Use of Biochar Prepared from the Açaí Seed as Adsorbent for the Uptake of Catechol from Synthetic Effluents.

This work proposes a facile methodology for producing porous biochar material (ABC) from açaí kernel residue, produced by chemical impregnation with ZnCl2 (1:1) and pyrolysis at 650.0 °C. The characterization was achieved using several techniques, and the biochar material was employed as an adsorbent to remove catechol. The results show that ABC carbon has hydrophilic properties. The specific surface area and total pore volume are 1315 m2·g−1 and 0.7038 cm3·g−1, respectively. FTIR revealed the presence of oxygenated groups, which can influence catechol adsorption. The TGA/DTG indicated that the sample is thermally stable even at 580 °C. Adsorption studies showed that equilibrium was achieved in <50 min and the Avrami kinetic model best fits the experimental data, while Freundlich was observed to be the best-fitted isotherm model. Catechol adsorption on ABC biochar is governed by van der Waals forces and microporous and mesoporous filling mechanisms. The Qmax is 339.5 mg·g−1 (40 °C) with 98.36% removal of simulated effluent, showing that açaí kernel is excellent biomass to prepare good biochar that can be efficiently used to treat real industrial effluents.

Removal of pharmaceutical compounds from aqueous solution by novel activated carbon synthesized from lovegrass (Poaceae).

In this work, lovegrass (Cpa), an abundant grass of the Poaceae family, was employed as feedstock for the production of activated carbon in a conventional furnace using ZnCl2 as a chemical activator. The prepared material (Cpa-AC) was characterized by pH of the point of zero charges (pHpzc), Boehm's titration method, CHN/O elemental analysis, ATR-FTIR, N2 adsorption/desorption curves, and SEM. This carbon material was used for adsorption of acetylsalicylic acid (ASA) and sodium diclofenac (DFC). FTIR analysis identified the presence of O-H, N-H, O-C=O), C-O, and aromatic ring bulk and surface of (Cpa-AC) adsorbent. The quantification of the surface functional groups showed the presence of a large amount of acidic functional groups on the surface of the carbon material. The isotherms of adsorption and desorption of N2 confirm that the Cpa-AC adsorbent is mesopore material with a large surface area of 1040 m2 g-1. SEM results showed that the surface of Cpa-AC is rugous. The kinetic study indicates that the system followed the pseudo-second-order model (pH 4.0). The equilibrium time was achieved at 45 (ASA) and 60 min (DCF). The Liu isotherm model best fitted the experimental data. The maxima sorption capacities (Qmax) for ASA and DFC at 25 °C were 221.7 mg g-1 and 312.4 mg g-1, respectively. The primary mechanism of ASA and DFC adsorption was justified considering electrostatic interactions and π-π interactions between the Cpa-AC and the adsorbate from the solution.

Removal of amoxicillin from simulated hospital effluents by adsorption using activated carbons prepared from capsules of cashew of Para.

High-surface-area activated carbons were prepared from an agroindustrial residue, Bertholletia excelsa capsules known as capsules of Para cashew (CCP), that were utilized for removing amoxicillin from aqueous effluents. The activated carbons were prepared with the proportion of CCP:ZnCl2 1:1, and this mixture was pyrolyzed at 600 (CCP-600) and 700 °C (CCP700). The CCP.600 and CCP.700 were characterized by CHN/O elemental analysis, the hydrophobic/hydrophilic ratio, FTIR, TGA, Boehm titration, total pore volume, and surface area. These analyses show that the adsorbents have different polar groups, which confers a hydrophilic surface. The adsorbents presented surface area and total pore volume of 1457 m2 g-1 and 0.275 cm3 g-1 (CCP.600) and 1419 m2 g-1 and 0.285 cm3 g-1 (CCP.700). The chemical and physical properties of the adsorbents were very close, indicating that the pyrolysis temperature of 600 and 700 °C does not bring relevant differences in the physical and chemical properties of these adsorbents. The adsorption data of kinetics and equilibrium were successfully adjusted to Avrami fractional-order and Liu isotherm model. The use of the adsorbents for treatment of simulated hospital effluents, containing different organic and inorganic compounds, showed excellent removals (up to 98.04% for CCP.600 and 98.60% CCP.700). Graphical abstract.

