Intraparticle Diffusion Coefficient Research Articles

Effect of Organic Solvent on the Mass Transfer Mechanism of Coumarin 102 in a Single Octadecylsilyl Silica Gel/Organic Solvent-Water System by Laser Trapping and Fluorescence Microspectroscopy.

Understanding mass transfer kinetics within individual porous particles is crucial for theoretically explaining the retention and elution behaviors in chromatography and drug delivery. Using laser trapping and fluorescence microspectroscopy, we investigated the diffusion mechanism of coumarin 102 (C102) into single octadecylsilyl particle in acetonitrile (ACN)/water, N,N-dimethylformamide (DMF)/water, and 1-butanol (BuOH)/water solutions. The intraparticle diffusion behavior of C102 was evaluated using the spherical diffusion equation, allowing us to determine the intraparticle diffusion coefficients (Dintra): (8-10) × 10-9 cm2 s-1 for ACN, (10-16) × 10-9 cm2 s-1 for DMF, and (4-6) × 10-9 cm2 s-1 for BuOH. The obtained Dintra values were further analyzed using a pore and surface diffusion model. Thus, we revealed that the diffusion mechanism of C102 differed depending on the organic solvent: surface diffusion for ACN and DMF and pore and surface diffusions for BuOH were observed. This difference is attributed to the formation of a concentrated liquid phase of ACN and DMF at the interface of the alkyl chain and the bulk solution in the pore.

Kinetic and Mechanistic Modelling of Pyrimethanil Fungicide Adsorption onto Soils of Varying Physico-chemical Properties.

Pesticide transport in the environment is impacted by the kinetics of its adsorption onto soil. The adsorption kinetics of pyrimethanil was investigated in ten soil samples of varying physicochemical properties. The highest adsorption was in the soil having the maximum silt and CaCO3 contents, pH and electrical conductance but the lowest amorphous Fe oxides and CaCl2 extractable Mn. Pseudo-second order kinetics and intra-particle diffusion model best accounted the adsorption kinetics of pyrimethanil. The equilibrium adsorption estimated by pseudo-second order kinetics (q02) was significantly and positively correlated with CaCl2 extractable Cu content (r = 0.709) while rate coefficient (k02) had a negative correlation with crystalline iron oxides content (r = -0.675). The intra-particle diffusion coefficient (ki.d.) had inverse relationship with CaCl2 extractable Mn content in soils (r = -0.689). FTIR spectra showed a significant interaction of pyrimethanil with micronutrient cations. Adsorption kinetic parameters of pyrimethanil could be successfully predicted by soil properties. The findings may help to evolve fungicide management decisions.

Diffusion behavior of rhodamine 6G in single octadecylsilyl-functionalized silica particle revealed by fluorescence correlation spectroscopy.

We investigated the diffusion behavior of rhodamine 6G (Rh6G) within single octadecylsilyl-functionalized (ODS) silica particle in an acetonitrile (ACN)/water system using fluorescence correlation spectroscopy (FCS). FCS measurements were conducted at the center of the particle to exclusively determine the intraparticle diffusion coefficient (D). The obtained D values were analyzed based on a pore and surface diffusion model, the results of which indicate that surface diffusion primarily governs the intraparticle diffusion of Rh6G. Furthermore, an increase in the concentration of ACN (CACN) resulted in a corresponding increase in the surface diffusion coefficient (Ds), whereas the addition of NaCl did not significantly affect the Ds values. We attributed this dependence of Ds to the dielectric constant change in the interfacial liquid phase formed on the ODS layer. Specially, Ds values of (4.0 ± 0.5) × 10-7, (7.7 ± 1.1) × 10-7, (1.0 ± 0.3) × 10-6, and (1.1 ± 0.2) × 10-6cm2s-1 were obtained for CACN = 20, 30, 40, and 50vol%, respectively. We anticipate that this approach will contribute to advancing research on intraparticle mass transfer mechanisms.

Migration of l-Selenomethionine in the Water-Soil Interface Dominated by Iron Oxides.

