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Chemical treatment of sugarcane bagasse and its influence on glyphosate adsorption

Tratamento químico de bagaço de cana-de-açúcar e sua influência na adsorção de glifosato

ABSTRACT

Due to the production rates of sugarcane, nowadays, the sugarcane bagasse stemming in the sugar and alcohol industry is the agro-industrial waste produced in greater volume throughout in Brazil. In 2019, about 192 million tons of this waste were generated. The use of this waste has been the aim of researches around the world, with emphasis on applications that aim to meet the prerogatives of the concept of circular economy. Within this scenario, sugarcane bagasse (SB) was treated in an alkaline medium, forming an adsorbent material, SBNaOH. The effects of chemical treatment were evaluated for surface properties and for glyphosate removal in an aqueous medium. The adsorptive phenomenon was studied through isotherm tests. The results obtained were fitted to classical models of Langmuir, Freundlich and Dubinin-Radushkevich. The characterization indicated that the chemical treatment promoted an important change in the surface of the residue, increasing the surface area. SB and SBNAOH had a feasible behavior as adsorbent and good performance in the removal of the herbicide, presenting values greater than 65% of under all working conditions. The theoretical adsorption saturation governed by Dubinin-Radushkevich (qS) was in the order of 8.988 mg/g (R2=0.988) for SB at 120 minutes of contact and maximum adsorption capacity by Langmuir (Qmax) was 13.720 mg/g (R2=0.984) for SBNaOH at 40 minutes of contact. The process was governed by the exchange or sharing of electrons. The adsorbate is distributed heterogeneously on the SB surface, justifying the presence of active sites with greater ionic strength, and homogeneously on the SBNaOH surface (monolayer). In general, the treated sugarcane bagasse, coming from an agro-industrial residue, proved to be an alternative and promising biosorbent for the removal of glyphosate from aqueous systems, thus generating a new application of this residue.

Keywords
Biosorbent; Agro-industrial waste; Adsorption; Herbicide; Alkaline treatment

RESUMO

Em virtude dos índices de produção da cana-de-açúcar, o bagaço proveniente do processamento da cana na indústria sucroalcooleira é hoje o resíduo agroindustrial produzido em maior volume no Brasil. Em 2019 foram gerados cerca de 192 milhões de toneladas deste resíduo. A utilização deste resíduo tem sido alvo de pesquisas em todo o mundo, com destaque às aplicações que visam atender as prerrogativas do conceito de economia circular. Dentro desse cenário, o bagaço de cana-de açúcar (SB) foi tratado em meio alcalino, formando um material adsorvente, SBNaOH. Os efeitos do tratamento químico foram avaliados quanto a propriedades de superfície e quanto a remoção do herbicida glifosato em meio aquoso. O fenômeno adsortivo foi estudado por meio de ensaios de isotermas. Os resultados obtidos foram ajustados aos modelos clássicos de Langmuir, Freundlich e Dubinin-Radushkevich, onde cada material adsorvente se encaixou em um modelo diferente. A caracterização indicou que o tratamento químico promoveu alteração importante na superfície do resíduo, ampliando a área superficial. SB e o SBNaOH tiveram um comportamento favorável como adsorvente e boa performance na remoção do herbicida, apresentando valores maiores que 65% de em todas as condições de trabalho. A saturação teórica de adsorção regida por Dubinin-Radushkevich (qS) foi na ordem de 8,988 mg/g (R2=0,988) para o SB aos 120 minutos de contato e capacidade máxima encontrada por Langmuir (Qmáx) foi de 13,720 mg/g (R2=0,984) para o SBNaOH aos 40 minutos de contato. O processo foi governado por troca ou partilha de elétrons. O adsorvato se distribui de forma heterogênea na superfície SB, justificando a presença sítios ativos com maior força iônica, e homogeneamente sobre a superfície (monocamada) de SBNaOH. Em geral, o bagaço de cana tratado, provindo de um resíduo agroindustrial, se mostrou um biosorvente alternativo e promissor para remoção de glifosato de sistemas aquosos, gerando assim uma nova aplicação deste resíduo.

Palavras-chave
Biosorvente; Resíduos agroindustriais; Adsorção; Herbicida; Tratamento alcalino

1. INTRODUCTION

The world population has been growing in an alarming number. According to the United Nations (UN) in 2024 the total number of people will be superior to 8 billion, and in 2050, more than 9 billion; those numbers show an increase of 13.16% from 2012 to 2024 and 34.90% from 2012 to 2050 [11 United Nations, Department of Economic and Social Affairs Population Dynamics, 2019, Revision of World Population Prospects, Available in: https://population.un.org/wpp2019/. Accessed November 10 of 2020.
https://population.un.org/wpp2019/...
]. With the population growth, the demand for food, has been increasing and consequently the increase of world agricultural production. The intensive utilization of pesticides, fertilizers and genetic development of seeds, among other factors contributed to increase the world agricultural production [22 CARVALHO, F.P., “Pesticides, environment, and food safety”, Pesticides, Environment, and Food Safety, v. 6, n.2, pp. 48-60, 2017.]. Among the compounds that are more used in the agricultural field can highlight the herbicides, because eliminate plants that will compete with planted crops for nutrients [33 ZHAN, H., FENG, Y., FAN, X., et al., “Recent advances in glyphosate biodegradation”, Applied Microbiology and Biotechnology, v. 102, n. 12, pp. 5033–5043, 2018.]. Glyphosate (N-(phosphonomethyl)glycine) is the most widely used herbicide on earth with properties of a non-selective, systemic and emerging herbicide which its most important function is to control the growth of weeds and grasses [44 SILVA, A.S., FERNANDES, F.C.B., TOGNOLLI, J.O., et al., “A simple and green analytical method for determination of glyphosate in commercial formulations and water by diffuse reflectance spectroscopy”, Spectrochimica Acta Part A., v. 79, n. 5, pp. 1881– 1885, 2011.].