Conversion of Eragrostis plana Nees leaves to activated carbon by microwave-assisted pyrolysis for the removal of organic emerging contaminants from aqueous solutions.

Eragrostis plana Nees leaves, abundant lignocellulosic biomass, was used as carbon source for preparation of activated carbon, by using microwave-assisted pyrolysis and chemical activation. The novel activated carbon (MWEPN) was characterised by FTIR, CHN elemental analysis, Boehm's titration method, TGA, SEM, N2 adsorption/desorption curves and pH of the point of zero charge (pHpzc). Afterwards, the adsorbent was successfully employed for adsorption of the two emerging contaminants (caffeine and 2-nitrophenol). The results indicated that MWEPN had a predominantly mesoporous structure with a high surface area of 1250 m2 g-1. FTIR analysis indicated the presence of carbonyl, hydroxyl and carboxylic groups on the surface of MWEPN. The Boehm analysis showed the existence of the high amount of acid moieties on the surface of activated carbon. Adsorption kinetic indicated that the system followed the Avrami fractional order at the optimal pH of 7. The equilibrium time was attained at 30 min. The Liu isotherm model better described the isothermal data. Based on the Liu isotherm, the maximum sorption capacities (Qmax) of caffeine and 2-nitrophenol adsorbed onto activated carbon at 25 °C were 235.5 and 255.8 mg g-1, respectively.

Microwave-activated carbons from tucumã (Astrocaryum aculeatum) seed for efficient removal of 2-nitrophenol from aqueous solutions.

Activated carbons (ACs) prepared from tucumã seed (Astrocaryum aculeatum) were used for 2-nitrophenol removal from aqueous solutions. The ACs were characterized by elemental analysis, FTIR, N2 adsorption/desorption isotherms, TGA, hydrophobicity/hydrophilicity balance, and total of acidic and basic groups. The ACs showed to have hydrophilic surfaces and they presented high specific surface areas (up to 1318 m2 g-1). In batch optimization studies, maximum removal was obtained at pH 7, contact time of 30 min, adsorbent dosage 1.5 gL-1 and temperature of 50°C. The general-order kinetic model and Liu isotherm model best fit the kinetic and equilibrium adsorption data with a maximum adsorption capacity of 1382 mg g-1 at 50°C. Effect of temperature and thermodynamic studies revealed that the adsorption processes of 2-nitrophenol onto ACs are dependent on temperature and are exothermic and spontaneous, respectively. About the applicability of the ACs for treating simulated effluents, the tucumã seed-activated carbon showed an excellent outcome in the treatment of simulated effluents, evidencing its high efficiency for phenolic compound adsorption. Tucumã seed-ACs showed to be cost effective and highly efficient adsorbents for efficient removal of 2-nitrophenol from aqueous solutions.

Activated carbons from avocado seed: optimisation and application for removal of several emerging organic compounds.

In this study, avocado seed was successfully used as raw material for producing activated carbons by conventional pyrolysis. In order to determine the best condition to produce the activated carbons, a 22 full-factorial design of experiment (DOE) with three central points was employed by varying the temperature and time of pyrolysis. The two evaluated factors (temperature and time of pyrolysis) strongly influenced the SBET, pore volumes, hydrophobicity-hydrophilicity ratio (HI) and functional groups values; both factors had a negative effect over SBET, pore volumes and functional groups which means that increasing the values of factors leads to decrease of these responses; on the other hand, with regards to HI, both factors caused a positive effect which means that increasing their values, the HI has an enhancement over its values. The produced activated carbon exhibited high specific surface areas in the range of 1122-1584 m2 g-1. Surface characterisation revealed that avocado seed activated carbons (ASACs) have hydrophilic surfaces and have predominantly acidic groups on their surfaces. The prepared ASACs were employed in the adsorption of 25 emerging organic compounds such as 10 pharmaceuticals and 15 phenolic compounds which presented high uptake values for all emerging pollutants. It was observed that the activated carbon prepared at higher temperature of pyrolysis (700 °C), which generated less total functional groups and presented higher HI, was the activated carbon with higher sorption capacity for uptaking emerging organic contaminants. Based on results of this work, it is possible to conclude that avocado seed can be employed as a raw material to produce high surface area and very efficient activated carbons in relation to treatment of polluted waters with emerging organic pollutants.

