.date.accessioned.none.fl_str_mv 2024-04-04T20:02:54Z
dc.date.available.none.fl_str_mv 2024-04-04T20:02:54Z
dc.type.spa.fl_str_mv Artículo de revista
dc.type.coar.spa.fl_str_mv http://purl.org/coar/resource_type/c_2df8fbb1
dc.type.content.spa.fl_str_mv Text
dc.type.driver.spa.fl_str_mv info:eu-repo/semantics/article
dc.type.redcol.spa.fl_str_mv http://purl.org/redcol/resource_type/ART
dc.type.version.spa.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.coarversion.spa.fl_str_mv http://purl.org/coar/version/c_970fb48d4fbd8a85
format http://purl.org/coar/resource_type/c_2df8fbb1
status_str publishedVersion
dc.identifier.citation.spa.fl_str_mv da Silva Bruckmann, F.; Schnorr, C.E.; da Rosa Salles, T.; Nunes, F.B.; Baumann, L.; Müller, E.I.; Silva, L.F.O.; Dotto, G.L.; Bohn Rhoden, C.R. Highly Efficient Adsorption of Tetracycline Using Chitosan-Based Magnetic Adsorbent. Polymers 2022, 14, 4854. https:// doi.org/10.3390/polym14224854
dc.identifier.uri.none.fl_str_mv https://hdl.handle.net/11323/10936
dc.identifier.doi.none.fl_str_mv 10.3390/polym14224854
dc.identifier.eissn.spa.fl_str_mv 2073-4360
dc.identifier.instname.spa.fl_str_mv Corporación Universidad de la Costa
dc.identifier.reponame.spa.fl_str_mv REDICUC – Repositorio CUC
dc.identifier.repourl.spa.fl_str_mv https://repositorio.cuc.edu.co/
identifier_str_mv da Silva Bruckmann, F.; Schnorr, C.E.; da Rosa Salles, T.; Nunes, F.B.; Baumann, L.; Müller, E.I.; Silva, L.F.O.; Dotto, G.L.; Bohn Rhoden, C.R. Highly Efficient Adsorption of Tetracycline Using Chitosan-Based Magnetic Adsorbent. Polymers 2022, 14, 4854. https:// doi.org/10.3390/polym14224854
10.3390/polym14224854
2073-4360
Corporación Universidad de la Costa
REDICUC – Repositorio CUC
url https://hdl.handle.net/11323/10936
https://repositorio.cuc.edu.co/
dc.language.iso.spa.fl_str_mv eng
language eng
dc.relation.ispartofjournal.spa.fl_str_mv Polymers
dc.relation.references.spa.fl_str_mv 1. Nasiri, A.; Rajabi, S.; Amiri, A.; Fattahizade, M.; Hasani, O.; Lalehzari, A.; Hashemi, M. Adsorption of tetracycline using CuCoFe2O4@ Chitosan as a new and green magnetic nanohybrid adsorbent from aqueous solutions: Isotherm, kinetic and thermodynamic study. Arab. J. Chem. 2022, 15, 104014. [CrossRef]
2. Da Silva Bruckmann, F.; Ledur, C.M.; da Silva, I.Z.; Dotto, G.L.; Rhoden, C.R.B. A DFT theoretical and experimental study about tetracycline adsorption onto magnetic graphene oxide. J. Mol. Liq. 2022, 1188, 35337. [CrossRef]
3. Dai, Y.; Liu, M.; Li, J.; Yang, S.; Sun, Y.; Sun, Q.; Wang, S.; Lu, L.; Zhang, K.; Xu, J.; et al. A review on pollution situation and treatment methods of tetracycline in groundwater. Sep. Sci. Technol. 2020, 55, 1005–1021. [CrossRef]
4. Pollock, A.J.; Seibert, T.; Allen, D.B. Severe and persistent thyroid dysfunction associated with tetracycline-antibiotic treatment in youth. J. Pediatr. 2016, 173, 232–234. [CrossRef] [PubMed]
5. Ibrahim, A.A.; Salama, R.S.; El-Hakam, S.A.; Khder, A.S.; Ahmed, A.I. Synthesis of 12-tungestophosphoric acid supported on Zr/MCM-41 composite with excellent heterogeneous catalyst and promising adsorbent of methylene blue. Colloid Surf. A Physicochem. Eng. Asp. 2021, 631, 127753. [CrossRef]
6. Alshorifi, F.T.; Alswat, A.A.; Salama, R.S. Gold-selenide quantum dots supported onto cesium ferrite nanocomposites for the efficient degradation of rhodamine B. Heliyon 2022, 8, e09652. [CrossRef]
7. Alayli, A.; Nadaroglu, H.; Turgut, E. Nanobiocatalyst beds with Fenton process for removal of methylene blue. Appl. Water Sci. 2021, 11, 32. [CrossRef]
8. Sani, O.N.; Yazdani, M.; Taghavi, M. Catalytic ozonation of ciprofloxacin using γ-Al2O3 nanoparticles in synthetic and real wastewaters. J. Water Process Eng. 2019, 32, 100894. [CrossRef]
9. Bakry, A.M.; Alamier, W.M.; Salama, R.S.; El-Shall, M.S.; Awad, F.S. Remediation of water containing phosphate using ceria nanoparticles decorated partially reduced graphene oxide (CeO2-PRGO) composite. Surf. Interfaces 2022, 31, 102006. [CrossRef]
