Adsorption and ion exchange of toxic metals by Brazilian clays: clay selection and studies of equilibrium, thermodynamics, and binary ion exchange modeling.

In this study, four Brazilian clays (Bofe, Verde-lodo, commercial Fluidgel, and expanded commercial vermiculite) were evaluated for their adsorptive capacity and removal percentage in relation to different toxic metals (Ni2+, Cd2+, Zn2+, and Cu2+). The best results were obtained by expanded vermiculite, with cadmium removal reaching values of 95%. The most promising clay was modified by the sodification process, and the metal cadmium was used to evaluate the ion exchange process. The clays expanded vermiculite (EV) and VNa-sodified vermiculite were evaluated by equilibrium study at 25, 35, and 45 °C. At 25 °C, EV obtained a maximum adsorption capacity of 0.368 mmol/g and sodified vermiculite 0.480 mmol/g, which represents an improvement of 30.4% in modified clay capacity. At 45 °C, the sodified vermiculite reached 0.970 mmol/g adsorption capacity. The Langmuir, Redlich-Peterson Freundlich, and Dubinin-Raduskevich models were adjusted to the results. Langmuir provided the best fit among the models. The thermodynamic quantities (ΔS, ΔH, and ΔG) demonstrated that the process is spontaneous and endothermic and the metal is captured by physisorption and chemisorption in the studied temperature range. For the ion exchange equilibrium, the binary Langmuir and binary Langmuir-Freundlich models were adjusted to the expanded vermiculite and sodified vermiculite isotherms, respectively. Both models were predictive. Thermal analysis indicated good heat resistance even after material modification. The apparent and real densities demonstrated that after each treatment or contamination, the clayey material undergoes contraction in its structure. An improved efficiency of the adsorbent was found after sodification.

Self-assembly mucoadhesive beads of κ-carrageenan/sericin for indomethacin oral extended release.

Oral drug administration, especially when composed of mucoadhesive delivery systems, has been a research trend due to increased residence time and contact with the mucosa, potentially increasing drug bioavailability and stability. In this context, this study aimed to develop self-assembly mucoadhesive beads composed of blends of κ-carrageenan and sericin (κ-Car/Ser) loaded with the anti-inflammatory drug indomethacin (IND). We investigated the swelling, adhesion behaviour, and mechanical/physical properties of the beads, assessing their effects on cell viability, safety and permeation characteristics in both 2D and triple-culture model. The swelling ratio of the beads indicated pH-responsiveness, with maximum water absorption at pH 6.8, and strong mucoadhesion, increasing primarily with higher polymer concentrations. The beads exhibited thermal stability and no chemical interaction with IND, showing improved mechanical properties. Furthermore, the beads remained stable during accelerated and long-term storage studies. The beads were found to be biocompatible, and IND encapsulation improved cell viability (>70 % in both models, 79 % in VN) and modified IND permeation through the models (6.3 % for F5 formulation (κ-Car 0.90 % w/v | Ser 1.2 % w/v| IND 3.0 g); 10.9 % for free IND, p < 0.05). Accordingly, κ-Car/Ser/IND beads were demonstrated to be a promising IND drug carrier to improve oral administration while mitigating the side effects of non-steroidal anti-inflammatories.

Enhanced degradation and removal of ciprofloxacin and ofloxacin through advanced oxidation and adsorption processes using environmentally friendly modified carbon nanotubes.

This study explores the utilization of adsorption and advanced oxidation processes for the degradation of ofloxacin (OFL) and ciprofloxacin (CIP) using a green functionalized carbon nanotube (MWCNT-OH/COOH-E) as adsorbent and catalyst material. The stability and catalytic activity of the solid material were proved by FT-IR and TG/DTG, which also helped to elucidate the reaction mechanisms. In adsorption kinetic studies, both antibiotics showed similar behavior, with an equilibrium at 30 min and 60% removal. The adsorption kinetic data of both antibiotics were well described by the pseudo-first-order (PFO) model. Different advanced oxidation processes (AOPs) were used, and the photolytic degradation was not satisfactory, whereas heterogeneous photocatalysis showed high degradation (⁓ 70%), both processes with 30 min of reaction. Nevertheless, ozonation and catalytic ozonation have resulted in the highest efficiencies, 90%, and 70%, respectively, after 30-min reaction. For AOP data modeling, the first-order model better described CIP and OFL in photocatalytic and ozonation process. Intermediates were detected by MS-MS analysis, such as P313, P330, and P277 for ciprofloxacin and P391 and P332 for ofloxacin. The toxicity test demonstrated that a lower acute toxicity was observed for the photocatalysis method samples, with only 3.1 and 1.5 TU for CIP and OFL, respectively, thus being a promising method for its degradation, due to its lower risk of inducing the proliferation of bacterial resistance in an aquatic environment. Ultimately, the analysis of MWCNT reusability showed good performance for 2 cycles and regeneration of MWCNT with ozone confirmed its effectiveness up to 3 cycles.

