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The aim of the present research is to show the development of a sustainability-oriented lab that teaches adsorption concepts in a virtual environment based on the premise "learning-through-play". Kinetic results in the virtual environment are contrasted to those obtained experimentally when diverse adsorbents prepared from Agave Bagasse (Raw Fibers, Hydrothermal Fibers, and Activated Fibers) were synthesized. Comparison between virtual and real-life experiments involving removal of methylene blue in solution showed that a pseudo-first-order model could describe adsorption kinetics satisfactorily. The study is complemented with a characterization of the adsorbents through SEM, nitrogen adsorption isotherms, FTIR and Raman. In addition, the environmental impact of the synthesis of adsorbents was evaluated through well-known methodologies (GAPI, NEMI, and Eco-Scale), which agree that raw fibers are the most eco-friendly material. This research provides an exciting opportunity to advance our knowledge on developing new technologies for teaching in engineering and to compliment real-life practices that consider environmental impacts with virtual experiments.

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Dye effluents cause diverse environmental problems. Methylene blue (MB) dye stands out since it is widely used in the textile industry. To reduce the pollution caused by the MB, we developed biosorbents from tucumã seeds, where the in natura seeds were treated with NaOH (BT) and H3PO4 (AT) solutions and characterized by Boehm titration, point of zero charges, FTIR, TGA, BET, and SEM. It was observed that the acid groups predominate on the surface of the three biosorbents. The process was optimized for all biosorbents at pH = 8, 7.5 g/L, 240 min, C0 = 250 mg/L, and 45 ℃. BT was more efficient in removing MB (96.20%; QMax = 35.71 mg/g), while IT and AT removed around 60% in similar conditions. The adsorption process best fits Langmuir and Redlich-Peterson isotherms, indicating a hybrid adsorption process (monolayer and multilayer) and pseudo-second-order kinetics. Thermodynamic data confirmed an endothermic and spontaneous adsorption process, mainly for BT. MB was also recovered through a desorption process with ethanol, allowing the BT recycling and reapplication of the dye. Thus, an efficient and sustainable biosorbent was developed, contributing to reducing environmental impacts.

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In this study, sugarcane bagasse ash (SCBA), obtained as residue from the sugar mill, was used as an adsorbent for Acid Red 27 (AR27) removal from aqueous solutions. The ash characterization data showed 23.63% of organic compounds and silica (α-SiO2) as the most expressive inorganic compound (confirmed by X-ray diffractogram), the BET surface area had a value of 62.79 m2.g-1 and the pHpzc was 8.45. Regarding the adsorptive tests, the optimal initial pH to the dye removal was 2.0. The adsorption equilibrium reached in about 4 h contact time and optimum SCBA dosage was found to be 4 g.L-1. The pseudo-second order model best represented the adsorption kinetics. The Freundlich equation presented the best fit to the equilibrium data for the removal of AR27 by ash, with maximum adsorption capacity of 15 mg.g-1 at pH 2.0. Thermodynamic study indicate that AR27 adsorption on SCBA occurs through a physisorption mechanism, with ΔHºads < 15 kJ.mol-1. The ΔHºads evaluated by Vant' Hoff equation was explained as a combination of water desorption enthalpy, ΔHºW and isosteric like enthalpy, ΔHºD for the dye adsorption in liquid environment. The ΔHºD = 9.2 kJ.mol-1 was calculated from Clausius-Clapeyron approach. The effects of coexisting anions on the adsorption and regeneration and reuse of the adsorbent were also investigated. This study suggests that SCBA, which was used without any pretreatment, has the potential to be applied as a low-cost adsorbent to mitigate effluents contamination with AR27 dye at low concentrations.

