Elucidating the adsorption mechanism of herbicide diuron onto activated carbons via steric, energetic and thermodynamic investigations.

The residues of the species Calophyllum inophyllum and Manihot esculenta were carbonized after impregnation with ZnCl2 to produce two different activated carbons (ACs). These adsorbents were subsequently used in the removal of the toxic herbicide Diuron. Both the produced adsorbents present function...

Full description

Autores:
Yanan, Chen
Ali, Jawad
Sellaoui, Lotfi
Dhaoudi, Fatma
Franco, Dison S.P.
Georgin, Jordana
Erto, Alessandro
Vieillard, Julien
Badawi, Michael
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:11323/13604
Acceso en línea:
https://hdl.handle.net/11323/13604
https://repositorio.cuc.edu.co/
Palabra clave:
Activated carbon
Adsorption
Herbicide Diuron
Modelling
Thermodynamic study
Rights
openAccess
License
Atribución 4.0 Internacional (CC BY 4.0)
id RCUC2_76941a175c026396d8a43ae70d49216d
oai_identifier_str oai:repositorio.cuc.edu.co:11323/13604
network_acronym_str RCUC2
network_name_str REDICUC - Repositorio CUC
repository_id_str
dc.title.eng.fl_str_mv Elucidating the adsorption mechanism of herbicide diuron onto activated carbons via steric, energetic and thermodynamic investigations.
title Elucidating the adsorption mechanism of herbicide diuron onto activated carbons via steric, energetic and thermodynamic investigations.
spellingShingle Elucidating the adsorption mechanism of herbicide diuron onto activated carbons via steric, energetic and thermodynamic investigations.
Activated carbon
Adsorption
Herbicide Diuron
Modelling
Thermodynamic study
title_short Elucidating the adsorption mechanism of herbicide diuron onto activated carbons via steric, energetic and thermodynamic investigations.
title_full Elucidating the adsorption mechanism of herbicide diuron onto activated carbons via steric, energetic and thermodynamic investigations.
title_fullStr Elucidating the adsorption mechanism of herbicide diuron onto activated carbons via steric, energetic and thermodynamic investigations.
title_full_unstemmed Elucidating the adsorption mechanism of herbicide diuron onto activated carbons via steric, energetic and thermodynamic investigations.
title_sort Elucidating the adsorption mechanism of herbicide diuron onto activated carbons via steric, energetic and thermodynamic investigations.
dc.creator.fl_str_mv Yanan, Chen
Ali, Jawad
Sellaoui, Lotfi
Dhaoudi, Fatma
Franco, Dison S.P.
Georgin, Jordana
Erto, Alessandro
Vieillard, Julien
Badawi, Michael
dc.contributor.author.none.fl_str_mv Yanan, Chen
Ali, Jawad
Sellaoui, Lotfi
Dhaoudi, Fatma
Franco, Dison S.P.
Georgin, Jordana
Erto, Alessandro
Vieillard, Julien
Badawi, Michael
dc.subject.proposal.eng.fl_str_mv Activated carbon
Adsorption
Herbicide Diuron
Modelling
Thermodynamic study
topic Activated carbon
Adsorption
Herbicide Diuron
Modelling
Thermodynamic study
description The residues of the species Calophyllum inophyllum and Manihot esculenta were carbonized after impregnation with ZnCl2 to produce two different activated carbons (ACs). These adsorbents were subsequently used in the removal of the toxic herbicide Diuron. Both the produced adsorbents present functional groups characteristic of structures containing lignin and cellulose. These groups are positioned in amorphous and disorganized arrangements. The activation process formed a porous carbon exoskeleton with a surface area of 468 m2 g−1 (AC Calophyllum inophyllum) and 614 m2 g−1 (AC Manihot esculenta), respectively. Adsorption tests of herbicide Diuron are performed at different temperatures, indicating better performances for the adsorbent derived from Manihot esculenta (Qmax = 220 mg/g). A physical model derived from statistical physics, which assumes the formation of two layers of Diuron molecules on the ACs surface is successfully used to analyze the adsorption mechanism. The theoretical analysis of model parameters shows that the number of herbicide molecules captured per adsorption site increases with temperature for both the tested adsorbents, suggesting that an endothermic aggregation process occurs. The calculation of the adsorption energies confirms that Diuron adsorption on the surface of both the adsorbents is based on physical forces. Finally, three thermodynamic parameters are analyzed to attribute a new macroscopic description of the adsorption mechanism.
publishDate 2023
dc.date.issued.none.fl_str_mv 2023-07
dc.date.accessioned.none.fl_str_mv 2024-10-30T15:41:01Z
dc.date.available.none.fl_str_mv 2024-10-30T15:41:01Z
dc.type.none.fl_str_mv Artículo de revista
dc.type.coar.none.fl_str_mv http://purl.org/coar/resource_type/c_2df8fbb1
dc.type.content.none.fl_str_mv Text
dc.type.driver.none.fl_str_mv info:eu-repo/semantics/article
dc.type.redcol.none.fl_str_mv http://purl.org/redcol/resource_type/ART
dc.type.version.none.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.coarversion.none.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.none.fl_str_mv Chen Yanan, Jawad Ali, Lotfi Sellaoui, Fatma Dhaoudi, Dison S.P. Franco, Jordana Georgin, Alessandro Erto, Julien Vieillard, Michael Badawi, Elucidating the adsorption mechanism of herbicide Diuron onto activated carbons via steric, energetic and thermodynamic investigations, Journal of Water Process Engineering, Volume 53, 2023, 103910, ISSN 2214-7144, https://doi.org/10.1016/j.jwpe.2023.103910.
dc.identifier.uri.none.fl_str_mv https://hdl.handle.net/11323/13604
dc.identifier.doi.none.fl_str_mv 10.1016/j.jwpe.2023.103910
dc.identifier.eissn.none.fl_str_mv 2214-7144
dc.identifier.instname.none.fl_str_mv Corporación Universidad de la Costa
dc.identifier.reponame.none.fl_str_mv REDICUC - Repositorio CUC
dc.identifier.repourl.none.fl_str_mv https://repositorio.cuc.edu.co/
identifier_str_mv Chen Yanan, Jawad Ali, Lotfi Sellaoui, Fatma Dhaoudi, Dison S.P. Franco, Jordana Georgin, Alessandro Erto, Julien Vieillard, Michael Badawi, Elucidating the adsorption mechanism of herbicide Diuron onto activated carbons via steric, energetic and thermodynamic investigations, Journal of Water Process Engineering, Volume 53, 2023, 103910, ISSN 2214-7144, https://doi.org/10.1016/j.jwpe.2023.103910.
10.1016/j.jwpe.2023.103910
2214-7144
Corporación Universidad de la Costa
REDICUC - Repositorio CUC
url https://hdl.handle.net/11323/13604
https://repositorio.cuc.edu.co/
dc.language.iso.none.fl_str_mv eng
language eng
dc.relation.ispartofjournal.none.fl_str_mv Journal of Water Process Engineering
dc.relation.references.none.fl_str_mv D.S.P. Franco, J. Georgin, E.C. Lima, L.F.O. Silva, Journal of Water Process Engineering Advances made in removing paraquat herbicide by adsorption technology: a review, J. Water Process Eng. 49 (2022), 102988, https://doi.org/ 10.1016/j.jwpe.2022.102988.
L. Rani, K. Thapa, N. Kanojia, N. Sharma, S. Singh, A.S. Grewal, A.L. Srivastav, J. Kaushal, An extensive review on the consequences of chemical pesticides on human health and environment, J. Clean. Prod. 283 (2021), 124657, https://doi. org/10.1016/j.jclepro.2020.124657.
S. Khalid, M. Shahid, B. Murtaza, I. Bibi, Natasha, M. Asif Naeem, N.K. Niazi, A critical review of different factors governing the fate of pesticides in soil under biochar application, Sci. Total Environ. 711 (2020), 134645, https://doi.org/ 10.1016/j.scitotenv.2019.134645.
