Euterpe oleracea-based biochar for clonazepam adsorption: synthesis, characterization, adsorption properties, and toxicity assays
The consumption of açaí fruit (Euterpe oleracea) has largely increased worldwide, resulting in a significant increase in the demand for its pulp. As a result, the small producing communities end up with large amounts of açaí endocarp residues, creating local environmental pollution problems. Therefo...
- Autores:
-
Santos, Ronald K. S.
Schnorr, Carlos Eduardo
Silva Oliveira, Luis Felipe
Nascimento, Bruna F.
Cavalcanti, Jorge V. F. L.
Vieira, Yasmin
Dotto, Guilherme Luiz
da Motta Sobrinho, Maurício Alves
- Tipo de recurso:
- Article of investigation
- Fecha de publicación:
- 2023
- Institución:
- Corporación Universidad de la Costa
- Repositorio:
- REDICUC - Repositorio CUC
- Idioma:
- eng
- OAI Identifier:
- oai:repositorio.cuc.edu.co:11323/10465
- Acceso en línea:
- https://hdl.handle.net/11323/10465
https://repositorio.cuc.edu.co/
- Palabra clave:
- Biochar
Emerging contaminant
Clonazepam
Adsorption
Açaí
- Rights
- embargoedAccess
- License
- Atribución 4.0 Internacional (CC BY 4.0)
id |
RCUC2_7bd1a122b69f0f63a9e669a36219ff3e |
---|---|
oai_identifier_str |
oai:repositorio.cuc.edu.co:11323/10465 |
network_acronym_str |
RCUC2 |
network_name_str |
REDICUC - Repositorio CUC |
repository_id_str |
|
dc.title.eng.fl_str_mv |
Euterpe oleracea-based biochar for clonazepam adsorption: synthesis, characterization, adsorption properties, and toxicity assays |
title |
Euterpe oleracea-based biochar for clonazepam adsorption: synthesis, characterization, adsorption properties, and toxicity assays |
spellingShingle |
Euterpe oleracea-based biochar for clonazepam adsorption: synthesis, characterization, adsorption properties, and toxicity assays Biochar Emerging contaminant Clonazepam Adsorption Açaí |
title_short |
Euterpe oleracea-based biochar for clonazepam adsorption: synthesis, characterization, adsorption properties, and toxicity assays |
title_full |
Euterpe oleracea-based biochar for clonazepam adsorption: synthesis, characterization, adsorption properties, and toxicity assays |
title_fullStr |
Euterpe oleracea-based biochar for clonazepam adsorption: synthesis, characterization, adsorption properties, and toxicity assays |
title_full_unstemmed |
Euterpe oleracea-based biochar for clonazepam adsorption: synthesis, characterization, adsorption properties, and toxicity assays |
title_sort |
Euterpe oleracea-based biochar for clonazepam adsorption: synthesis, characterization, adsorption properties, and toxicity assays |
dc.creator.fl_str_mv |
Santos, Ronald K. S. Schnorr, Carlos Eduardo Silva Oliveira, Luis Felipe Nascimento, Bruna F. Cavalcanti, Jorge V. F. L. Vieira, Yasmin Dotto, Guilherme Luiz da Motta Sobrinho, Maurício Alves |
dc.contributor.author.none.fl_str_mv |
Santos, Ronald K. S. Schnorr, Carlos Eduardo Silva Oliveira, Luis Felipe Nascimento, Bruna F. Cavalcanti, Jorge V. F. L. Vieira, Yasmin Dotto, Guilherme Luiz da Motta Sobrinho, Maurício Alves |
dc.subject.proposal.eng.fl_str_mv |
Biochar Emerging contaminant Clonazepam Adsorption Açaí |
topic |
Biochar Emerging contaminant Clonazepam Adsorption Açaí |
description |
The consumption of açaí fruit (Euterpe oleracea) has largely increased worldwide, resulting in a significant increase in the demand for its pulp. As a result, the small producing communities end up with large amounts of açaí endocarp residues, creating local environmental pollution problems. Therefore, chemical and physical routes were investigated for producing açaí endocarp adsorbents to propose a locally viable solution for this problem. The adsorption properties of the produced biochars were tested for clonazepam (CZM) removal, and the toxicity of the final solutions was evaluated. The results revealed that the chemical route generated biochar with about twice the surface area and pore volume (762 m2 g−1 and 0.098 cm3 g−1) than the physical route (498 m2 g−1 and 0.048 cm3 g−1). Furthermore, the Sips isotherm better described the CZM adsorption equilibrium for both biochars, with qs values of 26.94 and 61.86 mg g−1 for the physical- and chemical-activated adsorbents. Moreover, recycling studies were performed, and the chemical-activated biochar was stable for up to three cycles, reaching removal rates superior to 80%. Besides, the final toxicity decreased after the adsorptive treatment. Therefore, chemical activation can be used as a simple and effective method for producing stable and compelling adsorbents as an elegant way of adding value to the residues from açaí production, helping solve local environmental problems. |
publishDate |
2023 |
dc.date.accessioned.none.fl_str_mv |
2023-09-11T18:56:48Z |
dc.date.available.none.fl_str_mv |
2023-09-11T18:56:48Z 2024-02-25 |
dc.date.issued.none.fl_str_mv |
2023-02-25 |
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/draft |
dc.type.coarversion.spa.fl_str_mv |
http://purl.org/coar/version/c_b1a7d7d4d402bcce |
format |
http://purl.org/coar/resource_type/c_2df8fbb1 |
status_str |
draft |