Its application in large areas of cultivation and possible excessive use makes the glyphosate appear more between researches. Although it is considered non-toxic in the last few years it is preoccupying the whole world because of its direct and indirect possible effects on health [55 AMARANTE JÚNIOR, O.P., SANTOS, T.C.R., “Glyphosate: properties, toxicity, use and legislation”, Química Nova, v. 25, n.4, pp. 589-593, 2002.]. The effect to the human body from this herbicide had been demonstrated in a temporary study (2001 to 2015) in adults who live in the northeast of Germany which showed the concentrations of glyphosate on its limit and beyond quantification limit in these people´s urine [66 CONRAD, A., SCHROTER-KERMANI, C., HOPPE, H.W., et al., “Glyphosate in German adults – Time trend (2001 to 2015) of human exposure to a widely used herbicide”. International Journal of Hygiene and Environmental Health, v. 220, n. 1, pp. 8-16, Jan. 2017.]. MARTÍNEZ et al. [77 MARTÍNEZ, M.A., ARES, I., RODRÍGUEZ, J.L., et al., “Neurotransmitter changes in rat brain regions following glyphosate exposure”. Environmental Research, v. 161, pp. 212–219, 2018.] reported alterations in neurotransmitters in mice brain after exposure to glyphosate. Meanwhile in zebrafish the glyphosate caused alteration in morphological and behavioral parameters [88 BRIDI, D., ALTENHOFEN, S., GONZALEZ, J.B., et al., “Glyphosate and Roundup® alter morphology and behavior in zebrafish”, Toxicology, v. 392, n. 32–39, 2017.]. Furthermore, the contamination in the air, soil and water for excessive use of pesticides become a constant concern in last years [99 VAN BRUGGEN, A.H.C., HE, M.M., SHIN, K., et al., “Environmental and health effects of the herbicide glyphosate”, Science of the Total Environment, v. 616–617, pp. 255–268, 2018.].

Due to high mobility of water bodies, it becomes the main concern since even when the herbicide is applied to the soil in large quantities, the contaminating residues are leached into groundwater sources [1010 DYNIA, J.F. “Nitrate Retention and Leaching in Variable Charge Soils of a watershed in São Paulo State, Brazil”, Commun. Soil Sci. Plant Anal., v. 31, n. 5-6, pp. 777-791, 2000.]. This possibility of contaminants leaching makes the water available to the human, animal and plant population even more scarce. Unfortunately, about 1.2 billion people in the world do not have safe, potable and affordable water for their use, due their own activities including extensive use of pesticides, herbicides and, fertilizers [1111 MITIKU, A.A. “A Review on Water Pollution: Causes, Effects and Treatment methods”, Int. J. Pharm. Sci. Rev. Res., v. 60, n. 2, pp. 94-101, 2020.].

Once this contaminant reaches water bodies removal and remediation pathways such as coagulation [1212 BONGIOVANI, M.C., KONRADT-MORAES, L.C., BERGAMASCO, R., et al., “The benefits of using natural coagulants to obtain potable water”, Acta Scientiarum Technology, v. 32, n. 2, pp. 167-170, 2010.], membrane filtration [1313 YUAN, J., DUAN, J., SAINT, C.P., et al., “Removal of glyphosate and aminomethylphosphonic acid from synthetic water by nanofiltration”, Environmental Technology, v. 19, n. 11, pp. 1384 – 1392, 2017.] and advanced oxidative processes (AOPs) [1414 MATAMOROS, V., SALA, L., SALVADÓ, V., “Evaluation of a biologically-based filtration water reclamation plant for removing emerging contaminants: A pilot plant study”, Bioresource Technology, v. 104, pp. 243-249, 2012., 1515 SERNA-GALVIS, E.A., SILVA-AGREDO, J., GIRALDO, A.L., et al., “Comparison of route, mechanism and extent of treatment for the degradation of β-lactam antibiotic by TiO2 photocatalysis, sonochemistry, electrochemistry and the photo-Fenton system”, Chemical Engineering Journal, v. 284, pp. 953–962, 2016.], are being studied. Among these, the adsorption process seems to be the most promising removal pathways of this contaminant [1616 HERATH, I., KUMARATHILAKA, P., AL-WABEL, M.I., et al., “Mechanistic modeling of glyphosate interaction with rice husk derived engineered biochar”, Microporous and Mesoporous Materials, v. 225, n. 280-288, 2016., 1717 RODRIGUEZ-NARVAEZ, O.M., PERALTA-HERNANDEZ, J.M., GOONETILLEKE, A., BANDALA, E.R., “Treatment technologies for emerging contaminants in water: A review”, Chemical Engineering Journal, v. 323, pp. 361-380, 2017.]. Because of the large amount produced, being non-toxic and low cost, agricultural residues such as fruit [1818 GUIZA, S. “Biosorption of heavy metal from aqueous solution using cellulosic waste orange peel”, Ecological Engineering, v. 99, pp. 134–140, 2017., 1919 LEANDRO-SILVA, E., PIPI, A.R.F., MAGDALENA, A.G., et al., “Aplicação dos modelos de Langmuir e Freundlich no estudo da casca de banana como bioadsorvente de cobre (II) em meio aquoso”. Revista Matéria, v.25, n.2, 2020.], sawdust [2020 NJIMOU, J.R., MĂICĂNEANU, A., INDOLEAN, C., et al., “Removal of Cd(II) from synthetic wastewater by alginate–Ayous wood sawdust (Triplochiton scleroxylon) composite material”, Environmental Technology, v. 37, n. 11, pp. 1369–1381, 2016.], rice husks [2121 VITHANAGE, M., MAYAKADUWA, S.S., HERATH, I., et al. “Kinetics, thermodynamics and mechanistic studies of carbofuran removal using biochars from tea waste and rice husks”, Chemosphere, v. 150, pp. 781-789, 2016.], coconut fibers [2222 HENR, Y.K.K., JAROSŁAW, C., WITOLD, Z., “Peat and coconut fiber as biofilters for chromium adsorption from contaminated wastewaters”, Environmental Science and Pollution Research, v. 23, pp. 527–534, 2016., 2323 MERCI, A., REZENDE, M.I., CONSTANTINO, L.V., et al. “Evaluation of different factors in the removal of remazol brilliant blue from aqueous solutions by adsorption in sugarcane and green coconut fibers”. Revista Matéria, v.24, n.3, 2019.] and sugarcane bagasse [2424 XING, Y., LIU, D., ZHANG, L. “Enhanced adsorption of Methylene Blue by EDTAD-modified sugarcane bagasse and photocatalytic regeneration of the adsorbent”. Desalination, v. 259, n. 1-3, pp. 187–219, 2010.

