Experimental Breakthrough Curves Research Articles

Investigating advection–dispersion behavior for simulation of HTO and 238Pu transport in argillaceous shale with different varying degrees of weathering

Abstract Exploring the migration behavior of radioactive nuclides in the surrounding rock media of the disposal site is the basis for the safety evaluation of radioactive waste disposal sites. In this study, the column experiment was employed to evaluate the nuclide migration behavior in the surrounding rock medium of a near-surface disposal site in China and to investigate the advection–dispersion behavior of tritium (HTO) and plutonium-238 (238Pu) in highly weathered argillaceous shale with different degree of weathering. A reasonable numerical model was selected to fit the experimental breakthrough curves (BTCs) and obtain relevant migration parameters. The results showed that: (1) the breakthrough curves of HTO and 238Pu in fractured media with varying degrees of weathering exhibited clear “peak forward” and “tail dragging” phenomena; (2) the stream tube model can better fit the BTCs of the nuclides in the highly weathered fractures and obtain the average dispersion coefficient <D>, average distribution coefficient <K d>, and other parameters; (3) the two-region non-equilibrium model can better fit the BTCs of the nuclides in the penetrating fractures and weak weathering fractures and obtain the volumetric water content of the mobile liquid region (θ m), distribution coefficient (K d), and other parameters.

Flow and contaminant transport dynamics in clay-amended barriers through flushing experiments and multi-porosity-based modeling

Clay-amended barriers are widely used to prevent hazardous leachate percolation from landfill to subsurface. The performance of these barriers is mostly evaluated through numerical simulations with limited experimental investigation through leachate flushing experiments. To bridge this gap, contaminant loading and its flushing experiments were carried out to assess the performance of clay-amended composite materials as landfill liners. River sand (Sa), loamy soil (Ns), and alternative waste materials like fly ash (Fa) and flushed silt (Si) were used to prepare the composites. Composites fulfilling the hydraulic conductivity (<10−7 cm/s) and compressive strength (200 kPa) criteria were selected for contaminant loading and its flushing experiments to understand the fate of fluoride ions. The experimentally determined hydraulic conductivity (Ks) values for all the composites were in the order of 10−8 cm/s. The experimental breakthrough curves exhibited skewed shape, long tailing, and dual peaks. Dual porosity and dual permeability with immobile water models were employed to simulate these curves, revealing that preferential flow pathways and random chemical sorption sites significantly affect solute transport in clay-amended barriers. Further, scanning electron microscopy and energy-dispersive X-ray spectroscopy were employed to trace the preferred path of fluoride ions through the barrier. The removal efficiency and temporal moments were used to determine the percentage mass retained, mean arrival time, and spreading within the barrier. The highest solute mass was retained by sand-clay barrier (SaB30) (91%), followed by loam-clay barrier (NsB30) (59%), fly ash-clay barrier (FaB30) (38%), and silt-clay barrier (SiB30) (4%) with the least mass. The lowest mean arrival time was calculated for NsB30 (269 h) and the highest for SaB30 (990 h), with FaB30 (384 h) and SiB30 (512 h) having values in between. This study concludes that validating the design hypothesis of clay-amended barriers through contaminant loading and its flushing studies leads to an effective and sustainable design.

Continuous multi-column capture of monoclonal antibodies with convective diffusive membrane adsorbers.

Downstream processing is the bottleneck in the continuous manufacturing of monoclonal antibodies (mAbs). To overcome throughput limitations, two different continuous processes with a novel convective diffusive protein A membrane adsorber (MA) were investigated: the rapid cycling parallel multi-column chromatography (RC-PMCC) process and the rapid cycling simulated moving bed (RC-BioSMB) process. First, breakthrough curve experiments were performed to investigate the influence of the flow rate on the mAb dynamic binding capacity and to calculate the duration of the loading steps. In addition, customized control software was developed for an automated MA exchange in case of pressure increase due to membrane fouling to enable robust, uninterrupted, and continuous processing. Both processes were performed for 4 days with 0.61 g L-1 mAb-containing filtrate and process performance, product purity, productivity, and buffer consumption were compared. The mAb was recovered with a yield of approximately 90% and productivities of 1010 g L-1 d-1 (RC-PMCC) and 574 g L-1 d-1 (RC-BioSMB). At the same time, high removal of process-related impurities was achieved with both processes, whereas the buffer consumption was lower for the RC-BioSMB process. Finally, the attainable productivity for perfusion bioreactors of different sizes with suitable MA sizes was calculated to demonstrate the potential to operate both processes on a manufacturing scale with bioreactor volumes of up to 2000 L.