Organic selenium (Se) accounts for up to 10-80% of total Se in soils, and l-selenomethionine (SeMet) is a typical organic Se species. However, the migration of SeMet in soils remains elusive. This study investigated the solid-liquid distribution, adsorption, desorption by phosphate, and self-oxidization of SeMet in solution under the influence of ferrihydrite, goethite, and hematite through batch experiments. Iron oxides could adsorb a much larger amount of SeMet than inorganic Se. At the initial Se element concentrations of 0-200 mg/L, the solid/liquid partition coefficient of SeMet was constant, which was 0.41, 0.43, and 0.50 on ferrihydrite, goethite, and hematite, respectively. In addition, the adsorption process of SeMet on the three iron oxides could be well described by the linear driving force model. Accordingly, the intraparticle diffusion coefficient of SeMet in ferrihydrite, goethite, and hematite was 1.4 × 103, 7.9 × 104, and 1.2 × 105 nm2/min, respectively. The adsorption of SeMet on the three iron oxides was slightly influenced by the pH and the coexisting ions, such as Cl-, NO3-, SO42-, and H2PO4-. The desorption ratio of SeMet on the three iron oxides by phosphate was lower than 2.5%. SeMet would aggregate the nanoparticles of iron oxides, resulting in a synergistic effect on the adsorption of phosphate. The oxidization ratio of SeMet was 23.9% in the solution, while it decreased to 17.1-17.5% in iron oxide suspensions. For this oxidization process, the three iron oxides exhibited varying effects to decelerate SeMet oxidation, as represented by the equivalent reaction. The findings of this study reveal the migration of SeMet in the water-soil interface under the influence of iron oxides, which can improve the understanding of Se cycling in the environment as well as provide some guidance for the better utilization of Se in soils and environmental remediation of Se pollution.

Evolution of myoglobin diffusion mechanisms: exploring pore and surface diffusion in a single silica particle.

This study elucidates the mass transfer mechanism of myoglobin (Mb) within a single silica particle with a 50nm pore size at various pH levels (6.0, 6.5, 6.8, and 7.0). Investigation of Mb distribution ratio (R) and distribution kinetics was conducted using absorption microspectroscopy. The highest R was observed at pH 6.8, near the isoelectric point of Mb, as the electrostatic repulsion between Mb molecules on the silica surface decreased. The time-course absorbance of Mb in the silica particle was rigorously analyzed based on a first-order reaction, yielding the intraparticle diffusion coefficient of Mb (Dp). Dp-(1 + R)-1 plots at different pH values were evaluated using the pore and surface diffusion model. Consequently, we found that at pH 6.0, Mb diffused in the silica particle exclusively through surface diffusion, whereas pore diffusion made a more substantial contribution at higher pH. Furthermore, we demonstrated that Mb diffusion was hindered by slow desorption, associated with the electrostatic charge of Mb. This comprehensive analysis provides insights into the diffusion mechanisms of Mb at acidic, neutral, and basic pH conditions.

Removal of antibiotics, bacterial toxicity, and occurrence of antibiotic resistance genes in secondary hospital effluents treated with granular activated carbon and the impact of preceding chlorination