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The removal of dyes from effluents of textile industries represents a technological challenge, due to their significant environmental impact. The application of halloysite (Hal) and palygorskite (Pal) clay minerals as adsorbents for the removal of Congo red (CR) and methylene blue (MB) was evaluated in this work. The materials were applied both in natural and acid-treated forms, and characterized by XRD, XPS, SEM-EDS, FTIR, and N2 adsorption-desorption isotherm techniques to identify their properties and main active sites. The adsorbents showed potential to remove CR (> 98%) and MB (> 85%) within 180 min, using 0.3 g adsorbent and initial dye concentration of 250 mg L-1. Semi-empirical quantum mechanical calculations (SQM) confirmed the interaction mechanism between dyes and the adsorbents via chemisorption (- 69.0 kcal mol-1 < Eads < - 28.8 kcal mol-1), which was further observed experimentally due to the high fit of adsorption data to pseudo-second order kinetic model (R2 > 0.99) and Langmuir isotherm (R2 > 0.98). The use of Pal and Hal to remove dyes was proven to be economically and environmentally viable for industrial application.

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Contamination of water by toxic dyes is a serious environmental problem. Adsorbents prepared by an environmentally safe route have stood out for application in pollutant removal. Herein, iron oxide-based nanomaterial composed of Fe(III)-OOH and Fe(II/III) bound to proanthocyanidins, with particles in the order of 20 nm, was prepared by green synthesis assisted by extract of açaí (Euterpe oleracea Mart.) berry seeds from an agro-industrial residue. The nanomaterial was applied in the adsorption of cationic dyes. Screening tests were carried out for methylene blue (MB), resulting in an outstanding maximum adsorption capacity of 531.8 mg g-1 at 343 K, pH 10, 180 min. The kinetics followed a pseudo-second-order model and the isotherm of Fritz-Schülnder provided the best fit. Thermodynamic data show an endothermic process with entropy increase, typical of chemisorption. The proposed mechanism is based on the multilayer formation over a heterogeneous adsorbent surface, with chemical and electrostatic interactions of MB with the iron oxide nanoparticles and with the proanthocyanidins. The high adsorption efficiency was attributed to the network formed by the polymeric proanthocyanidins that entangled and protected the iron oxide nanoparticles, which allowed the reuse of the nanomaterial for seven cycles without loss of adsorption efficiency.

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A grafting of N1-(3-trimethoxysilylpropyl)diethylenetriamine (TMSPDETA) on natural clay was carried out to obtain an organic-inorganic hybrid clay material that was applied as an adsorbent to the uptake of Reactive Blue 19 (RB-19) and Reactive Green 19 (RG-19) dyes from aqueous wastewaters. This research demonstrates the effect of TMSPDETA contents on amino-functionalized clay materials' hydrophobic/hydrophilic behavior. The resultant material was utilized to uptake reactive dyes in aqueous solutions. The clay@TMSPDETA hybrid material was characterized by isotherm of adsorption and desorption of nitrogen, FTIR, elemental analysis, TGA, pHpzc, total acidity, total basicity groups, and hydrophilic balance. The hybrid samples were more hydrophilic than the pristine clay for ratios from 0.1 up to 0.5 due to adding amino groups to the pristine clay. FTIR spectra suggest that TMSPDETA was grafted onto the clay. The hybrid material presents a surface area 2.17-fold (42.7 m2/g) lower than pristine clay (92.7 m2/g). The total volume of pores of hybrid material was 0.0822 cm3/g, and the pristine clay material was 0.127 cm3/g, corresponding to a diminution of the total pore volume (Vtot) of 1.54 times. The kinetic data followed the pseudo-second-order (PSO) model for RB-19 and RG-19 reactive dyes. The equilibrium data were better fitted to the Liu isotherm model, displaying a Qmax as 178.8 and 361.1 mg g-1 for RB-19 and RG-19, respectively, at 20.0 °C. The main mechanism of interactions of the reactive dyes with the hybrid clay is electrostatic interaction. The clay@TMSPDETA has a very good effect on treating synthetic dye-textile wastewater. The removal percentage of simulated wastewater was up to 97.67% and 88.34% using distilled water and plastic industry wastewater as the solvents, respectively. The clay@TMSPDETA-0.1 could be recycled up to 5 cycles of adsorption and desorption of both dyes, attaining recoveries of 98.42% (RB-19) and 98.32% (RG-19) using 0.1 M HCl + 10% ethanol.