dc.identifier.citation.spa.fl_str_mv |
Santos, R.K.S., Schnorr, C., Silva, L.F.O. et al. Euterpe oleracea-based biochar for clonazepam adsorption: synthesis, characterization, adsorption properties, and toxicity assays. Environ Sci Pollut Res 30, 52485–52497 (2023). https://doi.org/10.1007/s11356-023-26044-y |
dc.identifier.issn.spa.fl_str_mv |
0944-1344 |
dc.identifier.uri.none.fl_str_mv |
https://hdl.handle.net/11323/10465 |
dc.identifier.doi.none.fl_str_mv |
10.1007/s11356-023-26044-y |
dc.identifier.eissn.spa.fl_str_mv |
1614-7499 |
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 |
Santos, R.K.S., Schnorr, C., Silva, L.F.O. et al. Euterpe oleracea-based biochar for clonazepam adsorption: synthesis, characterization, adsorption properties, and toxicity assays. Environ Sci Pollut Res 30, 52485–52497 (2023). https://doi.org/10.1007/s11356-023-26044-y 0944-1344 10.1007/s11356-023-26044-y 1614-7499 Corporación Universidad de la Costa REDICUC - Repositorio CUC |
url |
https://hdl.handle.net/11323/10465 https://repositorio.cuc.edu.co/ |
dc.language.iso.spa.fl_str_mv |
eng |
language |
eng |
dc.relation.ispartofjournal.spa.fl_str_mv |
Environmental Science and Pollution Research |
dc.relation.references.spa.fl_str_mv |
Barrett EP, Joyner LG, Halenda PP (1951) The determination of pore volume and area distributions in porous substances. I. computations from nitrogen isotherms. J Am Chem Soc 73:373–380 Calisto V, Ferreira CIA, Oliveira JABP, Otero M, Esteves VI (2015) Adsorptive removal of pharmaceuticals from water by commercial and waste-based carbons. J. Environ. Manage. 152:83–90. https://doi.org/10.1016/J.JENVMAN.2015.01.019 Coughlan B, Larkin PM, Physical sorption in transition metal loaded molecular sieves: application of the Koble-Corrigan and other isotherm equations to the equilibria , Proc. R. Ir. Acad. B. 77 (1977) 383–395. https://www.jstor.org/stable/20494301 (accessed June 9, 2022). Cunha MR, Lima EC, Lima DR, da Silva RS, Thue PS, Seliem MK, Sher F, dos Reis GS, Larsson SH, Removal of captopril pharmaceutical from synthetic pharmaceutical-industry wastewaters: use of activated carbon derived from Butia catarinensis, J. Environ. Chem. Eng. 8 (2020) 104506. https://doi.org/10.1016/J.JECE.2020.104506. Fernández P, Regenjo M, Fernández AM, Lorenzo RA, Carro AM (2014) Optimization of ultrasound-assisted dispersive liquid–liquid microextraction for ultra performance liquid chromatography determination of benzodiazepines in urine and hospital wastewater. Anal. Methods. 6:8239–8246. https://doi.org/10.1039/C4AY01348D Flilissa A, Venkataraman S, Laouameur K, Beroual A, Flilissa O, Omine K, Chaabane T, A. Darchen, Surface modification of aluminum phosphate by sodium dodecylbenzenesulfonate (SDBS): a new nano-structured adsorbent for an improved removal of Ponceau S", J. Environ. Chem. Eng. 8 (2020) 103625. https://doi.org/10.1016/J.JECE.2019.103625. Gao Q, Liu H, Cheng C, Li K, Zhang J, Zhang C, Li Y (2013) Preparation and characterization of activated carbon from wool waste and the comparison of muffle furnace and microwave heating methods. Powder Technol. 249:234–240. https://doi.org/10.1016/J.POWTEC.2013.08.029 Georgin J, Franco DSP, Netto MS, Allasia D, Oliveira MLS, Dotto GL (2020) Evaluation of Ocotea puberula bark powder (OPBP) as an effective adsorbent to uptake crystal violet from colored effluents: alternative kinetic approaches. Environ. Sci. Pollut. Res. 27:25727–25739. https://doi.org/10.1007/S11356-020-08854-6/FIGURES/6 Gerber M, Lucia T, Corrêa L, Neto JEP, Corrêa EK (2017) Phytotoxicity of effluents from swine slaughterhouses using lettuce and cucumber seeds as bioindicators. Sci. Total Environ. 592:86–90 Guo Y, Qi J, Yang S, Yu K, Wang Z, Xu H (2003) Adsorption of Cr(VI) on micro- and mesoporous rice husk-based active carbon. Mater. Chem. Phys. 78:132–137. https://doi.org/10.1016/S0254-0584(02)00302-4 Guy M, Mathieu M, Anastopoulos IP, Martínez MG, Rousseau F, Dotto GL, Oliveira HP, Lima EC, Thyrel M, Larsson SH, Reis GS (2022) Process parameters optimization, characterization, and application of KOH-activated Norway spruce bark graphitic biochars for efficient azo dye adsorption. Molecules 27(2):456. https://doi.org/10.3390/molecules27020456 Hameed BH, Tan IAW, Ahmad AL (2008) Adsorption isotherm, kinetic modeling and mechanism of 2,4,6-trichlorophenol on coconut husk-based activated carbon. Chem. Eng. J. 144:235–244. https://doi.org/10.1016/J.CEJ.2008.01.028 Hey G, Grabic R, Ledin A, la Cour Jansen J, Andersen HR (2012) Oxidation of pharmaceuticals by chlorine dioxide in biologically treated wastewater. Chem. Eng. J. 185–186:236–242. https://doi.org/10.1016/J.CEJ.2012.01.093 Ho YS, McKay G (1998) Sorption of dye from aqueous solution by peat. Chem. Eng. J. 70:115–124. https://doi.org/10.1016/S0923-0467(98)00076-1 Honeychurch KC, Brooks J, Hart JP (2016) Development of a voltammetric assay, using screen-printed electrodes, for clonazepam and its application to beverage and serum samples. Talanta. 