Visible-light photoactivated proanthocyanidin and kappa-carrageenan coating with anti-adhesive properties against clinically relevant bacteria.

The increase of bacterial resistance to antibiotics is a growing concern worldwide and the search for new therapies could cost billions of dollars and countless lives. Inert surfaces are major sources of contamination due to easier adhesion and formation of bacterial biofilms, hindering the disinfection process. Therefore, the objective of this study was to develop a photoactivatable and anti-adhesive kappa-carrageenan coating using proanthocyanidin as a photosensitizer. The complete reduction (>5-log10 CFU/cm3) of culturable cells of Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa pathogens was achieved after 30 min of exposure to visible light (420 nm; 30 mW/cm2) with 5 % (w/v) of the photosensitizer. Cell membrane damage was confirmed by measuring potassium leakage, epifluorescence microscopy and bacterial motility analysis. Overall, visible light irradiation on coated solid surfaces mediated by proanthocyanidin showed no cytotoxicity and inactivated clinically important pathogens through the generation of reactive oxygen species, inhibiting bacterial initial adhesion. The developed coating is a promising alternative for a wide range of applications related to surface disinfection and food biopreservation.

Pirarucu hydroxyapatite applied to ternary competitive adsorption of synthetic basic dyes as contaminants of emerging concern: kinetic, equilibrium, and ANN studies.

This study investigated the single and multicomponent adsorption of three emerging pollutants, the basic dyes Rhodamine 6G (R6G), Auramine-O (AO), and Brilliant Green (BG) by using hydroxyapatite synthesized from Pirarucu scales as adsorbent (HAP). The adsorption process was studied using seven different systems: AO-single, R6G-single, BG-single, R6G + AO, BG + AO, BG + R6G, and R6G + AO + BG. For kinetics, the initial concentration of each adsorbate per system was 50 mg/L, the results showed that the singular adsorption of these dyes was best-represented by the pseudo-second-order model (qAO = 62.54 mg/g, qR6G = 7.91 mg/g, qBG = 62.40 mg/g), however, the multicomponent adsorption was well-fitted by a pseudo-first-order model (ternary system: qAO = 56.21 mg/g, qR6G = 14.95 mg/g, qBG = 60.62 mg/g). For equilibrium, the initial concentration of each adsorbate per system was 10-300 mg/L, and the single adsorption systems were best represented by the Langmuir model. Nonetheless, the results displayed in the multicomponent mixture showed the presence of inflection points of AO and R6G whenever BG was present in solution with C0 > 150 mg/L, thus indicating that BG has greater affinity with HAP. The presence of inflection points in the curves represented a limitation for applying traditional equilibrium models, thus, an artificial neural network (ANN) was applied to non-linear curve fit this process and satisfactorily predicted the kinetics and equilibrium data. Finally, the analysis of thermodynamics for the ternary mixture revealed that the adsorption process is spontaneous (ΔG < 0), endothermic (ΔH > 0), and increases to a disorganized state as the temperature rises (ΔS > 0).

Green synthesis of carbon nanotubes functionalized with iron nanoparticles and coffee husk biomass for efficient removal of losartan and diclofenac: Adsorption kinetics and ANN modeling studies.