D. Suzuki, R. Shoji, Toxicological effects of chlorophenols to green algae observed at various pH and concentration of humic acid, J. Hazard. Mater. 400 (2020), 123079, https://doi.org/10.1016/j.jhazmat.2020.123079
L.M. Ndjientcheu Yossa, S.K. Ouiminga, S.S. Sidibe, I.W.K. Ouedraogo, Synthesis of a cleaner potassium hydroxide-activated carbon from baobab seeds hulls and investigation of adsorption mechanisms for diuron: chemical activation as alternative route for preparation of activated carbon from baobab seeds hulls and adsorption, Sci. Afr. 9 (2020), e00476, https://doi.org/10.1016/j.sciaf.2020. e00476.
E.C. Catalkaya, F. Kargi, Advanced oxidation of Diuron by photo-Fenton treatment as a function of operating parameters, J. Environ. Eng. 134 (2008) 1006–1013, https://doi.org/10.1061/(asce)0733-9372(2008)134:12(1006).
S.M. Ihlaseh-Catalano, K.A. Bailey, A.P.F. Cardoso, H. Ren, R.C. Fry, J.L.V. de Camargo, D.C. Wolf, Dose and temporal effects on gene expression profiles of urothelial cells from rats exposed to diuron, Toxicology 325 (2014) 21–30, https:// doi.org/10.1016/J.TOX.2014.08.005.
J.A. Silva Moretto, J.P. Rueda Furlan, A.F. Tonelli Fernandes, A. Bauermeister, N. P. Lopes, E.G. Stehling, Alternative biodegradation pathway of the herbicide diuron, Int. Biodeterior. Biodegradation 143 (2019), 104716, https://doi.org/ 10.1016/J.IBIOD.2019.06.004.
Z. Tekin, E. Oztürk ¨ Er, O.T. ¨ Günkara, S. Bakırdere, A novel determination method for diuron in seaweed samples: combination of quadruple isotope dilution strategy with liquid chromatography - quadrupole time of flight - tandem mass spectrometry for superior accuracy and precision, J. Chromatogr. A 1611 (2020), 460612, https://doi.org/10.1016/J.CHROMA.2019.460612.
M.T. Islam, A.G. Hyder, R. Saenz-Arana, C. Hernandez, T. Guinto, M.A. Ahsan, B. Alvarado-Tenorio, J.C. Noveron, Removal of methylene blue and tetracycline from water using peanut shell derived adsorbent prepared by sulfuric acid reflux, J. Environ. Chem. Eng. 7 (2019), 102816, https://doi.org/10.1016/j. jece.2018.102816.
A.E. Smith, A.J. Aubin, Metabolites of [14C]-2,4-Dichlorophenoxyacetic acid in Saskatchewan soils, J. Agric. Food Chem. 39 (1991) 2019–2021, https://doi.org/ 10.1021/jf00011a029.
A. El Imache, S. Dousset, A. Satrallah, A. Dahchour, Effects of sewage sludge amendments on pesticide sorption and leaching through undisturbed Mediterranean soils, J. Environ. Sci. Health B 47 (2012) 161–167, https://doi.org/ 10.1080/03601234.2012.632260.
G.L. Dotto, G. McKay, Current scenario and challenges in adsorption for water treatment, J. Environ. Chem. Eng. 8 (2020), 103988, https://doi.org/10.1016/j. jece.2020.103988.
F. Dhaouadi, L. Sellaoui, S. Taamalli, F. Louis, A. El, M. Badawi, J. Georgin, D.S. P. Franco, L.F.O. Silva, Enhanced Adsorption of Ketoprofen and 2, 4-Dichlorophenoxyactic Acid on Physalis peruviana Fruit Residue Functionalized with H 2 SO4: Adsorption Properties and Statistical Physics Modeling Adri a 445, 2022, https://doi.org/10.1016/j.cej.2022.136773.
Y. Dehmani, J. Lain´e, A. Daouli, L. Sellaoui, A. Bonilla-Petriciolet, T. Lamhasni, S. Abouarnadasse, M. Badawi, Unravelling the adsorption mechanism of phenol on zinc oxide at various coverages via statistical physics, artificial neural network modeling and ab initio molecular dynamics, Chem. Eng. J. 452 (2023), 139171, https://doi.org/10.1016/j.cej.2022.139171.
L. Sellaoui, L.F.O. Silva, M. Badawi, J. Ali, N. Favarin, G.L. Dotto, A. Erto, Z. Chen, Adsorption of ketoprofen and 2- nitrophenol on activated carbon prepared from winery wastes: a combined experimental and theoretical study, J. Mol. Liq. 333 (2021), 115906, https://doi.org/10.1016/j.molliq.2021.115906.
L. Sellaoui, Z. Li, M. Badawi, G.L. Dotto, A. Bonilla-Petriciolet, Z. Chen, Origin of the outstanding performance of ZnAl and MgFe layered double hydroxides in the adsorption of 2-nitrophenol: a statistical physics assessment, J. Mol. Liq. 314 (2020), 113572, https://doi.org/10.1016/j.molliq.2020.113572.
M. Sbizzaro, S. C´esar Sampaio, R. Rinaldo dos Reis, F. de Assis Beraldi, D. Medina Rosa, C. Maria Branco de Freitas Maia, C. Saramago de Carvalho Marques dos Santos Cordovil, C. Tillvitz do Nascimento, E. Antonio da Silva, C. Eduardo Borba, Effect of production temperature in biochar properties from bamboo culm and its influences on atrazine adsorption from aqueous systems, J. Mol. Liq. 343 (2021), 117667, https://doi.org/10.1016/j.molliq.2021.117667.
Q.A. Binh, H.H. Nguyen, Investigation the isotherm and kinetics of adsorption mechanism of herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) on corn cob biochar, Bioresour. Technol. Rep. 11 (2020), 100520, https://doi.org/10.1016/j. biteb.2020.100520.
Y.L. Salomon, ´ J. Georgin, D.S.P. Franco, M.S. Netto, D.G.A. Piccilli, E.L. Foletto, D. Pinto, M.L.S. Oliveira, G.L. Dotto, Adsorption of atrazine herbicide from water by diospyros kaki fruit waste activated carbon, J. Mol. Liq. 347 (2022), 117990, https://doi.org/10.1016/j.molliq.2021.117990.
J.S. Lazarotto, K. da Boit Martinello, J. Georgin, D.S.P. Franco, M.S. Netto, D.G. A. Piccilli, L.F.O. Silva, E.C. Lima, G.L. Dotto, Preparation of activated carbon from the residues of the mushroom (Agaricus bisporus) production chain for the adsorption of the 2,4-dichlorophenoxyacetic herbicide, J. Environ. Chem. Eng. 9 (2021), https://doi.org/10.1016/j.jece.2021.106843.
I.P.P. Cansado, P.A.M. Mourao, ˜ J.A.F.L. Gomes, V. Almodovar, ˆ Adsorption of MCPA, 2,4-D and diuron onto activated carbons from wood composites, Ciencia e Tecnologia Dos Materiais 29 (2017) e224–e228, https://doi.org/10.1016/j. ctmat.2016.07.005.
P.T. Hernandes, D.S.P. Franco, J. Georgin, N.P.G. Salau, G.L. Dotto, Investigation of biochar from Cedrella fissilis applied to the adsorption of atrazine herbicide from an aqueous medium, J. Environ. Chem. Eng. 10 (2022), 107408, https://doi.org/ 10.1016/j.jece.2022.107408.
E. Tchikuala, P. Mour˜ ao, J. Nabais, Valorisation of natural fibres from African baobab wastes by the production of activated carbons for adsorption of Diuron, Procedia Eng. 200 (2017) 399–407, https://doi.org/10.1016/j. proeng.2017.07.056.
J.S. Lazarotto, K. da Boit Martinello, J. Georgin, D.S.P. Franco, M.S. Netto, D.G. A. Piccilli, L.F.O. Silva, E.C. Lima, G.L. Dotto, Application of araç´ a fruit husks (Psidium cattleianum) in the preparation of activated carbon with FeCl3 for atrazine herbicide adsorption, Chem. Eng. Res. Des. 180 (2022) 67–78, https://doi. org/10.1016/j.cherd.2022.01.044.
Y. Cao, S. Jiang, Y. Zhang, J. Xu, L. Qiu, L. Wang, Investigation into adsorption characteristics and mechanism of atrazine on nano-MgO modified fallen leaf biochar, J. Environ. Chem. Eng. 9 (2021), 105727, https://doi.org/10.1016/j. jece.2021.105727.