25 FIDELES, R.A., TEODORO, F.S., XAVIER, A.L.P., et al., “Trimellitated sugarcane bagasse: A versatile adsorbent for removal of cationic dyes from aqueous solution. Part II: Batch and continuous adsorption in a bicomponent system”, Journal of Colloid and Interface Science, v. 552, pp. 752-763, 2019.
- 2626 XAVIER, C.S.F., CRISPINIANO, F.F., NASCIMENTO, K.K.R., et al., “Secagem e avaliação do bagaço de cana-de-açúcar como adsorvente de corantes têxteis presentes em soluções aquosas”, Revista Matéria, v.26, n.1, 2021.], show as an alternative to this adsorption process.

Recently, the bagasse from the processing of the sugar-alcohol industry is the agricultural residue produced in a large volume in Brazil because of the high production of sugarcane (Saccharum officinarum) in the country. In 2019/2020 season were produced 642.7 tons of million of sugarcane [2727 CONAB (2020) - Companhia Nacional de Abastecimento, “Monitoring of the Brazilian sugarcane season”, Fourth survey - 2019/2020 Season, Brazilia, v. 6, n. 4, pp. 1-58, April 2020, Available in: http://www.conab.gov.br. Accessed May 10 of 2020.
http://www.conab.gov.br...
]. The quantities of sugarcane bagasse (SB) from this activity corresponds around 30% of the total cane crushed in the industry, generating large amount of residues [2828 SILVA, D.C., MELO, C.A., SOARES JUNIOR, F.H., et al., “Effect of the reaction medium on the immobilization of nutrients in hydrochars Obtained using sugarcane industry residues”, Bioresource Technology, v. 237, pp. 213-221, 2017.]. Being a lignocellulosic material in the form of biomass plant the sugarcane bagasse is constituted specially of cellulose (C5H10O5), hemicellulose (C5H8O4) and lignin (C7H10O3) [2929 GOUVEIA, E.R., NASCIMENTO, R.T., SOUTO-MAIOR, A.M., “Validation of methodology for the chemical characterization of sugar cane bagasse”, Química Nova, v. 32, n. 6, pp. 1500-1503, 2009., 3030 FERREIRA, V.F., ROCHA, D.R., “Potentiality and opportunity in the chemistry of sucrose and other sugars”, Química Nova, v. 32, n. 3, pp. 623-638, 2009.]. Cellulose is rich in hydroxyl which allows the molecule to go through countless of chemical modifications making it interesting to the production of new materials and with different applications [3131 FERREIRA, B.C.S., GIL, L.F., GURGEL, L.V.A., et al. “Obtaining a New Carboxylated Derivative of Microcrystalline Cellulose: An Easy and Solvent-Free Synthesise”, Revista Virtual de Química, v. 9, n. 1, pp. 431-451, 2017.].