This comprehensive investigation highlighted the complex adsorption behaviors of antibiotics onto granular activated carbon (GAC), the effectiveness of this adsorption in reducing bacterial toxicity, and the reduction of antibiotic resistance genes (ARGs) and antibiotic resistant bacteria (ARB) in hospital wastewater (HWW) effluents. Six GACs were characterized for their physicochemical properties, and their ability to adsorb six antibiotics in the background matrix of actual HWW was evaluated. Coconut shell-derived GAC (Co-U), which had the highest hydrophobicity and lowest content of oxygen-containing acidic functional groups, demonstrated the highest adsorption capacities for the tested antibiotics. Bacterial toxicity tests revealed that GACs could eliminate the bacterial toxicity from antibiotic intermediates present in chlorinated HWW. By contrast, the bacterial toxicity could not be removed by GACs in non-chlorinated HWW due to the greater presence of intermediate components identified by LC-MS/MS. The intraparticle diffusion coefficient of antibiotics adsorbed onto Co-U could be calculated by adsorption kinetics derived from the linear driving force model and the homogenous intraparticle diffusion model associated with the linear adsorption isotherms (0–150 μg/L). Meropenem and sulfamethoxazole exhibited the highest adsorption capacities in a single-solute solution compared to penicillin G, ampicillin, cetazidime, and ciprofloxacin. However, the greater adsorption capacities of meropenem and sulfamethoxazole disappeared in mixed-solute solutions, indicating the lowest adsorption competition. GAC can eliminate most ARGs while also promoting the growth of some ARB. Chlorination (free chlorine residues at 0.5 mg Cl2/L) did not significantly affect the overall composition of ARGs and ARB in HWW. However, the accumulation of ARGs and ARB on GAC in fixed bed columns was lower in chlorinated HWW than in non-chlorinated HWW due to an increase in the adsorption of intermediates.

Prediction of Plate Height Curves of Porous-Shell Pillar Array Columns Micro-Pillar Array Columns

We investigate band broadening in the most widely adopted configuration of micro-pillar array columns (μPACs)—specifically, a cylindrical pillar array where both the pillar walls and the channel bottom are coated with a thin layer of mesoporous material. The two-zone moment analysis method is adopted to investigate the dispersion properties of μPACs in a broad range of shell thicknesses, reduced fluid velocities, and retention factors. Three different models of the unit cell, of increasing complexity, have been implemented, namely a two-dimensional model and two different three-dimensional models with and without the retentive bottom layer, the presence of which seems to have a very significant effect on the plate height curves. Model predictions are compared with experimental van Deemter curves for uncoated and coated porous layers, and a robust relationship between the intra-particle (porous-zone) diffusion coefficient Dpz and the retention factor k′ is established.

An alternative general model for the effective longitudinal diffusion in chromatographic beds filled with ordered porous particles

The two-zone moment-analysis method for the determination of the dispersion tensor in hierarchical retentive porous media has been adopted to compute and model the effective longitudinal diffusion Deff, or equivalently the B-term band broadening, in chromatographic beds filled with ordered porous particles. On the one hand, this approach offers accurate numerical results for Deff while keeping computational expenses low. On the other hand, it also gives direct insight for the analytical modelling, readily revealings the two main essential quantities (resp. referred to as the mobile-zone and stationary-zone effective diffusion factors γm and γs) that contribute to Deff. Modelling these two main parameters provided us with two new analytical models for Deff: a general one, valid for diluted and concentrated packings and accurate in the whole range of relevant intra-particle diffusion coefficient Dpz, and an approximate one, reliable for diluted packings and accurate also for concentrated packings with low to intermediate values of Dpz. The large advantage of both models is that they do not need any fitting parameter because all the required information is incorporated into the experimentally accessible geometric obstruction factor in the mobile phase originating from the tortuosity of the through-pore space (limiting case of fully solid particles without any retention). These models hence serve as an alternative to the Effective Medium Theory (EMT) models used so far in the literature. To validate the theory, five ordered geometries have been investigated. The accuracy of the general model proposed has been quantified and found to be comparable with that of the 3rd order approximate Torquato model for four geometries, even for macro-porosities close to the close-packing limit. The case of a 2-d triangular array of ellipsoidal particles with different elongations is also investigated to show the general validity and applicability of the models.

Detailed analysis of the effective and intra-particle diffusion coefficient of proteins at elevated pressure in columns packed with wide-pore core-shell particles