147:510–515. https://doi.org/10.1016/J.TALANTA.2015.10.032 Kaplan SA, Alexander K, Jack M, Puglisi CV, de Silva JAF, Lee TL, Weinfeld RE (1974) Pharmacokinetic profiles of clonazepam in dog and humans and of flunitrazepam in dog. J. Pharm. Sci. 63:527–532. https://doi.org/10.1002/JPS.2600630407 Kasperiski FM, Lima EC, Umpierres CS, dos Reis GS, Thue PS, Lima DR, Dias SLP, Saucier C, da Costa JB (2018) Production of porous activated carbons from Caesalpinia ferrea seed pod wastes: highly efficient removal of captopril from aqueous solutions. J. Clean. Prod. 197:919–929. https://doi.org/10.1016/J.JCLEPRO.2018.06.146 Kerkhoff CM, da Boit Martinello K, Franco DSP, Netto MS, Georgin J, Foletto EL, Piccilli DGA, Silva LFO, Dotto GL (2021) Adsorption of ketoprofen and paracetamol and treatment of a synthetic mixture by novel porous carbon derived from Butia capitata endocarp. J Mol Liq 339:117184 Khoshroo A, Hosseinzadeh L, Sobhani-Nasab A, Rahimi-Nasrabadi M, Ahmadi F (2019) Silver nanofibers/ionic liquid nanocomposite based electrochemical sensor for detection of clonazepam via electrochemically amplified detection. Microchem. J. 145:1185–1190. https://doi.org/10.1016/J.MICROC.2018.12.049 Lagergren SK, About the theory of so-called adsorption of soluble substances, K. Sven. Vetenskapsakademiens Handl. (1898) 1–39. Langmuir I (1918) The adsorption of gases on plane surfaces of glass, mica and platinum. J. Am. Chem. Soc. 40:1361–1403. https://doi.org/10.1021/JA02242A004 Laouameur K, Flilissa A, Erto A, Balsamo M, Ernst B, Dotto GL, Benguerba Y (2021) Clorazepate removal from aqueous solution by adsorption onto maghnite: experimental and theoretical analysis. J Mol Liq 328:115430 Leichtweis J, Vieira Y, Welter N, Silvestri S, Dotto GL, Carissimi E (2022) A review of the occurrence, disposal, determination, toxicity and remediation technologies of the tetracycline antibiotic. Process Saf. Environ. Prot. 160:25–40. https://doi.org/10.1016/J.PSEP.2022.01.085 Li Y, Li Y, Zang H, Chen L, Meng Z, Li H, Ci L, Du Q, Wang D, Wang C, Li H, Xia Y (2018) ZnCl2-activated carbon from soybean dregs as a high efficiency adsorbent for cationic dye removal: isotherm, kinetic, and thermodynamic studies. Environ. Technol. 41:2013–2023. https://doi.org/10.1080/09593330.2018.1554006 Lima EC, Hosseini-Bandegharaei A, Moreno-Piraján JC, Anastopoulos I (2019) A critical review of the estimation of the thermodynamic parameters on adsorption equilibria. wrong use of equilibrium constant in the Van’t Hoof equation for calculation of thermodynamic parameters of adsorption,. J Mol Liq 273:425–434 Mbarki F, Selmi T, Kesraoui A, Seffen M (2022) Low-cost activated carbon preparation from corn stigmata fibers chemically activated using H3PO4, ZnCl2 and KOH: study of methylene blue adsorption, stochastic isotherm and fractal kinetic. Ind Crops Prod 178:114546 Mccabe WL, Smith JC, Harriott P; Unit operations of chemical engineering, 6th ed., 2010. Mendes PM, Becker R, Corrêa LB, Bianchi I, Dai Prá MA, Lucia T, Corrêa EK (2016) Phytotoxicity as an indicator of stability of broiler production residues. J. Environ. Manage. 167:156–159 Moura FCC, Rios RDF, Galvão BRL (2018) Emerging contaminants removal by granular activated carbon obtained from residual Macauba biomass. Environ. Sci. Pollut. Res. 25:26482–26492. https://doi.org/10.1007/S11356-018-2713-8/FIGURES/8 Nardi AE, Machado S, Ferreira Almada L, Paes F, Cardoso Silva A, Jose Marques R, Amrein R, Freire RC, Martin-Santos R, Cosci F, Hallak JE, Crippa JA, Arias-Carrion O (2013) Clonazepam for the treatment of panic disorder, curr. Drug Targets. 14:353–364. https://doi.org/10.2174/1389450111314030007 Nascimento, BF; Araujo, CMB; Nascimento, AC; Costa, GRB.; Gomes, BFML; Silva, MP; Santos, RKS; Motta Sobrinho, MA; Adsorption of reactive black 5 and basic blue 12 using biochar from gasification residues: batch tests and fixed-bed breakthrough predictions for wastewater treatment. Bioresource Technology Reports, v. 15, p. 100767, 2021. https://doi.org/10.1016/j.biteb.2021.100767 Nascimento GFO, Costa GRB, Araújo CMB, Ghislandi MG, Motta Sobrinho MA (2020) Graphene-based materials production and application in textile wastewater treatment: color removal and phytotoxicity using Lactuca sativa as bioindicator. Journal of Environmental Science and Health. Part A 55(1):97–106 Newcombe G, Hayes R, Drikas M (1993) Granular activated carbon: importance of surface properties in the adsorption of naturally occurring organics. Colloids Surfaces A Physicochem. Eng. Asp. 78:65–71. https://doi.org/10.1016/0927-7757(93)80311-2 Nunes CN, Egéa dos Anjos V, Pércio Quináia S, Determination of diazepam and clonazepam in natural water – a voltammetric study, electroanalysis. 