The presence of emerging contaminants in wastewater poses a global environmental challenge, requiring the development of innovative materials or methods for their treatment. This study focused on the production of green functionalized carbon nanotubes (CNTs) and using them in the adsorption of the pharmaceuticals Losartan (LOS) and Diclofenac (DIC). The efficiency of the methodology was verified by characterization techniques. Elemental composition analysis indicated a significant increase in the iron content after the green functionalization, proving the effectiveness of the method. Thermogravimetric analysis showed similar thermal degradation profiles for pristine CNTs and functionalized CNTs, indicating better post-functionalization thermal stability. BET analysis revealed mesoporous characteristics of CNTs, with increased surface area and pore volumes after functionalization. X-Ray diffraction confirmed the preservation of the lattice structure of the CNTs post-functionalization and post-adsorption, with changes in peak broadening suggesting surface modifications. LOS and DIC adsorption were evaluated via kinetic studies at four different concentrations (0.1-0.4 mmol/L) that were best represented by the pseudo-second order model, suggesting chemisorption mechanisms, with faster and higher uptakes for DIC (0.084-0.261 mmol/g; teq = 5 min) when compared to LOS (0.058-0.235 mmol/g; teq = 20 min). The curves were also studied via artificial neural networks (ANN) and revealed that the best ANN architecture for representing the experimental data is a network with [3 5 5 2] neurons trained using the Bayesian-Regularization algorithm and the Log-sigmoid (hidden layers) and Linear (output layer) transfer functions. The desorption study showed that CaCl2 had better performance in CNT regeneration, reaching its removal capacity above 50% up to 3 cycles, for both pharmaceuticals. These findings reveal the potential of the developed material as a promising adsorbent for targeted removal of pollutants, contributing to advances in the remediation of emerging contaminants and the application of artificial intelligence in adsorption research.

κ-Carrageenan/sericin polymer matrix modified with different crosslinking agents and thermal crosslinking: Improved release profile of mefenamic acid.

The crosslinking of the polymer matrix with compatible macromolecules results in a three-dimensional network structure that offers an enhancement in the controlled release properties of the material. In this sense, this work aimed to improve the release profile of mefenamic acid (MAC) through crosslinking strategies. κ-Carrageenan/sericin crosslinked blend was obtained by covalent and thermal crosslinking and the different formulations were characterized. The gastroresistant potential and release profile were evaluated in the dissolution assay. The effect and characterization of the particles were investigated. Multiple units presented high entrapment efficiency (94.11-104.25), high drug loading (36.50-47.50 %) and adequate particle size (1.34-1.57 mm) with rough surface and visually spherical shape. The Weibull model showed that drug release occurred by relaxation, erosion and Fickian diffusion. Material stability and absence of MAC -polymer interactions were demonstrated by FTIR and thermogravimetric analysis. DSC showed a stable character of MAC in the drug-loaded beads. Moreover, the application studies of κ-Car/Ser/carboxymethylcellulose in the in vitro intestine mode showed that the crosslinked blend increased cell viability (>85 %), while free MAC exhibited a cytotoxic effect. Finally, the crosslinked k-Car/Ser blend MAC -loaded showed promising properties of a sustained release form of anti-inflammatory drug.

Adsorption of contaminants by nanomaterials synthesized by green and conventional routes: a critical review.

Nanomaterials, due to their large surface area and selectivity, have stood out as an alternative for the adsorption of contaminants from water and effluents. Synthesized from green or traditional protocols, the main advantages and disadvantages of green nanomaterials are the elimination of the use of toxic chemicals and difficulty of reproducing the preparation of nanomaterials, respectively, while traditional nanomaterials have the main advantage of being able to prepare nanomaterials with well-defined morphological properties and the disadvantage of using potentially toxic chemicals. Thus, based on the particularities of green and conventional nanomaterials, this review aims to fill a gap in the literature on the comparison of the synthesis, morphology, and application of these nanomaterials in the adsorption of contaminants in water. Focusing on the adsorption of heavy metals, pesticides, pharmaceuticals, dyes, polyaromatic hydrocarbons, and phenol derivatives in water, for the first time, a review article explored and compared how chemical and morphological changes in nanoadsorbents synthesized by green and conventional protocols affect performance in the adsorption of contaminants in water. Despite advances in the area, there is still a lack of review articles on the topic.

Fluoranthene adsorption by graphene oxide and magnetic chitosan composite (mCS/GO).