To determine the efficiency that can be obtained in a packed-bed liquid-chromatography column for a particular analyte, a correct determination of the molecular and effective diffusion coefficients (Dm and Deff) of the analyte is required. The latter is usually obtained via peak parking experiments wherein the flow is stopped. As a result, the column pressure rapidly dissipates and the measurement is essentially conducted at ambient pressure. This is problematic for analytes whose retention depends on pressure, such as proteins and potentially other large (dipolar) molecules. In that case, a conventional peak parking experiment is expected to lead to large errors in Deff. To obtain a better estimate ofDeff, the present study reports on the use of a set-up enabling peak parking measurements under pressurized conditions. This approach allowed us to report, for the first time, Deff for proteins at elevated pressure under retained conditions. First, Deff was determined at a (average) pressure of about 105 bar for a set of proteins with varying size, namely: bradykinin, insulin, lysozyme, β-lactoglobulin, and carbonic anhydrase in a column packed with 400 Å core-shell particles. The obtained data were then compared to those of several small analytes: acetophenone, propiophenone, benzophenone, valerophenone, and hexanophenone. A clear trend between Deff and analyte size was observed. The set-up was then used to determine Deff of bradykinin and lysozyme at variable (average) pressures ranging from 28 bar to 430 bar. These experiments showed a decrease in intra-particle and surface diffusion with pressure, which was larger for lysozyme than bradykinin. The data show that pressurized peak parking experiments are vital to correctly determine Deff when the analyte retention varies significantly with pressure.

Feasibility of nitrate adsorption from aqueous solution by nitrogen and oxygen-modified pine bark biochar: experimental and computational approach

Efficient and economical wastewater treatment has presented itself as a global challenge. In this context, adsorption is one of the most effective methods to remove contaminants from wastewater. The present study evaluated the feasibility of chemically modified pine bark biochar’s nitrate adsorption ability. Pine bark biochar was modified with urea and sulfuric acid to remove nitrate from an aqueous solution. The physicochemical properties of the biochar samples, such as pH, pH at point of zero charges, surface atomic composition, surface morphology, and surface area, were evaluated. The equilibrium adsorption data were fitted to the Langmuir and Freundlich isotherm models. The kinetic data were fitted to different kinetic models (pseudo-first order, pseudo-second order, intraparticle diffusion, and Elovich). The adsorption data fitted well with the Langmuir and pseudo-first order models. The maximum nitrate adsorption capacity was found to be 1.548 mg g−1. Mass transfer studies were conducted to identify the rate-limiting step, values of the external mass transfer coefficient, and diffusion coefficient in the nitrate adsorption process by the modified biochar. The external mass transfer coefficients were in the range of 2.2 × 10–11–2.86 × 10–10 m s−1. The intraparticle diffusion coefficient ranged from 6.53 × 10–10 to 1.78 × 10–9 m2 s−1. The Biot number value less than 100 indicated that the adsorption was controlled by film diffusion. Interaction energies between nitrate ions and model biochar structures were calculated DFT-based quantum chemical software (Gaussian). The positive interaction energy values (2.3485–2.485 eV) suggested nitrate adsorption on model biochar structures was thermodynamically not feasible.Graphical

Pore Size Dependence of Mass Transfer of Zinc Myoglobin in a Single Mesoporous Silica Particle.

This study investigated the pore size dependence of the mass transfer of zinc myoglobin (ZnMb) in a single mesoporous silica particle through confocal fluorescence microspectroscopy. The ZnMb's fluorescence depth profile in the particle was analyzed by a spherical diffusion model, and the intraparticle diffusion coefficient was obtained. The intraparticle diffusion coefficient in the silica particle with various pore sizes (10, 15, 30, and 50 nm) was furthermore analyzed based on a pore and surface diffusion model. Although the mass transfer mechanism in all silica particles followed the pore and surface diffusion model, the adsorption and desorption of ZnMb affected the mass transfer depending on the pore size. The influence of the slow desorption of ZnMb became pronounced for large pore sizes (30 and 50 nm), which was revealed by simulation using a diffusion equation combined with the adsorption-desorption kinetics. The distribution of ZnMb was suppressed in small pore sizes (10 and 15 nm) owing to the adsorption of ZnMb onto the entrance of the pore. Thus, we revealed the mass transfer mechanism of ZnMb in the silica particle with different pore sizes.

