Experimental and modeling of potassium diclofenac uptake on activated carbon.

The presence of pharmaceuticals in wastewater resulting from human activities has driven researchers to explore effective treatment methods such as adsorption using activated carbon (AC). While AC shows promise as an adsorbent, further studies are essential to comprehend its entire interaction with pharmaceuticals. This article investigates the adsorption of potassium diclofenac (PD) onto AC using experimental and modeling approaches. Batch adsorption studies coupled with Fourier transform infrared spectroscopy (FTIR) were employed to clarify the adsorption mechanism of PD on AC. Various kinetic and isotherm adsorption models were applied to analyze the adsorbent-adsorbate interaction. The kinetics were best described by Avrami's fractional order (AFO) nonlinear model. Also, the intraparticle diffusion (IP) model reveals a three-stage adsorption process. The experimental equilibrium data fitted well with the three-parameter nonlinear Liu model, indicating a maximum adsorption capacity (Qmax) of 88.45 mg g-1 and suggesting monolayer or multilayer adsorption. Thermodynamic analysis showed favorable adsorption (ΔG° < 0), with an enthalpy change (ΔH° = -30.85 kJ mol-1) characteristic of physisorption involving hydrogen bonds and π-π interactions. The adsorption mechanism was attributed to forming a double layer (adsorbate-adsorbent and adsorbate-adsorbate).

Interaction of fluorene and its analogs with high-density polyethylene microplastics: An assessment of the adsorption mechanism to establish the effects of heteroatoms in the molecule.

The threat of microplastics (MP) pollution in aquatic ecosystems can be even more severe for they are able to interact with organic pollutants that can migrate to adjacent environments. The presence of heteroatoms in organic pollutants can directly influence adsorption onto MP. This research evaluated the adsorption of fluorene (FLN) and its heteroatom analogs dibenzothiophene (DBT), dibenzofuran (DBF) and carbazole (CBZ) onto high-density polyethylene (HDPE) MP from residual (HDPEres) and commercial (HDPEcom) sources. The Langmuir isotherm showed a better fit, while DBT showed higher maximum adsorption capacity (19.2 and 15.8 µmol g-1) followed by FLN (13.4 and 11.7 µmol g-1), and DBF (13.5 and 10.3 µmol g-1) to the HDPEcom and HDPEres, respectively, which indicates a direct correlation with the hydrophobicity of the molecules determined by Log Kow. In contrast, CBZ showed no significant interaction with MP, due to their polar characteristic, thus, no kinetic and thermodynamic parameters could be determined. The adsorption process of all PAH was determined to be exothermic and spontaneous, with low temperatures favoring the process. The pseudo-second-order kinetic models have fitted to the adsorption onto both HDPE; intraparticle diffusion was also observed. Computational studies, physical characterization techniques and batch adsorption experiments demonstrated that the mechanism is governed by hydrophobic interactions, with van der Waals forces as a secondary effect in the adsorption of FLN, DBT and DBF onto HDPEres and HDPEcom. Thus, allowing a deeper understanding of the interactions between HDPE MP and FLN as well with its derivatives.

High-Efficiency Removal of Lead and Nickel Using Four Inert Dry Biomasses: Insights into the Adsorption Mechanisms.

In this study, inert dry bioadsorbents prepared from corn cob residues (CCR), cocoa husk (CH), plantain peels (PP), and cassava peels (CP) were used as adsorbents of heavy metal ions (Pb2+ and Ni2+) in single-batch adsorption experiments from synthetic aqueous solutions. The physicochemical properties of the bioadsorbents and the adsorption mechanisms were evaluated using different experimental techniques. The results showed that electrostatic attraction, cation exchange, and surface complexation were the main mechanisms involved in the adsorption of metals onto the evaluated bioadsorbents. The percentage removal of Pb2+ and Ni2+ increased with higher adsorbent dosage, with Pb2+ exhibiting greater biosorption capacity than Ni2+. The bioadsorbents showed promising potential for adsorbing Pb2+ with monolayer adsorption capacities of 699.267, 568.794, 101.535, and 116.820 mg/g when using PP, CCR, CH, and CP, respectively. For Ni2+, Langmuir's parameter had values of 10.402, 26.984, 18.883, and 21.615, respectively, for PP, CCR, CH, and CP. Kinetics data fitted by the pseudo-second-order model revealed that the adsorption rate follows this order: CH > CP > CCR > PP for Pb2+, and CH > CCR > PP > CP for Ni2+. The adsorption mechanism was found to be controlled by ion exchange and precipitation. These findings suggest that the dry raw biomasses of corn cob residues, cocoa husk, cassava, and plantain peels can effectively remove lead and nickel, but further research is needed to explore their application in industrial-scale and continuous systems.