30 (2018) 109–118. https://doi.org/10.1002/ELAN.201700566. Pishnamazi M, Ghasemi S, Khosravi A, ZabihiSahebi A, Hasan-Zadeh A, Borghei SM (2021) Removal of Cu (ll) from industrial wastewater using poly (acrylamide-co-2-acrylamide-2-methyl propane sulfonic acid)/graphene oxide/sodium alginate hydrogel: isotherm, kinetics, and optimization study. J Water Process Eng 42:102144 Reis GS, Larsson SH, Thyrel M, Pham TN, Lima EC, Oliveira HP, Dotto GL (2021) Preparation and application of efficient biobased carbon adsorbents prepared from spruce bark residues for efficient removal of reactive dyes and colors from synthetic effluents. Coatings 11(7):772. https://doi.org/10.3390/coatings11070772 Reis, GS; Guy, M; Mathieu, M; Jebrane, M; Lima, EC; Thyrel, M; Dotto, GL; Larsson, SH; A comparative study of chemical treatment by MgCl2, ZnSO4, ZnCl2, and KOH on physicochemical properties and acetaminophen adsorption performance of biobased porous materials from tree bark residues. Colloids and Surfaces A: Physicochemical and Engineering Aspects, v. 642, p. 128626, 2022. https://doi.org/10.1016/j.colsurfa.2022.128626 Ribeiro LAS, Thim GP, Alvarez-Mendez MO, dos Reis Coutinho A, de Moraes NP, Rodrigues LA (2018) Preparation, characterization, and application of low-cost açaí seed-based activated carbon for phenol adsorption. Int. J. Environ. Res. 12:755–764. https://doi.org/10.1007/S41742-018-0128-5/TABLES/5 Rossetto R, Maciel GM, Bortolini DG, Ribeiro VR, Haminiuk CWI (2020) Acai pulp and seeds as emerging sources of phenolic compounds for enrichment of residual yeasts (Saccharomyces cerevisiae) through biosorption process. LWT 128:109447 Salem S, Teimouri Z, Salem A (2020) Fabrication of magnetic activated carbon by carbothermal functionalization of agriculture waste via microwave-assisted technique for cationic dye adsorption. Adv. Powder Technol. 31:4301–4309. https://doi.org/10.1016/J.APT.2020.09.007 Salomón YLO, Georgin J, Reis GS, Lima EC, Oliveira MLS, Franco DSP, Netto MS, Allasia D, Dotto GL (2020) Utilization of pacara earpod tree (Enterolobium contortisilquum) and ironwood (Caesalpinia leiostachya) seeds as low-cost biosorbents for removal of basic fuchsin. Environmental Science and Pollution Research 27(26):33307–33320. https://doi.org/10.1007/s11356-020-09471-z Sato MK, de Lima HV, Costa HN, Rodrigues S, Pedroso AJS, de Freitas Maia CMB (2019) Biochar from Acai agroindustry waste: study of pyrolysis conditions. Waste Manag. 96:158–167. https://doi.org/10.1016/J.WASMAN.2019.07.022 Sato MK, de Lima HV, Costa AN, Rodrigues S, Mooney SJ, Clarke M, Pedroso AJS, de Freitas Maia CMB (2020) Biochar as a sustainable alternative to Açaí waste disposal in Amazon, Brazil. Process Saf. Environ. Prot. 139:36–46. https://doi.org/10.1016/J.PSEP.2020.04.001 Sips R (1948) Combined form of Langmuir and Freundlich equations. J. Chem. Phys. 16:490–495 Starling MCVM, Amorim CC, Leão MMD (2019) Occurrence, control and fate of contaminants of emerging concern in environmental compartments in Brazil. J. Hazard. Mater. 372:17–36. https://doi.org/10.1016/J.JHAZMAT.2018.04.043 Sun K, Huang Q, Chi Y, Yan J (2018) Effect of ZnCl2-activated biochar on catalytic pyrolysis of mixed waste plastics for producing aromatic-enriched oil. Waste Manag. 81:128–137. https://doi.org/10.1016/J.WASMAN.2018.09.054 Thommes M, Kaneko K, Neimark AV, Olivier JP, Rodriguez-Reinoso F, Rouquerol J, Sing KSW (2015) Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure Appl. Chem. 87:1051–1069. https://doi.org/10.1515/PAC-2014-1117/PDF Tian D, Xu Z, Zhang D, Chen W, Cai J, Deng H, Sun Z, Zhou Y (2019) Micro–mesoporous carbon from cotton waste activated by FeCl3/ZnCl2: preparation, optimization, characterization and adsorption of methylene blue and eriochrome black T. J. Solid State Chem. 269:580–587. https://doi.org/10.1016/J.JSSC.2018.10.035 Uǧurlu M, Gürses A, Açikyildiz M (2008) Comparison of textile dyeing effluent adsorption on commercial activated carbon and activated carbon prepared from olive stone by ZnCl2 activation. Microporous Mesoporous Mater. 111:228–235. https://doi.org/10.1016/J.MICROMESO.2007.07.034 Vieira Y, dos Santos JMN, Georgin J, Oliveira MLS, Pinto D, Dotto GL (2021) An overview of forest residues as promising low-cost adsorbents. Gondwana Res. https://doi.org/10.1016/J.GR.2021.06.018 Vieira Y, Lima EC, Foletto EL, Dotto GL, Microplastics physicochemical properties, specific adsorption modeling and their interaction with pharmaceuticals and other emerging contaminants, Sci. Total Environ. (2020) 141981. https://doi.org/10.1016/j.scitotenv.2020.141981. Vieira Y, Pereira HA, Leichtweis J, Mistura CM, Foletto EL, Oliveira LFS, Dotto GL (2021) Effective treatment of hospital wastewater with high-concentration diclofenac and ibuprofen using a promising technology based on degradation reaction catalyzed by Fe0 under microwave irradiation. Sci Total Environ 783:146991 Vinh NV, Zafar M, Behera SK, Park HS (2015) Arsenic(III) removal from aqueous solution by raw and zinc-loaded pine cone biochar: equilibrium, kinetics, and thermodynamics studies. Int. J. Environ. Sci. Technol. 12:1283–1294. https://doi.org/10.1007/S13762-014-0507-1/TABLES/4 Xia D, Tan F, Zhang C, Jiang X, Chen Z, Li H, Zheng Y, Li Q, Wang Y (2016) ZnCl2-activated biochar from biogas residue facilitates aqueous As(III) removal. Appl. Surf. Sci. 377:361–369. https://doi.org/10.1016/J.APSUSC.2016.03.109 Yağmur HK, Kaya I (2021) Synthesis and characterization of magnetic ZnCl2-activated carbon produced from coconut shell for the adsorption of methylene blue. J Mol Struct 1232:130071 Zhang S, Zhu S, Zhang H, Liu X, Xiong Y (2020) Synthesis and characterization of rice husk-based magnetic porous carbon by pyrolysis of pretreated rice husk with FeCl3 and ZnCl2. J Anal Appl Pyrolysis 147:104806 |