Magnetic nanoparticles loaded hydrochar for effective Cr(VI) removal from water: Batch and column studies

Chromium considered as most toxic trace metal and is essential to remove it from aqueous using influential adsorbents. Hydrochar prepared from mango peels biomass by thermal activation process was applied to produce activated hydrochr (ACH) which further prepared magnetic nano-composite activated hydrochar (Fe3O4-ACH) material as an effectual sorbent and tested for adsorption of Cr(VI) ions. SEM/EDS, BET, FTIR, VSM, and XRD instruments were utilized to evaluate the characteristics of produced Fe3O4-ACH. The obtained results revealed that the nanoparticle modification increased the surface area and improved the adsorption ability of ACH. A vibrating sample magnetometer was applied for magnetic properties in which the external magnetic field responded by saturation magnetization leading to quickly adsorbed metal ions from water. The factorial design studies were achieved to optimize the removal conditions of metal ions. Equilibrium data for isotherms (Langmuir isotherm) and kinetic mechanisms (pseudo second order) well fitted with the models. The obtained adsorption capacity for Langmuir isotherm was 174.7 mg/g under optimized conditions (dose 0.03 g, contact time 120 min, Cr(VI) solution 50 mg/L). Practical applications of real water samples were studied by fixed-bed column adsorption. The obtained results revealed that the synthesized Fe3O4-ACH was promising for Cr(VI) removal with adsorption capacity of 60.24 mg/g at optimized conditions; bed height (1.3 cm), Cr(VI) ions concentration (50 mg/L) and flow rate (12 mL/min). The experimental breakthrough curve results were compared in a fixed-bed column and were successfully fitted with kinetic models. The given results of distribution and selectivity coefficients proven that Fe3O4-ACH composite has a greater adsorption selectivity than adsorption of Cr(VI). Furthermore, computational molecular modeling was performed to evaluate the interaction types between Cr(VI), Fe3O4, and ACH. The Cr(VI) adsorption mainly carried hydrogen bonding, π–π, hydrophobic and electrostatic interactions. Desorption of chromium ions from Fe3O4-ACH composite adsorbent was more effective with 94.1% desorption efficiency. An approximate cost analysis of 3.15 USD/Kg in a week was assumed for activated hydrochar which was cheaper than the commercially available activated carbon which cost 20 USD/Kg. The obtained results indicated that the produced Fe3O4-ACH composite is a capable adsorbent to decontaminate Cr(VI) from real water samples.

Hydrogen Sulfide Adsorption Mechanism and Breakthrough Curves of Highly Stable Na-, Na-H-, Ca- and K-Mordenites.

Hydrogen sulfide (H2S) is a hazardous gas found in natural gas and biogas, lethal over 100 ppm. When released into the atmosphere, it can turn into sulfur dioxide. One option to remove H2S is using porous materials such as zeolites. Among them, mordenite stands out due to its channel structure, wide availability, and low cost. In this work, we evaluated the H2S adsorption capacity of mordenite using a volumetric static method. The results show the adsorption capacity of H2S in mordenite varies with the exchanged cation. The highest was measured in Na-mordenite (~4.08 mmol H2S/g mordenite). The experimental breakthrough curves for this zeolite confirmed Langmuir-type adsorption and strong affinity between Na+ cations and H2S. Despite this interaction, the XRD diffractograms of Na-mordenite show that the material retained its crystalline structure. More information about the differences in the amount of H2S adsorbed in the zeolites caused by the change in exchanged cation was obtained by H2S adsorption followed by FTIR spectroscopy. The spectra show differences in the position of the peaks related to the different adsorption modes of H2S caused by a change in the polarizing power of the cations due to their charge and position inside the zeolite pores.