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The removal of heavy metals from wastewater is an environmental challenge which demands the use of environmentally friendly materials that promote a circular economy. This study aimed to apply a novel composite of an activated nanoclay/hydrocolloid in the removal of heavy metals from wastewater. A composite blended under pressure was prepared with spray-dried hydrocolloid derived from Nostoc sphaericum algae and activated nanoclay in an acid medium and 1M NaCl. The composite and components were analyzed through infrared (IR), X-ray (XR), ζ potential, cation exchange capacity (CEC), particle size, and SEM images. The composite was subjected to the adsorption of heavy metals (Pb, As, Zn, and Cd) at pH 4.5 and the removal percentage, kinetics, and adsorption isotherms were evaluated. It was observed that the activated nanoclay and the composite that presented a particle size of around 400 nm significantly increased (p-value < 0.05) the CEC, ζ potential, the functional groups, and chelating components, removing heavy metals above 99% for Pb, As 33%, Cd 15%, and Zn 10%. Adsorption kinetics was adjusted to the pseudo second-order model (R2 > 0.98), and the Langmuir and Freundlich models better represented the sorption isotherm at 20 °C. The formulated composite presents a good ability to remove heavy metals in wastewater.

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Modelling of liquid-solid batch adsorption based on mass transfer and conservation equations results in differential equations that may have or not an analytical solution. Even when analytical solutions are available, several simplified models can be considered for evaluating kinetic data of batch adsorption experiments. However, these simplified models are commonly used regardless of the premises considered in its development, and the analysis of the kinetic experiments based on these simplified models may be severely compromised. For this reason, this work presents a detailed development of the phenomenological models, and the hypotheses considered in its development are clearly stated. Typical simplified models derived from the phenomenological ones are obtained, and the conditions considered in the simplification are critically assessed. It was observed that the simplified models fail mainly for considering the concentration of the bulk phase constant over time or considering a linear adsorption isotherm. It must be emphasised that even when phenomenological models must be solved through numerical procedures, its use must be preferred, since the agreement with model premises and experimental conditions are closer, ensuring the quality of the kinetic data analysis.

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In this work, chitosan/alginate composites were developed by the gelation method with the addition of different amounts of activated carbon produced from tannery waste (ACTW). The performance of these composites was verified through the adsorption of the textile dye Remazol Brilliant Blue R (RBBR). A synergistic effect was observed by the addition of ACTW; with a specific surface area up to 45.584 m2/g, the maximum adsorption capacity was 300.96 mg/g. The synergy was due to the reduction in steric hindrance, with the adsorption capacity 1.2 times higher than expected. The material was regenerated with sodium hydroxide for 10 cycles. The composite containing 30% ACTW (AC30) was applied in the treatment of real textile effluent, with 30% reductions in the biochemical oxygen demand (BOD), 39% in the chemical oxygen demand (COD), 78% in turbidity, and 67% in color.

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The fluoride content in groundwater varies depending on geological configuration. Fluoride problems tend to occur in places where these minerals are most abundant in rocks. The objective of the present work was to synthesize four biopolymers based on chitosan-polyvinyl alcohol (Ch-PVA) cross-linked with sodium tripolyphosphate pentabasic (TPP) and ethylene glycol diglycidyl ether (EGDE) and determine their ability to remove fluoride from water. The characterization of the Ch-PVA beads was performed by way of Scanning Electron Microscopy (SEM) and Fourier-transform infrared spectroscopy (FTIR). The percentage of humidity and the point of zero charge were determined. The Ch-PVA beads showed a surface area of 63.87 m2 g-1, a pore size of 7.6 nm, a point of zero charge of 7.4, and 98.6% humidity. The kinetic adsorption study was adjusted to the pseudo-second-order model and the adsorption equilibrium data were adjusted to the Freundlich adsorption isotherm, showing a maximum fluoride adsorption capacity of 12.64 mg.g-1 at pH 7 and 30 °C, for the beads of Ch-PVA-NaOH-TPP. According to the thermodynamic parameters: -∆Go, +∆Ho and -∆So, fluoride adsorption is spontaneous, endothermic in nature and there is no random energy change in the solid/liquid interface during the adsorption process.