Effects of first-row transition metals and impregnation ratios on the physicochemical properties of microwave-assisted activated carbons from wood biomass.

First-row transition metals (Co, Ni, Cu and Zn) were successfully used in the preparation of activated carbons from wood biomass via microwave-assisted irradiation. Physical-chemical properties of the produced materials (MWAC) were studied by nitrogen adsorption-desorption curves, SEM, FTIR, UV-vis DRS and synchronous fluorescence spectroscopy, CHN elemental analysis, TGA/DTG, pHzpc, hydrophobic properties, and total acidity and basicity groups. Results showed that the metals were bound successfully in different amounts with surface functional groups of the wood biomass through ion exchange and surface complexation interaction during the impregnation step. Zn2+ and Cu2+ formed the most complexes. MWAC impregnated with Zn2+ showed higher pore volumes and surface areas, followed by Cu2+, Co2+ and Ni2+, independently of the ratio used. As the metal : biomass ratio was increased from 0.5 to 2, the surface area of MWAC increased from 300 to 620m2g-1 for Co-MC, 260 to 381m2g-1 for Ni-MC, 449 to 765m2g-1 for Cu-MC and from 572 to 1780m2g-1 for Zn-MC. The samples showed high values of carbon contents and oxygen-containing groups. An adsorption experiment revealed that samples prepared using ZnCl2 showed the highest sorption capacities (qe) for the tested adsorbates, followed by CuCl2, CoCl2 and NiCl2. These results matched with the surface areas and pore volumes trends, which were found to follow atomic number and melting point trends-Ni(II)bisphenol A>hydroquinone>4-nitro phenol>2-naphtol>paracetamol>caffeine>resorcinol.

Adsorption of Direct Blue 53 dye from aqueous solutions by multi-walled carbon nanotubes and activated carbon.

Multi-walled carbon nanotubes (MWCNT) and powder activated carbon (PAC) were used as adsorbents for adsorption of Direct Blue 53 dye (DB-53) from aqueous solutions. The adsorbents were characterised using Raman spectroscopy, N2 adsorption/desorption isotherms, and scanning and transmission electron microscopy. The effects of initial pH, contact time and temperature on adsorption capacity of the adsorbents were investigated. At pH 2.0, optimum adsorption of the dye was achieved by both adsorbents. Equilibrium contact times of 3 and 4 h were achieved by MWCNT and PAC adsorbents, respectively. The general order kinetic model provided the best fit of the experimental data compared to pseudo-first order and pseudo-second order kinetic adsorption models. For DB-53 dye, the equilibrium data (298-323 K) were best fitted to the Sips isotherm model. The maximum sorption capacity for adsorption of the dye occurred at 323 K, with the values of 409.4 and 135.2 mg g(-1) for MWCNT and PAC, respectively. Studies of adsorption/desorption were conducted and the results showed that DB-53 loaded MWCNT could be regenerated (97.85%) using a mixture 50% acetone + 50% of 3 mol L(-1) NaOH. Simulated dye house effluents were used to evaluate the application of the adsorbents for effluent treatment (removal of 99.87% and 97.00% for MWCNT and PAC, respectively, were recorded).

Antimicrobial membrane cellulose acetate containing ionic liquid and metal nanoparticles.