A.S. S´ anchez, Y.L. Silva, R.A. Kalid, E. Cohim, E.A. Torres, Waste bio-refineries for the cassava starch industry: new trends and review of alternatives, Renew. Sust. Energ. Rev. 73 (2017) 1265–1275, https://doi.org/10.1016/j.rser.2017.02.007. [28] D. Schwantes, A.C. Gonçalves, G.F. Coelho, M.A. Campagnolo, D.C. Dragunski, C.R. T. Tarley, A.J. Miola, E.A.V. Leismann, Chemical modifications of cassava peel as adsorbent material for metals ions from wastewater, J. Chem. 2016 (2016), https://doi.org/10.1155/2016/3694174.
O.C. Orororo, N.J. Tonukari, O.J. Avwioroko, T. Ezedom, Effect of Supplementation of Animal Feed with Dried Cassava (Manihot esculenta) Peels, and Stems of Vernonia amygdalina and Pennisetum purpereum on Some Biochemical Parameters in Pigs, Nigerian Society for Experimental Biology 14, 2014, pp. 177–183.
B.H. Beakou, K. El Hassani, M.A. Houssaini, M. Belbahloul, E. Oukani, A. Anouar, Novel activated carbon from Manihot esculenta Crantz for removal of methylene blue, Sustain. Environ. Res. 27 (2017) 215–222, https://doi.org/10.1016/j. serj.2017.06.003.
J. Wu, J. Yang, G. Huang, C. Xu, B. Lin, Hydrothermal carbonization synthesis of cassava slag biochar with excellent adsorption performance for rhodamine B, J. Clean. Prod. 251 (2020), 119717, https://doi.org/10.1016/j. jclepro.2019.119717.
A. Navya, S. Nandhini, S. Sivamani, G. Vasu, N. Sivarajasekar, A. HosseiniBandegharaei, Preparation and characterization of cassava stem biochar for mixed reactive dyes removal from simulated effluent, Desalin. Water Treat. 189 (2020) 440–451, https://doi.org/10.5004/dwt.2020.25635.
H. Deng, Y.F. Li, S.Q. Tao, A.Y. Li, Q.Y. Li, L.N. Hu, Efficient adsorption capability of banana and cassava biochar for malachite green: removal process and mechanism exploration, Environ. Eng. Res. 27 (2021), 200575-0, https://doi.org/ 10.4491/eer.2020.575.
X. Xie, H. Xiong, Y. Zhang, Z. Tong, A. Liao, Z. Qin, Preparation magnetic cassava residue microspheres and its application for Cu(II) adsorption, J. Environ. Chem. Eng. 5 (2017) 2800–2806, https://doi.org/10.1016/j.jece.2017.05.024.
J.C. Moreno-Piraj´ an, L. Giraldo, Adsorption of copper from aqueous solution by activated carbons obtained by pyrolysis of cassava peel, J. Anal. Appl. Pyrolysis 87 (2010) 188–193, https://doi.org/10.1016/j.jaap.2009.12.004.
M. Horsfall, A.A. Abia, A.I. Spiff, Kinetic studies on the adsorption of Cd2+, Cu2+ and Zn2+ ions from aqueous solutions by cassava (Manihot sculenta Cranz) tuber bark waste, Bioresour. Technol. 97 (2006) 283–291, https://doi.org/10.1016/j. biortech.2005.02.016.
S. Keily, C. Silva, A. Gomes, R. Henrique, D.L. Leite, E. Maria, M. Aroucha, Adsorç˜ ao de corante azul reativo BF-5G utilizando casca de Manihot Esculenta Crantz Adsorption of BF-5G reactive blue dye using Manihot Esculenta Crantz, 2022.
A. Arumugam, V. Ponnusami, Biodiesel production from Calophyllum inophyllum oil using lipase producing Rhizopus oryzae cells immobilized within reticulated foams, Renew. Energy 64 (2014) 276–282, https://doi.org/10.1016/j. renene.2013.11.016.
A. Arumugam, V. Ponnusami, Biodiesel production from Calophyllum inophyllum oil a potential non-edible feedstock: an overview, Renew. Energy 131 (2019) 459–471, https://doi.org/10.1016/j.renene.2018.07.059.
K. Mohanty, M. Jha, B.C. Meikap, M.N. Biswas, Removal of chromium (VI) from dilute aqueous solutions by activated carbon developed from Terminalia arjuna nuts activated with zinc chloride, Chem. Eng. Sci. 60 (2005) 3049–3059, https:// doi.org/10.1016/j.ces.2004.12.049.
J. Georgin, D. Pinto, D.S.P. Franco, M. Schadeck Netto, J.S. Lazarotto, D.G. Allasia, R. Tassi, L.F.O. Silva, G.L. Dotto, Improved adsorption of the toxic herbicide Diuron using activated carbon obtained from residual cassava biomass (Manihot esculenta), Molecules 27 (2022) 7574, https://doi.org/10.3390/ molecules27217574.
D.S.P. Franco, J. Georgin, C.G. Ramos, M.S. Netto, N.J. Ojeda, N.A. Vega, L. Meili, E.C. Lima, Mu. Naushad, The Production of Activated Biochar Using Calophyllum inophyllum Waste Biomass and Use as an Adsorbent for Removal of Diuron from the Water in Batch and Fixed Bed Column, Environ Sci Pollut Res, 2023, https://doi. org/10.1007/s11356-023-26048-8.
H.K. Chung, W.H. Kim, J. Park, J. Cho, T.Y. Jeong, P.K. Park, Application of Langmuir and Freundlich isotherms to predict adsorbate removal efficiency or required amount of adsorbent, J. Ind. Eng. Chem. 28 (2015) 241–246, https://doi. org/10.1016/j.jiec.2015.02.021.
R.F.T. Tagne, N.G. Ndifor-Angwagor, R.C.T. Temgoua, D.R.T. Tchuifon, T. Vintila, A.S. Ngueabouo, S.G. Anagho, Development of an electroanalytical method using activated rice husk-derived carbon for the detection of a paraquat herbicide, Carbon Trends 4 (2021), 100060, https://doi.org/10.1016/j.cartre.2021.100060.
S. Nanda, P. Mohanty, K.K. Pant, S. Naik, J.A. Kozinski, A.K. Dalai, Characterization of north American lignocellulosic biomass and biochars in terms of their candidacy for alternate renewable fuels, Bioenergy Res. 6 (2013) 663–677, https://doi.org/10.1007/s12155-012-9281-4.
P. Mohanty, S. Nanda, K.K. Pant, S. Naik, J.A. Kozinski, A.K. Dalai, Evaluation of the physiochemical development of biochars obtained from pyrolysis of wheat straw, timothy grass and pinewood: effects of heating rate, J. Anal. Appl. Pyrolysis 104 (2013) 485–493, https://doi.org/10.1016/j.jaap.2013.05.022.
R. Sharma, A. Sarswat, C.U. Pittman, D. Mohan, Cadmium and lead remediation using magnetic and non-magnetic sustainable biosorbents derived from Bauhinia purpurea pods, RSC Adv. 7 (2017) 8606–8624, https://doi.org/10.1039/ C6RA25295H.
S.V. Vassilev, D. Baxter, L.K. Andersen, C.G. Vassileva, T.J. Morgan, An overview of the organic and inorganic phase composition of biomass, Fuel 94 (2012) 1–33, https://doi.org/10.1016/j.fuel.2011.09.030.
J. Georgin, Y.L. de O. Salomon, ´ D.S.P.P. Franco, M.S. Netto, D.G.A. Piccilli, D. Perondi, L.F.O.O. Silva, E.L. Foletto, G.L. Dotto, G. Daniel, J. Georgin, Y.L.D. O. Salom, A. Piccilli, D. Perondi, L.F.O.O. Silva, E.L. Foletto, G.L. Dotto, Y.L. de O. Salomon, ´ D.S.P.P. Franco, M.S. Netto, D.G.A. Piccilli, D. Perondi, L.F.O.O. Silva, E.L. Foletto, G.L. Dotto, Development of highly porous activated carbon from Jacaranda mimosifolia seed pods for remarkable removal of aqueous-phase ketoprofen, J. Environ. Chem. Eng. 9 (2021), 105676, https://doi.org/10.1016/j. jece.2021.105676
Y. Zhou, X. Liu, Y. Xiang, P. Wang, J. Zhang, F. Zhang, J. Wei, L. Luo, M. Lei, L. Tang, Modification of biochar derived from sawdust and its application in removal of tetracycline and copper from aqueous solution: adsorption mechanism and modelling, Bioresour. Technol. 245 (2017) 266–273, https://doi.org/10.1016/ j.biortech.2017.08.178.