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The dyes used in textile industries are usually difficult to degrade in aquatic environments, being highly toxic to micro fauna and flora. Thus, textile wastewater treatments have been developed, among them, one that stands out is adsorption process. With the rise of nanomaterials applied to adsorption, graphene oxide (GO) shows promise in the removal of dyes. This work aimed to produce a more economical and environmentally friendly GO by reducing H2SO4 concentration during the synthesis. Adsorption tests were performed with methylene blue (MB) and brilliant blue (BB), adsorbent regeneration tests, as well as a kinetic study using real wastewater, and toxicological assays with lettuce seeds. Results showed that the sample produced with less H2SO4 (GO-21) performed better for MB (99% removal) and BB (29% removal); and recycling test showed that despite the decrease in removal efficiency, it remained high in the first cycles. Kinetics showed that equilibrium was reached in 30 min, removing 67.43% of color and 90.23% of the effluent's turbidity. Phytotoxicity assays indicated that the wastewater treated with GO-21 was the least toxic, compared to other wastewater samples analyzed. Therefore, GO has demonstrated its potential to be an effective and less toxic option to treat textile effluents.[Formula: see text].

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Today, fluoride represents one of the most often found, and resilient, pollutants threatening the health of millions of people around the globe. The use of biosorbents is an interesting alternative technique for the removal of fluorine-ions. Chitosan is a natural biopolymer with surface groups capable of removing fluorine; however, their lack of mechanical stability restricts its application. In the present work, we proposed that such limitations can be overcame by forming a composite with zeolite (ZCC). A proper zeolite-to-chitosan ration must be kept to prevent a collapse of the material's capacity. Two ZCCs at ratios of 1:1 and 1:3 were formed and tested for the removal of fluoride from aqueous solution. The composites were characterized by Electron Microscopy, FT-IR, N2 physisorption, and potentiometric titration techniques. During fluoride adsorption studies, the effects of pH and temperature were analysed and thermodynamic parameters for adsorption were calculated. The results demonstrated that there is a chemical interaction between the zeolite and chitosan components leading to a superior adsorption performance than if there was a simple physical mixture of the precursors. Maximum adsorption capacities were reached using the composite material with the lowest chitosan content due to reduced constriction of the zeolite pores and a better dispersion of overall the adsorption sites. Both pH and temperature had a significant, and negative, impact on the adsorption; these effects were discussed. The present work represents an advance in the development of functional biocomposites for the removal of pollutants from aqueous solutions.

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The purpose of this work is to make use of vegetables that, although widely found in nature, there are few applications. The weeds used here, Cyanthilium cinereum (L.) H. Rob (CCLHR) and Paspalum maritimum (PMT) found in the Amazon region of Belém state of Pará-Brazil, contribute to the problem of water contamination by the removal of the methylene blue dye through the biosorption process, taking advantage of other materials for economic viability and processing. The influences of parameters such as, biosorbent dose, contact time, and initial concentration of dye were examined. The characterizations were realized using SEM to verify the morphology of the material and spectroscopy in the FTIR region. As for the adsorption mechanism, the physical adsorption mechanism prevailed. The time required for the system to reach equilibrium for both biosorbents was from 50 min, following a kinetics described by the pseudo-second order model. The adsorption isotherm data for PMT were better adjusted to the Langmuir model and the biosorption capacity (qmax) value was (56.1798 mg/g). CCLHR was better adjusted to the Freundlich model and its maximum biosorption capacity was 76.3359 mg/g. Thus, these weed species are promising for the biosorption of methylene blue dye in effluents.

