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This study reports the use of multivariate tools to optimize the synthesis of a new agricultural-based biosorbent derived from sugarcane bagasse (SB) for the removal of Cd(II) and Pb(II) from aqueous solutions, as well as to optimize the process of desorption of these ions from the spent biosorbent using an acidic solution. The effects of the reaction parameters temperature (T), time (t), and the ratio of 1,2,3,4-butanetetracarboxylic acid dianhydride (BTCAD) to raw SB (wBTCAD wraw SB−1) on the chemical modification of raw SB with BTCAD and on the equilibrium adsorption capacity (qe) for Cd(II) and Pb(II) were investigated by application of a 23 Doehlert experimental design (DED), followed by optimization using a statistical desirability tool to produce the best adsorbent in terms of performance and cost. The best reaction condition was wBTCAD wraw SB−1 of 4.0 g g−1, t of 1 h, and T of 70 ºC. The optimal synthesis condition resulted in a modified sugarcane bagasse (MSB) that provided qe values for Cd(II) and Pb(II) of 0.50 and 0.61 mmol g−1, respectively, obtained under the following conditions: 0.311 mmol Cd(II) L−1, 0.632 mmol Pb(II) L−1, pH 5.0, 4 h, 0.2 g L−1 MSB, 130 rpm, and 25 °C. The desorption of Cd(II) and Pb(II) from MSB was investigated by a 22 DED, with optimization using the desirability tool to obtain the best desorption condition in terms of HNO3 solution concentration ( C HNO 3 ) and t. The desorption efficiencies for Cd(II) and Pb(II) were 90 ± 4% and 88 ± 3%, respectively, obtained using 0.7 mol L−1 HNO3, t of 42 min, and 1.0 g L−1 MSB-M(II) (M = Pb or Cd). Infrared spectroscopy was used to investigate the natures of the interactions involved in the adsorption of Cd(II) and Pb(II) on MSB, as well as possible changes in the chemical structure of MSB after desorption. The synthesis of MSB can be performed under mild reaction conditions (t = 1 h, T = 70 ºC), and the solvents used can be recovered by distillation. BTCA is commercially available at moderate cost and can alternatively be obtained employing microbial succinic acid, metal-free catalysis, and modest use of petrochemical feedstocks. Furthermore, MSB can be reused, which could contribute to increasing the economic feasibility of water and wastewater treatment processes. [ABSTRACT FROM AUTHOR]

A new one-pot synthesis method optimized by a 23 experimental design was developed to prepare a biosorbent, sugarcane bagasse cellulose succinate pyromellitate (SBSPy), for the removal of Cu(II) and Zn(II) from single-component aqueous solutions, in batch and continuous modes. The bi-functionalization of the biosorbent with ligands of different chemical structures increased its selectivity, improving its performance for removing pollutants from contaminated water. The succinate moiety favored Cu(II) adsorption, while the pyromellitate moiety favored Zn(II) adsorption. Sugarcane bagasse (SB) and SBSPy were characterized using several techniques. Analysis by 13C Multi-CP SS NMR and FTIR revealed the best order of addition of each anhydride that maximized the chemical modification of SB. The maximum adsorption capacities of SBSPy for Cu(II) and Zn(II), in batch mode, were 1.19 and 0.95 mmol g-1, respectively. Homogeneous surface diffusion, intraparticle diffusion, and Boyd models were used to determine the steps involved in the adsorption process. Isothermal titration calorimetry was used to assess changes in enthalpy of adsorption as a function of SBSPy surface coverage. Fixed-bed column adsorption of Cu(II) and Zn(II) was performed in three cycles, showing that SBSPy has potential to be used in water treatment. Breakthrough curves were well fitted by the Thomas and Bohart-Adams models. [ABSTRACT FROM AUTHOR]

Batch and continuous adsorption of Co2+ and Cu2+ from aqueous solutions by oxidized sugarcane bagasse (SBox) and oxidized cellulose (Cox) were investigated. The oxidation reaction of sugarcane bagasse and cellulose was made with a mixture of H3PO4‒NaNO2 to obtain SBox and Cox, with the introduction of high number of carboxylic acid functions, 4.5 and 4.8 mmol/g, respectively. The adsorption kinetics of Co2+ and Cu2+ on SBox and Cox were modeled using two models (pseudo-first-order and pseudo-second-order) and the rate-limiting step controlling the adsorption was evaluated by Boyd and intraparticle diffusion models. The Sips and Langmuir models better fitted the isotherms with values of maximum adsorption capacity Q max of 0.68 and 0.37 mmol/g for Co2+ and 1.20 and 0.57 mmol/g for Cu2+ adsorption on Cox and SBox, respectively. The reuse of both spent adsorbents was evaluated. Adsorption of Cu2+ and Co2+ on SBox in continuous was evaluated using a 22 factorial design with spatial time and initial metal concentration as independent variables and Q max and effective use of the bed as responses. The breakthrough curves were very well described by the Bohart–Adams original model and the Q max values for Co2+ and Cu2+ were 0.22 and 0.55 mmol/g. SBox confirmed to be a promising biomaterial for application on a large scale. [ABSTRACT FROM AUTHOR]