10. Anastopoulos, I.; Karamesouti, M.; Mitropoulos, A.C.; Kyzas, G.Z. A review for coffee adsorbents. J. Mol. Liq. 2017, 229, 555–565. [CrossRef]
11. Abegunde, S.M.; Idowu, K.S.; Adejuwon, O.M.; Adeyemi-Adejolu, T. A review on the influence of chemical modification on the performance of adsorbents. Environ. Dev. Sustain. 2020, 1, 100001. [CrossRef]
12. Periyasamy, S.; Viswanathan, N. Hydrothermal synthesis of hydrocalumite assisted biopolymeric hybrid composites for efficient Cr (VI) removal from water. New J. Chem. 2018, 42, 3371–3382. [CrossRef]
13. Da Rosa Salles, T.; De Bitencourt Rodrigues, H.; Da Silva Bruckmann, F.; Alves LC, S.; Mortari, S.R.; Rhoden CR, B. Graphene oxide optimization synthesis for application on laboratory of Universidade Franciscana. Discip. Sci. Sér. Ciên. Nat. Tecnol. 2020, 21, 15–26. [CrossRef]
14. Zhu, H.; Chen, T.; Liu, J.; Li, D. Adsorption of tetracycline antibiotics from an aqueous solution onto graphene oxide/calcium alginate composite fibers. RSC Adv. 2018, 8, 2616–2621. [CrossRef]
15. Da Silva Bruckmann, F.; Zuchetto, T.; Ledur, C.M.; dos Santos, C.L.; da Silva, W.L.; Fagan, S.B.; da Silva, I.Z.; Rhoden CR, B. Methylphenidate adsorption onto graphene derivatives: Theory and experiment. New J. Chem. 2022, 4283, 46–4291. [CrossRef]
16. Zhai, W.; He, J.; Han, P.; Zeng, M.; Gao, X.; He, Q. Adsorption mechanism for tetracycline onto magnetic Fe3O4 nanoparticles: Adsorption isotherm and dynamic behavior, location of adsorption sites and interaction bonds. Vacuum 2022, 195, 110634. [CrossRef]
17. Shahraki, S.; Delarami, H.S.; Khosravi, F.; Nejat, R. Improving the adsorption potential of chitosan for heavy metal ions using aromatic ring-rich derivatives. J. Colloid Interface Sci. 2020, 576, 79–89. [CrossRef]
18. Da Rosa Salles, T.; Da Silva Bruckamann, F.; Viana, A.R.; Krause, L.M.F.; Mortari, S.R.; Rhoden, C.R.B. Magnetic nanocrystalline cellulose: Azithromycin adsorption and in vitro biological activity against melanoma cells. J. Polym. Environ. 2022, 30, 2695–2713. [CrossRef]
19. Li, Z.; Sellaoui, L.; Gueddida, S.; Dotto, G.L.; Lamine, A.B.; Bonilla-Petriciolet, A.; Badawi, M. Adsorption of methylene blue on silica nanoparticles: Modelling analysis of the adsorption mechanism via a double layer model. J. Mol. Liq. 2020, 319, 114348. [CrossRef]
20. Giraldo, J.D.; Rivas, B.L. Direct ionization and solubility of chitosan in aqueous solutions with acetic acid. Polym. Bull. 2021, 78, 1465–1488. [CrossRef]
21. Nunes, F.B.; Da Silva Bruckmann, F.; Da Rosa Salles, T.; Rhoden, C.B.R. Study of phenobarbital removal from the aqueous solutions employing magnetite-functionalized chitosan. Environ. Sci. Pollut. Res. 2022, 29, 1–14. [CrossRef]
22. Bruckmann, F.S.; Rossato Viana, A.; Tonel, M.Z.; Fagan, S.B.; Garcia, W.J.D.S.; Oliveira, A.H.D.; Dorneles, L.S.; Mortari, S.R.; Da Silva, W.L.; Da Silva, I.Z.; et al. Influence of magnetite incorporation into chitosan on the adsorption of the methotrexate and in vitro cytotoxicity. Environ. Sci. Pollut. Res. 2022, 29, 70413–70434. [CrossRef]
23. Liu, E.; Zheng, X.; Xu, X.; Zhang, F.; Liu, E.; Wang, Y.; Li, C.; Yan, Y. Preparation of diethylenetriamine-modified magnetic chitosan nanoparticles for adsorption of rare-earth metal ions. New J. Chem. 2017, 41, 7739–7750. [CrossRef]
24. Rhoden, C.R.B.; Bruckmann, F.S.; Salles, T.R.; Kaufmann Jr, C.G.; Mortari, S.R. Study from the influence of magnetite onto removal of hydrochlorothiazide from aqueous solutions applying magnetic graphene oxide. J. Water Process. Eng. 2021, 43, 102262. [CrossRef]
25. Wang, X.; Tang, R.; Zhang, Y.; Yu, Z.; Qi, C. Preparation of a novel chitosan based biopolymer dye and application in wood dyeing. Polymers 2016, 8, 338. [CrossRef] [PubMed]
26. Zhang, L.Y.; Zhu, X.J.; Sun, H.W.; Chi, G.R.; Xu, J.X.; Sun, Y.L. Control synthesis of magnetic Fe3O4–chitosan nanoparticles under UV irradiation in aqueous system. Curr. Appl. Phys. 2010, 10, 828–833. [CrossRef]