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We investigated the adsorption of glyphosate onto five subtropical soils of Paraná and São Paulo states, Brazil, a region of intense agricultural activities, aiming at the determination of kinetic and isotherm adsorption parameters which enable the evaluation of the potential leaching of the herbicide. The adsorption was fast, being described by the pseudo-second order and intraparticle diffusion models, thus suggesting that mixed mechanisms are involved. The Oxisol containing the highest concentrations of metal oxides (209.5 g kg-1 Fe2O3 and 160.2 g kg-1 Al2O3) was the sample with the highest rate constant, indicating the adsorption sites are readily available. All the soils are rich in aluminum and iron oxides, explaining the Freundlich coefficients (KF) between 642 and 1360 mg1-1/n kg-1 L1/n, which are higher than most of the coefficients described for other soils around the world. The maximum desorption (15% of the adsorbed amount) was observed for the Oxisol. For the other soils, desorption ranged from 2 to 7%. These results suggest that the leaching of free glyphosate to nearby surface and groundwaters is unlikely unless excessive doses are used. The adsorption parameters are useful for managing the right doses applied to the crops, thus avoiding contamination of adjacent areas.

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The application of biosorption operation has gained attention in the removal and retrieval of toxic metal ions from water bodies. Wastewater from industrial activity generally presents great complexity due to the coadsorption of cations to the inactive biomass binding sites. In this work, the competitive biosorption of Cu(II) and Ag(I) ions was studied in batch systems. A kinetic study applying a non-acidified and acidified waste of Sargassum filipendula in equimolar and non-equimolar metal samples was carried out and the acidified biosorbent was selected due to higher removal rates and selectivity of silver ions. The assays were performed with 2 g L-1 of biosorbent concentration at 25 °C for 12 h and pH was controlled at around 5.0. Copper presented higher affinity for the biosorbent and a fast biosorption kinetic profile, while silver equilibrium times exhibited dependence on the copper concentration. External diffusion is the rate-limiting step in Cu(II) ion removal and it might also limit the kinetic rates of Ag(I) ions with intraparticle diffusion, depending on the initial concentration of metal cations. The ion-exchange mechanism is evidenced and complexation and electrostatic attraction mechanisms might be suggested, explained by simultaneous chemisorption and physisorption processes during the operation. Calcium and sodium were released in considerable amounts by the ion-exchange mechanism. Characterization analyses confirmed the role of several functional groups in the competitive biosorption accompanied by a homogenous covering of both metal ions on the surface of the particles. Particle porosity analyses revealed that the material is macroporous and an appreciable amount of macropores are filled with metal cations after biosorption.

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A quartz crystal microbalance method with dissipation (QCM-D) and attenuated total reflection Fourier-transform infrared (ATR-FTIRS) spectroscopy were used to study the adsorption of L-cysteine (L-Cys) on Pt. Through QCM-D, it was possible to verify that the viscoelastic properties of the adsorbed species play an important role in the adsorption, rendering Sauerbrey's equation inapplicable. The modelling of QCM-D data exposed two different processes for the adsorption reaction. The first one had an activation time and is fast, whereas the second is slow. These processes were also resolved by ATR-FTIRS and identified to be water and anion adsorption preceded by L-Cys adsorption. Both techniques reveal that the degree of surface coverage is pH dependent. Spectroscopic data indicate that the conformation of L-Cys(ads) changes with pH and that the structures do not fully agree with those proposed in literature for other metallic surfaces. The assembling of the adsorbed monolayer appeared to be very fast, and it was not possible to determine or quantify this kinetics. The conformation is also controlled by applied potential, and the anion adsorption and interfacial water depends on the conformation of the adsorbed molecules.