The oil industry faces the challenge of reducing its high polluting potential, due to the presence of aromatic pollutants, such as polycyclic aromatic hydrocarbons (PAHs). Efforts have been made to mitigate the impact of PAHs in industry through the development of detection technologies and the implementation of mitigation strategies. This study presents the adsorption of fluoranthene, through a magnetic composite of graphene oxide and chitosan as a method of remediation of produced water. The efficiency of the process was evaluated through kinetic, equilibrium, thermodynamic, and characterization analyses. The nanocomposite was able to remove 90.9% of FLT after 60 min and showed a maximum adsorption capacity of 28.22 mg/g, demonstrating that they can be implemented to remove fluoranthene. Kinetic and equilibrium experimental data showed that physisorption is the predominant adsorptive mechanism; however, the process is also influenced by chemisorption, which occurs through electrostatic interactions between the surface of the material and the adsorbate. The thermodynamic study showed that fluoranthene and graphene composite have high affinity, and that the adsorption is exothermic and spontaneous. The results presented in this paper indicate that the magnetic composite is a potential and sustainable adsorbent for fluoranthene remediation.

Propranolol adsorption onto multiwalled carbon nanotubes modified by green synthesis: pH, kinetic, and equilibrium studies.

This research investigated the adsorption of propranolol (PROP) by functionalized green carbon nanotubes (MWCNT-B), assessing the influence of pH, in addition to kinetic, equilibrium, and thermodynamic studies and reuse of the material. For this purpose, speciation of PROP and the point of zero charge (pHPZC) of MWCNT-B were performed, indicating a pKa of 9.67 and pHPZC of 3.31. The adsorption tests at different pH values revealed that in the range of pH 3 to 9, there is no significant variation in PROP uptake, despite this, at pH 11, the removal decreases. Regarding PROP adsorption, the equilibrium time ranged from 30 to 90 min, and the PFO model best represented the kinetic data. The Langmuir model was more predictive in representing isotherms (R2 > 0.95), and the adsorption process was spontaneous and favorable (ΔG < - 20 kJ mol-1) and indicated exothermic behavior (ΔH = - 33 kJ mol-1) for PROP removal. In addition, the material showed satisfactory thermal regeneration results and can be reused for four cycles. The results suggest that MWCNT-B is an attractive adsorbent and exhibits effective removal of propranolol from aqueous matrices.

Biosorption of europium and erbium from aqueous solutions using crosslinked sericin-alginate beads.

Critical metals such as rare earths are essential for important industrial applications and for producing high-tech materials. Currently, the development of alternative and non-conventional biomaterials has gained significant interest. This work investigated the use of crosslinked sericin-alginate-based natural polymeric particles for the removal of rare earths from water. Affinity tests showed that sericin-alginate/polyethylene glycol diglycidyl ether had the highest potential for capturing europium (0.258 mmol/g and 94.33%) and erbium (0.259 mmol/g and 94.55%). Next, erbium was selected based on the affinity with sericin-alginate/polyethylene glycol diglycidyl to investigate the effect of dose/pH, biosorption kinetics, isothermal equilibrium, desorption/reuse, and selectivity. The effect of dose and pH showed that 8.0 g/L (95.91%) and pH 5.0 (97.53%) were more efficient in capturing erbium. The biosorption kinetics showed that the equilibration time was reached within 210 min. The PSO and EMTR models effectively represented the kinetics data. The isothermal equilibrium revealed that the maximum uptake capacity for erbium was 0.641 mmol/g. The isothermal curves better fit the Dubinin-Radushkevich (55 °C) and Langmuir (25 and 40 °C) models. Thermodynamic quantitates indicated that erbium uptake was spontaneous, governed by entropic changes, and endothermic. The recovery of Er3+ was greater than 98% and the reuse of the eluent in the cycles enriched the Er3+ load 10-times (1.0 to 9.91 mmol/L). The beads also showed better performance for capturing Er3+ and Eu3+ with other coexisting ions. Characterization analyzes revealed the ion exchange mechanism between Ca2+/Er3+ prevailed in the Er3+ removal. Thus, the results pointed out that crosslinked sericin-alginate can be used as an alternative and promising biosorbent to remove and recover rare earths.

Multi-pollutant biosorption of organic and inorganic pollutants by brown algae waste from alginate production: batch and fixed-bed investigation.