27. da Silva Bruckmann, F.; Pimentel, A.C.; Viana, A.R.; da Rosa Salles, T.; Krause, L.M.F.; Mortari, S.R.; Silva, I.Z.; Rhoden, C.R.B. Synthesis, characterization and cytotoxicity evaluation of magnetic nanosilica in L929 cell line. Discip. Sci. Sér. Ciên. Nat. Tecnol. 2020, 21, 1–14. [CrossRef]
28. Peng, J.; Wang, X.; Lou, T. Preparation of chitosan/gelatin composite foam with ternary solvents of dioxane/acetic acid/water and its water absorption capacity. Polym. Bull. 2020, 77, 5227–5244. [CrossRef]
29. Hao, G.; Hu, Y.; Shi, L.; Chen, J.; Cui, A.; Weng, W.; Osako, K. Physicochemical characteristics of chitosan from swimming crab (Portunus trituberculatus) shells prepared by subcritical water pretreatment. Sci. Rep. 2021, 11, 1646. [CrossRef]
30. Prabha, G.; Raj, V. Preparation and characterization of chitosan—Polyethylene glycol-polyvinylpyrrolidone-coated superparamagnetic iron oxide nanoparticles as carrier system: Drug loading and in vitro drug release study. J. Biomed. Mater. Res. B Appl. Biomater. 2016, 104, 808–816. [CrossRef]
31. Ates, B.; Ulu, A.; Köytepe, S.; Noma, S.A.A.; Kolat, V.S.; Izgi, T. Magnetic-propelled Fe3O4–chitosan carriers enhance L-asparaginase catalytic activity: A promising strategy for enzyme immobilization. RSC Adv. 2018, 8, 36063–36075. [CrossRef] [PubMed]
32. Pylypchuk, I.V.; Kołody ´nska, D.; Kozioł, M.; Gorbyk, P.P. Gd-DTPA adsorption on chitosan/magnetite nanocomposites. Nanoscale Res. Lett. 2016, 11, 168. [CrossRef] [PubMed]
33. Freire, T.M.; Fechine, L.M.; Queiro, D.C.; Freire, R.M.; Denardin, J.C.; Ricardo, N.M.; Rodrigues, T.N.B.; Gondim, D.R.; Junior, I.J.S.; Fechine, P. Magnetic Porous Controlled Fe3O4–Chitosan Nanostructure: An Ecofriendly Adsorbent for Efficient Removal of Azo Dyes. Nanomaterials 2020, 10, 1194. [CrossRef] [PubMed]
34. Yu, F.; Ma, J.; Han, S. Adsorption of tetracycline from aqueous solutions onto multi-walled carbon nanotubes with different oxygen contents. Sci. Rep. 2014, 4, 5326. [CrossRef] [PubMed]
35. Croitoru, C.; Roata, I.C.; Pascu, A.; Stanciu, E.M. Diffusion and controlled release in physically crosslinked poly (vinyl alcohol)/iota-carrageenan hydrogel blends. Polymers 2020, 12, 1544. [CrossRef] [PubMed]
36. Hu, X.; Zhao, Y.; Wang, H.; Tan, X.; Yang, Y.; Liu, Y. Efficient removal of tetracycline from aqueous media with a Fe3O4 nanoparticles@ graphene oxide nanosheets assembly. Int. J. Environ. Res. Public Health 2017, 14, 1495. [CrossRef]
37. Liao, Q.; Rong, H.; Zhao, M.; Luo, H.; Chu, Z.; Wang, R. Strong adsorption properties and mechanism of action with regard to tetracycline adsorption of double-network polyvinyl alcohol-copper alginate gel beads. J. Hazard. Mater. 2022, 422, 126863. [CrossRef]
38. Ji, L.; Chen, W.; Bi, J.; Zheng, S.; Xu, Z.; Zhu, D.; Alvarez, P.J. Adsorption of tetracycline on single-walled and multi-walled carbon nanotubes as affected by aqueous solution chemistry. Environ. Toxicol. Chem. 2010, 29, 2713–2719. [CrossRef]
39. Liang, J.; Fang, Y.; Luo, Y.; Zeng, G.; Deng, J.; Tan, X.; Tang, N.; Li, X.; He, X.; Feng, C.; et al. Magnetic nanoferromanganese oxides modified biochar derived from pine sawdust for adsorption of tetracycline hydrochloride. Environ. Sci. Pollut. Res. 2019, 26, 5892–5903. [CrossRef]
40. Yang, Y.; Hu, X.; Zhao, Y.; Cui, L.; Huang, Z.; Long, J.; Xu, J.; Deng, J.; Wu, C.; Liao, W. Decontamination of tetracycline by thiourea-dioxide–reduced magnetic graphene oxide: Effects of pH, ionic strength, and humic acid concentration. J. Colloid Interface Sci. 2017, 495, 68–77. [CrossRef]
41. Martins, A.C.; Pezoti, O.; Cazetta, A.L.; Bedin, K.C.; Yamazaki, D.A.; Bandoch, G.F.; Asefa, T.; Visentainer, J.V.; Almeida, V.C. Removal of tetracycline by NaOH-activated carbon produced from macadamia nut shells: Kinetic and equilibrium studies. Chem. Eng. J. 2015, 260, 291–299. [CrossRef]
42. Gupta, S.S.; Bhattacharyya, K.G. Kinetics of adsorption of metal ions on inorganic materials: A review. Adv. Colloid Interface Sci. 2011, 162, 39–58. [CrossRef] [PubMed]