A sustainable approach to combat industrial air pollution using commercially available and engineered gas-phase adsorbents

The occurrence of benzene, toluene, ethylbenzene, and xylene (BTEX) in the environment has human health and ecological consequences; hence, it is essential to remediate the gas-phase industrial plume before its release. A laboratory-scale experimental apparatus was designed to investigate single-component gas-phase adsorption of BTEX compounds on commercially available granular activated carbon (CGAC) and laboratory-developed Mesquite-derived granular activated carbon (MDAC). The physical properties of CGAC and MDAC show that these adsorbents have a high N2 BET surface area, with CGAC exhibiting microporosity features. The single-component adsorption of BTEX was modeled by considering the transport of BTEX by axial dispersion, convective transport, and accumulation in the adsorbent bed at isothermal conditions. A linear driving force model was used to examine the mass transfer process. The experimental breakthrough curves showed good agreement with the modeled breakthrough curves. The modeling parameters demonstrated the dominance of intraparticle diffusion with a negligible external diffusion of BTEX onto CGAC and MDAC. The analysis of experimental data validated the modeled dynamic behavior of BTEX adsorption onto CGAC and MDAC. Overall, BTEX compounds followed Langmuir isotherms for both adsorbents, with intra-particle diffusion as a dominant gas phase adsorption mechanism.

Investigation of the removal of color and heavy metal from wastewater using activated sludge continuous system and application of models

In the continuous system studies, the natural state of the activated sludge was used in the fixed bed column and fluidized bed column, and the studies were carried out with the synthetic solution wastewater similar to the metal coating industry. Experiments at operating conditions of bed heights 20 cm, initial Cu2+, Ni2+, and Methylene Blue concentrations of 100 mg/L, pH 5.0 and flow rates 2 mL/min were performed to study the performance of the fixed bed column and fluidized bed column. It is seen that the removal efficiencies of the fixed bed and fluidized bed column are very close to each other. Thomas, Yoon-Nelson and Bohart-Adams models were applied to the data obtained in the fixed bed column system. It has been observed that there is a good agreement between the experimental breakthrough curves and the model predictions. In addition, regeneration of activated sludge with 0.1 M HCl and a reuse experiments were carried out, and it was observed that the efficiency decreased considerably in the second use. The results are promising and shall serve to design the activated sludge based fixed bed column and fluidized bed column to obtain cleaner and sustainable treatment of industrial wastewaters containing Cu, Ni and Methylene Blue.

Study of methane upgrading using an activated carbon 3D-printed adsorbent

Although Maxsorb is a commercially available powder-form material, to be used in adsorption-based processes, its handling is easier if used with a structured geometry. Indeed, in the monolithic form, activated carbons have shown the potential to be used in adsorption-based applications. The use of additive manufacturing (AM) allows the development of structured adsorbents with adaptable geometries. In this work, Maxsorb activated carbon was 3D-printed into a monolithic structure using a polymeric binding agent, carboxymethylcellulose (CMC). The monolith was obtained through direct writing of filaments of an ink containing the adsorbent and the binding agent in a layered way, according to a pre-established pattern. The material was comprehensively characterized by N2 physisorption at 77 K and CO2 adsorption at 273 K to analyze the porous structure, SEM, and mercury porosimetry to evaluate the macrostructure porosity. To examine the affinity of CH4 and N2 with the adsorbent, pure adsorption equilibrium isotherms of these two gases on the 3D-printed monolith were measured at 303, 333, and 373 K by a gravimetric method. The adsorption capacities were compared to the ones of the original powder. The activated carbon materials showed a higher affinity to CH4. Furthermore, the adsorption equilibrium data of CO2 and Ar were also assessed. For all gases, the adsorption capacities decreased upon shaping. The monolith's CH4/N2 ideal selectivity was compared with its pristine powder (2.84 vs. 3.54). The CH4/N2 separation performance was also assessed through dynamic breakthrough tests. The experimental breakthrough curves were well predicted using a mathematical model.