D.S.P. Franco, J. Georgin, M.S. Netto, K. da Boit Martinello, L.F.O. Silva, Preparation of activated carbons from fruit residues for the removal of naproxen (NPX): analytical interpretation via statistical physical model, J. Mol. Liq. 356 (2022), 119021, https://doi.org/10.1016/j.molliq.2022.119021.
C.M. Kerkhoff, K. da Boit Martinello, D.S.P. Franco, M.S. Netto, J. Georgin, E. L. Foletto, D.G.A. Piccilli, L.F.O. Silva, G.L. Dotto, Adsorption of ketoprofen and paracetamol and treatment of a synthetic mixture by novel porous carbon derived from Butia capitata endocarp, J. Mol. Liq. 339 (2021), 117184, https://doi.org/ 10.1016/j.molliq.2021.117184.
R. Ramirez, C.E. Schnorr, J. Georgin, M.S. Netto, D.S.P. Franco, E. Carissimi, D. Wolff, L.F.O. Silva, G.L. Dotto, Transformation of residual açai fruit (Euterpe oleracea) seeds into porous adsorbent for efficient removal of 2,4-dichlorophenoxyacetic acid herbicide from waters, Molecules 27 (2022) 7781, https://doi.org/ 10.3390/molecules27227781.
J. Georgin, F.C. Drumm, P. Grassi, D. Franco, D. Allasia, G.L. Dotto, F. Caroline, D. Patrícia, G. Dison, F. Guilherme, L. Dotto, Potential of Araucaria angustifolia bark as adsorbent to remove gentian violet dye from aqueous effluents, Water Sci. Technol. 78 (2018) 1693–1703, https://doi.org/10.2166/wst.2018.448.
P.T. Hernandes, M.L.S.S. Oliveira, J. Georgin, D.S.P.P. Franco, D. Allasia, G. L. Dotto, Adsorptive decontamination of wastewater containing methylene blue dye using golden trumpet tree bark (Handroanthus albus), Environ. Sci. Pollut. Res. 26 (2019) 31924–31933, https://doi.org/10.1007/s11356-019-06353-x.
P. Grassi, F.C. Drumm, J. Georgin, D.S.P. Franco, G.L. Dotto, E.L. Foletto, S.L. Jahn, Application of Cordia trichotoma sawdust as an effective biosorbent for removal of crystal violet from aqueous solution in batch system and fixed-bed column, Environ. Sci. Pollut. Res. 28 (2021) 6771–6783, https://doi.org/10.1007/s11356- 020-11005-6.
K.S.W. Sing, Reporting physisorption data for gas / solid systems with special reference to the determination of S, Pure Appl. Chem. 54 (1982) 2201–2218, https://doi.org/10.1515/iupac.57.0007.
M. Thommes, K. Kaneko, A.V. Neimark, J.P. Olivier, F. Rodriguez-Reinoso, J. Rouquerol, K.S.W. Sing, Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC technical report), Pure Appl. Chem. 87 (2015) 1051–1069, https://doi.org/10.1515/pac-2014-1117.
R. Ramirez, C.E. Schnorr, J. Georgin, M.S. Netto, D.S.P. Franco, E. Carissimi, D. Wolff, L.F.O. Silva, G.L. Dotto, Transformation of residual Açai fruit (Euterpe oleracea) seeds into porous adsorbent for efficient removal of 2,4-dichlorophenoxyacetic acid herbicide from waters, Molecules 27 (2022) 7781, https://doi.org/ 10.3390/molecules27227781.
Y. Vieira, J.P. Silveira, G.L. Dotto, S. Knani, J. Vieillard, J. Georgin, D.S.P. Franco, E.C. Lima, Mechanistic insights and steric interpretations through statistical physics modelling and density functional theory calculations for the adsorption of the pesticides atrazine and diuron by Hovenia dulcis biochar, J. Mol. Liq. 367 (2022), 120418, https://doi.org/10.1016/J.MOLLIQ.2022.120418.
J.S. Lazarotto, K. da Boit Martinello, J. Georgin, D.S.P. Franco, M.S. Netto, D.G. A. Piccilli, L.F.O. Silva, E.C. Lima, G.L. Dotto, Preparation of activated carbon from the residues of the mushroom (Agaricus bisporus) production chain for the adsorption of the 2,4-dichlorophenoxyacetic herbicide, J. Environ. Chem. Eng. 9 (2021), 106843, https://doi.org/10.1016/j.jece.2021.106843.
L. Sellaoui, A. Gomez-Avil ´ ´es, F. Dhaouadi, J. Bedia, A. Bonilla-Petriciolet, S. Rtimi, C. Belver, Adsorption of emerging pollutants on lignin-based activated carbon: analysis of adsorption mechanism via characterization, kinetics and equilibrium studies, Chem. Eng. J. 452 (2023), 139399, https://doi.org/10.1016/j. cej.2022.139399.
F. Dhaouadi, L. Sellaoui, G.L. Dotto, A. Bonilla-Petriciolet, A. Erto, A.B. Lamine, Adsorption of methylene blue on comminuted raw avocado seeds: interpretation of the effect of salts via physical monolayer model, J. Mol. Liq. 305 (2020), 112815, https://doi.org/10.1016/j.molliq.2020.112815.
L.M. Ndjientcheu Yossa, S.K. Ouiminga, S.S. Sidibe, I.W.K. Ouedraogo, Synthesis of a cleaner potassium hydroxide-activated carbon from baobab seeds hulls and investigation of adsorption mechanisms for diuron: chemical activation as alternative route for preparation of activated carbon from baobab seeds hulls and adsorption of diuron, Sci. Afr. 9 (2020), e00476, https://doi.org/10.1016/J. SCIAF.2020.E00476.
E. Tchikuala, P. Mour˜ ao, J. Nabais, Valorisation of natural fibres from African baobab wastes by the production of activated carbons for adsorption of Diuron, Procedia Eng. 200 (2017) 399–407, https://doi.org/10.1016/j. proeng.2017.07.056.
A. Wong, F.M. De Oliveira, C.R.T. Tarley, M. Del Pilar Taboada Sotomayor, Study on the cross-linked molecularly imprinted poly(methacrylic acid) and poly(acrylic acid) towards selective adsorption of diuron, React. Funct. Polym. 100 (2016) 26–36, https://doi.org/10.1016/j.reactfunctpolym.2016.01.006.
M. Al Bahri, L. Calvo, M.A. Gilarranz, J.J. Rodriguez, Activated carbon from grape seeds upon chemical activation with phosphoric acid: application to the adsorption of diuron from water, Chem. Eng. J. 203 (2012) 348–356, https://doi.org/ 10.1016/j.cej.2012.07.053.
A.M. De Souza, C.F. De Oliveira, V.B. De Oliveira, F. Cesar, M. Betim, O.G. Miguel, M.D. Miguel, A.M. De Souza, Traditional uses, phytochemistry, and antimicrobial activities of eugenia species – a review, Planta Med. 84 (2018) 1232–1248.
G.-C. Chen, X.-Q. Shan, Z.-G. Pei, H. Wang, L.-R. Zheng, J. Zhang, Y.-N. Xie, Adsorption of diuron and dichlobenil on multiwalled carbon nanotubes as affected by lead, J. Hazard. Mater. 188 (2011) 156–163, https://doi.org/10.1016/j. jhazmat.2011.01.095.