Efficient removal of veterinary drugs from aqueous solutions using magnetically separable carbonaceous materials derived from cobalt and iron metal-organic frameworks.

Rapid synthesis of carbon-based magnetic materials derived from cobalt and iron metal-organic frameworks (MOFs), ZIF-67, and MIL-100(Fe), by microwave-assisted method, followed by carbonization under a N2 atmosphere is described in this study. The carbon-derived MOFs (CDMs) were evaluated for the removal of the emerging pollutants sulfadiazine (SDZ) and flumequine (FLU) used as veterinary drugs. The study aimed to link the adsorption behavior with their surface properties and elemental composition. C-ZIF-67 and C-MIL-100(Fe) showed hierarchical porous structures with specific surface areas of 295.6 and 163.4 m2 g-1, respectively. The Raman spectra of the CDMs show the characteristic D and G bands associated with defect-rich carbon and sp2 graphitic carbon, respectively. The CDMs exhibit cobalt species (Co3O4, CoO, and Co) in C-ZIF-67 and iron species (Fe2O3, Fe3O4, and Fe) in C-MIL-100 (Fe) which are related to the magnetic behavior of CDMs. C-ZIF-67 and C-MIL-100 (Fe) had saturation magnetization values of 22.9 and 53.7 emu g-1, respectively, allowing easy solid-liquid separation using a magnet. SDZ and FLU removal rates on CDMs follow pseudo-second-order kinetics, and adsorption isotherms fit the Langmuir model based on regression coefficient values. Adsorption thermodynamics calculations showed that the adsorption of SDZ and FLU by CDMs was a thermodynamically favorable process. Therefore, these properties of C-ZIF-67 and C-MIL-100 (Fe) and their regeneration ability facilitate their use as adsorbents for emerging pollutants.

Surface Adsorption Mechanism between Lead(II,IV) and Nanomaghemite Studied on Polluted Water Samples Collected from the Peruvian Rivers Mantaro and Cumbaza.

Real water remediation is an important issue that requires the development of novel adsorbents with remarkable adsorption properties, permitting reusability. In this work, the surface and adsorption properties of bare magnetic iron oxide nanoparticles were systematically studied, before and after the application of a maghemite nanoadsorbent in two real Peruvian effluents severely contaminated with Pb(II), Pb(IV), Fe(III), and others. We were able to describe the Fe and Pb adsorption mechanisms that occurred at the particle surface. 57Fe Mössbauer and X-ray photoelectron spectroscopy results together with kinetic adsorption analyses gave evidence for two involved surface mechanisms: (i) surface deprotonation of maghemite nanoparticles (isoelectric point of pH = 2.3), forming Lewis sites bonding Pb complexes; and (ii) the formation of a thin inhomogeneous secondary layer of iron oxyhydroxide and adsorbed Pb compounds, as favored by surface physicochemical conditions. The magnetic nanoadsorbent enhanced the removal efficiency to values of ca. 96% and provided adsorptive properties with reusability due to the conserved morphological, structural, and magnetic properties. This makes it favorable for large-scale industrial applications.

Brilliant blue FCF dye adsorption using magnetic activated carbon from Sapelli wood sawdust.

Sapelli wood sawdust-derived magnetic activated carbon (SWSMAC) was produced by single-step pyrolysis using KOH and NiCl2 as activating and magnetization agents. SWSMAC was characterized by several techniques (SEM/EDS, N2 adsorption/desorption isotherms, FTIR, XRD, VSM, and pHPZC) and applied in the brilliant blue FCF dye adsorption from an aqueous medium. The obtained SWSMAC was a mesoporous material and showed good textural properties. Metallic nanostructured Ni particles were observed. Also, SWSMAC exhibited ferromagnetic properties. In the adsorption experiments, adequate conditions were an adsorbent dosage of 0.75 g L-1 and a solution pH of 4. The adsorption was fast, and the pseudo-second-order demonstrated greater suitability to the kinetic data. The Sips model fitted the equilibrium data well, and the maximum adsorption capacity predicted by this model was 105.88 mg g-1 (at 55 °C). The thermodynamic study revealed that the adsorption was spontaneous, favorable, and endothermic. Besides, the mechanistic elucidation suggested that electrostatic interactions, hydrogen bonding, π-π interactions, and n-π interactions were involved in the brilliant blue FCF dye adsorption onto SWSMAC. In summary, an advanced adsorbent material was developed from waste by single-step pyrolysis, and this material effectively adsorbs brilliant blue FCF dye.