In this study, four different adsorbent materials: commercial powdered activated carbon (PAC) from pine tree (PAC-I) and coconut shell (PAC-III) agricultural crop wastes, coal (PAC-II), and carbon nanotubes (CNT) were tested and compared for the removal of sulfamethoxazole (SMX) from spiked aqueous solutions. The kinetic, extrathermodynamic, and thermodynamic parameters for the adsorption of SMX on PACs and CNT were also determined. The results indicate that PAC-I was the best adsorbent for SMX adsorption. SMX adsorption was only favorable with PAC-I and CNT, leading to Gibbs free energies in the range of −39 to −44 kJ mol −1 and showing that the adsorption process was spontaneous in all temperature ranges (15–45 °C) tested. Langmuir model best described SMX adsorption on PAC-I and led to maximum adsorption capacity of ∼131 mg g −1 (at 25 °C), which was ∼4.6 times higher than that observed for CNT. The mechanism of SMX adsorption on PAC-I and CNT was suggested with basis on thermodynamic and extrathermodynamic parameters. The kinetic studies showed the pseudo-second-order model best described SMX adsorption, yielding k 2 values of 0.0035 and 0.0016 g mg −1 min −1 for PAC-I and CNT, respectively. [ABSTRACT FROM AUTHOR]

A bioadsorbent (CEDA) capable of adsorbing As(V) and Cu(II) simultaneously was prepared by tosylation of microcrystalline cellulose (MC) and nucleophilic substitution of the tosyl group by ethylenediamine. MC, tosyl cellulose, and CEDA were characterized by elemental C, H, N, and S analysis, infrared spectroscopy, and 13C solid-state nuclear magnetic resonance spectroscopy. The adsorption of As(V) and Cu(II) on CEDA was evaluated as a function of solution pH, contact time, and initial solute concentration. The maximum adsorption capacities of CEDA for As(V) and Cu(II) were 1.62 and 1.09 mmol g−1, respectively. The interactions of As(V) and Cu(II) with CEDA were elucidated using thermodynamic parameters, molecular quantum mechanics calculations, and experiments with ion exchange of Cd(II) by Cu(II), and As(V) by SO 4 2−. Adsorption enthalpies were determined as a function of surface coverage of the CEDA, using isothermal titration calorimetry, with Δ ads H ° values of −32.24 ± 0.07 and −93 ± 2 kJ mol−1 obtained for As(V) and Cu(II), respectively. The potential to reuse CEDA was evaluated and the interference of other ions in the adsorption of As(V) and Cu(II) was investigated. Multi-component experiments showed that Cd(II), Co(II), Ni(II), and Pb(II) did not interfere in the adsorption of Cu(II), while SO 4 2− inhibited As(V) adsorption. [ABSTRACT FROM AUTHOR]

In the second part of this series of studies, the bicomponent adsorption of safranin-T (ST) and auramine-O (AO) on trimellitated sugarcane bagasse (STA) was evaluated using equimolar dye aqueous solutions at two pH values. Bicomponent batch adsorption was investigated as a function of contact time, solution pH and initial concentration of dyes. Bicomponent kinetic data were fitted by the pseudo-first-order and pseudo-second-order models and the competitive model of Corsel. Bicomponent equilibrium data were fitted by the real adsorbed solution theory model. The antagonistic interactions between ST and AO in the adsorption systems studied contributed to obtain values of maximum adsorption capacity in mono- (Q max,mono) and bicomponent (Q max,multi) lower than unity (Q max,multi / Q max,mono at pH 4.5 for ST of 0.75 and AO of 0.37 and at pH 7 for ST of 0.94 and AO of 0.43). Mono- and bicomponent adsorption of dyes in a fixed-bed column was evaluated at pH 4.5. The breakthrough curves were fitted by the Thomas and Bohart-Adams original models. Desorption of ST in a fixed-bed column was studied. The results obtained from the bicomponent batch and continuous adsorption showed that the presence of ST most affected the AO adsorption than the presence of AO affected the ST adsorption. [ABSTRACT FROM AUTHOR]