In function of the quantity produced, physical and chemical characteristics, such as environment and low cost the sugarcane bagasse has been studied in several areas including animal nutrition [3232 GUNUN, N., WANAPAT, M., GUNUN, P., et al., “Effect of treating sugarcane bagasse with urea and calcium hydroxide on feed intake, digestibility, and rumen fermentation in beef cattle”, Tropical Animal Health and Production, v. 48, pp. 1123-1128, 2016.], construction [3333 CASTRO, T.R., MARTINS, C.H. “Evaluation of the addition of sugarcane bagasse ashes in mixed mortars”, Ambiente Construído, v. 16, n. 3, pp. 137-151, 2016.] and biocomposites [3434 PAIVA, F.F.G., DE MARIA, V.P.K., TORRES, G.B., et al., “Sugarcane bagasse fiber as semi-reinforcement filler in natural rubber composite sandals”, Journal of Material Cycles and Waste Management, v. 2, n. 2, pp. 326-335, 2019.]. Its versatility allows to be used as a biosorbent in the removal of water contaminants including dyes [3535 TAHIR, H., SULTAN, M., AKHTAR, N., et al., “Application of natural and modified sugar cane bagasse for the removal of dye from aqueous solution”, Journal of Saudi Chemical Society, v. 20, n. 1, pp. 115-121, 2016., 3636 UTOMO, H.D., PHOON, R.Y.N., SHEN, Z., et al., “Removal of Methylene Blue Using Chemically Modified Sugarcane Bagasse”, Natural Resources, v. 6, n. 4, pp. 209-220, 2015.], metal ions [3737 MANH, K.N., MINH, T.H., THI, T.P., et al. “Performance Comparison of Chemically Modified Sugarcane Bagasse for Removing Cd(II) in Water Environment”, Journal of Renewable Materials, v. 7, n. 5, pp. 414-427, 2019.], medicines [3838 CARVALHO, R.S., ARGUELHO, M.L.P.M., FACCIOLI, G.G., et al. “Use of orange bagasse biocarbon for the removal of tetracycline in wastewater”, Revista Matéria, v.24, n.3, 2019.] and pesticides [3939 TOLEDO-JALDIN, H.P., SÁNCHEZ-MENDIETA, V., BLANCO-FLORES, A., et al., “Low-cost sugarcane bagasse and peanut shell magnetic-composites applied in the removal of carbofuran and iprodione pesticides”, Environmental Science and Pollution Research, v. 27, pp. 7872–7885, 2020.]. Furthermore, researchers about biochar production from waste has demonstrated the removal of caffeine [4040 ANASTOPOULOS, I., KATSOUROMALLI, A., PASHALIDIS, I., “Oxidized biochar obtained from pine needles as a novel adsorbent to remove caffeine from aqueous solutions”, Journal of Molecular Liquids, v. 304, pp. 11266, 2020.], oxytetracycline [4141 ZHANG, M., MENG, J., LIU, Q., et al., “Corn stover–derived biochar for efficient adsorption of oxytetracycline from wastewater”, Journal of Materials Research, v. 34, n. 17, pp. 3050-3060, 2019.] and copper [4242 SAMARAWEERA, H., PITTMAN JR, C.U., THIRUMALAI, R.V.K.G., et. al., “Characterization of graphene/pine wood biochar hybrids: Potential to remove aqueous Cu2+”, Environmental Research, v. 192, pp. 110283, 2021.] an easier adsorption even though assigned process and consequently obtaining costs in the adsorbent. CUBA et al. [4343 CUBA, R.M.F., GUIMARÃES, M.S., TERÁN, F.J.C., “Production of biochar from sugarcane bagasse to remove glyphosate (commercial formulation) in aqueous medium”, In: 1° South American Congress on Solid Waste and Sustainability, Gramado, Rio Grande do Sul, Brazil, 12 – 14 June 2018.] used sugarcane bagasse in the biochar production to remove glyphosate demonstrating that the use of sugarcane bagasse as raw material to produce charcoal chemically activated shows that it is favorable to the formulation removal based on glyphosate.

Based on the above considerations, its notorious the relevance of waste used from clean source in the adsorption process for the water decontamination. Because of the low number of studies in relations to adsorption of pesticides in the sugarcane bagasse its potential to generate new materials and the exacerbated in the use of glyphosate in agriculture. The present study aims use the sugarcane bagasse treated and untreated as adsorbent material to glyphosate removal.

MATERIALS AND METHODS

Commercial active Roundup® Original DI herbicide glyphosate (N-(phosphonomethyl) glycine) was used for this study obtained in the local market. The sugarcane bagasse was donated from Usina Alto Alegre S/A sugar-alcohol industry located in Santo Inácio-Paraná- Brazil. Sodium hydroxide (99% purity; NaOH; Synth), Ninhydrin (99% purity; C9H6O4; Chemical Dynamics) and sodium molybdate (99% purity; Na2MoO4.2H2O; Synth). All chemicals were used as received.

2.1 Sugarcane bagasse fibers processing and treatment

For the removal of impurities in the sugarcane bagasse it was washed in running water during 48 hours and later on washed in deionized water. The fibers were dried in an oven at 60 °C for 72 h until the mass stabilized. Finally, the fibers were micronized and sieved to obtain particles between 0.15 and 0.11 mm (100 and 140 mesh). This process resulted in the sugarcane bagasse (SB).

The chemical treatment of the sugarcane bagasse fibers was carried out with the main purpose of removing the lignin and increasing cellulose access. For this procedure it used sodium hydroxide solution, 10% w/v (NaOH) and 50 g of sugarcane bagasse according to the methodology described by SANCHEZ et al. [4444 SANCHEZ, E.M.S., CAVANI, C.S., LEAL, C.V., et al., “Unsaturated polyester resin composite with sugar cane bagasse: influence of treatment on the fibers properties”, Polímeros, v. 20, n. 3, pp. 194–200, 2010.]. Briefly, the waste was immersed in alkaline solution under agitation for 24 hours in room temperature (25ºC±2ºC). After this time, the fibers were removed from the solution and washed with deionized water until its pH neutralization. The resulting of the bagasse was dried in the oven for 5 hours at 100 ° C. The treated bagasse is called SBNaOH.