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Chitosan particles (CH) were obtained from seafood processing wastes (shrimp shells) and physicochemically characterized; deacetylation degree of CH was measured by Infrared Spectroscopy (FTIR) and potentiometric titration; polymer molecular weight was determined by intrinsic viscosity measurements. Reticulated micro/nanoparticles of chitosan (MCH) with an average diameter close to 100nm were synthesized by ionic gelation of chitosan using tripolyphosphate (TPP), and characterized by SEM, size distribution and Zeta-potential. Detoxification capacities of CH and MCH were tested analyzing the removal of hexavalent chromium Cr(VI) from contaminated water, at different initial chromium concentrations. The effect of pH on adsorption capacity of CH and MCH was experimentally determined and analyzed considering the Cr(VI) stable complexes (anions) formed, the presence of protonated groups in chitosan particles and the addition of the reticulating agent (TPP). Chitosan crosslinking was necessary to adsorb Cr(VI) at pH<2 due to the instability of CH particles in acid media. Langmuir isotherm described better than Freundlich and Temkin equations the equilibrium adsorption data. Pseudo-second order rate provided the best fitting to the kinetic data in comparison to pseudo-first order and Elovich equations. Chemical analysis to determine the oxidation state of the adsorbed Cr, showed that Cr(VI) was adsorbed on CH particles without further reduction; in contrast Cr(VI) removed from the solution was reduced and bound to the MCH as Cr(III). The reduction of toxic Cr(VI) to the less or nontoxic Cr(III) by the reticulated chitosan micro/nanoparticles can be considered a very efficient detoxification technique for the treatment of Cr(VI) contaminated water.

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Although adsorption is an essential step in the enzymatic hydrolysis of lignocellulosic materials, literature reports controversial results in relation to the adsorption of the cellulolitic enzymes on different biomasses/pretreatments, which makes difficult the description of this phenomenon in hydrolysis mathematical models. In this work, the adsorption of these enzymes on Avicel and sugarcane bagasse pretreated by the hydrothermal bagasse (HB) and organosolv bagasse (OB) methods was evaluated. The results have shown no significant adsorption of ß-glucosidase on Avicel or HB. Increasing solids concentration from 5% (w/v) to 10% (w/v) had no impact on the adsorption of cellulase on the different biomasses if stirring rates were high enough (>100 rpm for Avicel and >150 rpm for HB and OB). Adsorption equilibrium time was low for Avicel (10 Min) when compared with the lignocellulosic materials (120 Min). Adsorption isotherms determined at 4 and 50 °C have shown that for Avicel there was a decrease in the maximum adsorption capacity (Emax) with the temperature increase, whereas for HB increasing temperature increased Emax . Also, Emax increased with the content of lignin in the material. Adsorption studies of cellulase on lignin left after enzymatic digestion of HB show lower but significant adsorption capacity (Emax = 11.92 ± 0.76 mg/g).

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Formation water from oilfields is one of the major environmental issues related to the oil industry. This research investigated oil adsorption onto nanoparticles of hydrophobic alumina and alumina nanoparticles functionalized with a petroleum vacuum residue (VR) at 2 and 4wt% to reduce the amount of oil in oil-saltwater emulsions at different pH values (5, 7 and 9). The initial concentration of crude oil in water ranged from 100 to 500mg/L. The change in oil concentration after adsorption was determined using a UV-vis spectrophotometer. The results indicated that all of the systems performed more effectively at a pH of 7 and using Al/4VR material. The oil adsorption was higher for neutral and acid systems compared with basic ones, and it was improved by increasing the amount of VR on the surface of the alumina. Additionally, the amount of NaCl adsorbed onto nanoparticles was estimated for different mixtures. The adsorption equilibrium and kinetics were evaluated using the Dubinin-Astakhov model, the Brunauer-Emmet-Teller model, and pseudo-first- and pseudo-second-order models, with a better fitting to the Brunauer-Emmet-Teller model and pseudo-second-order model.