Sugarcane bagasse cellulose succinate trimellitate (SBST) was prepared by a one-pot synthesis method. The synthesis of this novel mixed ester was investigated by a 23-factorial design. The parameters investigated were time, temperature, and succinic anhydride mole fraction (χ SA). The responses evaluated were the adsorption capacity (q Co2+ and q Ni2+), weight gain (wg), and number of carboxylic acid groups (n T,COOH). 13C Multiple Cross-Polarization solid-state NMR spectroscopy, 1H NMR relaxometry, and Fourier-transform infrared spectroscopy were used to elucidate the SBST structure. The best SBST reaction conditions were 100 °C, 660 min, and χ SA of 0.2, which yielded SBST with a wg of 57.1%, n T,COOH of 4.48 mmol g−1, and q Co2+ and q Ni2+ of 0.900 and 0.963 mmol g−1, respectively. The maximum adsorption capacities (Q max) (pH 5.75, 25 °C) estimated by the Redlich-Peterson model for Co2+ and Ni2+ were 1.16 and 1.29 mmol g−1. The Δ ads H ° values for Co2+ and Ni2+ adsorption obtained by isothermal titration calorimetry were 8.03 and 6.94 kJ mol−1. Regeneration and reuse of SBST were investigated and the best conditions applied for fixed-bed column adsorption in five consecutive cycles. SBST was fully desorbed and Q max values for Co2+ (0.95 mmol g−1) and Ni2+ (1.02 mmol g−1) were estimated using the Bohart-Adams model. [ABSTRACT FROM AUTHOR]

Graphical abstract Abstract Sugarcane bagasse cellulose mixed ester succinate phthalate (SBSPh) was synthesized by a novel one-pot reaction method. The effects of temperature, time and mole fraction of succinic anhydride (χ SA) on the responses weight gain (wg), number of carboxylic acid groups (n T,COOH), and adsorption capacity (q) of Co2+ and Ni2+ were evaluated by a 23 experimental design. The chemical structure of the material was elucidated by Fourier transform infrared, 13C Multiple Cross-Polarization solid-state NMR spectroscopy and 1H NMR relaxometry. The best SBSPh synthesis condition (100 °C, 11 h, χ SA of 0.2) yielded a wg of 59.1%, n T,COOH of 3.41 mmol g−1, and values of q Co 2+ and q Ni 2+ of 0.348 and 0.346 mmol g−1, respectively. The Sips model fitted better the equilibrium data, and the maximum adsorption capacities (pH 5.75 and 25 °C) estimated by this model were 0.62 and 0.53 mmol g−1 for Co2+ and Ni2+, respectively. The Δ ads H ° values estimated by isothermal titration calorimetry were 8.43 and 7.79 kJ mol−1 for Co2+ and Ni2+, respectively. Desorption and re-adsorption efficiencies were evaluated by a 22 experimental design, which showed that SBSPh adsorbent can be recovered and reused without significant loss of adsorption capacity. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Bifunctionalized chitosan(C4) was synthesized for removal of both Cu2+ and Cr6+. • C4 was insoluble in water in a pH range of 1–10. • The maximum adsorption capacity of C4 for Cu2+ adsorption at pH 5.5 was 2.60 mmol/g. • The maximum adsorption capacity of C4 for Cr6+ adsorption at pH 2.0 was 3.50 mmol/g. • The re-adsorption efficiency of C4 was 106% for Cu2+ and 44% for oxyanions of Cr6+. Abstract This study describes the chemical modification of chitosan to produce a novel bifunctionalized adsorbent material (C4) for the removal of Cu2+ and oxyanions of Cr6+ from a single aqueous solution. The chemical modifications allowed C4 to be insoluble under acidic conditions, improving the chemical properties of the modified chitosan in aqueous solution. C4 adsorbent was synthesized by reaction of the amino group of chitosan with 2-pyridinecarboxaldehyde, a reduction of imine group, followed by esterification with EDTA dianhydride (EDTAD). C4 was characterized by solid-state 13C nuclear magnetic resonance, infrared spectroscopy, and elemental analysis. The adsorption studies of Cu2+ and oxyanions of Cr6+ in a batch mode were evaluated as a function of the contact time (kinetics), solution pH, and initial metal ion concentration. The maximum adsorption capacities (Q max) of C4 for the adsorption of Cu2+ (pH 5.5) and Cr6+ (pH 2.0) were 2.60 and 3.50 mmol/g, respectively. The reusability of the recovered C4 adsorbent was also evaluated. [ABSTRACT FROM AUTHOR]