Stable metallic Au(0), Ag(0) and Pt(0) nanoparticle-containing membrane films (20 microm thickness) were obtained by combining irregularly shaped nanoparticles of monomodal size distributions (11 +/- 1.5 nm Au(0), 8.9 +/- 2.1 nm Ag(0) and 2.8 +/- 0.4 nm Pt(0)) in the ionic liquid (IL) 1-n-butyl-3-methylimidazolium bis(trifluoromethane sulfonyl)imide (BMI x (NTf)2) with a syrup of cellulose acetate (CA) in acetone. The presence of small and stable Au(0), Ag(0) or Pt(0) nanoparticles induced an augmentation in the CA/IL film surface areas. The addition of the IL to the membrane resulted in an increase of its elasticity and a decrease in its tenacity and toughness, whereas its stress at break was not influenced. High antimicrobial activity was observed in membranes containing Au(0), Ag(0) and Pt(0) metal concentrations as low as 1 mg of metal per 5 g of CA. The CA/IL/nanoparticle combination enhanced the activity and durability of the metal nanoparticles and provided greater antimicrobial activity against E. coli and S. aureus bacteria.

Application of carbon adsorbents prepared from Brazilian-pine fruit shell for the removal of reactive orange 16 from aqueous solution: Kinetic, equilibrium, and thermodynamic studies.

Activated (AC-PW) and non-activated (C-PW) carbonaceous materials were prepared from the Brazilian-pine fruit shell (Araucaria angustifolia) and tested as adsorbents for the removal of reactive orange 16 dye (RO-16) from aqueous effluents. The effects of shaking time, adsorbent dosage and pH on the adsorption capacity were studied. RO-16 uptake was favorable at pH values ranging from 2.0 to 3.0 and from 2.0 to 7.0 for C-PW and AC-PW, respectively. The contact time required to obtain the equilibrium using C-PW and AC-PW as adsorbents was 5 and 4h at 298 K, respectively. The fractionary-order kinetic model provided the best fit to experimental data compared with other models. Equilibrium data were better fit to the Sips isotherm model using C-PW and AC-PW as adsorbents. The enthalpy and entropy of adsorption of RO-16 were obtained from adsorption experiments ranging from 298 to 323 K.

Metal nanoparticle/ionic liquid/cellulose: new catalytically active membrane materials for hydrogenation reactions.

Transition metal-containing membrane films of 10, 20, and 40 µm thickness were obtained by the combination of irregularly shaped nanoparticles with monomodal size distributions of 4.8 ± 1.1 nm (Rh(0)) and 3.0 ± 0.4 nm (Pt(0)) dispersed in the ionic liquid (IL) 1-n-butyl-3-methylimidazolium bis(trifluoromethane sulfonyl)imide (BMI·(NTf)(2)) with a syrup of cellulose acetate (CA) in acetone. The Rh(0) and Pt(0) metal concentration increased proportionally with increases in film thickness up to 20 µm, and then the material became metal saturated. The presence of small and stable Rh(0) or Pt(0) nanoparticles induced an augmentation in the CA/IL film surface areas. The augmentation of the IL content resulted in an increase of elasticity and decrease in tenacity and toughness, whereas the stress at break was not influenced. The introduction of IL probably causes an increase in the separation between the cellulose macromolecules that results in a higher flexibility, lower viscosity, and better formability of the cellulose material. The nanoparticle/IL/CA combinations exhibit an excellent synergistic effect that enhances the activity and durability of the catalyst for the hydrogenation of cyclohexene. The nanoparticle/IL/cellulose acetate film membranes display higher catalytic activity (up to 7353 h(-1) for the 20 µm film of CA/IL/Pt(0)) and stability than the nanoparticles dispersed only in the IL.

Pecan nutshell as biosorbent to remove Cu(II), Mn(II) and Pb(II) from aqueous solutions.