43. Agarry, S.E.; Aworanti, O.A. Kinetics, Isothermal and Thermodynamic Modelling Studies of Hexavalent Chromium Ions Adsorption from Simulated Wastewater onto Parkia biglobosa-Sawdust Derived Acid-Steam. Act. Carbon. Appl. J. Envir. Eng. Sci. 2017, 3, 58–76. [CrossRef]
44. De Souza, F.M.; Dos Santos, O.A.A.; Vieira, M.G.A. Adsorption of herbicide 2,4-D from aqueous solution using organo-modified bentonite clay. Environ. Sci. Pollut. Res. 2019, 26, 18329–18342. [CrossRef]
45. Gago, D.; Chagas, R.; Ferreira, L.M.; Velizarov, S.; Coelhoso, I. A novel cellulose-based polymer for efficient removal of methylene blue. Membranes 2020, 10, 13. [CrossRef]
46. Cazalbou, S.; Bertrand, G.; Drouet, C. Tetracycline-loaded biomimetic apatite: An adsorption study. J. Phys. Chem. B 2015, 119, 3014–3024. [CrossRef] [PubMed]
47. Acosta, R.; Fierro, V.; De Yuso, A.M.; Nabarlatz, D.; Celzard, A. Tetracycline adsorption onto activated carbons produced by KOH activation of tyre pyrolysis char. Chemosphere 2016, 149, 168–176. [CrossRef]
48. Chaabane, L.; Beyou, E.; Baouab, M.H.V. Preparation of a novel zwitterionic graphene oxide-based adsorbent to remove of heavy metal ions from water: Modeling and comparative studies. Adv. Powder Technol. 2021, 32, 2502–2516. [CrossRef]
49. Wojtacha-Rychter, K.; Howaniec, N.; Smoli ´nski, A. Effect of porous structure of coal on propylene adsorption from gas mixtures. Sci. Rep. 2020, 10, 11277. [CrossRef]
50. Liu, W.; Zhang, Y.; Wang, S.; Bai, L.; Deng, Y.; Tao, J. Effect of pore size distribution and amination on adsorption capacities of polymeric adsorbents. Molecules 2021, 26, 5267. [CrossRef]
51. Huízar-Félix, A.M.; Aguilar-Flores, C.; Martínez-de-la Cruz, A.; Barandiarán, J.M.; Sepúlveda-Guzmán, S.; Cruz-Silva, R. Removal of tetracycline pollutants by adsorption and magnetic separation using reduced graphene oxide decorated with α-Fe2O3 nanoparticles. Nanomaterials 2019, 9, 313. [CrossRef] [PubMed]
52. Ranjbari, S.; Tanhaei, B.; Ayati, A.; Khadempir, S.; Sillanpää, M. Efficient tetracycline adsorptive removal using tricaprylmethylammonium chloride conjugated chitosan hydrogel beads: Mechanism, kinetic, isotherms and thermodynamic study. Int. J. Biol. Macromol. 2020, 155, 421–429. [CrossRef] [PubMed]
53. Zhang, Z.; Ding, C.; Li, Y.; Ke, H.; Cheng, G. Efficient removal of tetracycline hydrochloride from aqueous solution by mesoporous cage MOF-818. SN Appl. Sci. 2020, 2, 669. [CrossRef]
54. Erdem, S.; Öztekin, M.; Açıkel, Y.S. Investigation of tetracycline removal from aqueous solutions using halloysite/chitosan nanocomposites and halloysite nanotubes/alginate hydrogel beads. Environ. Nanotechnol. Monit. Manag. 2021, 16, 100576. [CrossRef]
55. Rathod, M.; Haldar, S.; Basha, S. Nanocrystalline cellulose for removal of tetracycline hydrochloride from water via biosorption: Equilibrium, kinetic and thermodynamic studies. Ecol. Eng. 2015, 84, 240–249. [CrossRef]
56. Lin, Y.; Xu, S.; Li, J. Fast and highly efficient tetracyclines removal from environmental waters by graphene oxide functionalized magnetic particles. Chem. Eng. J. 2013, 225, 679–685. [CrossRef]
57. Chen, Y.; Wang, F.; Duan, L.; Yang, H.; Gao, J. Tetracycline adsorption onto rice husk ash, an agricultural waste: Its kinetic and thermodynamic studies. J. Mol. Liq. 2016, 222, 487–494. [CrossRef]
dc.relation.citationendpage.spa.fl_str_mv 19
dc.relation.citationstartpage.spa.fl_str_mv 1
dc.relation.citationissue.spa.fl_str_mv 22
dc.relation.citationvolume.spa.fl_str_mv 14
dc.rights.eng.fl_str_mv © 2022 by the authors. Licensee MDPI, Basel, Switzerland.
dc.rights.license.spa.fl_str_mv Atribución 4.0 Internacional (CC BY 4.0)
dc.rights.uri.spa.fl_str_mv https://creativecommons.org/licenses/by/4.0/
dc.rights.accessrights.spa.fl_str_mv info:eu-repo/semantics/openAccess
dc.rights.coar.spa.fl_str_mv http://purl.org/coar/access_right/c_abf2
rights_invalid_str_mv Atribución 4.0 Internacional (CC BY 4.0)
© 2022 by the authors. Licensee MDPI, Basel, Switzerland.