Three-zone simulated moving bed for the separation of chlorogenic acid and caffeine fractions in the liquid extract of spent coffee grounds

Spent Coffee Grounds (SCG) is an agricultural residue obtained in a large quantity from local cafes in Thailand. In order to handle this waste effectively, the valorization of SCG is essential. SCG consists of beneficial phenolic compounds with antioxidative properties and caffeine, which can be recovered through extraction followed by separation and purification processes. In this work, water extraction of SCG was carried out. The volumetric composition of the liquid extract of SCG was then adjusted with an organic solvent, and the obtained mixture was used as the feed for subsequent separation. For the separation method of the SCG extract, a single chromatographic column was employed to separate a group of phenolic compounds (represented by chlorogenic acid) and a group of contaminants (represented by caffeine). The volumetric composition of the mobile phase was varied to determine the condition suitable for the separation of chlorogenic acid and caffeine in a C18 column. Adsorption parameters were determined and used to formulate the mathematical models describing the adsorption dynamics of those two bioactive compounds in the experimental breakthrough curves of standard solutions and the liquid extract of SCG. Furthermore, the three-zone simulated moving bed system (TZ-SMB) was designed to continuously separate fractions of chlorogenic acid and caffeine in the liquid extract of SCG. The adsorption parameters were employed in the optimization of TZ-SMB operating conditions using triangle theory, conducted via computer simulation. The experimental result of water extraction revealed that the yields of chlorogenic acid and caffeine were 0.292 and 0.583 mg/g dried SCG, respectively, using solid-to-liquid ratio of 1 g: 30 mL and temperature of 75 °C. The separation result in a single chromatographic column showed that the mobile phase consisting of acetonitrile, water, and formic acid (10: 90: 1.5 vol%) provided the linear adsorption isotherms for both chlorogenic acid and caffeine, and the chromatographic peaks of all compounds in the liquid extract of SCG were well separated. The simulated results of TZ-SMB at the optimal point revealed that the flow rates of desorbent, feed, extract product, and raffinate product were 0.626, 0.115, 0.081, and 0.593 mL/min, respectively, with the switching time of 20 min. At this point, the relative purities of caffeine in the extract product and chlorogenic acid in the raffinate product were 99.45 % and 98.88 %, respectively, with the maximum productivity of 0.045 mg/mL⋅h. In addition, for demonstration purposes, the lab-scale TZ-SMB experiment was conducted to show the separation of chlorogenic acid and caffeine in the liquid extract of SCG. The operating point from the triangle separation region was chosen based on the sensitivity of flow rate that ensured the criteria of purity. The experimental results showed that the relative purities of caffeine in extract product and chlorogenic acid in raffinate product were both 100 %, verifying the successful separation.

Effective removal of arsenic from contaminated groundwater using an iron-based metal-organic framework

This study investigates the potential of an iron-based metal–organic framework (MOF) material, Fe-benzene-1,3,5-tricarboxylate (Fe-BTC), for arsenic removal from water. We conducted batch and column experiments to evaluate the effects of varying mass dosages of MOF and pH ranges on arsenic adsorption. Our batch experiments revealed that increasing the mass of Fe-BTC MOF led to higher adsorption capacity. Furthermore, within the range of pH values analyzed, Fe-BTC demonstrated stable arsenic adsorption capacity, suggesting that pH conditions did not significantly affect its performance. In the column experiments, we used granitic material amended with compost and compared arsenic concentration breakthrough curves with and without the presence of MOF to assess its efficiency in arsenic removal. Without MOF, we observed rapid arsenic arrival followed by a slow increase in concentration, indicating anomalous transport dynamics induced by the compost. The addition of MOF resulted in prolonged arsenic arrival and a stabilized lower concentration, indicating effective arsenic adsorption. Fe-BTC MOF exhibited a six-fold increase in arsenic adsorption compared to its absence when added to the soil material. We employed a fractional order advection–dispersion equation model to characterize and predict the physical and chemical dynamics in the column experiments. The transport model accurately matched the arsenic breakthrough curves in the column experiments by capturing the non-Fickian transport and sorption chemical dynamics. The model indicated that compost had an insignificant impact on arsenic adsorption due to flow heterogeneity, while higher dosages of MOF resulted in increased arsenic adsorption and non-Fickian dynamics.