L. Sellaoui, S. Knani, A. Erto, M.A. Hachicha, A. Ben Lamine, Equilibrium isotherm simulation of tetrachlorethylene on activated carbon using the double layer model with two energies: steric and energetic interpretations, Fluid Phase Equilib. 408 (2016) 259–264, https://doi.org/10.1016/j.fluid.2015.09.022.
dc.relation.citationendpage.none.fl_str_mv 9
dc.relation.citationstartpage.none.fl_str_mv 1
dc.relation.citationissue.none.fl_str_mv 103910
dc.relation.citationvolume.none.fl_str_mv 53
dc.rights.eng.fl_str_mv © 2023
dc.rights.license.none.fl_str_mv Atribución 4.0 Internacional (CC BY 4.0)
dc.rights.uri.none.fl_str_mv https://creativecommons.org/licenses/by/4.0/
dc.rights.accessrights.none.fl_str_mv info:eu-repo/semantics/openAccess
dc.rights.coar.none.fl_str_mv http://purl.org/coar/access_right/c_abf2
rights_invalid_str_mv Atribución 4.0 Internacional (CC BY 4.0)
© 2023
https://creativecommons.org/licenses/by/4.0/
http://purl.org/coar/access_right/c_abf2
eu_rights_str_mv openAccess
dc.format.extent.none.fl_str_mv 9 páginas
dc.format.mimetype.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Elsevier Ltd
dc.publisher.place.none.fl_str_mv United Kingdom
publisher.none.fl_str_mv Elsevier Ltd
dc.source.none.fl_str_mv https://www.sciencedirect.com/science/article/pii/S2214714423004294?via%3Dihub
institution Corporación Universidad de la Costa
bitstream.url.fl_str_mv https://repositorio.cuc.edu.co/bitstreams/be9c04d5-03ab-49fc-bdaa-309da29bfa8a/download
https://repositorio.cuc.edu.co/bitstreams/24cb67ac-a232-4888-903c-93194651d96d/download
https://repositorio.cuc.edu.co/bitstreams/2afedb65-73bd-4beb-b9a6-00fb059b6ba1/download
https://repositorio.cuc.edu.co/bitstreams/9f7611c4-e26d-4c35-948c-d923ada70f6a/download
bitstream.checksum.fl_str_mv 38248b56ff8dbed9ecca46e1e8022c7f
73a5432e0b76442b22b026844140d683
991136b5bf5c4276c199003f71709d9a
f89efc9a9e6762e9e0692d18724195ea
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_ 1828166836173144064
spelling Atribución 4.0 Internacional (CC BY 4.0)© 2023https://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccesshttp://purl.org/coar/access_right/c_abf2Yanan, ChenAli, JawadSellaoui, LotfiDhaoudi, FatmaFranco, Dison S.P.Georgin, JordanaErto, AlessandroVieillard, JulienBadawi, Michael2024-10-30T15:41:01Z2024-10-30T15:41:01Z2023-07Chen Yanan, Jawad Ali, Lotfi Sellaoui, Fatma Dhaoudi, Dison S.P. Franco, Jordana Georgin, Alessandro Erto, Julien Vieillard, Michael Badawi, Elucidating the adsorption mechanism of herbicide Diuron onto activated carbons via steric, energetic and thermodynamic investigations, Journal of Water Process Engineering, Volume 53, 2023, 103910, ISSN 2214-7144, https://doi.org/10.1016/j.jwpe.2023.103910.https://hdl.handle.net/11323/1360410.1016/j.jwpe.2023.1039102214-7144Corporación Universidad de la CostaREDICUC - Repositorio CUChttps://repositorio.cuc.edu.co/The residues of the species Calophyllum inophyllum and Manihot esculenta were carbonized after impregnation with ZnCl2 to produce two different activated carbons (ACs). These adsorbents were subsequently used in the removal of the toxic herbicide Diuron. Both the produced adsorbents present functional groups characteristic of structures containing lignin and cellulose. These groups are positioned in amorphous and disorganized arrangements. The activation process formed a porous carbon exoskeleton with a surface area of 468 m2 g−1 (AC Calophyllum inophyllum) and 614 m2 g−1 (AC Manihot esculenta), respectively. Adsorption tests of herbicide Diuron are performed at different temperatures, indicating better performances for the adsorbent derived from Manihot esculenta (Qmax = 220 mg/g). A physical model derived from statistical physics, which assumes the formation of two layers of Diuron molecules on the ACs surface is successfully used to analyze the adsorption mechanism. The theoretical analysis of model parameters shows that the number of herbicide molecules captured per adsorption site increases with temperature for both the tested adsorbents, suggesting that an endothermic aggregation process occurs. The calculation of the adsorption energies confirms that Diuron adsorption on the surface of both the adsorbents is based on physical forces. Finally, three thermodynamic parameters are analyzed to attribute a new macroscopic description of the adsorption mechanism.9 páginasapplication/pdfengElsevier LtdUnited Kingdomhttps://www.sciencedirect.com/science/article/pii/S2214714423004294?via%3DihubElucidating the adsorption mechanism of herbicide diuron onto activated carbons via steric, energetic and thermodynamic investigations.Artículo 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_970fb48d4fbd8a85Journal of Water Process EngineeringD.S.P. Franco, J. Georgin, E.C. Lima, L.F.O. Silva, Journal of Water Process Engineering Advances made in removing paraquat herbicide by adsorption technology: a review, J. Water Process Eng. 49 (2022), 102988, https://doi.org/ 10.1016/j.jwpe.2022.102988.L. Rani, K. Thapa, N. Kanojia, N. Sharma, S. Singh, A.S. Grewal, A.L. Srivastav, J. Kaushal, An extensive review on the consequences of chemical pesticides on human health and environment, J. Clean. Prod. 283 (2021), 124657, https://doi. org/10.1016/j.jclepro.2020.124657.S. Khalid, M. Shahid, B. Murtaza, I. Bibi, Natasha, M. Asif Naeem, N.K. Niazi, A critical review of different factors governing the fate of pesticides in soil under biochar application, Sci. Total Environ. 711 (2020), 134645, https://doi.org/ 10.1016/j.scitotenv.2019.134645.D. Suzuki, R. Shoji, Toxicological effects of chlorophenols to green algae observed at various pH and concentration of humic acid, J. Hazard. Mater. 400 (2020), 123079, https://doi.org/10.1016/j.jhazmat.2020.123079L.M. Ndjientcheu Yossa, S.K. Ouiminga, S.S. Sidibe, I.W.K. Ouedraogo, Synthesis of a cleaner potassium hydroxide-activated carbon from baobab seeds hulls and investigation of adsorption mechanisms for diuron: chemical activation as alternative route for preparation of activated carbon from baobab seeds hulls and adsorption, Sci. Afr. 9 (2020), e00476, https://doi.org/10.1016/j.sciaf.2020. e00476.E.C. Catalkaya, F. Kargi, Advanced oxidation of Diuron by photo-Fenton treatment as a function of operating parameters, J. Environ. Eng. 134 (2008) 1006–1013, https://doi.org/10.1061/(asce)0733-9372(2008)134:12(1006).S.M. Ihlaseh-Catalano, K.A. Bailey, A.P.F. Cardoso, H. Ren, R.C. Fry, J.L.V. de Camargo, D.C. Wolf, Dose and temporal effects on gene expression profiles of urothelial cells from rats exposed to diuron, Toxicology 325 (2014) 21–30, https:// doi.org/10.1016/J.TOX.2014.08.005.J.A. Silva Moretto, J.P. Rueda Furlan, A.F. Tonelli Fernandes, A. Bauermeister, N. P. Lopes, E.G. Stehling, Alternative