The reuse of biomass waste has been gaining attention in adsorption processes to remove pollutants of emerging concern from water and wastewater. In this work, the potential of alginate-extracted macro-algae waste to uptake synthetic dyes and metal cations was evaluated in comparison with raw algae. In affinity assays, both materials were able to remove metal cations and cationic dyes up to maximum rates, and no significant removal was observed for an anionic dye in an acidic medium. Competition was observed in multi-component systems of metal cations and dyes. For binary samples containing organic and inorganic contaminants, kinetic modeling evidenced the distinct nature of both types of adsorbates. Pb(II) biosorption was best described as a first-order process, while second-order and Elovich models better fitted methyl blue (MB) uptake data. For equimolar binary samples, the Sips isothermal model fitted the experimental data more satisfactorily at room temperature. Isotherms for 20, 30, 40, and 60 °C exhibited favorable adsorption profiles with spontaneous ΔG values for both raw macro-algae and waste from alginate extraction. Maximum adsorption capacities were competitive with previous reports in the literature for a wide range of biomaterials, pointing to the slightly higher efficiency with algae waste in batch experiments. In elution tests, HNO3 (0.5 M) showed the best recovery rates of metal cations. Continuous biosorption operation revealed the performance of the brown algae waste was considerably more efficient than raw algae with breakthrough biosorption capacities up to 3.96 and 0.97 mmol.g-1 for the removal of Pb(II) and MB, respectively. A total of 3.0 g of algae and algae waste were able to deliver 1.20 and 1.62 L of contaminant-free water, respectively. XPS analyses corroborate previous assays that pointed to the prevalence of physisorption with evidence of complexation, ionic exchange, and hydrogen displacement mechanisms.

Carbonaceous adsorbent as green silica by-product applied to the treatment of contaminated effluent by pesticide commonly sprayed on rice cultivation.

Grain cultivation and its impacts on the environment have been the focus of many studies, especially due to generated solid waste and the wide use of agrochemicals aiming for greater productivity. In this context, the present study proposes a new and consistent step in constructing self-sustainability in rice farming. The proposed stage includes reusing green silica waste as an adsorbent to treat effluents contaminated by pesticides directly applied to rice cultivation. After nano silica production through the rice husks burning, followed by basic leaching and acid precipitation, a carbonaceous material remains. This material, naturally impregnated by Na2SiO3, was washed and dried, characterized, and used to remove the pesticide 2,4-dichlorophenoxyacetic acid (2,4-D). The adsorption essays were performed at 2,4-D at low concentrations (between 1 and 10 mg L-1) at different temperatures. The washed and dried porous carbon (WDPC) surface is irregular and presents slit-shaped channels. The FT-IR analysis identified the siloxane, carbonyl, carboxylate, and methylene functional groups available to interact with the pesticide molecules. The washing/drying process eliminated impurities, improving the surface area from 539.67 to 619.67 cm2 g-1 and pore volume from 0.29 to 0.44 cm3 g-1. Concerning the adsorption of 2,4-D on WDPC, the best pH was 6.0, where around 75% of the pesticide was removed from the water. The equilibrium isotherms presented an S-shaped form indicating a multilayer and cooperative adsorption, with maximum adsorption capacities of 7.504 and 7.736 mg g-1. The estimated ∆Gads, ΔHads, and ΔSads values suggested that pesticide adsorption was spontaneous, exothermic, and favorable. Finally, WDPC demonstrated a good potential to uptake 2,4-D from water, contributing to self-sustainability in rice farming.

Development and characterization of crosslinked k-carrageenan/sericin blend with covalent agents or thermal crosslink for indomethacin extended release.

Modified release of multiparticulate pharmaceutical forms is a key therapeutic strategy to reduce side effects and toxicity caused by high and repeated doses of immediate-release oral drugs. This research focused on the encapsulation of indomethacin (IND) in the crosslinked k-Car/Ser polymeric matrix by covalent and thermal methods to evaluate drug delivery modulation and properties of the crosslinked blend. Therefore, the entrapment efficiency (EE %), drug loading (DL %) and physicochemical properties of the particles were investigated. The particles presented a spherical shape and a rough surface with a mean diameter of 1.38-2.15 mm (CCA) and 1.56-1.86 mm (thermal crosslink). FTIR investigation indicated the presence of IDM in the particles and X-ray pattern showed the maintenance of crystallinity of IDM. The in vitro release in acidic medium (pH 1.2) and phosphate buffer saline solution (pH 6.8) was 1.23-6.81 % and 81-100 %, respectively. Considering the results, the formulations remained stable after 6 months. The Weibull equation was adequately fitted for all formulations and a diffusion mechanism, swelling and relaxation of chain were observed. IDM-loaded k-carrageenan/sericin/CMC increases cell viability (> 75 % for neutral red and > 81 % for MTT). Finally, all formulations present gastro-resistance, pH response and altered release and have the potential to be used as drug delivery careers.