dc.relation.citationendpage.spa.fl_str_mv |
52497 |
dc.relation.citationstartpage.spa.fl_str_mv |
52485 |
dc.relation.citationvolume.spa.fl_str_mv |
30 |
dc.rights.eng.fl_str_mv |
© 2023 Springer Nature |
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/embargoedAccess |
dc.rights.coar.spa.fl_str_mv |
http://purl.org/coar/access_right/c_f1cf |
rights_invalid_str_mv |
Atribución 4.0 Internacional (CC BY 4.0) © 2023 Springer Nature https://creativecommons.org/licenses/by/4.0/ http://purl.org/coar/access_right/c_f1cf |
eu_rights_str_mv |
embargoedAccess |
dc.format.extent.spa.fl_str_mv |
1 página |
dc.format.mimetype.spa.fl_str_mv |
application/pdf |
dc.publisher.spa.fl_str_mv |
Springer Science + Business Media |
dc.publisher.place.spa.fl_str_mv |
Germany |
dc.source.spa.fl_str_mv |
https://link.springer.com/article/10.1007/s11356-023-26044-y |
institution |
Corporación Universidad de la Costa |
bitstream.url.fl_str_mv |
https://repositorio.cuc.edu.co/bitstreams/2f4287d7-a18b-4729-a528-02a902b851b1/download https://repositorio.cuc.edu.co/bitstreams/40f439ae-affb-4c8c-a11d-bb1457f07c34/download https://repositorio.cuc.edu.co/bitstreams/3875ae55-762a-4ff4-8a95-dcd8782229de/download https://repositorio.cuc.edu.co/bitstreams/5832377c-5ca2-4307-8cbd-82e0e66081ac/download |
bitstream.checksum.fl_str_mv |
5b4e0321e4a2e8984c5f83e1a4ceb981 2f9959eaf5b71fae44bbf9ec84150c7a fb18d49d9166263b19eb6885e6edcd71 7d6c1080366d821ab49e31cb04260509 |
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_ |
1811760684763971584 |
spelling |
Atribución 4.0 Internacional (CC BY 4.0)© 2023 Springer Naturehttps://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/embargoedAccesshttp://purl.org/coar/access_right/c_f1cfSantos, Ronald K. S.Schnorr, Carlos EduardoSilva Oliveira, Luis FelipeNascimento, Bruna F.Cavalcanti, Jorge V. F. L.Vieira, YasminDotto, Guilherme Luizda Motta Sobrinho, Maurício Alves2023-09-11T18:56:48Z2024-02-252023-09-11T18:56:48Z2023-02-25Santos, R.K.S., Schnorr, C., Silva, L.F.O. et al. Euterpe oleracea-based biochar for clonazepam adsorption: synthesis, characterization, adsorption properties, and toxicity assays. Environ Sci Pollut Res 30, 52485–52497 (2023). https://doi.org/10.1007/s11356-023-26044-y0944-1344https://hdl.handle.net/11323/1046510.1007/s11356-023-26044-y1614-7499Corporación Universidad de la CostaREDICUC - Repositorio CUChttps://repositorio.cuc.edu.co/The consumption of açaí fruit (Euterpe oleracea) has largely increased worldwide, resulting in a significant increase in the demand for its pulp. As a result, the small producing communities end up with large amounts of açaí endocarp residues, creating local environmental pollution problems. Therefore, chemical and physical routes were investigated for producing açaí endocarp adsorbents to propose a locally viable solution for this problem. The adsorption properties of the produced biochars were tested for clonazepam (CZM) removal, and the toxicity of the final solutions was evaluated. The results revealed that the chemical route generated biochar with about twice the surface area and pore volume (762 m2 g−1 and 0.098 cm3 g−1) than the physical route (498 m2 g−1 and 0.048 cm3 g−1). Furthermore, the Sips isotherm better described the CZM adsorption equilibrium for both biochars, with qs values of 26.94 and 61.86 mg g−1 for the physical- and chemical-activated adsorbents. Moreover, recycling studies were performed, and the chemical-activated biochar was stable for up to three cycles, reaching removal rates superior to 80%. Besides, the final toxicity decreased after the adsorptive treatment. Therefore, chemical activation can be used as a simple and effective method for producing stable and compelling adsorbents as an elegant way of adding value to the residues from açaí production, helping solve local environmental problems.1 páginaapplication/pdfengSpringer Science + Business MediaGermanyhttps://link.springer.com/article/10.1007/s11356-023-26044-yEuterpe oleracea-based biochar for clonazepam adsorption: synthesis, characterization, adsorption properties, and toxicity assaysArtículo de revistahttp://purl.org/coar/resource_type/c_2df8fbb1Textinfo:eu-repo/semantics/articlehttp://purl.org/redcol/resource_type/ARTinfo:eu-repo/semantics/drafthttp://purl.org/coar/version/c_b1a7d7d4d402bcceEnvironmental Science and Pollution ResearchBarrett EP, Joyner LG, Halenda PP (1951) The determination of pore volume and area distributions in porous substances. I. computations from nitrogen isotherms. J Am Chem Soc 73:373–380Calisto V, Ferreira CIA, Oliveira JABP, Otero M, Esteves VI (2015) Adsorptive removal of pharmaceuticals from water by commercial and waste-based carbons. J. Environ. Manage. 