2.2 Characterizatio

The determination of the point of zero charge (pHpzc) was based on GIACOMNI et al. [4545 GIACOMNI, F., MENEGAZZO, M.A.B., SILVA, M.G., et al., “Point of zero charge of protein fibers, an important characteristic for dyeing”, Revista Matéria, v. 22, n. 2, 2017.], which it kept in contact 0.1 g of adsorbent with 10 mL of the aqueous solutions of 100 mg L-1 of glyphosate with 11 different initial pH conditions (1 to 11). The pHpzc of the samples were obtained when calculating the average between the final points of pH tended the same value.

The specific surface area was determined by Brunauer-Emmett-Teller (BET) analyses, using ASAP 2020 (196 ºC - 0 ºC), and pore volume and diameter were calculated using the Barrett-Johner-Halenda method (BJH). The morphology of fibers was determined using Scanning Electron Microscopy (SEM), the images were obtained in a Carls Zeiss microscope EVO-LS 15 model.

2.3 Herbicide Solution and Analysis

Using the methodology proposed by TZASKOS et al.[4646 TZASKOS, D.F., MARCOVICZ, C., DIAS, N.M.P., et al. “Development of sampling for quantification of glyphosate in natural waters”, Agricultural Sciences, v. 36, n. 4, pp. 399-405, 2012.] calibration curve was prepared from a stock solution of 100 mg L-1 of glyphosate. A volume of 1.5 mL of glyphosate solution with aliquots ranging from 0.5 to 10 mg L-1 were transferred to glass vials and 1.5 mL of 5% ninhydrin and 1.5 mL of 5% of sodium molybdate were added to each of the vials. The vials were sealed and kept in a water bath in a temperature of 85-95° C for 12 minutes. Then the samples were cooled to room temperature (25ºC±2ºC) and were quantitatively transferred to volumetric flasks and added 8 mL of MilliQ water. Then the reading was performed by Spectrophotometer-1800, SHIMADZU spectrophotometer at 570 nm.

From this data was constructed a calibration curve with the absorbance as a function of glyphosate concentration in the range from 0.5 to 10 mg L-1. For the baseline of the instrument 1,5 mL of ninhydrin and sodium molybdate solution was used, to a total volume of 4,5 mL. The coefficient od determination (R-squared) was 0.99589.

2.4 Adsorption tests

The pH study of adsorption tests was performed in which the value between the pH range analyzed those results in a larger glyphosate removal. To evaluate this effect the pH solution was adjusted in nine different conditions (2.0 to 10.0) with hydrochloric acid solution and/or NaOH at 0.5 M.

The kinetics adsorption studies were performed through the contact of 0.1g of the adsorbent to 10 mL of contaminated solution (glyphosate concentration of 100 mg L-1) added in glass vials and agitated by a mechanical stirrer at room temperature (25ºC±2ºC) and a gap of 10 min to 24 hours and pH 5 and 9 to the SB and SBNaOH, respectively. After the adsorption time the adsorbents were separated from the aqueous solutions by centrifugation at 4000 rpm for 30 min and so the supernatant was collected. Sequentially, the remain amount of glyphosate was analyzed with the quoted procedure before (item 2.3). All experiments were conducted in triplicates.

The amount of glyphosate adsorbed at equilibrium (qe) was calculated by Equation (1).

q e = ( C 0 C f ) V m (1)

Where: qe (mg g-1) is the adsorption capacity at the equilibrium; C0 (mg L-1) corresponding the initial concentration of glyphosate in the solution, Cf (mg L-1) the concentration of glyphosate at equilibrium, V (L) is the volume of the glyphosate solution and m (g) is the mass of the sugarcane bagasse.

2.5 Adsorption isotherms

For the adsorption of isotherm studies were utilized fixed amounts of adsorbents were used, 0.1 g for 10 mL of contaminated solution. The concentrations range were 5 - 10 - 20 - 30 - 40 - 50 - 60 - 80 and 100 mg L-1, time of 2 hours at pH 6 to SB and 40 min at pH 9 to SBNaOH. The glyphosate adsorption capacity (qe) was calculated by Equation 1 and the removal percentage calculated by Equation 2.

% Removal = [ C 0 C F C 0 ] 100 (2)

In order to describe the interactive behavior between the glyphosate and sugarcane bagasse, were calculated the adsorption balance through nonlinear models by LANGMUIR, FREUNDLICH [4747 NASCIMENTO, R.F., LIMA, A.C.A., VIDAL, C.B., et al., “Adsorption - Theoretical and Environmental Aspects”, Postgraduate Studies Collection - Universidade Federal do Ceará – UFC; 2014.] and DUBININ-RADUSHKEVICH [4848 FOO, K.Y., HAMEED, B.H. “Insights into the modeling of adsorption isotherm systems”, Chemical Engineering Journal, v. 156, n. 1, pp. 2–10, 2010.], according with the Equation (3), (4) and (5), respectively.

q e = Q max K l C e / [ 1 + ( K l C e ) ] (3)
q e = K f C e 1 / n (4)
q e = ( q s ) exp ( K a d ε 2 ) (5)

Where: qe (mg g-1); is the amount of glyphosate adsorbed at equilibrium on the sugarcane bagasse; qmax (g.mg-1) is the amount of glyphosate adsorbed at saturation; Kl (L g-1) is the Langmuir adsorption equilibrium that represents surface affinity; Ce (mg L-1) is the concentration of glyphosate in the liquid phase at equilibrium; Kf (mg g-1); n is an empirical parameter (dimensionless) of Freundlich model, where n provides an indication whether the isotherm is favorable or unfavorable. For D-R isotherm, qs indicate the theoretical isotherm saturation capacity (mg/g), Kad is the constant related to the adsorption energy (mol2 kJ-2), and ε is the Dubinin–Radushkevich isotherm constant.