https://creativecommons.org/licenses/by/4.0/
http://purl.org/coar/access_right/c_abf2
eu_rights_str_mv openAccess
dc.format.extent.spa.fl_str_mv 19 páginas
dc.format.mimetype.spa.fl_str_mv application/pdf
dc.publisher.spa.fl_str_mv MDPI AG
dc.publisher.place.spa.fl_str_mv Switzerland
dc.source.spa.fl_str_mv https://www.mdpi.com/2073-4360/14/22/4854
institution Corporación Universidad de la Costa
bitstream.url.fl_str_mv https://repositorio.cuc.edu.co/bitstreams/e61f29ee-67c4-4ffc-8f8e-764e616f0f7b/download
https://repositorio.cuc.edu.co/bitstreams/72eb73b8-857a-4f6e-bcce-6928f856ec0d/download
https://repositorio.cuc.edu.co/bitstreams/193da81c-a65d-4b95-ac8b-5a4781292b03/download
https://repositorio.cuc.edu.co/bitstreams/5e773783-9b90-44ad-b7ee-4568e24cef02/download
bitstream.checksum.fl_str_mv 52890781da1141efddb5a82d9a68096f
2f9959eaf5b71fae44bbf9ec84150c7a
379284d40ce0304845d1b6c3e885b5fb
ee7e61fae7f0ecd4f420e074ca8b201e
bitstream.checksumAlgorithm.fl_str_mv MD5
MD5
MD5
MD5
repository.name.fl_str_mv Repositorio de la Universidad de la Costa CUC
repository.mail.fl_str_mv repdigital@cuc.edu.co
_version_ 1811760789439119360
spelling Atribución 4.0 Internacional (CC BY 4.0)© 2022 by the authors. Licensee MDPI, Basel, Switzerland.https://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccesshttp://purl.org/coar/access_right/c_abf2Bruckmann, FrancieleSchnorr, Carlos Eduardoda Rosa Salles, TheodoroBatista Nunes, FrancianeBaumann, LuizaIrineu Müller, EdsonSilva Oliveira, Luis FelipeDotto, Guilherme LuizBohn Rhoden, Cristiano Rodrigo2024-04-04T20:02:54Z2024-04-04T20:02:54Z2022-11-11da Silva Bruckmann, F.; Schnorr, C.E.; da Rosa Salles, T.; Nunes, F.B.; Baumann, L.; Müller, E.I.; Silva, L.F.O.; Dotto, G.L.; Bohn Rhoden, C.R. Highly Efficient Adsorption of Tetracycline Using Chitosan-Based Magnetic Adsorbent. Polymers 2022, 14, 4854. https:// doi.org/10.3390/polym14224854https://hdl.handle.net/11323/1093610.3390/polym142248542073-4360Corporación Universidad de la CostaREDICUC – Repositorio CUChttps://repositorio.cuc.edu.co/Herein, tetracycline adsorption employing magnetic chitosan (CS·Fe3O4) as the adsorbent is reported. The magnetic adsorbent was synthesized by the co-precipitation method and characterized through FTIR, XRD, SEM, and VSM analyses. The experimental data showed that the highest maximum adsorption capacity was reached at pH 7.0 (211.21 mg g−1). The efficiency of the magnetic adsorbent in tetracycline removal was dependent on the pH, initial concentration of adsorbate, and the adsorbent dosage. Additionally, the ionic strength showed a significant effect on the process. The equilibrium and kinetics studies demonstrate that Sips and Elovich models showed the best adjustment for experimental data, suggesting that the adsorption occurs in a heterogeneous surface and predominantly by chemical mechanisms. The experimental results suggest that tetracycline adsorption is mainly governed by the hydrogen bonds and cation–π interactions due to its pH dependence as well as the enhancement in the removal efficiency with the magnetite incorporation on the chitosan surface, respectively. Thermodynamic parameters indicate a spontaneous and exothermic process. Finally, magnetic chitosan proves to be efficient in TC removal even after several adsorption/desorption cycles.19 páginasapplication/pdfengMDPI AGSwitzerlandhttps://www.mdpi.com/2073-4360/14/22/4854Highly efficient adsorption of tetracycline using chitosan-based magnetic adsorbentArtículo de revistahttp://purl.org/coar/resource_type/c_2df8fbb1Textinfo:eu-repo/semantics/articlehttp://purl.org/redcol/resource_type/ARTinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/version/c_970fb48d4fbd8a85Polymers1. Nasiri, A.; Rajabi, S.; Amiri, A.; Fattahizade, M.; Hasani, O.; Lalehzari, A.; Hashemi, M. Adsorption of tetracycline using CuCoFe2O4@ Chitosan as a new and green magnetic nanohybrid adsorbent from aqueous solutions: Isotherm, kinetic and thermodynamic study. Arab. J. Chem. 2022, 15, 104014. [CrossRef]2. Da Silva Bruckmann, F.; Ledur, C.M.; da Silva, I.Z.; Dotto, G.L.; Rhoden, C.R.B. A DFT theoretical and experimental study about tetracycline adsorption onto magnetic graphene oxide. J. Mol. Liq. 2022, 1188, 35337. [CrossRef]3. Dai, Y.; Liu, M.; Li, J.; Yang, S.; Sun, Y.; Sun, Q.; Wang, S.; Lu, L.; Zhang, K.; Xu, J.; et al. A review on pollution situation and treatment methods of tetracycline in groundwater. Sep. Sci. Technol. 2020, 55, 1005–1021. [CrossRef]4. Pollock, A.J.; Seibert, T.; Allen, D.B. Severe and persistent thyroid dysfunction associated with tetracycline-antibiotic treatment in youth. J. Pediatr. 