biodegradation pathway of the herbicide diuron, Int. Biodeterior. Biodegradation 143 (2019), 104716, https://doi.org/ 10.1016/J.IBIOD.2019.06.004.Z. Tekin, E. Oztürk ¨ Er, O.T. ¨ Günkara, S. Bakırdere, A novel determination method for diuron in seaweed samples: combination of quadruple isotope dilution strategy with liquid chromatography - quadrupole time of flight - tandem mass spectrometry for superior accuracy and precision, J. Chromatogr. A 1611 (2020), 460612, https://doi.org/10.1016/J.CHROMA.2019.460612.M.T. Islam, A.G. Hyder, R. Saenz-Arana, C. Hernandez, T. Guinto, M.A. Ahsan, B. Alvarado-Tenorio, J.C. Noveron, Removal of methylene blue and tetracycline from water using peanut shell derived adsorbent prepared by sulfuric acid reflux, J. Environ. Chem. Eng. 7 (2019), 102816, https://doi.org/10.1016/j. jece.2018.102816.A.E. Smith, A.J. Aubin, Metabolites of [14C]-2,4-Dichlorophenoxyacetic acid in Saskatchewan soils, J. Agric. Food Chem. 39 (1991) 2019–2021, https://doi.org/ 10.1021/jf00011a029.A. El Imache, S. Dousset, A. Satrallah, A. Dahchour, Effects of sewage sludge amendments on pesticide sorption and leaching through undisturbed Mediterranean soils, J. Environ. Sci. Health B 47 (2012) 161–167, https://doi.org/ 10.1080/03601234.2012.632260.G.L. Dotto, G. McKay, Current scenario and challenges in adsorption for water treatment, J. Environ. Chem. Eng. 8 (2020), 103988, https://doi.org/10.1016/j. jece.2020.103988.F. Dhaouadi, L. Sellaoui, S. Taamalli, F. Louis, A. El, M. Badawi, J. Georgin, D.S. P. Franco, L.F.O. Silva, Enhanced Adsorption of Ketoprofen and 2, 4-Dichlorophenoxyactic Acid on Physalis peruviana Fruit Residue Functionalized with H 2 SO4: Adsorption Properties and Statistical Physics Modeling Adri a 445, 2022, https://doi.org/10.1016/j.cej.2022.136773.Y. Dehmani, J. Lain´e, A. Daouli, L. Sellaoui, A. Bonilla-Petriciolet, T. Lamhasni, S. Abouarnadasse, M. Badawi, Unravelling the adsorption mechanism of phenol on zinc oxide at various coverages via statistical physics, artificial neural network modeling and ab initio molecular dynamics, Chem. Eng. J. 452 (2023), 139171, https://doi.org/10.1016/j.cej.2022.139171.L. Sellaoui, L.F.O. Silva, M. Badawi, J. Ali, N. Favarin, G.L. Dotto, A. Erto, Z. Chen, Adsorption of ketoprofen and 2- nitrophenol on activated carbon prepared from winery wastes: a combined experimental and theoretical study, J. Mol. Liq. 333 (2021), 115906, https://doi.org/10.1016/j.molliq.2021.115906.L. Sellaoui, Z. Li, M. Badawi, G.L. Dotto, A. Bonilla-Petriciolet, Z. Chen, Origin of the outstanding performance of ZnAl and MgFe layered double hydroxides in the adsorption of 2-nitrophenol: a statistical physics assessment, J. Mol. Liq. 314 (2020), 113572, https://doi.org/10.1016/j.molliq.2020.113572.M. Sbizzaro, S. C´esar Sampaio, R. Rinaldo dos Reis, F. de Assis Beraldi, D. Medina Rosa, C. Maria Branco de Freitas Maia, C. Saramago de Carvalho Marques dos Santos Cordovil, C. Tillvitz do Nascimento, E. Antonio da Silva, C. Eduardo Borba, Effect of production temperature in biochar properties from bamboo culm and its influences on atrazine adsorption from aqueous systems, J. Mol. Liq. 343 (2021), 117667, https://doi.org/10.1016/j.molliq.2021.117667.Q.A. Binh, H.H. Nguyen, Investigation the isotherm and kinetics of adsorption mechanism of herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) on corn cob biochar, Bioresour. Technol. Rep. 11 (2020), 100520, https://doi.org/10.1016/j. biteb.2020.100520.Y.L. Salomon, ´ J. Georgin, D.S.P. Franco, M.S. Netto, D.G.A. Piccilli, E.L. Foletto, D. Pinto, M.L.S. Oliveira, G.L. Dotto, Adsorption of atrazine herbicide from water by diospyros kaki fruit waste activated carbon, J. Mol. Liq. 347 (2022), 117990, https://doi.org/10.1016/j.molliq.2021.117990.J.S. Lazarotto, K. da Boit Martinello, J. Georgin, D.S.P. Franco, M.S. Netto, D.G. A. Piccilli, L.F.O. Silva, E.C. Lima, G.L. Dotto, Preparation of activated carbon from the residues of the mushroom (Agaricus bisporus) production chain for the adsorption of the 2,4-dichlorophenoxyacetic herbicide, J. Environ. Chem. Eng. 9 (2021), https://doi.org/10.1016/j.jece.2021.106843.I.P.P. Cansado, P.A.M. Mourao, ˜ J.A.F.L. Gomes, V. Almodovar, ˆ Adsorption of MCPA, 2,4-D and diuron onto activated carbons from wood composites, Ciencia e Tecnologia Dos Materiais 29 (2017) e224–e228, https://doi.org/10.1016/j. ctmat.2016.07.005.P.T. Hernandes, D.S.P. Franco, J. Georgin, N.P.G. Salau, G.L. Dotto, Investigation of biochar from Cedrella fissilis applied to the adsorption of atrazine herbicide from an aqueous medium, J. Environ. Chem. Eng. 10 (2022), 107408, https://doi.org/ 10.1016/j.jece.2022.107408.E. Tchikuala, P. Mour˜ ao, J. Nabais, Valorisation of natural fibres from African baobab wastes by the production of activated carbons for adsorption of Diuron, Procedia Eng. 200 (2017) 399–407, https://doi.org/10.1016/j. proeng.2017.07.056.J.S. Lazarotto, K. da Boit Martinello, J. Georgin, D.S.P. Franco, M.S. Netto, D.G. A. Piccilli, L.F.O. Silva, E.C. Lima, G.L. Dotto, Application of araç´ a fruit husks (Psidium cattleianum) in the preparation of activated carbon with FeCl3 for atrazine herbicide adsorption, Chem. Eng. Res. Des. 180 (2022) 67–78, https://doi. org/10.1016/j.cherd.2022.01.044.Y. Cao, S. Jiang, Y. Zhang, J. Xu, L. Qiu, L. Wang, Investigation into adsorption characteristics and mechanism of atrazine on nano-MgO modified fallen leaf biochar, J. Environ. Chem. Eng. 9 (2021), 105727, https://doi.org/10.1016/j. jece.2021.105727.A.S. S´ anchez, Y.L. Silva, R.A. Kalid, E. Cohim, E.A. Torres, Waste bio-refineries for the cassava starch industry: new trends and review of alternatives, Renew. Sust. Energ. Rev. 73 (2017) 1265–1275, https://doi.org/10.1016/j.rser.2017.02.007. [28] D. Schwantes, A.C. Gonçalves, G.F. Coelho, M.A. Campagnolo, D.C. Dragunski, C.R. T. Tarley, A.J. Miola, E.A.V. Leismann, Chemical modifications of cassava peel as adsorbent material for metals ions from wastewater, J. Chem. 2016 (2016), https://doi.org/10.1155/2016/3694174.O.C. Orororo, N.J. Tonukari, O.J. Avwioroko, T. Ezedom, Effect of Supplementation of Animal Feed with Dried Cassava (Manihot esculenta) Peels, and Stems of Vernonia amygdalina and Pennisetum purpereum on Some Biochemical Parameters in Pigs, Nigerian Society for Experimental Biology 14, 2014, pp. 177–183.B.H. Beakou, K. El Hassani, M.A. Houssaini, M. Belbahloul, E. Oukani, A. Anouar, Novel activated carbon from Manihot esculenta Crantz for removal of methylene blue, Sustain. Environ. Res. 27 (2017) 215–222, https://doi.org/10.1016/j. serj.2017.06.003.J. Wu, J. Yang, G. Huang, C. Xu, B. Lin, Hydrothermal carbonization synthesis of cassava slag biochar with excellent adsorption performance for rhodamine B, J. Clean. Prod. 251 (2020), 119717, https://doi.org/10.1016/j. jclepro.2019.119717.A. Navya, S. Nandhini, S. Sivamani, G. Vasu, N. Sivarajasekar, A. HosseiniBandegharaei, Preparation and characterization of cassava stem biochar for mixed reactive dyes removal from simulated effluent, Desalin. Water Treat. 