3. RESULTS AND DISCUSSION

The chemical treatment of the sugarcane bagasse surface with alkaline solution of sodium hydroxide it was possible the majority remove of lignin and the increased exposure to cellulose in consequent increase of roughness and surface area of material. This was observed by PAIVA et al. [3434 PAIVA, F.F.G., DE MARIA, V.P.K., TORRES, G.B., et al., “Sugarcane bagasse fiber as semi-reinforcement filler in natural rubber composite sandals”, Journal of Material Cycles and Waste Management, v. 2, n. 2, pp. 326-335, 2019.] when those treated sugarcane bagasse with alkaline solution for composites production. The treatment of sugarcane bagasse with sodium hydroxide caused swelling in the fibers, increasing the interior surface of the cellulose causing the decrease of crystallinity that is necessary for the lignin breakdown [4949 ALVIRA, P., TOMÁS-PEJÓ, E., BALLESTEROS, M., et al. “Pretreatment technologies for an efficient bioethanol production process based on enzymatic hydrolysis: A review”, Bioresource Technology, v. 101, n. 13, pp. 4851-5486, 2010.] explain the significant increase of the surface area and pore volume of the fibers treated as shown in Table 1.

Table 1
BET and BJH surface parameters of raw sugarcane bagasse (SB) and treated (SBNaOH).

It can be observed that a variation in the results of the surface area SB (0.114 m2 g-1) in the present study and one reported by MOUBARIK & NABIL [5050 MOUBARIK, A., GRIMI, N., “Valorization of olive stone and sugar cane bagasse by-products as biosorbents for the removal of cadmium from aqueous solution”, Food Research International, v. 73, pp. 169-175, 2015.] (0.487 m2 g-1). This variation between the value of literature and this work can be considered not significant once these fibers properties can slightly vary because of the production factors, such as: planting conditions, seasonality factors, irrigation volumes like the way the plant is harvested.

The samples morphology was analyzed by SEM. The Figure 1 shows SB (a - b) and SBNaOH (c-d). The SB images shows an ordered uniform and smooth structure which is associated with the presence of amorphous constituents such as lignin and hemicellulose, as well as wax and extracts as reported by LI et al. [5151 LI, X., TABIL, L.G., PANIGRAHI, S., “Chemical Treatments of Natural Fiber for Use in Natural Fiber-Reinforced Composites: A Review”. Journal of Polymers and the Environment, v. 15, pp. 25-33, 2007.]. While in the SBNaOH images the fibrils were exposed due to the effect of lignin removal that causes the fibrillation process indicating the disorganization in the cellulose structure, confirming the increase of roughness and structure surface area (Table 1) result corroborated by AGUIAR and LUCENA [5252 AGUIAR, C.M., LUCENA, S.L., “Cellulases production by Aspergillus niger and cellulase deactivation kinetic”, Acta Scientiarum Technology, v. 33, n.4, pp. 385-391, 2011.]. However, the alkaline treatment promotes the release of new active sites thus allowing a better interaction between the bagasse and the contaminant.

Figure 1
Scanning electron microscopy images of SB (a) 100 X; b) 700 X; and SBNaOH (c) 100 X; (d) 700 X.

Using the plot of final pH vs initial pH for the SB and SBNaOH, it is possible evaluate the stabilization trend at a given pH, regardless of the initial conditions, which we call pHPZC. The investigation in the adsorption efficiency of glyphosate in different pH`s such as the determination of the point of zero charge (pHPZC) the adsorbents is justified because the adsorption process is dependent on the pH which affects the surface charge ionization level and adsorbate species [4545 GIACOMNI, F., MENEGAZZO, M.A.B., SILVA, M.G., et al., “Point of zero charge of protein fibers, an important characteristic for dyeing”, Revista Matéria, v. 22, n. 2, 2017.]. According Figure 2 the point of zero charge (pHPZC) was obtained at pH 6.36 and pH 9.12, for SB and SBNaOH, respectively.

Figure 2
pH at the point of zero charge (pHpzc) of SB and SBNaOH.

The adsorption study of the pH indicates what value between the analyzed pH range which results in greater glyphosate removal. According to pHPZC, for SBNaOH the optimum adsorption pH would be higher than for SB adsorbent reaching more active sites for adsorption. As observed in Figure 3 the pH value which showed a greater SB removal was the pH 5 approximately 67% while for SBNaOH was the pH 9 with 86%.

Figure 3
Glyphosate removal percentage as a function of effect pH on the adsorption and dissociation onto SB and SBNAOH.