2016, 173, 232–234. [CrossRef] [PubMed]5. Ibrahim, A.A.; Salama, R.S.; El-Hakam, S.A.; Khder, A.S.; Ahmed, A.I. Synthesis of 12-tungestophosphoric acid supported on Zr/MCM-41 composite with excellent heterogeneous catalyst and promising adsorbent of methylene blue. Colloid Surf. A Physicochem. Eng. Asp. 2021, 631, 127753. [CrossRef]6. Alshorifi, F.T.; Alswat, A.A.; Salama, R.S. Gold-selenide quantum dots supported onto cesium ferrite nanocomposites for the efficient degradation of rhodamine B. Heliyon 2022, 8, e09652. [CrossRef]7. Alayli, A.; Nadaroglu, H.; Turgut, E. Nanobiocatalyst beds with Fenton process for removal of methylene blue. Appl. Water Sci. 2021, 11, 32. [CrossRef]8. Sani, O.N.; Yazdani, M.; Taghavi, M. Catalytic ozonation of ciprofloxacin using γ-Al2O3 nanoparticles in synthetic and real wastewaters. J. Water Process Eng. 2019, 32, 100894. [CrossRef]9. Bakry, A.M.; Alamier, W.M.; Salama, R.S.; El-Shall, M.S.; Awad, F.S. Remediation of water containing phosphate using ceria nanoparticles decorated partially reduced graphene oxide (CeO2-PRGO) composite. Surf. Interfaces 2022, 31, 102006. [CrossRef]10. Anastopoulos, I.; Karamesouti, M.; Mitropoulos, A.C.; Kyzas, G.Z. A review for coffee adsorbents. J. Mol. Liq. 2017, 229, 555–565. [CrossRef]11. Abegunde, S.M.; Idowu, K.S.; Adejuwon, O.M.; Adeyemi-Adejolu, T. A review on the influence of chemical modification on the performance of adsorbents. Environ. Dev. Sustain. 2020, 1, 100001. [CrossRef]12. Periyasamy, S.; Viswanathan, N. Hydrothermal synthesis of hydrocalumite assisted biopolymeric hybrid composites for efficient Cr (VI) removal from water. New J. Chem. 2018, 42, 3371–3382. [CrossRef]13. Da Rosa Salles, T.; De Bitencourt Rodrigues, H.; Da Silva Bruckmann, F.; Alves LC, S.; Mortari, S.R.; Rhoden CR, B. Graphene oxide optimization synthesis for application on laboratory of Universidade Franciscana. Discip. Sci. Sér. Ciên. Nat. Tecnol. 2020, 21, 15–26. [CrossRef]14. Zhu, H.; Chen, T.; Liu, J.; Li, D. Adsorption of tetracycline antibiotics from an aqueous solution onto graphene oxide/calcium alginate composite fibers. RSC Adv. 2018, 8, 2616–2621. [CrossRef]15. Da Silva Bruckmann, F.; Zuchetto, T.; Ledur, C.M.; dos Santos, C.L.; da Silva, W.L.; Fagan, S.B.; da Silva, I.Z.; Rhoden CR, B. Methylphenidate adsorption onto graphene derivatives: Theory and experiment. New J. Chem. 2022, 4283, 46–4291. [CrossRef]16. Zhai, W.; He, J.; Han, P.; Zeng, M.; Gao, X.; He, Q. Adsorption mechanism for tetracycline onto magnetic Fe3O4 nanoparticles: Adsorption isotherm and dynamic behavior, location of adsorption sites and interaction bonds. Vacuum 2022, 195, 110634. [CrossRef]17. Shahraki, S.; Delarami, H.S.; Khosravi, F.; Nejat, R. Improving the adsorption potential of chitosan for heavy metal ions using aromatic ring-rich derivatives. J. Colloid Interface Sci. 2020, 576, 79–89. [CrossRef]18. Da Rosa Salles, T.; Da Silva Bruckamann, F.; Viana, A.R.; Krause, L.M.F.; Mortari, S.R.; Rhoden, C.R.B. Magnetic nanocrystalline cellulose: Azithromycin adsorption and in vitro biological activity against melanoma cells. J. Polym. Environ. 2022, 30, 2695–2713. [CrossRef]19. Li, Z.; Sellaoui, L.; Gueddida, S.; Dotto, G.L.; Lamine, A.B.; Bonilla-Petriciolet, A.; Badawi, M. Adsorption of methylene blue on silica nanoparticles: Modelling analysis of the adsorption mechanism via a double layer model. J. Mol. Liq. 2020, 319, 114348. [CrossRef]20. Giraldo, J.D.; Rivas, B.L. Direct ionization and solubility of chitosan in aqueous solutions with acetic acid. Polym. Bull. 2021, 78, 1465–1488. [CrossRef]21. Nunes, F.B.; Da Silva Bruckmann, F.; Da Rosa Salles, T.; Rhoden, C.B.R. Study of phenobarbital removal from the aqueous solutions employing magnetite-functionalized chitosan. Environ. Sci. Pollut. Res. 2022, 29, 1–14. [CrossRef]22. Bruckmann, F.S.; Rossato Viana, A.; Tonel, M.Z.; Fagan, S.B.; Garcia, W.J.D.S.; Oliveira, A.H.D.; Dorneles, L.S.; Mortari, S.R.; Da Silva, W.L.; Da Silva, I.Z.; et al. Influence of magnetite incorporation into chitosan on the adsorption of the methotrexate and in vitro cytotoxicity. Environ. Sci. Pollut. Res. 2022, 29, 70413–70434. [CrossRef]23. Liu, E.; Zheng, X.; Xu, X.; Zhang, F.; Liu, E.; Wang, Y.; Li, C.; Yan, Y. Preparation of diethylenetriamine-modified magnetic chitosan nanoparticles for adsorption of rare-earth metal ions. New J. Chem. 2017, 41, 7739–7750. [CrossRef]24. Rhoden, C.R.B.; Bruckmann, F.S.; Salles, T.R.; Kaufmann Jr, C.G.; Mortari, S.R. Study from the influence of magnetite onto removal of hydrochlorothiazide from aqueous solutions applying magnetic graphene oxide. J. Water Process. Eng. 2021, 43, 102262. [CrossRef]25. Wang, X.; Tang, R.; Zhang, Y.; Yu, Z.; Qi, C. Preparation of a novel chitosan based biopolymer dye and application in wood dyeing. Polymers 2016, 8, 338. [CrossRef] [PubMed]26. Zhang, L.Y.; Zhu, X.J.; Sun, H.W.; Chi, G.R.; Xu, J.X.; Sun, Y.L. Control synthesis of magnetic Fe3O4–chitosan nanoparticles under UV irradiation in aqueous system. Curr. Appl. Phys. 2010, 10, 828–833. [CrossRef]27. da Silva Bruckmann, F.; Pimentel, A.C.; Viana, A.R.; da Rosa Salles, T.; Krause, L.M.F.; Mortari, S.R.; Silva, I.Z.; Rhoden, C.R.B. Synthesis, characterization and cytotoxicity evaluation of magnetic nanosilica in L929 cell line. Discip. Sci. Sér. Ciên. Nat. Tecnol. 