In the present study we reported for the first time the feasibility of pecan nutshell (PNS, Carya illinoensis) as an alternative biosorbent to remove Cu(II), Mn(II) and Pb(II) metallic ions from aqueous solutions. The ability of PNS to remove the metallic ions was investigated by using batch biosorption procedure. The effects such as, pH, biosorbent dosage on the adsorption capacities of PNS were studied. Four kinetic models were tested, being the adsorption kinetics better fitted to fractionary-order kinetic model. Besides that, the kinetic data were also fitted to intra-particle diffusion model, presenting three linear regions, indicating that the kinetics of adsorption should follow multiple sorption rates. The equilibrium data were fitted to Langmuir, Freundlich, Sips and Redlich-Peterson isotherm models. Taking into account a statistical error function, the data were best fitted to Sips isotherm model. The maximum biosorption capacities of PNS were 1.35, 1.78 and 0.946mmolg(-1) for Cu(II), Mn(II) and Pb(II), respectively.

Methylene blue biosorption from aqueous solutions by yellow passion fruit waste.

The yellow passion fruit (Passiflora edulis Sims. f. flavicarpa Degener) (YPFW) a powdered solid waste, was tested as biosorbent for the removal of a cationic dye, methylene blue (MB), from aqueous solutions. Adsorption of MB onto this low-cost natural adsorbent was studied by batch adsorption at 25 degrees C. The effects of shaking time, biosorbent dosage and pH on adsorption capacity were studied. In alkaline pH region the adsorption of MB was favorable. The contact time required to obtain the maximum adsorption was 48 h at 25 degrees C. Four kinetic models were tested, being the adsorption kinetics better fitted to pseudo-first order and ion exchange kinetic models. The ion exchange and pseudo-first order constant rates were 0.05594 and 0.05455 h(-1), respectively. The equilibrium data were fitted to Langmuir, Freundlich, Sips and Redlich-Peterson isotherm models. Taking into account the analysis of the normal distribution of the residuals (difference of q(measured)-q(model)), the data were best fitted to Sips isotherm model. The maximum amount of MB adsorbed on YPFW biosorbent was 44.70 mg g(-1).

Adsorption of Cu(II) on Araucaria angustifolia wastes: determination of the optimal conditions by statistic design of experiments.

Wastes of Araucaria angustifolia (named pinhão) natural (PW) and also loaded with Congo red (CRP) were tested as low-cost adsorbents for Cu(II) removal from aqueous solutions. In order to reduce the total number of experiments to achieve the best conditions of the batch adsorption procedure, three sets of statistical designs of experiments were carried-out for each adsorbent. Initially, a full 2(4) factorial design for each adsorbent with two central points (18 experiments) were performed, to optimize the following factors: mass of adsorbent (m), pH, time of contact (t) and initial metallic ion concentration (Co). These results indicated that almost all the main factors and its interactions were significant. It was verified for both adsorbents, that a mass of 30.0mg leaded to higher Cu(II) uptake and that the best pH for Cu(II) adsorption was 5.6. In order to continue the batch adsorption optimization of the systems, a central composite surface analysis design with two factors (Co, t) containing 13 experiments, divided in to four cube points, four axial points and five centre points was carried-out for each adsorbent. By performing these two sets of statistical design of experiments, the best conditions for Cu(II) uptake using pinhão wastes (PW) and pinhão wastes loaded with Congo red (CRP) using batch adsorption system, where: m=30.0mg of adsorbent; pH 5.6; t=2.5h. After optimizing the batch adsorption system by statistical design of experiments, isotherms for Cu(II) uptake using PW and CRP were performed. These isotherms fitted to the linear Langmuir and Freundlich models.

Structure and property studies of hybrid xerogels containing bridged positively charged 1,4-diazoniabicycle[2.2.2]octane dichloride.

