Corn cob reuse in the adsorption of a commercial formulation of glyphosate

Marcelino, Nayara Valéria Assis; Cuba, Renata Medici Frayne; Teran, Francisco Javier Cuba

doi:10.1590/S1413-415220200088

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Artigo Técnico • Eng. Sanit. Ambient. 26 (4) • Jul-Aug 2021 • https://doi.org/10.1590/S1413-415220200088 copy

Corn cob reuse in the adsorption of a commercial formulation of glyphosate

Authorship SCIMAGO INSTITUTIONS RANKINGS

ABSTRACT

In this study a biochar was produced from corn cob (BCA), which was activated with phosphoric acid to verify its potential for removal of herbicide glyphosate (GLF) (commercial formula) in aqueous media. BCA was characterized by X-ray diffraction spectroscopy, infrared spectroscopy, sorption and desorption of N2, scanning electron microscope, and zero charge potential. Kinetic results of adsorption were adjusted to pseudo-first and pseudo-second order reactions. The adsorption process was studied to verify if it followed Freundlich and Langmuir isotherms, and the thermodynamic parameter was calculated for 23 ^oC, 43 ^cC and 63 ^oC. The results showed that adsorption of GLF on BCA depended on temperature, adsorbent mass, and pH. The best results were obtained for the temperature of 63 ^oC with 0.25 g de GLF and pH = 7.0, conditions that presented 62.3% of GLF removal and low adsorption capacity (2.67 mg. g⁻¹). That was probably due to the porous nature of BCA and co-adsorption of other constituents that were present in the commercial formula of GLF. The adsorption kinetics was represented by the model of pseudo-second order and considered fast, taking 15 min to reach 98% of the maximum adsorption capacity. The isotherm data were well represented by the Freundlich model. Finally, the thermodynamic study demonstrated that the adsorption of GLF is of endothermic nature (ΔHº > 0) and endergonic (ΔGº > 0). The results confirmed that BCA from corn cob is an adsorbent capable of removing GLF (commercial formula) from aqueous media. However, the endothermic nature of the process can compromise its performance in water treatment processes.

corn cob; herbicide; activated carbon; water treatment

Adsorvente	Tempo de equilíbrio	Referência
BCA de sabugo de milho	1 hora	Presente estudo
CA comercial impregnado com Fe e Mn	24 horas	Yamaguchi, Rubio e Bergamasco (2019YAMAGUCHI, N.U.; RUBIO, A.J.; BERGAMASCO, R. Carvão ativado impregnado com manganês e ferro para adsorção de glifosato: Cinética, isotermas e estudos termodinâmicos. Ambiente & Água, v. 14, p. 6, 2019. https://doi.org/10.4136/ambi-agua.2414 https://doi.org/10.4136/ambi-agua.2414... )
BCA da casca de eucalipto	2 horas	Sen, Datta e Mondal (2019SEN, K.; DATTA, J.K.; MONDAL, N.K. Glyphosate adsorption by Eucalyptus camaldulensis bark-mediated char and optimization through response surface modeling Applied Water Science, v. 9, n. 7, p. 162, 2019. https://doi.org/10.1007/s13201-019-1036-3 https://doi.org/10.1007/s13201-019-1036-... )
BC da casca de arroz	1,5 hora	Herath et al. (2016HERATH, I.; KUMARATHILAKA, P.; AL-WABEL, M.I; ABDULJABBAR, A.; AHMAD, M.; USMAN, A.R.A; VITHANAGE, M. Mechanistic modeling of glyphosate interaction with rice husk derived engineered biochar. Microporous and Mesoporous Materials, v. 225, p. 280-288, 2016. https://doi.org/10.1016/j.micromeso.2016.01.017 https://doi.org/10.1016/j.micromeso.2016... )
CA de folhas de palma	4 horas	Salman, Abid e Muhammed (2012SALMAN, J.M.; ABID, F.M.; MUHAMMED, A.A. Batch study for pesticide glyphosate adsorption onto palm oil fronds activated carbon. Asian Journal of Chemistry, v. 24, n. 12, p. 5646-5648, 2012.)
CA resíduo do tratamento de água	20 horas	Hu et al. (2011HU, Y.S.; ZHAO, Y.Q.; SOROHAN, B. Removal of glyphosate from aqueous environment by adsorption using water industrial residual. Desalination, v. 271, n. 1-3, p. 150-156, 2011. https://doi.org/10.1016/j.desal.2010.12.014 https://doi.org/10.1016/j.desal.2010.12.... )
CA de jornal de desperdício	3 dias	Nourouzi, Chuah e Choong (2010NOUROUZI, M.M.; CHUAH, T.G.; CHOONG, T.S.Y. Adsorption of glyphosate onto activated carbon derived from waste newspaper. Desalination and Water Treatment, v. 24, n. 1-3, p. 321-326, 2010. https://doi.org/10.5004/dwt.2010.1461 https://doi.org/10.5004/dwt.2010.1461... )