2020, 21, 1–14. [CrossRef]28. Peng, J.; Wang, X.; Lou, T. Preparation of chitosan/gelatin composite foam with ternary solvents of dioxane/acetic acid/water and its water absorption capacity. Polym. Bull. 2020, 77, 5227–5244. [CrossRef]29. Hao, G.; Hu, Y.; Shi, L.; Chen, J.; Cui, A.; Weng, W.; Osako, K. Physicochemical characteristics of chitosan from swimming crab (Portunus trituberculatus) shells prepared by subcritical water pretreatment. Sci. Rep. 2021, 11, 1646. [CrossRef]30. Prabha, G.; Raj, V. Preparation and characterization of chitosan—Polyethylene glycol-polyvinylpyrrolidone-coated superparamagnetic iron oxide nanoparticles as carrier system: Drug loading and in vitro drug release study. J. Biomed. Mater. Res. B Appl. Biomater. 2016, 104, 808–816. [CrossRef]31. Ates, B.; Ulu, A.; Köytepe, S.; Noma, S.A.A.; Kolat, V.S.; Izgi, T. Magnetic-propelled Fe3O4–chitosan carriers enhance L-asparaginase catalytic activity: A promising strategy for enzyme immobilization. RSC Adv. 2018, 8, 36063–36075. [CrossRef] [PubMed]32. Pylypchuk, I.V.; Kołody ´nska, D.; Kozioł, M.; Gorbyk, P.P. Gd-DTPA adsorption on chitosan/magnetite nanocomposites. Nanoscale Res. Lett. 2016, 11, 168. [CrossRef] [PubMed]33. Freire, T.M.; Fechine, L.M.; Queiro, D.C.; Freire, R.M.; Denardin, J.C.; Ricardo, N.M.; Rodrigues, T.N.B.; Gondim, D.R.; Junior, I.J.S.; Fechine, P. Magnetic Porous Controlled Fe3O4–Chitosan Nanostructure: An Ecofriendly Adsorbent for Efficient Removal of Azo Dyes. Nanomaterials 2020, 10, 1194. [CrossRef] [PubMed]34. Yu, F.; Ma, J.; Han, S. Adsorption of tetracycline from aqueous solutions onto multi-walled carbon nanotubes with different oxygen contents. Sci. Rep. 2014, 4, 5326. [CrossRef] [PubMed]35. Croitoru, C.; Roata, I.C.; Pascu, A.; Stanciu, E.M. Diffusion and controlled release in physically crosslinked poly (vinyl alcohol)/iota-carrageenan hydrogel blends. Polymers 2020, 12, 1544. [CrossRef] [PubMed]36. Hu, X.; Zhao, Y.; Wang, H.; Tan, X.; Yang, Y.; Liu, Y. Efficient removal of tetracycline from aqueous media with a Fe3O4 nanoparticles@ graphene oxide nanosheets assembly. Int. J. Environ. Res. Public Health 2017, 14, 1495. [CrossRef]37. Liao, Q.; Rong, H.; Zhao, M.; Luo, H.; Chu, Z.; Wang, R. Strong adsorption properties and mechanism of action with regard to tetracycline adsorption of double-network polyvinyl alcohol-copper alginate gel beads. J. Hazard. Mater. 2022, 422, 126863. [CrossRef]38. Ji, L.; Chen, W.; Bi, J.; Zheng, S.; Xu, Z.; Zhu, D.; Alvarez, P.J. Adsorption of tetracycline on single-walled and multi-walled carbon nanotubes as affected by aqueous solution chemistry. Environ. Toxicol. Chem. 2010, 29, 2713–2719. [CrossRef]39. Liang, J.; Fang, Y.; Luo, Y.; Zeng, G.; Deng, J.; Tan, X.; Tang, N.; Li, X.; He, X.; Feng, C.; et al. Magnetic nanoferromanganese oxides modified biochar derived from pine sawdust for adsorption of tetracycline hydrochloride. Environ. Sci. Pollut. Res. 2019, 26, 5892–5903. [CrossRef]40. Yang, Y.; Hu, X.; Zhao, Y.; Cui, L.; Huang, Z.; Long, J.; Xu, J.; Deng, J.; Wu, C.; Liao, W. Decontamination of tetracycline by thiourea-dioxide–reduced magnetic graphene oxide: Effects of pH, ionic strength, and humic acid concentration. J. Colloid Interface Sci. 2017, 495, 68–77. [CrossRef]41. Martins, A.C.; Pezoti, O.; Cazetta, A.L.; Bedin, K.C.; Yamazaki, D.A.; Bandoch, G.F.; Asefa, T.; Visentainer, J.V.; Almeida, V.C. Removal of tetracycline by NaOH-activated carbon produced from macadamia nut shells: Kinetic and equilibrium studies. Chem. Eng. J. 2015, 260, 291–299. [CrossRef]42. Gupta, S.S.; Bhattacharyya, K.G. Kinetics of adsorption of metal ions on inorganic materials: A review. Adv. Colloid Interface Sci. 2011, 162, 39–58. [CrossRef] [PubMed]43. Agarry, S.E.; Aworanti, O.A. Kinetics, Isothermal and Thermodynamic Modelling Studies of Hexavalent Chromium Ions Adsorption from Simulated Wastewater onto Parkia biglobosa-Sawdust Derived Acid-Steam. Act. Carbon. Appl. J. Envir. Eng. Sci. 2017, 3, 58–76. [CrossRef]44. De Souza, F.M.; Dos