Lignocellulosic biomass functionalized with EDTA dianhydride for removing Cu (II) and dye from wastewater: Batch and fixed-bed column adsorption

This work aims to introduce new chelating materials based on lignocellulosic biomass from Gundelia Tournefortii (GT). In terms of functionalization, GT has been modified using ethylenediaminetetraacetic dianhydride (EDTAD). Functionalized/modified Gundelia Tournefortii (EGT) and GT were characterized by the Fourier Transform Infra-red (FTIR), Scanning Electron Microscopy (SEM), Energy Dispersive X-ray (EDX), and X-ray Diffraction (XRD) analyses. In this regard, adsorption experiments (continuous fixed-bed column, batch) have been conducted using EGT to adsorb contaminants (Cu (II) and dye). The batch tests investigate the optimum condition, factors like: duration of experiment, the value of pH, EGT amount, and the initial concentration of the prepared solution. According to experimental data, sorption followed Langmuir isotherm. Besides, the most suitable kinetics model was pseudo-second-order. The capacity of this adsorbent reached 156.78 mg/g as the maximum amount. In terms of fixed-bed column study, functional items such as flow rate, bed depth, inflow concentration on EGT performance in the continuous adsorption column were assessed. Results confirmed that the enhancement in the inflow concentration and bed length, and flow rate decline, reinforced EGT removal capability. The dynamic capacity of this adsorbent is projected to reach 15.61 mg/g as the maximum amount in certain conditions. Modeling of experimental breakthrough curve demonstrated that the Thomas model is better described rather than Yoon-Nelson and Adams-Bohart models. Also, the results indicated that the Lignocellulosic biomass had dye (Direct Red 23: DR23) removal ability.

Experimental Design and Breakthrough Curve Modeling of Fixed-Bed Columns Utilizing a Novel 3D Coconut-Based Polyurethane-Activated Carbon Composite Adsorbent for Lead Sequestration

This study presents a novel polyurethane-activated carbon composite (PACC) as an effective and sustainable adsorbent for treating lead-ion-contaminated waters. The PACC was characterized using Scanning Electron Microscopy with Energy Dispersive X-ray (SEM-EDX), Fourier Transform Infrared Spectroscopy (FTIR), Brunauer, Emmett, and Teller (BET) surface area analyzer, X-ray Diffraction (XRD), and Thermogravimetric Analyzer (TGA) to evaluate its physicochemical and thermal properties. Furthermore, the PACC was employed in an experimental column adsorption setup to investigate its adsorption performance and to develop a dynamic method suitable for industrial implementation. Parameters such as bed height (50, 100, 150 mm), flow rate (4, 6, 8 mL min−1), pH (2, 4, 6), and initial metal-ion concentrations (10, 50, 100 mg L−1) were examined. The experimental data exhibited strong agreement with the Thomas and Yoon–Nelson models (R2 ≥ 0.96), indicating efficient adsorption mechanisms. Remarkably, the used adsorbent has the potential for facile regeneration without substantial loss in capacity. The PACC demonstrated excellent adsorption performance for lead ions in aqueous solutions in a fixed-bed column system. Thus, the novel PACC material holds the potential for scalable application in industrial settings to address water pollution challenges, especially in regions with uncontrolled effluent discharge.

Revealing the infiltration process and retention mechanisms of surface applied free DNA tracer through soil under flood irrigation

It has been recently demonstrated that free DNA tracers have the potential in tracing water flow and contaminant transport through the vadose zone. However, whether the free DNA tracer can be used in flood irrigation area to track water flow and solute/contaminant transport is still unclear. To reveal the infiltration process and retention mechanisms of surface applied free DNA tracer through soil under flood irrigation, we tested the fate and transport behavior of surface applied free DNA tracers through packed saturated sandy soil columns with a 10 cm water head mimicking flood irrigation. From the experimental breakthrough curves and by fitting a two-site kinetic sorption model (R2 = 0.83–0.91 and NSE = 0.79–0.89), adsorption/desorption rates could be obtained and tracer retention profiles could be simulated. Together these results revealed that 1) the adsorption of free DNA was dominantly to clay particles in the soil, which took up 1.96 % by volume, but took up >97.5 % by surface area and densely cover the surface of sand particles; and 2) at a pore water pH of 8.0, excluding the 4.9 % passing through and 3.1 % degradation amount, the main retention mechanisms in the experimental soil were ligand exchange (42.0 %), Van der Waals interactions (mainly hydrogen bonds), electrostatic forces and straining (together 44.7 %), and cation bridge (5.3 %). To our knowledge, this study is the first to quantify the contribution of each of the main retention mechanisms of free synthetic DNA tracers passing through soil. Our findings could facilitate the application of free DNA tracer to trace vadose zone water flow and solute/contaminant transport under flood irrigation and other infiltration conditions.