Adsorption kinetics of ciprofloxacin and ofloxacin by green-modified carbon nanotubes.

This paper investigated the uptake of CIP and OFL in single and multicomponent adsorptive systems using modified carbon nanotubes (CNTs) as adsorbent material. The characterization analyses of the pre- and post-process material by XPS, TG/DTG, FT-IR, SEM/EDS, and XRD helped in the elucidation of the mechanisms, indicating greater involvement of n-n and π -π interactions. In the kinetic studies, the simple systems with CIP and OFL were similar, both showed equilibrium time around 20/30 min and increased adsorptive capacity with increasing initial drug concentration. In the multicomponent system, different fractions of CIP and OFL were tested and the time to reach equilibrium also varied between 20 and 30 min. In general, the adsorption capacity of CIP is slightly lower than that of OFL under the conditions tested. The selectivity analysis of the system showed that the selectivity's of the two drugs are identical in equimolar fractions. The mathematical modeling of the kinetic data indicated that in monocomponent systems, the model of pseudo-second order (PSO) adequately described both CIP and OFL kinetics. Furthermore, with the implementation of Artificial Neural Networks (ANN), it was possible to obtain a more assertive prediction of the behavior of single and binary systems.

Cerium biosorption onto alginate/vermiculite-based particles functionalized with ionic imprinting: Kinetics, equilibrium, thermodynamic, and reuse studies.

Cerium is an essential element for several applications in industry, therefore, recovering it from secondary sources is a promising strategy from an economic and environmental perspective. For this purpose, biosorption is a low-cost and effective alternative. The present work evaluated the recovery of Ce3+ from aqueous solutions using alginate/vermiculite-based particles (ALEV) functionalized by ionic imprinting. From the kinetic assays, it was verified that the uptake of Ce3+ followed the pseudo-second-order model and was mainly controlled by external diffusion. The Langmuir model better described the equilibrium data, and a maximum biosorption capacity of 0.671 mmol/g at 45 °C was attained. The evaluation of the thermodynamic quantities revealed that the process occurs spontaneously and endothermically. The particles reuse and Ce3+ recovery were achieved using 0.1 mol/L HCl or 1.0 mol/L CaCl2 solutions for up to four cycles of biosorption/desorption. The biosorbent was characterized before and posted Ce3+ biosorption to investigate the morphology, textural properties, crystallinity, thermal resistance, composition, and functional groups of the biosorbent.

Comparative effect of mesoporous carbon doping on the adsorption of pharmaceutical drugs in water: Theoretical calculations and mechanism study.

In this study, mesoporous doped-carbons were synthesized from sucrose, a natural source, boric acid and cyanamide as precursors, generating B- or N-doped carbon. These materials were characterized by FTIR, XRD, TGA, Raman, SEM, TEM, BET, and XPS, confirming the preparation of a tridimensional doped porous structure. B-MPC and N-MPC showed a high surface specific area above 1000 m2/g. The effect of B and N doping on mesoporous carbon was evaluated on the adsorption of emerging pollutants from water. Diclofenac sodium and paracetamol were used in adsorption assays, reaching removal capacities of 78 and 101 mg.g-1, respectively. Kinetic and isothermal studies indicate the chemical nature of adsorption controlled by external and intraparticle diffusion and multilayer formation due to strong adsorbent/adsorbate interactions. DFT-based calculations and adsorption assays infer that the main attractive forces are hydrogen bonds and Lewis acid-base interactions.

Amazon raw clay as a precursor of a clay-based adsorbent: experimental study and DFT analysis for the adsorption of Basic Yellow 2 dye.