Santos, O.A.A.; Vieira, M.G.A. Adsorption of herbicide 2,4-D from aqueous solution using organo-modified bentonite clay. Environ. Sci. Pollut. Res. 2019, 26, 18329–18342. [CrossRef]45. Gago, D.; Chagas, R.; Ferreira, L.M.; Velizarov, S.; Coelhoso, I. A novel cellulose-based polymer for efficient removal of methylene blue. Membranes 2020, 10, 13. [CrossRef]46. Cazalbou, S.; Bertrand, G.; Drouet, C. Tetracycline-loaded biomimetic apatite: An adsorption study. J. Phys. Chem. B 2015, 119, 3014–3024. [CrossRef] [PubMed]47. Acosta, R.; Fierro, V.; De Yuso, A.M.; Nabarlatz, D.; Celzard, A. Tetracycline adsorption onto activated carbons produced by KOH activation of tyre pyrolysis char. Chemosphere 2016, 149, 168–176. [CrossRef]48. Chaabane, L.; Beyou, E.; Baouab, M.H.V. Preparation of a novel zwitterionic graphene oxide-based adsorbent to remove of heavy metal ions from water: Modeling and comparative studies. Adv. Powder Technol. 2021, 32, 2502–2516. [CrossRef]49. Wojtacha-Rychter, K.; Howaniec, N.; Smoli ´nski, A. Effect of porous structure of coal on propylene adsorption from gas mixtures. Sci. Rep. 2020, 10, 11277. [CrossRef]50. Liu, W.; Zhang, Y.; Wang, S.; Bai, L.; Deng, Y.; Tao, J. Effect of pore size distribution and amination on adsorption capacities of polymeric adsorbents. Molecules 2021, 26, 5267. [CrossRef]51. Huízar-Félix, A.M.; Aguilar-Flores, C.; Martínez-de-la Cruz, A.; Barandiarán, J.M.; Sepúlveda-Guzmán, S.; Cruz-Silva, R. Removal of tetracycline pollutants by adsorption and magnetic separation using reduced graphene oxide decorated with α-Fe2O3 nanoparticles. Nanomaterials 2019, 9, 313. [CrossRef] [PubMed]52. Ranjbari, S.; Tanhaei, B.; Ayati, A.; Khadempir, S.; Sillanpää, M. Efficient tetracycline adsorptive removal using tricaprylmethylammonium chloride conjugated chitosan hydrogel beads: Mechanism, kinetic, isotherms and thermodynamic study. Int. J. Biol. Macromol. 2020, 155, 421–429. [CrossRef] [PubMed]53. Zhang, Z.; Ding, C.; Li, Y.; Ke, H.; Cheng, G. Efficient removal of tetracycline hydrochloride from aqueous solution by mesoporous cage MOF-818. SN Appl. Sci. 2020, 2, 669. [CrossRef]54. Erdem, S.; Öztekin, M.; Açıkel, Y.S. Investigation of tetracycline removal from aqueous solutions using halloysite/chitosan nanocomposites and halloysite nanotubes/alginate hydrogel beads. Environ. Nanotechnol. Monit. Manag. 2021, 16, 100576. [CrossRef]55. Rathod, M.; Haldar, S.; Basha, S. Nanocrystalline cellulose for removal of tetracycline hydrochloride from water via biosorption: Equilibrium, kinetic and thermodynamic studies. Ecol. Eng. 2015, 84, 240–249. [CrossRef]56. Lin, Y.; Xu, S.; Li, J. Fast and highly efficient tetracyclines removal from environmental waters by graphene oxide functionalized magnetic particles. Chem. Eng. J. 2013, 225, 679–685. [CrossRef]57. Chen, Y.; Wang, F.; Duan, L.; Yang, H.; Gao, J. Tetracycline adsorption onto rice husk ash, an agricultural waste: Its kinetic and thermodynamic studies. J. Mol. Liq. 2016, 222, 487–494. [CrossRef]1912214AntibioticsEmerging pollutantsIron oxide nanoparticlesMagnetic nanocompositesPublicationORIGINALHighly Efficient Adsorption of Tetracycline Using Chitosan-Based Magnetic Adsorbent.pdfHighly Efficient Adsorption of Tetracycline Using Chitosan-Based Magnetic Adsorbent.pdfArtículoapplication/pdf5677343https://repositorio.cuc.edu.co/bitstreams/e61f29ee-67c4-4ffc-8f8e-764e616f0f7b/download52890781da1141efddb5a82d9a68096fMD51LICENSElicense.txtlicense.txttext/plain; charset=utf-814828https://repositorio.cuc.edu.co/bitstreams/72eb73b8-857a-4f6e-bcce-6928f856ec0d/download2f9959eaf5b71fae44bbf9ec84150c7aMD52TEXTHighly Efficient Adsorption of Tetracycline Using Chitosan-Based Magnetic Adsorbent.pdf.txtHighly Efficient Adsorption of Tetracycline Using Chitosan-Based Magnetic Adsorbent.pdf.txtExtracted texttext/plain78603https://repositorio.cuc.edu.co/bitstreams/193da81c-a65d-4b95-ac8b-5a4781292b03/download379284d40ce0304845d1b6c3e885b5fbMD53THUMBNAILHighly Efficient Adsorption of Tetracycline Using Chitosan-Based Magnetic Adsorbent.pdf.jpgHighly Efficient Adsorption of Tetracycline Using Chitosan-Based Magnetic Adsorbent.pdf.jpgGenerated Thumbnailimage/jpeg15909https://repositorio.cuc.edu.co/bitstreams/5e773783-9b90-44ad-b7ee-4568e24cef02/downloadee7e61fae7f0ecd4f420e074ca8b201eMD5411323/10936oai:repositorio.cuc.edu.co:11323/109362024-09-17 11:09:48.388https://creativecommons.org/licenses/by/4.0/© 2022 by the authors. Licensee MDPI, Basel, Switzerland.open.accesshttps://repositorio.cuc.edu.coRepositorio de la Universidad de la Costa CUCrepdigital@cuc.edu.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

Publicaciones similares