In the second part of this series of studies, the monocomponent adsorption of Cu 2+ , Co 2+ and Ni 2+ onto STA adsorbent in a fixed-bed column was investigated and optimized using a 2 2 central composite design. The process variables studied were: initial metal ion concentration and spatial time, and the optimized responses were: adsorption capacity of the bed ( Q max ), efficiency of the adsorption process ( EAP ), and effective use of the bed ( H ). The higher Q max for Cu 2+ , Co 2+ and Ni 2+ were 1.060, 0.800 and 1.029 mmol/g, respectively. The breakthrough curves were modeled by the original Thomas and Bohart-Adams models. The changes in enthalpy (Δ ads H °) of adsorption of the metal ions onto STA were determined by isothermal titration calorimetry (ITC). The values of Δ ads H ° were in the range of 3.0–6.8 kJ/mol, suggesting that the adsorption process involved physisorption. Desorption ( E des ) and re-adsorption ( E re-ads ) of metal ions from the STA adsorbent were also investigated in batch mode, and the optimum conditions were applied for three cycles of adsorption/desorption in a fixed bed column. For these cycles, the lowest values of E des and E re-ads were 95 and 92.3%, respectively, showing that STA is a promising candidate for real applications on a large scale. [ABSTRACT FROM AUTHOR]

Trimellitated-sugarcane bagasse (STA) was used as an environmentally friendly adsorbent for removal of the basic dyes auramine-O (AO) and safranin-T (ST) from aqueous solutions at pH 4.5 and 7.0. Dye adsorption was evaluated as a function of STA dosage, agitation speed, solution pH, contact time, and initial dye concentration. Pseudo-first- and pseudo-second-order, Elovich, intraparticle diffusion, and Boyd models were used to model adsorption kinetics. Langmuir, Dubinin-Radushkevich, Redlich-Peterson, Sips, Hill-de Boer, and Fowler-Guggenheim models were used to model adsorption isotherms, while a Scatchard plot was used to evaluate the existence of different adsorption sites. Maximum adsorption capacities for removal of AO and ST were 1.005 and 0.638 mmol g −1 at pH 4.5, and 1.734 and 1.230 mmol g −1 at pH 7.0, respectively. Adsorption enthalpy changes obtained by isothermal titration calorimetry (ITC) ranged from −21.07 ± 0.25 to −7.19 ± 0.05 kJ mol −1 , indicating that both dyes interacted with STA by physisorption. Dye desorption efficiencies ranged from 41 to 51%, and re-adsorption efficiencies ranged from 66 to 87%, showing that STA can be reused in new adsorption cycles. ITC data combined with isotherm studies allowed clarification of adsorption interactions. [ABSTRACT FROM AUTHOR]

In the third part of this series of studies, the adsorption of the basic textile dyes auramine-O (AO) and safranin-T (ST) on a carboxylated cellulose derivative (CTA) were evaluated in mono- and bi-component spiked aqueous solutions. Adsorption studies were developed as a function of solution pH, contact time, and initial dye concentration. Adsorption kinetic data were modeled by monocomponent kinetic models of pseudo-first- (PFO), pseudo-second-order (PSO), intraparticle diffusion, and Boyd, while the competitive kinetic model of Corsel was used to model bicomponent kinetic data. Monocomponent adsorption equilibrium data were modeled by the Langmuir, Sips, Fowler-Guggenhein, Hill de-Boer, and Konda models, while the IAST and RAST models were used to model bicomponent equilibrium data. Monocomponent maximum adsorption capacities for AO and ST at pH 4.5 were 2.841 and 3.691 mmol g −1 , and at pH 7.0 were 5.443 and 4.074 mmol g −1 , respectively. Bicomponent maximum adsorption capacities for AO and ST at pH 7.0 were 1.230 and 3.728 mmol g −1 . Adsorption enthalpy changes (Δ ads H ) were obtained using isothermal titration calorimetry. The values of Δ ads H ranged from −18.83 to −5.60 kJ mol −1 , suggesting that physisorption controlled the adsorption process. Desorption and re-adsorption of CTA was also evaluated. [ABSTRACT FROM AUTHOR]