Adsorvente	q_eqexp	Pseudoprimeira ordem	Pseudossegunda ordem
BCA de sabugo de milho	1,49	q_eqcal = 1,249 k₁ = 0,467 R² = 0,8164	q_eqcal = 1,3781 k₂ = 0,4184 R² = 0,9987

Modelo isotérmico	Temperatura (°C)	Parâmetros
Freundlich	23	K_F	3,79
		n	1,78
		R²	0,93
	43	K_F	4,29
		n	1,04
		R²	0,81
	63	K_F	1,82
		n	1,73
		R²	0,99
Langmuir	23	q_máx	1,26
		K_L	0,3422
		R²	0,63
		RL	0,69
	43	q_máx	1,02
		K_L	0,2961
		R² RL	0,89 0,91
	63	q_máx	2,67
		K_L	0,6745
		R²	0,96
		RL	0,30

Adsorvente	q_máx	Referência
CA comercial impregnado com Fe e Mn	9,19 mg.g⁻¹ (mesoporoso)	Yamaguchi, Rubio e Bergamasco (2019YAMAGUCHI, N.U.; RUBIO, A.J.; BERGAMASCO, R. Carvão ativado impregnado com manganês e ferro para adsorção de glifosato: Cinética, isotermas e estudos termodinâmicos. Ambiente & Água, v. 14, p. 6, 2019. https://doi.org/10.4136/ambi-agua.2414 https://doi.org/10.4136/ambi-agua.2414... )
CA da casca de eucalipto	66,76 mg.g⁻¹ (microporoso)	Sen, Datta e Mondal (2019SEN, K.; DATTA, J.K.; MONDAL, N.K. Glyphosate adsorption by Eucalyptus camaldulensis bark-mediated char and optimization through response surface modeling Applied Water Science, v. 9, n. 7, p. 162, 2019. https://doi.org/10.1007/s13201-019-1036-3 https://doi.org/10.1007/s13201-019-1036-... )
CA funcionalizado com óxido de grafeno	3,7 mg.g⁻¹ (mesoporoso)	Marin et al. (2019MARIN, P.; BERGAMASCO, R.; MÓDENES, A.N.; PARAISO, P.R.; HAMOUDI, S. Synthesis and characterization of graphene oxide functionalized with MnFe2O4 and supported on activated carbon for glyphosate adsorption in fixed bed column. Process Safety and Environmental Protection, v. 123, p. 59-71, 2019. https://doi.org/10.1016/j.psep.2018.12.027 https://doi.org/10.1016/j.psep.2018.12.0... )
BC da casca de arroz	123 mg.g⁻¹ (microporoso)	Herath et al. (2016HERATH, I.; KUMARATHILAKA, P.; AL-WABEL, M.I; ABDULJABBAR, A.; AHMAD, M.; USMAN, A.R.A; VITHANAGE, M. Mechanistic modeling of glyphosate interaction with rice husk derived engineered biochar. Microporous and Mesoporous Materials, v. 225, p. 280-288, 2016. https://doi.org/10.1016/j.micromeso.2016.01.017 https://doi.org/10.1016/j.micromeso.2016... )
BC de resíduo de indústria de bioenergia	44 mg.g⁻¹ (microporoso)	Mayakaduwa et al. (2016MAYAKADUWA, S.S.; KUMARATHILAKA, P.; HERATH, I.; AHMAD, M.; AL-WABEL, M.; OK, Y.S.; USMAN, A.; ABDULJABBAR, A.; VITHANAGE, M. Equilibrium and kinetic mechanisms of woody biochar on aqueous glyphosate removal. Chemosphere, v. 144, p. 2516-2521, 2016. https://doi.org/10.1016/j.chemosphere.2015.07.080 https://doi.org/10.1016/j.chemosphere.20... )
CA de jornal de desperdício	48 mg.g⁻¹ (microporoso)	Nourouzi, Chuah e Choong (2010NOUROUZI, M.M.; CHUAH, T.G.; CHOONG, T.S.Y. Adsorption of glyphosate onto activated carbon derived from waste newspaper. Desalination and Water Treatment, v. 24, n. 1-3, p. 321-326, 2010. https://doi.org/10.5004/dwt.2010.1461 https://doi.org/10.5004/dwt.2010.1461... )
BCA de sabugo de milho	2,67 mg.g⁻¹ (mesoporoso)	Presente estudo

Parâmetros termodinâmicos
T (°C)	K_D	∆Gº (KJ.mol⁻¹)	∆Hº (KJ.mol⁻¹)	∆Sº (KJ.mol⁻¹ K)
23	0,177	4,25	21,7	0,06
43	0,120	5,58
63	0,077	7,16

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[1] * Autora correspondente: nayara.valeria@hotmail.com

Diâmetro médio dos grãos	0,07 mm
Área superficial	34,126 m².g⁻¹
Volume total de poros	0,0498 cm³.g⁻¹
Tipologia	Mesoporosa
Morfologia	Superfície irregular
Composição elementar	C, O, Na e P
Estrutura cristalina	Sólido amorfo
pH_PCZ	8,0