Tray drying of medical cannabis inflorescences at industrial scale: Kinetics measurement and modeling towards the implementation of statistical process control

The production of medical cannabis in compliance with the guidelines of Good Manufacturing Practice requires a science-based control strategy for the process. In this work, we hypothesized that industrial tray drying process of cannabis inflorescences can be achieved through an accurate selection and fitting of mechanistic models. In total, three industrial runs were measured and modeled from an initial moisture content of 70–72 wt% to a final content of ≤12 wt%. The temperature, relative humidity, and flow rate of convection air were kept constant at 20 °C, 50 %, and 9800 m3h−1. A two-period model based on external resistance and intraparticle diffusion (FUMM+SPPM) was the best to describe the process, with a fitting error of 16.9 %. A control chart was conceived using FUMM+SPPM and a non-linear relation for the standard deviation along time. The suitability of the FUMM+SPPM was demonstrated with a validation run, resulting in a prediction error of 11.5 %; and where the upper and lower control limits of the control chart were respected. A sensitivity analysis showed that the initial moisture uncertainty can offset by 11.6 % the duration of the drying process. A deeper analysis on the fitted intraparticle diffusion coefficients points the migration of water to resemble osmotic movement. Globally, this study validates the adopted pathway to launch and improve a statistical process control for the tray drying of medical cannabis inflorescences.

Pore connectivity influences mass transport in natural rocks: Pore structure, gas diffusion and batch sorption studies

Six rocks (one granodiorite, one limestone, two chalks, one mudstone, and one dolostone) with different extents of heterogeneity at six different particle sizes (from 75 to 8000 μm) were studied to describe the effects of pore connectivity on mass transport. The methods applied were (i) porosity measurement of granular rocks, (ii) analyses of gas-phase diffusive transport in a bed of packed particles, along with a solid quartz method at these six particle sizes being developed to identify the contribution of intraparticle diffusion, and (iii) batch sorption tests of multiple ions (anions and cations) with subsequent analyses of inductively coupled plasma-mass spectrometry. Granular porosity measurement results reveal that with decreasing particle sizes, the effective porosities for the “heterogenous” group of rocks (Grimsel granodiorite and Edwards limestone) increase, whereas the porosities of another “homogeneous” group (two Israel chalk samples, Japan mudstone, and Wyoming dolostone) remain constant. Gas diffusion results show that the intraparticle gas diffusion coefficient among these two sample groups, varying in the magnitude of 10-8 to 10-6 m2/s, are not directly correlated to the porosity differences. Moreover, the batch sorption work displays a different affinity of rocks for various tracers. For Grimsel granodiorite, Japan mudstone, and Wyoming dolostone, the adsorption capacity of Sm3+ and Eu3+ increases as the particle size decreases. In general, this integrated research of grain size distribution, granular rock porosity, intraparticle diffusivity, and ionic sorption capacity gives insights into the pore connectivity effect on both physical and chemical transport behaviors for different lithologies and/or different particle sizes.

Sorption efficiency of Pb2+ ions using (bio)nano-composite magnetic gelled beads

The rapidly expanding world of nanotechnology is captivating researchers in fields as diverse as health, nutrition, agriculture and the environment. Many works have been carried out over the last ten years on nanoparticles in the field of water treatment due to their unique properties. They can potentially improve adsorption, catalysis, magnetic separation and promising processes. Solving the difficulties associated with water treatment using nanotechnology requires the development of innovative solutions and the design of a recoverable product. In the present study, we evaluated the adsorption efficiency of lead ions (Pb2+) by using new gelled magnetic (bio)nano-composite beads, based on magnetic nanoparticles (MNPs), sodium alginate (SA), polyvinyl alcohol (PVA) and calcium carbonate (CC). First, the physical characteristics of these magnetic (bio)nano-composites gelled beads were determined. Then, the discontinuous adsorption of (Pb2+) ions was studied by examining some parameters related to kinetics and the effect of pH. The corresponding obtained results show that these beads are more effective in pH range 6–9, since the sorbed amount is very fast at the start of contact and kinetics follow the 2nd order model. The removal yield of 99 % is reached after 300 min. The values ​​of the intra-particle diffusion coefficients (Df and Dp) are equal to 0.32*10-8 and 2.49*10-8 m2/s, respectively. The shape of isotherm is of type III, and it is well described by the Freundlich model. The obtained results revealed that these magnetic (bio)nano-composite gelled beads seems to be very effective in treating water contaminated with Pb2+ cations and without negative impact on the environment.