152:83–90. https://doi.org/10.1016/J.JENVMAN.2015.01.019Coughlan B, Larkin PM, Physical sorption in transition metal loaded molecular sieves: application of the Koble-Corrigan and other isotherm equations to the equilibria , Proc. R. Ir. Acad. B. 77 (1977) 383–395. https://www.jstor.org/stable/20494301 (accessed June 9, 2022).Cunha MR, Lima EC, Lima DR, da Silva RS, Thue PS, Seliem MK, Sher F, dos Reis GS, Larsson SH, Removal of captopril pharmaceutical from synthetic pharmaceutical-industry wastewaters: use of activated carbon derived from Butia catarinensis, J. Environ. Chem. Eng. 8 (2020) 104506. https://doi.org/10.1016/J.JECE.2020.104506.Fernández P, Regenjo M, Fernández AM, Lorenzo RA, Carro AM (2014) Optimization of ultrasound-assisted dispersive liquid–liquid microextraction for ultra performance liquid chromatography determination of benzodiazepines in urine and hospital wastewater. Anal. Methods. 6:8239–8246. https://doi.org/10.1039/C4AY01348DFlilissa A, Venkataraman S, Laouameur K, Beroual A, Flilissa O, Omine K, Chaabane T, A. Darchen, Surface modification of aluminum phosphate by sodium dodecylbenzenesulfonate (SDBS): a new nano-structured adsorbent for an improved removal of Ponceau S", J. Environ. Chem. Eng. 8 (2020) 103625. https://doi.org/10.1016/J.JECE.2019.103625.Gao Q, Liu H, Cheng C, Li K, Zhang J, Zhang C, Li Y (2013) Preparation and characterization of activated carbon from wool waste and the comparison of muffle furnace and microwave heating methods. Powder Technol. 249:234–240. https://doi.org/10.1016/J.POWTEC.2013.08.029Georgin J, Franco DSP, Netto MS, Allasia D, Oliveira MLS, Dotto GL (2020) Evaluation of Ocotea puberula bark powder (OPBP) as an effective adsorbent to uptake crystal violet from colored effluents: alternative kinetic approaches. Environ. Sci. Pollut. Res. 27:25727–25739. https://doi.org/10.1007/S11356-020-08854-6/FIGURES/6Gerber M, Lucia T, Corrêa L, Neto JEP, Corrêa EK (2017) Phytotoxicity of effluents from swine slaughterhouses using lettuce and cucumber seeds as bioindicators. Sci. Total Environ. 592:86–90Guo Y, Qi J, Yang S, Yu K, Wang Z, Xu H (2003) Adsorption of Cr(VI) on micro- and mesoporous rice husk-based active carbon. Mater. Chem. Phys. 78:132–137. https://doi.org/10.1016/S0254-0584(02)00302-4Guy M, Mathieu M, Anastopoulos IP, Martínez MG, Rousseau F, Dotto GL, Oliveira HP, Lima EC, Thyrel M, Larsson SH, Reis GS (2022) Process parameters optimization, characterization, and application of KOH-activated Norway spruce bark graphitic biochars for efficient azo dye adsorption. Molecules 27(2):456. https://doi.org/10.3390/molecules27020456Hameed BH, Tan IAW, Ahmad AL (2008) Adsorption isotherm, kinetic modeling and mechanism of 2,4,6-trichlorophenol on coconut husk-based activated carbon. Chem. Eng. J. 144:235–244. https://doi.org/10.1016/J.CEJ.2008.01.028Hey G, Grabic R, Ledin A, la Cour Jansen J, Andersen HR (2012) Oxidation of pharmaceuticals by chlorine dioxide in biologically treated wastewater. Chem. Eng. J. 185–186:236–242. https://doi.org/10.1016/J.CEJ.2012.01.093Ho YS, McKay G (1998) Sorption of dye from aqueous solution by peat. Chem. Eng. J. 70:115–124. https://doi.org/10.1016/S0923-0467(98)00076-1Honeychurch KC, Brooks J, Hart JP (2016) Development of a voltammetric assay, using screen-printed electrodes, for clonazepam and its application to beverage and serum samples. Talanta. 147:510–515. https://doi.org/10.1016/J.TALANTA.2015.10.032Kaplan SA, Alexander K, Jack M, Puglisi CV, de Silva JAF, Lee TL, Weinfeld RE (1974) Pharmacokinetic profiles of clonazepam in dog and humans and of flunitrazepam in dog. J. Pharm. Sci. 63:527–532. https://doi.org/10.1002/JPS.2600630407Kasperiski FM, Lima EC, Umpierres CS, dos Reis GS, Thue PS, Lima DR, Dias SLP, Saucier C, da Costa JB (2018) Production of porous activated carbons from Caesalpinia ferrea seed pod wastes: highly efficient removal of captopril from aqueous solutions. J. Clean. Prod. 197:919–929. https://doi.org/10.1016/J.JCLEPRO.2018.06.146Kerkhoff CM, da Boit Martinello K, Franco DSP, Netto MS, Georgin J, Foletto EL, Piccilli DGA, Silva LFO, Dotto GL (2021) Adsorption of ketoprofen and paracetamol and treatment of a synthetic mixture by novel porous carbon derived from Butia capitata endocarp. J Mol Liq 339:117184Khoshroo A, Hosseinzadeh L, Sobhani-Nasab A, Rahimi-Nasrabadi M, Ahmadi F (2019) Silver nanofibers/ionic liquid nanocomposite based electrochemical sensor for detection of clonazepam via electrochemically amplified detection. Microchem. J. 145:1185–1190. https://doi.org/10.1016/J.MICROC.2018.12.049Lagergren SK, About the theory of so-called adsorption of soluble substances, K. Sven. Vetenskapsakademiens Handl. (1898) 1–39.Langmuir I (1918) The adsorption of gases on plane surfaces of glass, mica and platinum. J. Am. Chem. Soc. 40:1361–1403. https://doi.org/10.1021/JA02242A004Laouameur K, Flilissa A, Erto A, Balsamo M, Ernst B, Dotto GL, Benguerba Y (2021) Clorazepate removal from aqueous solution by adsorption onto maghnite: experimental and theoretical analysis. J Mol Liq 328:115430Leichtweis J, Vieira Y, Welter N, Silvestri S, Dotto GL, Carissimi E (2022) A review of the occurrence, disposal, determination, toxicity and remediation technologies of the tetracycline antibiotic. Process Saf. Environ. Prot. 160:25–40. https://doi.org/10.1016/J.PSEP.2022.01.085Li Y, Li Y, Zang H, Chen L, Meng Z, Li H, Ci L, Du Q, Wang D, Wang C, Li H, Xia Y (2018) ZnCl2-activated carbon from soybean dregs as a high efficiency adsorbent for cationic dye removal: isotherm, kinetic, and thermodynamic studies. Environ. Technol. 