The compound di-3-n-propyltrimethoxysilane (1,4-diazoniabicycle[2.2.2]octane) dichloride, [(MeO)3Si(CH2)3N+ (CH2CH2)3N+ (CH2)3Si(OME)3]Cl2 was obtained and was used as a precursor reagent to obtain hybrid xerogels where the organic molecule was bonded to a silica framework by reacting the ends of both sides of the precursor reagent. That is, both -Si(OME)3 groups react with tetraethylorthosilicate (TEOS) by hydrolysis-condensation reactions. The resulting hybrid xerogels with variable C/Si mole ratios were prepared and analyzed and their textural characteristics determined. The samples prepared presented micropores with diameter 1.5 nm, the chain length of which matched with the estimated length of the organic bridging group. The charged organic bridging groups allow the immobilization of hexacyanoferrate ions by an ion exchange process. The electron transfer process of the hexacyanoferrate anionic complex confined in the pores of the matrices was studied by cyclovoltammetry.

Statistical design of experiments as a tool for optimizing the batch conditions to Cr(VI) biosorption on Araucaria angustifolia wastes.

In order to reduce the total number of experiments for achieving the best conditions for Cr(VI) uptake using Araucaria angustifolia (named pinhão) wastes as a biosorbent, three statistical design of experiments were carried out. A full 2(4) factorial design with two blocks and two central points (20 experiments) was experimented (pH, initial metallic ion concentration-C(o), biosorbent concentration-X and time of contact-t), showing that all the factors were significant; besides, several interactions among the factors were also significant. These results led to the performance of a Box-Behnken surface analysis design with three factors (X, C(o) and t) and three central points and just one block (15 experiments). The performance of these two statistical designs of experiments led to the best conditions for Cr(VI) biosorption on the pinhão wastes using a batch system, where: pH 2.0; C(o) = 1200 mg l(-1) Cr(VI); X = 1.5 g l(-1) of biosorbent; t = 8 h. The maximum Cr(VI) uptake in these conditions was 125 mg g(-1). After evaluating the best Cr(VI) biosorption conditions on pinhão wastes, a new Box-Behnken surface analysis design was employed in order to verify the effects of three concomitant ions (Cl(-), NO(3)(-) and PO(4)(3-)) on the biosorption of Cr(VI) as a dichromate on the biosorbent (15 experiments). These results showed that the tested anions did not show any significant effect on the Cr(VI) uptake by pinhão wastes. In order to evaluate the pinhão wastes as a biosorbent in dynamic system, a glass column was fulfilled with pinhão wastes (4.00 g) as biosorbent, and it was fed with 25.0 mg l(-1) Cr(VI) at pH 2.0 and 2.5 ml min(-1). The breakpoint was attained when concentrations of effluent of the column attained the value of 0.05 mg l(-1) Cr(VI) using 5550 ml of the metallic ion solution. In these conditions, the biosorbent was able to remove completely Cr(VI) from aqueous solution with a ratio of Cr(VI) effluent volume/biosorbent volume of 252.3.

Monitoramento ambiental do glifosato e do seu metabólitoácido aminometilfosfônico) na água de lavoura de arroz irrigado / Environmental monitoring of glyphosate and its metabolite (aminomethylphosphonic acid) in tillage water of irrigable rice

Monitorou-se a presença do herbicida Glifosato e do seu metabólito, ácido aminometilfosfônico (AMPA), em amostrasde águas coletadas em área orizícola, submetida a plantio direto. Níveis de Glifosato em concentraçöes acima do limite máximo permitido (7,0 ug/L) pela Agência de Proteçäo Ambiental dos Estados Unidos (Environmental Protection Agency) foram detectados. A presença do metabólito AMPA, nas águas dos canais de irrigaçäo, foi detectada até 120 dias após a aplicaçäo (DAA). Pode-se dizer que determinado nível de segurança será alcançado nas águas de lançamento da granja para o Arroio Bretanhas, 120 DAA da formulaçäode Glifosato. Como näo foi observada deserçäo do Glifosato em Gleyssolo Haplico Ta Eutrófico pode-se inferir que a concentraçäo do mesmo permaneceu como resíduo ligado. Assim, a dissipaçäo do herbicida nesse solo pode ser reflexo, entre outros fatores, da formaçäo de resíduo ligado, determinando desta forma o seu destino e/ou comportamento no ambiente.