189 (2020) 440–451, https://doi.org/10.5004/dwt.2020.25635.H. Deng, Y.F. Li, S.Q. Tao, A.Y. Li, Q.Y. Li, L.N. Hu, Efficient adsorption capability of banana and cassava biochar for malachite green: removal process and mechanism exploration, Environ. Eng. Res. 27 (2021), 200575-0, https://doi.org/ 10.4491/eer.2020.575.X. Xie, H. Xiong, Y. Zhang, Z. Tong, A. Liao, Z. Qin, Preparation magnetic cassava residue microspheres and its application for Cu(II) adsorption, J. Environ. Chem. Eng. 5 (2017) 2800–2806, https://doi.org/10.1016/j.jece.2017.05.024.J.C. Moreno-Piraj´ an, L. Giraldo, Adsorption of copper from aqueous solution by activated carbons obtained by pyrolysis of cassava peel, J. Anal. Appl. Pyrolysis 87 (2010) 188–193, https://doi.org/10.1016/j.jaap.2009.12.004.M. Horsfall, A.A. Abia, A.I. Spiff, Kinetic studies on the adsorption of Cd2+, Cu2+ and Zn2+ ions from aqueous solutions by cassava (Manihot sculenta Cranz) tuber bark waste, Bioresour. Technol. 97 (2006) 283–291, https://doi.org/10.1016/j. biortech.2005.02.016.S. Keily, C. Silva, A. Gomes, R. Henrique, D.L. Leite, E. Maria, M. Aroucha, Adsorç˜ ao de corante azul reativo BF-5G utilizando casca de Manihot Esculenta Crantz Adsorption of BF-5G reactive blue dye using Manihot Esculenta Crantz, 2022.A. Arumugam, V. Ponnusami, Biodiesel production from Calophyllum inophyllum oil using lipase producing Rhizopus oryzae cells immobilized within reticulated foams, Renew. Energy 64 (2014) 276–282, https://doi.org/10.1016/j. renene.2013.11.016.A. Arumugam, V. Ponnusami, Biodiesel production from Calophyllum inophyllum oil a potential non-edible feedstock: an overview, Renew. Energy 131 (2019) 459–471, https://doi.org/10.1016/j.renene.2018.07.059.K. Mohanty, M. Jha, B.C. Meikap, M.N. Biswas, Removal of chromium (VI) from dilute aqueous solutions by activated carbon developed from Terminalia arjuna nuts activated with zinc chloride, Chem. Eng. Sci. 60 (2005) 3049–3059, https:// doi.org/10.1016/j.ces.2004.12.049.J. Georgin, D. Pinto, D.S.P. Franco, M. Schadeck Netto, J.S. Lazarotto, D.G. Allasia, R. Tassi, L.F.O. Silva, G.L. Dotto, Improved adsorption of the toxic herbicide Diuron using activated carbon obtained from residual cassava biomass (Manihot esculenta), Molecules 27 (2022) 7574, https://doi.org/10.3390/ molecules27217574.D.S.P. Franco, J. Georgin, C.G. Ramos, M.S. Netto, N.J. Ojeda, N.A. Vega, L. Meili, E.C. Lima, Mu. Naushad, The Production of Activated Biochar Using Calophyllum inophyllum Waste Biomass and Use as an Adsorbent for Removal of Diuron from the Water in Batch and Fixed Bed Column, Environ Sci Pollut Res, 2023, https://doi. org/10.1007/s11356-023-26048-8.H.K. Chung, W.H. Kim, J. Park, J. Cho, T.Y. Jeong, P.K. Park, Application of Langmuir and Freundlich isotherms to predict adsorbate removal efficiency or required amount of adsorbent, J. Ind. Eng. Chem. 28 (2015) 241–246, https://doi. org/10.1016/j.jiec.2015.02.021.R.F.T. Tagne, N.G. Ndifor-Angwagor, R.C.T. Temgoua, D.R.T. Tchuifon, T. Vintila, A.S. Ngueabouo, S.G. Anagho, Development of an electroanalytical method using activated rice husk-derived carbon for the detection of a paraquat herbicide, Carbon Trends 4 (2021), 100060, https://doi.org/10.1016/j.cartre.2021.100060.S. Nanda, P. Mohanty, K.K. Pant, S. Naik, J.A. Kozinski, A.K. Dalai, Characterization of north American lignocellulosic biomass and biochars in terms of their candidacy for alternate renewable fuels, Bioenergy Res. 6 (2013) 663–677, https://doi.org/10.1007/s12155-012-9281-4.P. Mohanty, S. Nanda, K.K. Pant, S. Naik, J.A. Kozinski, A.K. Dalai, Evaluation of the physiochemical development of biochars obtained from pyrolysis of wheat straw, timothy grass and pinewood: effects of heating rate, J. Anal. Appl. Pyrolysis 104 (2013) 485–493, https://doi.org/10.1016/j.jaap.2013.05.022.R. Sharma, A. Sarswat, C.U. Pittman, D. Mohan, Cadmium and lead remediation using magnetic and non-magnetic sustainable biosorbents derived from Bauhinia purpurea pods, RSC Adv. 7 (2017) 8606–8624, https://doi.org/10.1039/ C6RA25295H.S.V. Vassilev, D. Baxter, L.K. Andersen, C.G. Vassileva, T.J. Morgan, An overview of the organic and inorganic phase composition of biomass, Fuel 94 (2012) 1–33, https://doi.org/10.1016/j.fuel.2011.09.030.J. Georgin, Y.L. de O. Salomon, ´ D.S.P.P. Franco, M.S. Netto, D.G.A. Piccilli, D. Perondi, L.F.O.O. Silva, E.L. Foletto, G.L. Dotto, G. Daniel, J. Georgin, Y.L.D. O. Salom, A. Piccilli, D. Perondi, L.F.O.O. Silva, E.L. Foletto, G.L. Dotto, Y.L. de O. Salomon, ´ D.S.P.P. Franco, M.S. Netto, D.G.A. Piccilli, D. Perondi, L.F.O.O. Silva, E.L. Foletto, G.L. Dotto, Development of highly porous activated carbon from Jacaranda mimosifolia seed pods for remarkable removal of aqueous-phase ketoprofen, J. Environ. Chem. Eng. 9 (2021), 105676, https://doi.org/10.1016/j. jece.2021.105676Y. Zhou, X. Liu, Y. Xiang, P. Wang, J. Zhang, F. Zhang, J. Wei, L. Luo, M. Lei, L. Tang, Modification of biochar derived from sawdust and its application in removal of tetracycline and copper from aqueous solution: adsorption mechanism and modelling, Bioresour. Technol. 245 (2017) 266–273, https://doi.org/10.1016/ j.biortech.2017.08.178.D.S.P. Franco, J. Georgin, M.S. Netto, K. da Boit Martinello, L.F.O. Silva, Preparation of activated carbons from fruit residues for the removal of naproxen (NPX): analytical interpretation via statistical physical model, J. Mol. Liq. 356 (2022), 119021, https://doi.org/10.1016/j.molliq.2022.119021.C.M. Kerkhoff, K. da Boit Martinello, D.S.P. Franco, M.S. Netto, J. Georgin, E. L. Foletto, D.G.A. Piccilli, L.F.O. Silva, G.L. Dotto, Adsorption of ketoprofen and paracetamol and treatment of a synthetic mixture by novel porous carbon derived from Butia capitata endocarp, J. Mol. Liq. 339 (2021), 117184, https://doi.org/ 10.1016/j.molliq.2021.117184.R. Ramirez, C.E. Schnorr, J. Georgin, M.S. Netto, D.S.P. Franco, E. Carissimi, D. Wolff, L.F.O. Silva, G.L. Dotto, Transformation of residual açai fruit (Euterpe oleracea) seeds into porous adsorbent for efficient removal of 2,4-dichlorophenoxyacetic acid herbicide from waters, Molecules 27 (2022) 7781, https://doi.org/ 10.3390/molecules27227781.J. Georgin, F.C. Drumm, P. Grassi, D. Franco, D. Allasia, G.L. Dotto, F. Caroline, D. Patrícia, G. Dison, F. Guilherme, L. Dotto, Potential of Araucaria angustifolia bark as adsorbent to remove gentian violet dye from aqueous effluents, Water Sci. Technol. 