Characterization of dynamic adsorption regimes in synthetic and natural porous structures using lattice Boltzmann simulations

This paper presents the first systematic study on the characterization of dynamic adsorption regimes of gas in porous media using the ratio of inter- to intraparticle diffusion coefficients. The effect of the ratio between the two diffusion coefficients on the adsorption dynamics was investigated in combination with the adsorbent particles size and the disorder parameter, which numerically describes pore space heterogeneity, by mathematical modelling using the lattice Boltzmann simulations for fluid flow and the convective-diffusive transport of an adsorbate dissolved in a fluid. To characterize the dynamic adsorption regimes, for the first time, a relationship between the surface and total adsorption amount was used. The obtained results during simulations in two-dimensional synthetic porous structures showed that the size of the adsorbent particle strongly affects the surface and the total adsorption dynamics. An increase in the particle size promotes an increase in the rate of surface adsorption. Depending on the ratio of inter- to intraparticle diffusion coefficients, increasing particle size promotes either an acceleration or slowdown of the total adsorption dynamics. The results revealed in two-dimensional structures were verified by simulations in three-dimensional digital models of natural sandstones, which were obtained using X-ray computed tomography.

On the occurrence of very low intra-particle diffusion rates in zwitterionic hydrophilic interaction liquid chromatography polymer columns

Intra-particle diffusion is investigated in particle-packed and monolithic zwitterionic hydrophilic interaction liquid chromatography (HILIC) polymer columns. For this purpose, plate heights are first measured over a broad range of velocities for polar compounds with zone retention factors between k″ = 2 and 10 on all column types, multiplied with the corresponding velocity, and extrapolated to zero velocity. The thus obtained B-term coefficients are additionally verified via peak parking experiments and indicate a very low degree of longitudinal diffusion in all columns, that moreover seems to be independent of the zone retention factor. This is in contrast to earlier observations on reversed-phase liquid chromatography columns and bare silica HILIC columns. To obtain more insight into the reasons for these low levels of longitudinal diffusion, the experimentally obtained effective diffusion coefficients are modeled to equations derived from the effective medium theory, such as the models developed by Torquato and Jefrey & Hashin. It is, however, demonstrated that these models fail to adequately describe effective diffusion in the studied zwitterionic HILIC columns, due to the low degree of intraparticle diffusion in these stationary phases. Fitting the experimental effective diffusion coefficients to the two limiting cases of the effective medium theory, i.e., the pure parallel-connection and pure serial-connection case, it is observed that to stay within these limits, intraparticle diffusion must be extremely low, i.e., Dpz/Dm ≤ 0.01, indicating that the diffusion inside the pores is at least 100 times smaller than the bulk diffusion coefficient. There are several possible explanations for these low intraparticle diffusion coefficients, such as a strongly hindered diffusion in the polymer matrix, extremely low surface diffusion rates in the aqueous layer adsorbed onto the stationary phase and/or the occurrence of slow localized adsorption events.

Adsorption Effect and Adsorption Mechanism of High Content Zeolite Ceramsite on Asphalt VOCs.

In order to meet the requirements of industrial-scale fixed beds and develop an excellent adsorbent for asphalt VOCs. Zeolite ceramsite containing binder was prepared and successfully applied to the inhibition of asphalt VOCs. The results showed that prepared zeolite ceramsite possessed a high degree of crystallinity, and its main crystal phase is zeolite. The micropores with a pore size of 0.88 nm dominated the pore size distribution of the material. The adsorption experiment of asphalt VOCs showed a lower VOCs adsorption effect of 8.72% at a small dosage of 5%, while at a large dosage of 50%, the adsorption effect of VOCs exceeded 45%. This might be caused by the quite small external specific surface area, which occupied only 8.3% of the total specific surface area, and the low intraparticle diffusion coefficient due to the micropores. Meanwhile, the kinetics diameters of most aromatic hydrocarbons, which were comparable to the pore size of micropores, and the increase in the intraparticle diffusion resistance of aliphatic hydrocarbon molecules were the important factors in obtaining high adsorption of aromatic hydrocarbons in asphalt VOCs. Furthermore, the results indicated that the particulate adsorbent with a microporous structure should be mixed into the asphalt as a fine aggregate rather than an asphalt modifier for better asphalt VOCs adsorption effect.