Single adsorption of diclofenac and ronidazole from aqueous solution on commercial activated carbons: effect of chemical and textural properties.

The importance of the textural and physicochemical characteristics upon the adsorption capacity of the commercial activated carbons (ACs) Coconut, Wood, Merck, Darco, and Norit towards ronidazole (RNZ) and diclofenac (DCF) from water solution was investigated thoroughly in this work. At pH = 7, Coconut AC and Wood AC presented the highest adsorption capacity towards RNZ (444 mg/g) and DCF (405 mg/g). The maximum mass of RNZ adsorbed onto Coconut AC was higher in this study than those outlined previously in other works. Besides, the maximum capacity of Wood AC for adsorbing DCF was comparable to those found for other ACs. The adsorption capacity of all the ACs was increased by surface area and was favored by incrementing the acidic site concentration. The π-π stacking interactions were the predominant adsorption mechanism for the RNZ and DCF adsorption on ACs, and the acidic sites favored the adsorption capacity by activating the π-π stacking. Electrostatic interactions did not influence the adsorption of RNZ on Coconut AC, but electrostatic repulsion decreased that of DCF on Wood AC. The adsorption of DCF on Wood AC was reversible but not that of RNZ on Coconut AC. Besides, the adsorption of RNZ and DCF on the Coconut and Wood ACs was endothermic in the range of 15-25 °C.

The Effect of La3+ on the Methylene Blue Dye Removal Capacity of the La/ZnTiO3 Photocatalyst, a DFT Study.

Theoretically, lanthanum can bond with surface oxygens of ZnTiO3 to form La-O-Ti bonds, resulting in the change of both the band structure and the electron state of the surface. To verify this statement, DFT calculations were performed using a model with a dispersed lanthanum atom on the surface (101) of ZnTiO3. The negative heat segmentation values obtained suggest that the incorporation of La on the surface of ZnTiO3 is thermodynamically stable. The bandgap energy value of La/ZnTiO3 (2.92 eV) was lower than that of ZnTiO3 (3.16 eV). TDOS showed that the conduction band (CB) and the valence band (VB) energy levels of La/ZnTiO3 are denser than those of ZnTiO3 due to the participation of hybrid levels composed mainly of O2p and La5d orbitals. From the PDOSs, Bader's charge analysis, and ELF function, it was established that the La-O bond is polar covalent. MB adsorption on La/ZnTiO3 (-200 kJ/mol) was more favorable than on ZnTiO3 (-85 kJ/mol). From the evidence of this study, it is proposed that the MB molecule first is adsorbed on the surface of La/ZnTiO3, and then the electrons in the VB of La/ZnTiO3 are photoexcited to hybrid levels, and finally, the MB molecule oxidizes into smaller molecules.

Reducing the negative impact of ceftriaxone and doxycycline in aqueous solutions using ferrihydrite/plant-based composites: mechanism pathway.

The adsorption of ceftriaxone (CET) and doxycycline (DOX) from aqueous solution using ferrihydrite/plant-based composites (silica rice husk) to reduce their negative impact on the ecosystem was adequately studied. On the other hand, phosphate and humic acid are often found in water and soil; in view of this, their effects on the adsorption of CET and DOX were investigated. The results showed that the removal of ceftriaxone decreased with an increase in pH, while that of doxycycline did not. Ferrihydrite with 10% silica rice husk (Fh-10%SRH) has the highest maximum adsorption capacity of 139 and 178 mg g-1 for CET and DOX, respectively, at room temperature based on Liu's adsorption isotherm. This implies that the presence of silica rice husk increases CET and DOX uptake due to an increase in the pore volume of FH-10%SRH. The results showed that phosphate had a significant inhibition role on CET adsorption and minor on DOX, whereas humic acid salt affected neither case. Increase in temperature up to 333 K favored the adsorption of both contaminants. The proposed adsorption mechanisms of ceftriaxone are electrostatic interaction, n-π interaction, and hydrogen bond, while that of DOX entails n-π interaction and hydrogen bond.

Experimental and Theoretical Insights on Methylene Blue Removal from Wastewater Using an Adsorbent Obtained from the Residues of the Orange Industry.