Glyphosate belongs to the phosphonated amino acids group and like the precursor glycine can be separated in two charges being one positive in the amino group and one negative in the phosphonate group [5353 MAYAKADUWA, S.S., KUMARATHILAKA, P., HERATH, I., “Equilibrium and kinetic mechanisms of woody biochar on aqueous glyphosate removal”, Chemosphere, v. 144, pp. 2516-2521, 2016.]. In a pH < 2.6 the glyphosate shows a positive liquid charge, in a pH = 2.6 the glyphosate is neutral and the negative charges increase with pH > 2.6 [5454 CARNEIRO, R.T.A., TAKETA, T.B., NETO, R.J.G., et al., “Removal of glyphosate herbicide from water using biopolymer membranes”, Journal of Environmental Management, v. 151, pp. 353-360, 2015.]. MAYAKADUWA et al. [5353 MAYAKADUWA, S.S., KUMARATHILAKA, P., HERATH, I., “Equilibrium and kinetic mechanisms of woody biochar on aqueous glyphosate removal”, Chemosphere, v. 144, pp. 2516-2521, 2016.] and ESSANDOH et al. [5555 ESSANDOH, M., KUNWAR, B., PITTIMAN, J.R.C.U., et al., “Sorptive removal of salicylic acid and ibuprofen from aqueous solutions using pine wood fast pyrolysis biochar”, Chemical Engineering Journal, v. 265, pp. 219-227, 2015.] reported that when the pHpzc is lower than the pH of the solution the adsorbent surface will be negatively charged while when the pHPZC is higher than the pH of the solution the adsorbent surface tends to be positively charged.

For the SB the pHPZC is greater than the pH solution and the glyphosate molecule in the values of pH 5 (Figure 3) has a prevalence of negative charges, value similar to that used by CUBA et al. [4343 CUBA, R.M.F., GUIMARÃES, M.S., TERÁN, F.J.C., “Production of biochar from sugarcane bagasse to remove glyphosate (commercial formulation) in aqueous medium”, In: 1° South American Congress on Solid Waste and Sustainability, Gramado, Rio Grande do Sul, Brazil, 12 – 14 June 2018.] therefore in this case the removal occurs with the interaction of positive biosorbent charges and negative charges of glyphosate phosphonate group. For SBNaOH the pHPZC value is equal to the pH solution indicating the adsorbent matrix surface has the same amount of positive and negative charges being this way the adsorption occurs by a ligand exchange between the sugarcane bagasse hydroxyl treated with sodium hydroxide and glyphosate phosphonic portion of P-O- group similar reported by PICCOLO et al. [5656 PICCOLO, A., CELANO, G., PIETRAMELLARA, G. “Adsorption of the herbicide glyphosate on a metal-humic acid complex”, Science of The Total Environment, v. 123-124, pp. 77-82, 1992.].

The percentual kinetic study of glyphosate removal in function to time was performed taking in consideration the pH values. Analyzing Figure 4 it is established that the kinetics process was fast for both adsorbents in 40 minutes happens 81.4% of removal to SBNaOH while for the SB has showed a percentage of removal of 77.2% in the first two hours and the maximum removal of 77.9% in 24 hours.

Figure 4
% Glyphosate removal in function of adsorption time on SB and SBNAOH (concentration of of 100 mg L-1).

Observing the data can be noted a reduction in the glyphosate removal percentage after obtaining the maximum samples removal. Such fact can be explained because the bagasse has initially various empty places which were progressively filled until an equilibrium point was reached. When the amount of adsorption glyphosate increased like forces of repulsion between adsorbed molecules made more difficult the adsorption on the rest sites, reducing consequently the adsorption rate making it possible the desorption phenomenon that can occur in the biosorbent surface [5454 CARNEIRO, R.T.A., TAKETA, T.B., NETO, R.J.G., et al., “Removal of glyphosate herbicide from water using biopolymer membranes”, Journal of Environmental Management, v. 151, pp. 353-360, 2015.].

The results in the application of nonlinear models of Langmuir, Freundlich and Dubinin-Radushkevich in the obtained experimental data are shown in Figure 5 (A and B), that shows glyphosate adsorbed at equilibrium (qe) as function of concentration of glyphosate in the liquid phase at equilibrium (Ce). The values of the calculated parameters are shown in Table 2.

Figure 5
Experimental and predicted adsorption isotherms for glyphosate for the Langmuir, Freundlich and Dubinin-Radushkevich non-linear models for (A) SB and (B) SBNAOH.
Table 2
Freundlich and Langmuir isotherm parameters for glyphosate removal using SB and SBNaOH.

It is important to note that all isotherm models applied in that work had satisfactory behavior for both adsorbent materials, with similar adjustments for tested models when consider R2. However, even with similar coefficient of determination, each type of adsorbent present better fits for different model.

The sugarcane bagasse adsorbent (SB) was adjusted for both models, the high R2 values (Langmuir and Freundlich) and the n value (Freundlich) which was showed in Table 2 is greater than 1 indicating that the adsorption is favorable a result confirmed by KL and the 1/N value is 0.075. NASCIMENTO et al. [4747 NASCIMENTO, R.F., LIMA, A.C.A., VIDAL, C.B., et al., “Adsorption - Theoretical and Environmental Aspects”, Postgraduate Studies Collection - Universidade Federal do Ceará – UFC; 2014.] explained the as higher the n value is lower the 1/n value will be implying in a greater interaction between the glyphosate and the sugarcane bagasse. However, the Dubinin-Raduchkevich (D-R) fitted slightly better for those fibers. The D–R isotherm model was developed to account for the effect of the porous structure assuming that the adsorption process was related to micropore volume on the adsorbent walls [5757 HU, Q., ZHANG, Z. “Application of Dubinin–Radushkevich isotherm model at the solid/solution interface: A theoretical analysis”, Journal of Molecular Liquids, v. 277, n. 1, pp. 646-648, 2019.]. Which is in accordance with the SEM discussion, where the SB has amorphous part in its structure.