41:2013–2023. https://doi.org/10.1080/09593330.2018.1554006Lima EC, Hosseini-Bandegharaei A, Moreno-Piraján JC, Anastopoulos I (2019) A critical review of the estimation of the thermodynamic parameters on adsorption equilibria. wrong use of equilibrium constant in the Van’t Hoof equation for calculation of thermodynamic parameters of adsorption,. J Mol Liq 273:425–434Mbarki F, Selmi T, Kesraoui A, Seffen M (2022) Low-cost activated carbon preparation from corn stigmata fibers chemically activated using H3PO4, ZnCl2 and KOH: study of methylene blue adsorption, stochastic isotherm and fractal kinetic. Ind Crops Prod 178:114546Mccabe WL, Smith JC, Harriott P; Unit operations of chemical engineering, 6th ed., 2010.Mendes PM, Becker R, Corrêa LB, Bianchi I, Dai Prá MA, Lucia T, Corrêa EK (2016) Phytotoxicity as an indicator of stability of broiler production residues. J. Environ. Manage. 167:156–159Moura FCC, Rios RDF, Galvão BRL (2018) Emerging contaminants removal by granular activated carbon obtained from residual Macauba biomass. Environ. Sci. Pollut. Res. 25:26482–26492. https://doi.org/10.1007/S11356-018-2713-8/FIGURES/8Nardi AE, Machado S, Ferreira Almada L, Paes F, Cardoso Silva A, Jose Marques R, Amrein R, Freire RC, Martin-Santos R, Cosci F, Hallak JE, Crippa JA, Arias-Carrion O (2013) Clonazepam for the treatment of panic disorder, curr. Drug Targets. 14:353–364. https://doi.org/10.2174/1389450111314030007Nascimento, BF; Araujo, CMB; Nascimento, AC; Costa, GRB.; Gomes, BFML; Silva, MP; Santos, RKS; Motta Sobrinho, MA; Adsorption of reactive black 5 and basic blue 12 using biochar from gasification residues: batch tests and fixed-bed breakthrough predictions for wastewater treatment. Bioresource Technology Reports, v. 15, p. 100767, 2021. https://doi.org/10.1016/j.biteb.2021.100767Nascimento GFO, Costa GRB, Araújo CMB, Ghislandi MG, Motta Sobrinho MA (2020) Graphene-based materials production and application in textile wastewater treatment: color removal and phytotoxicity using Lactuca sativa as bioindicator. Journal of Environmental Science and Health. Part A 55(1):97–106Newcombe G, Hayes R, Drikas M (1993) Granular activated carbon: importance of surface properties in the adsorption of naturally occurring organics. Colloids Surfaces A Physicochem. Eng. Asp. 78:65–71. https://doi.org/10.1016/0927-7757(93)80311-2Nunes CN, Egéa dos Anjos V, Pércio Quináia S, Determination of diazepam and clonazepam in natural water – a voltammetric study, electroanalysis. 30 (2018) 109–118. https://doi.org/10.1002/ELAN.201700566.Pishnamazi M, Ghasemi S, Khosravi A, ZabihiSahebi A, Hasan-Zadeh A, Borghei SM (2021) Removal of Cu (ll) from industrial wastewater using poly (acrylamide-co-2-acrylamide-2-methyl propane sulfonic acid)/graphene oxide/sodium alginate hydrogel: isotherm, kinetics, and optimization study. J Water Process Eng 42:102144Reis GS, Larsson SH, Thyrel M, Pham TN, Lima EC, Oliveira HP, Dotto GL (2021) Preparation and application of efficient biobased carbon adsorbents prepared from spruce bark residues for efficient removal of reactive dyes and colors from synthetic effluents. Coatings 11(7):772. https://doi.org/10.3390/coatings11070772Reis, GS; Guy, M; Mathieu, M; Jebrane, M; Lima, EC; Thyrel, M; Dotto, GL; Larsson, SH; A comparative study of chemical treatment by MgCl2, ZnSO4, ZnCl2, and KOH on physicochemical properties and acetaminophen adsorption performance of biobased porous materials from tree bark residues. Colloids and Surfaces A: Physicochemical and Engineering Aspects, v. 642, p. 128626, 2022. https://doi.org/10.1016/j.colsurfa.2022.128626Ribeiro LAS, Thim GP, Alvarez-Mendez MO, dos Reis Coutinho A, de Moraes NP, Rodrigues LA (2018) Preparation, characterization, and application of low-cost açaí seed-based activated carbon for phenol adsorption. Int. J. Environ. Res. 12:755–764. https://doi.org/10.1007/S41742-018-0128-5/TABLES/5Rossetto R, Maciel GM, Bortolini DG, Ribeiro VR, Haminiuk CWI (2020) Acai pulp and seeds as emerging sources of phenolic compounds for enrichment of residual yeasts (Saccharomyces cerevisiae) through biosorption process. LWT 128:109447Salem S, Teimouri Z, Salem A (2020) Fabrication of magnetic activated carbon by carbothermal functionalization of agriculture waste via microwave-assisted technique for cationic dye adsorption. Adv. Powder Technol. 