Chemical and thermochemical transformations were performed on orange peel to obtain materials that were characterized and further tested to explore their potential as adsorbents for the removal of methylene blue (MB) from aqueous solutions. The results show the high potential of some of these materials for MB adsorption not only due to the surface area of the resulting substrate but also to the chemistry of the corresponding surface functional groups. Fitting of the kinetic as well as the equilibrium experimental data to different models suggests that a variety of interactions are involved in MB adsorption. The overall capacities for these substrates (larger than 192.31 mg g-1) were found to compare well with those reported for activated carbon and other adsorbents of agro-industrial origin. According to these results and complementary with theoretical study using Density Functional Theory (DFT) approximations, it was found that the most important adsorption mechanisms of MB correspond to: (i) electrostatic interactions, (ii) H-bonding, and (iii) π (MB)-π (biochar) interactions. In view of these findings, it can be concluded that adsorbent materials obtained from orange peel, constitute a good alternative for the removal of MB dye from aqueous solutions.

Sustainable production of nanoporous carbons: Kinetics and equilibrium studies in the removal of atrazine.

Nanoporous carbons have been prepared from mangosteen peels-derived chars by physical activation under CO2 flow as a function of temperature. As an example of circular bioeconomy, these sustainable adsorbents were used to remove atrazine, a common pesticide from the agroindustry. Several adsorption models such as Langmuir (two parameter), Sips and Redlich-Peterson (three parameters) were applied to verify the influence of carbon's properties on the uptake of atrazine. Additional kinetic models (pseudo-first order, pseudo-second order and Avrami's) allowed to establish that a mixture of physisorption and chemisorption describes the interaction between the nanoporous carbons and atrazine. As a general fact, an important diffusion of atrazine from the bulk of solution to the surface of carbons was observed. All samples were able to remove atrazine, but the highest uptake was found in the carbon with the highest contribution of micropores to the total pore of volume and with the lowest content of basic surface groups. Several correlations between the kinetic and equilibrium parameters for the atrazine adsorption were found as a function of the textural properties and surface chemistry. Based on the kinetics and equilibrium parameters, the present work proposes a mechanism for the atrazine adsorption on nanoporous carbons contributing to the understanding of the interactions between pollutant molecules and the surface functional groups on nanoporous carbons in the liquid-solid interface.

Chitosan-iron oxide hybrid composite: mechanism of hexavalent chromium removal by central composite design and theoretical calculations.

In this study, the synthesis of iron oxide stabilized by chitosan was carried out for the application and optimization in the removal process of aqueous Cr(VI) by central composite design (CCD). The calculation of these effects allowed to know, quantitatively, the variables and the interaction between them that could affect the Cr(VI) removal process. It was also verified that the most favorable conditions for chromium removal were the following: pH 5.0, Cr(VI) concentration of 130 mg L-1, adsorbent mass of 5 mg, and Fe(II) content of 45% (w/w) in the CT-Fe beads. The adsorption kinetics performed under these conditions showed that the chitosan/iron hybrid composite is an adsorbent material with high chromium removal capacity (46.12 mg g-1). It was found that all variables were statistically significant. However, it was observed that the variable that most affected Cr(VI) removal was the pH of the solution, followed by the concentration of chromium ions in solution and the interaction between them. Therefore, the studied experimental conditions are efficient in chromium adsorption, besides the operational simplicity coming from statistical design. Theoretical calculations showed that the most stable chitosan was that with Fe(II) in the structure, that is, in the reaction mechanism, there is no competition of Fe(II) with Cr(III, VI) in the available sites of chitosan. Thus, the theoretical calculations show that the proposed Cr(VI) removal is effective.

Adsorption mechanisms of hexavalent chromium from aqueous solutions on modified activated carbons.

Functional groups of the activated carbon play the major role in metals removal from aqueous solutions and, for this reason, different treatments can be used to modify the adsorbent surface improving the adsorption capacity for a particular pollutant. In this research, oxidation with nitric acid, heating under an inert atmosphere, and ammonia treatment were applied to modify the activated carbon surface. The modified adsorbents were used for the removal of hexavalent chromium (Cr(VI)) from aqueous solutions at different concentrations (10-500 mg L-1), pH 6, and 25 °C. Adsorption mechanisms of Cr(VI) on the activated carbon were proposed based on the surface chemistry, adsorption/reduction, and desorption experiments. Findings demonstrate that acid functional groups of the activated carbon had an important effect on the hexavalent chromium removal. For instance, a high reduction of Cr(VI) to Cr(III) (50%) was obtained by the oxidized adsorbents, whereas the heat treated adsorbents achieved a low reduction (35%), but the ammonia-treated activated carbon achieved the lowest reduction (20%). The heat-treated adsorbent showed the best Cr(VI) adsorption capacity (48 mg g-1), especially at equilibrium Cr(VI) concentration lower than 200 mg L-1, and the fastest adsorption kinetics among the studied adsorbents. Furthermore, the highest Cr(VI) desorption (90%) was achieved with 0.1 N NaOH-NaCl solutions. In summary, an anionic/reduction coupled adsorption mechanism of Cr(VI) seems to be feasible, and the heat-treated activated carbon is an interesting option for sequestering Cr(VI) species from aqueous effluents.