78 (2018) 1693–1703, https://doi.org/10.2166/wst.2018.448.P.T. Hernandes, M.L.S.S. Oliveira, J. Georgin, D.S.P.P. Franco, D. Allasia, G. L. Dotto, Adsorptive decontamination of wastewater containing methylene blue dye using golden trumpet tree bark (Handroanthus albus), Environ. Sci. Pollut. Res. 26 (2019) 31924–31933, https://doi.org/10.1007/s11356-019-06353-x.P. Grassi, F.C. Drumm, J. Georgin, D.S.P. Franco, G.L. Dotto, E.L. Foletto, S.L. Jahn, Application of Cordia trichotoma sawdust as an effective biosorbent for removal of crystal violet from aqueous solution in batch system and fixed-bed column, Environ. Sci. Pollut. Res. 28 (2021) 6771–6783, https://doi.org/10.1007/s11356- 020-11005-6.K.S.W. Sing, Reporting physisorption data for gas / solid systems with special reference to the determination of S, Pure Appl. Chem. 54 (1982) 2201–2218, https://doi.org/10.1515/iupac.57.0007.M. Thommes, K. Kaneko, A.V. Neimark, J.P. Olivier, F. Rodriguez-Reinoso, J. Rouquerol, K.S.W. Sing, Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC technical report), Pure Appl. Chem. 87 (2015) 1051–1069, https://doi.org/10.1515/pac-2014-1117.R. Ramirez, C.E. Schnorr, J. Georgin, M.S. Netto, D.S.P. Franco, E. Carissimi, D. Wolff, L.F.O. Silva, G.L. Dotto, Transformation of residual Açai fruit (Euterpe oleracea) seeds into porous adsorbent for efficient removal of 2,4-dichlorophenoxyacetic acid herbicide from waters, Molecules 27 (2022) 7781, https://doi.org/ 10.3390/molecules27227781.Y. Vieira, J.P. Silveira, G.L. Dotto, S. Knani, J. Vieillard, J. Georgin, D.S.P. Franco, E.C. Lima, Mechanistic insights and steric interpretations through statistical physics modelling and density functional theory calculations for the adsorption of the pesticides atrazine and diuron by Hovenia dulcis biochar, J. Mol. Liq. 367 (2022), 120418, https://doi.org/10.1016/J.MOLLIQ.2022.120418.J.S. Lazarotto, K. da Boit Martinello, J. Georgin, D.S.P. Franco, M.S. Netto, D.G. A. Piccilli, L.F.O. Silva, E.C. Lima, G.L. Dotto, Preparation of activated carbon from the residues of the mushroom (Agaricus bisporus) production chain for the adsorption of the 2,4-dichlorophenoxyacetic herbicide, J. Environ. Chem. Eng. 9 (2021), 106843, https://doi.org/10.1016/j.jece.2021.106843.L. Sellaoui, A. Gomez-Avil ´ ´es, F. Dhaouadi, J. Bedia, A. Bonilla-Petriciolet, S. Rtimi, C. Belver, Adsorption of emerging pollutants on lignin-based activated carbon: analysis of adsorption mechanism via characterization, kinetics and equilibrium studies, Chem. Eng. J. 452 (2023), 139399, https://doi.org/10.1016/j. cej.2022.139399.F. Dhaouadi, L. Sellaoui, G.L. Dotto, A. Bonilla-Petriciolet, A. Erto, A.B. Lamine, Adsorption of methylene blue on comminuted raw avocado seeds: interpretation of the effect of salts via physical monolayer model, J. Mol. Liq. 305 (2020), 112815, https://doi.org/10.1016/j.molliq.2020.112815.L.M. Ndjientcheu Yossa, S.K. Ouiminga, S.S. Sidibe, I.W.K. Ouedraogo, Synthesis of a cleaner potassium hydroxide-activated carbon from baobab seeds hulls and investigation of adsorption mechanisms for diuron: chemical activation as alternative route for preparation of activated carbon from baobab seeds hulls and adsorption of diuron, Sci. Afr. 9 (2020), e00476, https://doi.org/10.1016/J. SCIAF.2020.E00476.E. Tchikuala, P. Mour˜ ao, J. Nabais, Valorisation of natural fibres from African baobab wastes by the production of activated carbons for adsorption of Diuron, Procedia Eng. 200 (2017) 399–407, https://doi.org/10.1016/j. proeng.2017.07.056.A. Wong, F.M. De Oliveira, C.R.T. Tarley, M. Del Pilar Taboada Sotomayor, Study on the cross-linked molecularly imprinted poly(methacrylic acid) and poly(acrylic acid) towards selective adsorption of diuron, React. Funct. Polym. 100 (2016) 26–36, https://doi.org/10.1016/j.reactfunctpolym.2016.01.006.M. Al Bahri, L. Calvo, M.A. Gilarranz, J.J. Rodriguez, Activated carbon from grape seeds upon chemical activation with phosphoric acid: application to the adsorption of diuron from water, Chem. Eng. J. 203 (2012) 348–356, https://doi.org/ 10.1016/j.cej.2012.07.053.A.M. De Souza, C.F. De Oliveira, V.B. De Oliveira, F. Cesar, M. Betim, O.G. Miguel, M.D. Miguel, A.M. De Souza, Traditional uses, phytochemistry, and antimicrobial activities of eugenia species – a review, Planta Med. 84 (2018) 1232–1248.G.-C. Chen, X.-Q. Shan, Z.-G. Pei, H. Wang, L.-R. Zheng, J. Zhang, Y.-N. Xie, Adsorption of diuron and dichlobenil on multiwalled carbon nanotubes as affected by lead, J. Hazard. Mater. 188 (2011) 156–163, https://doi.org/10.1016/j. jhazmat.2011.01.095.L. Sellaoui, S. Knani, A. Erto, M.A. Hachicha, A. Ben Lamine, Equilibrium isotherm simulation of tetrachlorethylene on activated carbon using the double layer model with two energies: steric and energetic interpretations, Fluid Phase Equilib. 408 (2016) 259–264, https://doi.org/10.1016/j.fluid.2015.09.022.9110391053Activated carbonAdsorptionHerbicide DiuronModellingThermodynamic studyPublicationORIGINALElucidating the adsorption mechanism of herbicide diuron onto activated carbons via steric, energetic and thermodynamic investigations..pdfElucidating the adsorption mechanism of herbicide diuron onto activated carbons via steric, energetic and thermodynamic investigations..pdfapplication/pdf1166981https://repositorio.cuc.edu.co/bitstreams/be9c04d5-03ab-49fc-bdaa-309da29bfa8a/download38248b56ff8dbed9ecca46e1e8022c7fMD51LICENSElicense.txtlicense.txttext/plain; charset=utf-815543https://repositorio.cuc.edu.co/bitstreams/24cb67ac-a232-4888-903c-93194651d96d/download73a5432e0b76442b22b026844140d683MD52TEXTElucidating the adsorption mechanism of herbicide diuron onto activated carbons via steric, energetic and thermodynamic investigations..pdf.txtElucidating the adsorption mechanism of herbicide diuron onto activated carbons via steric, energetic and thermodynamic investigations..pdf.txtExtracted texttext/plain67040https://repositorio.cuc.edu.co/bitstreams/2afedb65-73bd-4beb-b9a6-00fb059b6ba1/download991136b5bf5c4276c199003f71709d9aMD53THUMBNAILElucidating the adsorption mechanism of herbicide diuron onto activated carbons via steric, energetic and thermodynamic investigations..pdf.jpgElucidating the adsorption mechanism of herbicide diuron onto activated carbons via steric, energetic and thermodynamic investigations..pdf.jpgGenerated Thumbnailimage/jpeg14580https://repositorio.cuc.edu.co/bitstreams/9f7611c4-e26d-4c35-948c-d923ada70f6a/downloadf89efc9a9e6762e9e0692d18724195eaMD5411323/13604oai:repositorio.cuc.edu.co:11323/136042024-10-31 03:01:59.628https://creativecommons.org/licenses/by/4.0/© 2023open.accesshttps://repositorio.cuc.edu.coRepositorio de la Universidad de la Costa CUCrepdigital@cuc.edu.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