A novel method for fabrication of a binary oxide biochar composite for oxidative adsorption of arsenite: Characterization, adsorption mechanism and mass transfer modeling

Arsenite [As(III)] is more mobile and toxic than arsenate [As(V)], making it more difficult and more critical to remove from water. The oxidative adsorption of As(III) is preferred due to its cost and time effectiveness. The chemical mixing process is a common method for preparation of biochar composites, but it is not time-efficient for homogeneous metal impregnation and is challenging to achieve consistent and reproducible physicochemical properties of the composite. The mixing method is even more challenging if two metal oxides are utilized in preparing engineered biochars. The current study proposes a novel microwave- and electrochemical-assisted technique to overcome the shortcomings of the mixing method and create a binary-oxide biochar composite with oxidation and adsorption capabilities. In addition, a new procedure was used to develop a diffusional mass transfer model combined with a genetic algorithm to characterize the adsorption process. Characterization of the fabricated biochar indicated that the deposited Fe and Mn oxides on the biochar surface included a mixture of Mn(II,III,IV) oxides and poorly crystalline α-FeOOH, respectively. The adsorption results suggested a hybrid adsorption mechanism with a high probability of a homogeneous monolayer adsorption process. Based on XANES analyses, no reduction to As(III) was observed for the As(V) adsorbed onto adsorbent, while 79% of the adsorbed As(III) was oxidized to As(V). The intraparticle diffusion and external mass transfer coefficients were estimated using a diffusional mass transfer model. Based on the modeling results, the adsorption of As onto the fabricated adsorbent was mainly controlled by external mass transfer. Overall the As(III) adsorption capacity of untreated biomass increased from 62 to 21,426 μg/g through the modification, indicating the high potential of the proposed procedure for preparation of adsorbents with improved oxidation and adsorption performance.

Solketal Removal from Aqueous Solutions Using Activated Carbon and a Metal-Organic Framework as Adsorbents.

The worldwide rise in biodiesel production has generated an excess of glycerol, a byproduct of the process. One of the most interesting alternative uses of glycerol is the production of solketal, a bioadditive that can improve the properties of both diesel and gasoline fuels. Even with its promising future, not much research has been performed on its toxicity in aqueous environments. In this work, solketal adsorption has been tested with two different commercial adsorbents: an activated carbon (Hydrodarco 3000) and a metal–organic framework (MIL-53). Diclofenac and caffeine were also chosen as emerging contaminants for comparison purposes. The effect of various parameters, such as the adsorbent mass or initial concentration of pollutants, has been studied. Adsorption kinetics with a better fit to a pseudo-second-order model, intraparticle diffusion, and effective diffusion coefficient were studied as well. Various isotherm equation models were employed to study the equilibrium process. The results obtained indicate that activated carbon is more effective in removing solketal from aqueous solutions than the metal–organic framework.

A new multi-mechanism adsorption kinetic model and its relation to mass transfer coefficients

A new multi-mechanism kinetic model for batch adsorption is proposed. A dimensionless parameter in the model serves as a mechanism indicator in the sense that the model converts to the pseudo-first-order (PFO), the Vermeulen (intraparticle diffusion) and the film diffusion models as the dimensionless parameter changes its values. Expressions relating the model parameters and the mass transfer coefficients are obtained which allow for the estimation of the film mass transfer and the intraparticle diffusion coefficients from `show that the estimated mass transfer coefficients are in reasonable agreement with literature values.