When analyzing the coefficients of determination (R2), the treated sugarcane bagasse (SBNaOH) showed better fit in Langmuir isotherm, where the herbicide molecules are adsorbed in monolayer. That result corroborate with the experiments of ABREU et al. [5858 ABREU, M.B., ANDRADE, J.R., TURBIANI, F.R.B., et al., “Aplicação de carvão ativado de bagaço de cana-de-açúcar na adsorção de Cd (II) e Cu(II)”. In: Congresso Brasileiro de Sistemas Particulados – ENEMP, Universidade Federal de São Carlos, São Carlos, SP, 2015.] with sugarcane biochar for the adsorption of Cadmium (Cd), and CARVALHO et al. [5959 CARVALHO, R.S., ARGUELHO, M.L.P.M., FACCIOLI, G.G., et al., “Utilização do biocarvão de bagaço de laranja na remoção de tetraciclina em água residuária”, Revista Matéria, v.26, n.2, 2021.] who studied orange peel biochar for tetracycline removal. Analyzing the SBNaOH for the Langmuir model was noticed that the maximum adsorbed amount in the experiment (Table 2) was 13.720 mg.g-1 while the RL factor (separation factor at 100 mg.L-1) was 0.767 mgL-1 indicating that adsorption was favorable (0 <RL <1) that is the adsorbate prefer the solid phase than the liquid [4747 NASCIMENTO, R.F., LIMA, A.C.A., VIDAL, C.B., et al., “Adsorption - Theoretical and Environmental Aspects”, Postgraduate Studies Collection - Universidade Federal do Ceará – UFC; 2014.]. The fit in Langmuir model proposed that adsorption occurs by covering the monolayer of glyphosate molecules above surface of SBNaOH that is each site is responsible by adsorption of only one molecule cannot to occurs additional adsorption [6060 BANERJEE, S., CHATTOPADHYAYA, M.C., “Adsorption characteristics for the removal of a toxic dye, tartrazine from aqueous solutions by a low cost agricultural by product”, Arabian Journal of Chemistry, v. 10, n. 2, pp. S1629-S1638, 2017.], further assuming that the adsorption takes with active sites of the adsorbent with equal affinity for the adsorbate in which interferences in the adsorption of neighboring sites are disregarded [5959 CARVALHO, R.S., ARGUELHO, M.L.P.M., FACCIOLI, G.G., et al., “Utilização do biocarvão de bagaço de laranja na remoção de tetraciclina em água residuária”, Revista Matéria, v.26, n.2, 2021.].

4. CONCLUSIONS

The use of sugarcane bagasse (SB) and chemically treated sugarcane (SBNaOH) showed as favorable to the glyphosate removal in the studied conditions being with pH 5 for SB and pH 9 for SBNaOH at room temperature. SB adsorbent showed removal efficiency of 77% (qS 8.988 mg g-1) occurred in 2 hours with an adsorption plateau, fitting to all tested models (Langmuir, Freundlich and Dubinin-Radushkevich) with showed a similar coefficient of determination. However, the Dubinin-Radushkevich fitted better for those fibers due their amorphous and porous structure of lignin and hemicellulose compounds.

The SBNaOH showed a similar behavior, with small difference between the R2. This adsorbent present fast adsorption with 81% of removal in 40 min and maximum capacity of adsorption of 13.720 mg g-1 (Qmax). In this case it occurred adjust for the Langmuir model, therefore the adsorption occurs by covering the monolayers of glyphosate molecules over the surface bagasse.

All factors involved in the study showed that the alkaline treatment in sugarcane bagasse and final glyphosate adsorption fulfill the proposed objective providing biosorbent with capacity of maximum removal higher than untreated material as well a smaller taken time for adsorption.

As shown in previous literature - mentioned in this work - the alkaline treatment for natural fibers has been shown to be very efficient and viable for different applications. In this case it was no different, the treatment proved to be efficient in improving the adsorbent material for herbicide removal. As it is a cheap alkaline, easy to handle, and with small amount of waste, this type of treatment has been feasible in terms of cost/benefit.

Therefore, presenting a possibility alkaline treatment to increase efficiency in the lignocellulosic fibers such as aqueous solutions decontamination agents. Hence, the perspectives for this material and its future application in the industry are very favorable, however more evaluations such as the effect of temperature and recyclability must be carried out.

ACKNOWLEDGEMENTS

The authors would like to acknowledge the financial support from “Coordenação de Aperfeiçoamento de Pessoal de Nível Superior” (CAPES - Brazil) - Finance Code 001 and “Conselho Nacional de Desenvolvimento Científico e Tecnológico” (CNPq). The authors also thank “LabMMEV- FCT/UNESP” by microscopy images.

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Publication Dates

  • Publication in this collection
    13 May 2022
  • Date of issue
    2022

History

  • Received
    11 Feb 2021
  • Accepted
    19 Sept 2021
Laboratório de Hidrogênio, Coppe - Universidade Federal do Rio de Janeiro, em cooperação com a Associação Brasileira do Hidrogênio, ABH2 Av. Moniz Aragão, 207, 21941-594, Rio de Janeiro, RJ, Brasil, Tel: +55 (21) 3938-8791 - Rio de Janeiro - RJ - Brazil
E-mail: revmateria@gmail.com