31:4301–4309. https://doi.org/10.1016/J.APT.2020.09.007Salomón YLO, Georgin J, Reis GS, Lima EC, Oliveira MLS, Franco DSP, Netto MS, Allasia D, Dotto GL (2020) Utilization of pacara earpod tree (Enterolobium contortisilquum) and ironwood (Caesalpinia leiostachya) seeds as low-cost biosorbents for removal of basic fuchsin. Environmental Science and Pollution Research 27(26):33307–33320. https://doi.org/10.1007/s11356-020-09471-zSato MK, de Lima HV, Costa HN, Rodrigues S, Pedroso AJS, de Freitas Maia CMB (2019) Biochar from Acai agroindustry waste: study of pyrolysis conditions. Waste Manag. 96:158–167. https://doi.org/10.1016/J.WASMAN.2019.07.022Sato MK, de Lima HV, Costa AN, Rodrigues S, Mooney SJ, Clarke M, Pedroso AJS, de Freitas Maia CMB (2020) Biochar as a sustainable alternative to Açaí waste disposal in Amazon, Brazil. Process Saf. Environ. Prot. 139:36–46. https://doi.org/10.1016/J.PSEP.2020.04.001Sips R (1948) Combined form of Langmuir and Freundlich equations. J. Chem. Phys. 16:490–495Starling MCVM, Amorim CC, Leão MMD (2019) Occurrence, control and fate of contaminants of emerging concern in environmental compartments in Brazil. J. Hazard. Mater. 372:17–36. https://doi.org/10.1016/J.JHAZMAT.2018.04.043Sun K, Huang Q, Chi Y, Yan J (2018) Effect of ZnCl2-activated biochar on catalytic pyrolysis of mixed waste plastics for producing aromatic-enriched oil. Waste Manag. 81:128–137. https://doi.org/10.1016/J.WASMAN.2018.09.054Thommes M, Kaneko K, Neimark AV, Olivier JP, Rodriguez-Reinoso F, Rouquerol J, Sing KSW (2015) Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure Appl. Chem. 87:1051–1069. https://doi.org/10.1515/PAC-2014-1117/PDFTian D, Xu Z, Zhang D, Chen W, Cai J, Deng H, Sun Z, Zhou Y (2019) Micro–mesoporous carbon from cotton waste activated by FeCl3/ZnCl2: preparation, optimization, characterization and adsorption of methylene blue and eriochrome black T. J. Solid State Chem. 269:580–587. https://doi.org/10.1016/J.JSSC.2018.10.035Uǧurlu M, Gürses A, Açikyildiz M (2008) Comparison of textile dyeing effluent adsorption on commercial activated carbon and activated carbon prepared from olive stone by ZnCl2 activation. Microporous Mesoporous Mater. 111:228–235. https://doi.org/10.1016/J.MICROMESO.2007.07.034Vieira Y, dos Santos JMN, Georgin J, Oliveira MLS, Pinto D, Dotto GL (2021) An overview of forest residues as promising low-cost adsorbents. Gondwana Res. https://doi.org/10.1016/J.GR.2021.06.018Vieira Y, Lima EC, Foletto EL, Dotto GL, Microplastics physicochemical properties, specific adsorption modeling and their interaction with pharmaceuticals and other emerging contaminants, Sci. Total Environ. (2020) 141981. https://doi.org/10.1016/j.scitotenv.2020.141981.Vieira Y, Pereira HA, Leichtweis J, Mistura CM, Foletto EL, Oliveira LFS, Dotto GL (2021) Effective treatment of hospital wastewater with high-concentration diclofenac and ibuprofen using a promising technology based on degradation reaction catalyzed by Fe0 under microwave irradiation. Sci Total Environ 783:146991Vinh NV, Zafar M, Behera SK, Park HS (2015) Arsenic(III) removal from aqueous solution by raw and zinc-loaded pine cone biochar: equilibrium, kinetics, and thermodynamics studies. Int. J. Environ. Sci. Technol. 12:1283–1294. https://doi.org/10.1007/S13762-014-0507-1/TABLES/4Xia D, Tan F, Zhang C, Jiang X, Chen Z, Li H, Zheng Y, Li Q, Wang Y (2016) ZnCl2-activated biochar from biogas residue facilitates aqueous As(III) removal. Appl. Surf. Sci. 377:361–369. https://doi.org/10.1016/J.APSUSC.2016.03.109Yağmur HK, Kaya I (2021) Synthesis and characterization of magnetic ZnCl2-activated carbon produced from coconut shell for the adsorption of methylene blue. J Mol Struct 1232:130071Zhang S, Zhu S, Zhang H, Liu X, Xiong Y (2020) Synthesis and characterization of rice husk-based magnetic porous carbon by pyrolysis of pretreated rice husk with FeCl3 and ZnCl2. J Anal Appl Pyrolysis 147:104806524975248530BiocharEmerging contaminantClonazepamAdsorptionAçaíPublicationORIGINALEuterpe oleracea-based biochar for clonazepam adsorption.pdfEuterpe oleracea-based biochar for clonazepam adsorption.pdfArtículoapplication/pdf60921https://repositorio.cuc.edu.co/bitstreams/2f4287d7-a18b-4729-a528-02a902b851b1/download5b4e0321e4a2e8984c5f83e1a4ceb981MD51LICENSElicense.txtlicense.txttext/plain; charset=utf-814828https://repositorio.cuc.edu.co/bitstreams/40f439ae-affb-4c8c-a11d-bb1457f07c34/download2f9959eaf5b71fae44bbf9ec84150c7aMD52TEXTEuterpe oleracea-based biochar for clonazepam adsorption.pdf.txtEuterpe oleracea-based biochar for clonazepam adsorption.pdf.txtExtracted texttext/plain1879https://repositorio.cuc.edu.co/bitstreams/3875ae55-762a-4ff4-8a95-dcd8782229de/downloadfb18d49d9166263b19eb6885e6edcd71MD53THUMBNAILEuterpe oleracea-based biochar for clonazepam adsorption.pdf.jpgEuterpe oleracea-based biochar for clonazepam adsorption.pdf.jpgGenerated Thumbnailimage/jpeg16109https://repositorio.cuc.edu.co/bitstreams/5832377c-5ca2-4307-8cbd-82e0e66081ac/download7d6c1080366d821ab49e31cb04260509MD5411323/10465oai:repositorio.cuc.edu.co:11323/104652024-09-16 16:48:52.286https://creativecommons.org/licenses/by/4.0/© 2023 Springer Natureopen.accesshttps://repositorio.cuc.edu.coRepositorio de la Universidad de la Costa CUCrepdigital@cuc.edu.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 |