Stabilized landfill leachate treatment using Guadua amplexifolia bamboo as a source of activated carbon: kinetics study.

In the present study, the characteristics of leachate generated from dumpsite called 'Zapote' located in southern region of Tamaulipas, Mexico were evaluated. The adsorption of non-biodegradable organic matter measured as chemical oxygen demand (COD), color and heavy metals from leachate on activated carbon (AC) prepared in acid media from Guadua amplexifolia bamboo has been studied. In addition, the computation of kinetic parameters during the adsorption process as well as the most probable mechanisms was determined. The ACs were analyzed by using scanning electron microscopy and Fourier transform infrared spectroscopy. The experimental data showed that the ACs removed up to 81.4% of color and reduced COD up to 91.6% after 9 h of reaction at 60°C. For heavy metals, the maximum adsorption uptake was achieved at pH = 8.0 within 20 min with removal percentages of 87.0% (Pb(II)), 43.0% (Cu(II)) and 30.5% (Ni(II)). A pseudo-second-order model explained the adsorption kinetics most effectively for Pb, Ni and Cu, while a pseudo-first order was found for Zn. The AC synthesized from the G. amplexifolia species could be potentially used as an effective adsorbent in the reduction of COD, and removal of color and heavy metals.

Efficient fluoride removal using Al-Cu oxide nanoparticles supported on steel slag industrial waste solid.

A SSW/Al-Cu formed from an industrial solid waste and Al-Cu Nps are utilized for the removal of fluoride from aqueous solutions. The SSW/Al-Cu was obtained by a chemical reduction method. The SSW/Al-Cu was characterized by TEM, SEM, FT-IR, XRD, BET, and pHzpc techniques. The Nps were formed as bimetallic oxides and deposited in the form of spheroidal particles forming agglomerations. The sizes of these particles range from 1 to 3 nm. The surface area and average pore width of SSW/Al-Cu were 2.99 m2/g and 17.09 nm, respectively. The adsorption kinetics were better described using the second-order model, pointing to chemical adsorption with an equilibrium time of 540 min. The thermodynamic parameters obtained here confirm the spontaneous and endothermic nature of the process. The percentage of fluoride removal was 89.5% using the four-bladed disk turbine, and computational fluid dynamics (CFD) modeling demonstrated that using the four-bladed disk turbine helped improve the fluoride removal process. The maximum adsorption capacity was 3.99 mg/g. The Langmuir-Freundlich model best describes the adsorption process, which occurred by a combination of mechanisms, such as electrostatic interactions between the ions involved in the process. This study proves that the chemical modification of this waste solid created an efficient bimetallic nanomaterial for fluoride removal. Furthermore, the method of preparation of these nanocomposites is quite scalable.

Driving forces for the adsorption of a His-tag Chagas antigen. A rational approach to design bio-functional surfaces.

In order to rationally design a bio-functional surface based on the adsorption of a His-tag antigen, three requirements have to be considered: the bio-recognition element, the driving forces for the adsorption process and the detection mode of the bio-recognition event. This work is focused on the study of the adsorption mechanism of the His-tag H49 Chagas antigen on Ni(II) modified substrates. In order to construct the bio-functional surface, the gen of the H49 Chagas antigen was modified to incorporate His6 moiety at the N-terminal (His6-H49). Then, its physical adsorption and bio-affinity interaction with the solid substrate was studied by reflectometry. Besides His-Ni(II) bio-affinity interactions, His6-H49 was also physically adsorbed on Ni(II) modified substrates, leading to randomly oriented antigens. These loosely attached bio-molecules were partially removed using conditions of electrostatic repulsion. On the other hand, bio-affinity interactions, resulting in site-oriented molecules on the substrate, were only removable by specific competitors for Ni(II) surface sites. Finally, the surface bio-activity was determined from the peak separations of voltammetry waves due to the change of the electron transfer kinetics of a redox probe through the bio-functional surface (working electrode).