A clay-based adsorbent (CBA) was purified from a sustainable precursor (raw clay, RC), which was obtained from the Amazon region in Brazil. The CBA was characterized using X-ray diffraction (XRD), Fourier Transform Infrared spectroscopy (FTIR), Brunauer-Emmet-Teller surface area (SBET, RC = 23.386 m2.g-1, CBA = 33.020 m2.g-1), Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDS), thermogravimetric analysis (TGA), cation exchange capacity (CEC, CBA = 44.75 cmol/kg), and point of zero charge analyses (pHPZC, CBA = 2.20). Subsequently, CBA was used to adsorb basic yellow 2 (BY2) dye from aqueous solutions. A CBA dosage (1 g/L), initial concentration of dye (C0 = 15 mg/L), and pH (5.6) were ideal conditions for the BY2 dye removal of ~ 98%. The BY2 kinetics was better represented by the pseudo-first-order (PFO) model while the BY2 equilibrium was well represented by the Sips model, with a maximum adsorption capacity of qms = 18.04 mg/g at 28 °C. The negative values of ΔG° and ΔH° showed that the studied process is spontaneous and exothermic, while the values of isosteric heat (∆Hst, -16 to -20 kJ/mol) suggest a predominance of physical interactions. The molecular chemical reactivity of BY2 was investigated using quantum chemical descriptors calculated based on Density Functional Theory (DFT) optimization of the dye molecule, and the results revealed a large energy gap value (4.3900 eV) and considerable chemical hardness (η = 2.1950 eV). Therefore, the correlation between DFT and experimental results consistently sustains that BY2 dye tends to be adsorbed on the CBA surface by electrostatic interactions, thus, this is the possible adsorption mechanism of this process.

Hybrid process of adsorption and electrochemically based green regeneration of bentonite clay for ofloxacin and ciprofloxacin removal.

Removal of emerging contaminants, such as antibiotics, from wastewater by adsorption is a simple, low-cost, and high-performance process; however, regeneration and reuse of the exhausted adsorbent are necessary to make the process economically viable. This study aimed to investigate the possibility of electrochemical-based regeneration of clay-type materials. For this, the calcined Verde-lodo (CVL) clay was saturated with the antibiotics ofloxacin (OFL) and ciprofloxacin (CIP) in one-component systems by an adsorption process and then subjected to photo-assisted electrochemical oxidation (0.45 A, 0.05 mol/L NaCl, UV-254 nm, and 60 min), which promotes both pollutant degradation and adsorbent regeneration. The external surface of the CVL clay was investigated by X-ray photoelectron spectroscopy before and after the adsorption process. The influence of regeneration time was evaluated for the CVL clay/OFL and CVL clay/CIP systems, and the results demonstrate high regeneration efficiencies after 1 h of photo-assisted electrochemical oxidation. Clay stability during regeneration was investigated by four successive cycles in different aqueous matrices (ultrapure water, synthetic urine, and river water). The results indicated that the CVL clay is relatively stable under the photo-assisted electrochemical regeneration process. Furthermore, CVL clay was able to remove antibiotics even in the presence of natural interfering agents. The hybrid adsorption/oxidation process applied here demonstrated the electrochemical-based regeneration potential of CVL clay for the treatment of emerging contaminants, since it can be operated quickly (1h of treatment) and with lower consumption of energy (3.93 kWh kg-1) than the traditional method of thermal regeneration (10 kWh kg-1).

Optimization of kappa-carrageenan cationization using experimental design for model-drug release and investigation of biological properties.

Cationization is a promising chemical modification technique that improves properties by attaching permanent positive charges to the backbone of biopolymers. Carrageenan is a widely available and non-toxic polysaccharide, commonly used in food industry but with low solubility in cold water. We performed a central composite design experiment to check the parameters that most influence the degree of cationic substitution and the film solubility. Hydrophilic quaternary ammonium groups on the carrageenan backbone enhance interaction in drug delivery systems and create active surfaces. Statistical analysis indicated that within the studied range, only the molar ratio between the cationizing reagent and the repeating disaccharide unit of carrageenan had a significant effect. Optimized parameters using 0.086 g of sodium hydroxide and glycidyltrimethylammonium/disaccharide repeating unit of 6.83 achieved 65.47 % degree of substitution and 4.03 % solubility. Characterizations confirmed the effective incorporation of cationic groups into the commercial structure of carrageenan and thermal stability improvement of the derivatives.