In the second part of this series of studies, the competitive adsorption of three binary systems Cu 2+ –Co 2+ , Cu 2+ –Ni 2+ and Co 2+ –Ni 2+ on a carboxylated cellulose derivative (CTA) was evaluated in binary equimolar (1:1) metal–ion aqueous solutions. Bicomponent adsorption studies were developed as a function of contact time and initial metal ion concentration. Bicomponent adsorption kinetic data was modeled by monocomponent kinetic models of pseudo-first- (PFO) and pseudo-second-order (PSO) and a competitive kinetic model of Corsel. Bicomponent adsorption isotherm data was modeled by the ideal adsorbed solution theory (IAST) and real adsorbed solution theory (RAST) models. The monocomponent isotherm models implemented into the IAST were the Langmuir and Sips models, whereas for the RAST model only the Langmuir model was implemented because this model provided the best prediction of the bicomponent isotherm data. The surface of the CTA adsorbent after bicomponent adsorption of metal ions was also examined by SEM-EDX. The effect of one metal ion on the adsorption capacity of another metal ion was discussed in detail with basis on the kinetic and thermodynamics parameters. The selectivity and performance of the CTA adsorbent for the removal of Cu 2+ , Co 2+ and Ni 2+ was also evaluated and discussed. [ABSTRACT FROM AUTHOR]

This study describes the synthesis of a new chitosan derivative (C2) with zwitterionic characteristics and its use for the removal of cationic species Cu 2+ , Co 2+ , and Ni 2+ and anionic species of Cr 6+ in a single aqueous solution. The new adsorbent was synthesized by quaternization of the amine group of chitosan and esterification of hydroxyl groups with EDTA dianhydride. These combined reactions gave both cationic and anionic characteristics to C2 with the release of quaternary ammonium groups and carboxylic groups. The capacity of C2 to adsorb Cu 2+ , Co 2+ , Ni 2+ , and oxyanions of Cr 6+ was evaluated in a batch process with different contact times, pH values, and initial concentrations. Adsorption isotherms were best fitted to the Langmuir and Sips models. The maximum adsorption capacities ( Q max ) of C2 for adsorption of Cu 2+ , Co 2+ , Ni 2+ , and Cr 6+ were 0.698, 1.125, 0.725, and 1.910 mmol/g, respectively. The Δ ads G ° values were in the range from −20 to −28 kJ/mol. These values suggest a mixed mechanism controlling adsorption. Desorption studies using an aqueous solution consisting of 0.1 mol/L HNO 3 were carried out. The reusability of the recovered C2 adsorbent after desorption was also evaluated. [ABSTRACT FROM AUTHOR]

This study describes, in detail, the chemical modification of sugarcane bagasse with phthalic anhydride to produce a carboxylate-functionalized sugarcane bagasse (SPA). The optimized modification conditions yielded SPA with a percent weight gain of 77.08% and an amount of carboxylic acid groups of 4.76 mmol/g. The SPA was characterized by PZC, FTIR, elemental analysis, TGA, and SEM-EDX. An SPA adsorbent was used to remove Co 2+ , Cu 2+ , and Ni 2+ from aqueous solution in mono- and multicomponent systems in batch mode. The adsorption kinetics followed a pseudo-second-order model. The adsorption rate constants assumed the following order: k 2,Co 2+ > k 2,Ni 2+ > k 2,Cu 2+ . Four mono- and multicomponent isotherm models were used to model the adsorption data. Monocomponent data were well described by the Langmuir model, whereas bicomponent data were well described by the modified extended Langmuir and P -Factor models. The maximum adsorption capacities ( Q max,mono ) for the Langmuir model were 0.561, 0.935, and 0.932 mmol/g for Co 2+ , Cu 2+ , and Ni 2+ , respectively. Adsorption in bicomponent systems revealed that Cu 2+ suppressed the adsorption of Co 2+ and Ni 2+ , whereas Ni 2+ suppressed the adsorption of Co 2+ . Desorption studies revealed that the SPA adsorbent could be fully desorbed with a 1 mol/L HNO 3 solution. [ABSTRACT FROM AUTHOR]

A new carboxylate-functionalized sugarcane bagasse (SMA) was prepared via a solvent-free procedure involving esterification of sugarcane bagasse with Meldrum's acid. The optimized conditions provided SMA with a percent weight gain of 86.0% and 4.69 ± 0.20 mmol/g of carboxylic acid groups. SMA was characterized by FTIR, TGA, elemental analysis and SEM. Kinetic experiments showed that the amount of crystal violet adsorbed increased with increasing temperature and equilibrium was reached at 12 h. Adsorption kinetics followed a pseudo-second-order model. The Arrhenius and Eyring models were used to obtain the activation energy and changes in free energy, enthalpy, and entropy of activation for the adsorption process. The calculated activation energy (14.14 kJ/mol) suggested physical adsorption of CV onto SMA. The equilibrium data were well fitted to the Langmuir and Sips isotherms. Maximum adsorption capacity was 692.1 mg/g at 45 °C. Thermodynamic parameters such as changes in free energy, enthalpy and entropy were also determined. [ABSTRACT FROM AUTHOR]