Multi-objective optimization of breakthrough times for hydrogen purification through layered bed pressure swing adsorption based on genetic algorithm and artificial neural network model

Hydrogen purification from steam methane reforming (SMR) by pressure swing adsorption (PSA) technology is a common method to obtain high-purity hydrogen. The breakthrough time can well reflect the adsorption dynamics and help PSA cycle design. In order to avoid time-consuming and labor-intensive breakthrough curve experiments, it is very necessary to develop a fast and accurate surrogate model. In this study, a genetic algorithm (GA) and artificial neural network (ANN) are combined to predict and optimize breakthrough times of adsorbates in activated carbon/zeolite layered beds. Using the Latin hypercube sampling strategy, training data sets of GA-optimized ANN (GA-ANN) obtains from the physical model of adsorption, heat and mass transfer model. The genetic algorithm (GA) optimizes the weights and biases of ANN for better performance. The ANN topology has 4 input variables (superficial velocity, activated carbon height, adsorption pressure and feed temperature) and 3 output variables (breakthrough times of CH4, CO and CO2). The number of neurons in the hidden layer for the GA-ANN model was optimized as 7 to predict and optimize the maximum breakthrough time of SMR with a four-component (H2/CH4/CO/CO2) system. The sensitivity analysis displays that relative importance to the breakthrough time is in the order of superficial velocity (40.88%) > adsorption pressure (24.55%) > activated carbon height (21.04%) > feed temperature (13.53%). To obtain high-purity hydrogen, the GA-ANN model combined with multi-objective GA optimization is used to maximize the breakthrough times of CH4 and CO. The GA-ANN surrogate model proposed in this paper can not only accurately and quickly achieve the purpose of predicting the system breakthrough time with a high correlation coefficient (R = 0.9937) but also obtains the optimal operating conditions of PSA hydrogen purification.

Nano-impregnation on metakaolin backbone for enhanced removal of Cu(II) and Mn(II) ions in a binary system using fixed bed column

This paper presents a comprehensive study on the synthesis and characterization of a novel composite material composed of metakaolin (MK), cellulose nanofibers (CNF), graphene oxide (GO), and zinc oxide (ZnO) for the efficient removal of heavy metals from wastewater. The main objective of this research was to enhance the removal efficiency of Cu(II) and Mn(II) ions in a binary system using a fixed bed column adsorption technique while investigating the effect of impregnating the nanomaterials. The synthesized samples were subjected to a thorough characterization using various techniques. These analyses provided insights into the structural properties and morphology of the composite material. The adsorption performance of the MK/CNF/GO/ZnO composite was evaluated through breakthrough curve analysis and kinetic modeling. The MDR model provided good fits with R2 values of 0.962 and 0.967 for Cu(II) and Mn(II) respectively. Based on the experimental breakthrough curve data, the saturation and breakthrough capacities of the composite material were calculated to be 5.97 mg/g and 4.84 mg/g for Cu(II) and Mn(II) respectively, achieved after a saturation time of 102 min for Cu(II) and 128 min for Mn(II). The results demonstrated a synergistic effect between GO and CNF, resulting in enhanced adsorption efficiency. The incorporation of ZnO nanoparticles further improved the adsorption capacity due to their high surface area, providing additional active sites for adsorption. The results showed that combining CNF, GO, and ZnO in a composite resulted in extended breakthrough and exhaustion times compared to the combination of CNF and GO alone.

Phenomenological modeling and simulation of competitive biosorption of ternary heavy metal systems in a fixed bed column

Phenomenological mathematical modeling was applied to describe the dynamic behavior of the biosorption of ternary heavy metal systems in fixed-bed columns. The modeling approach hereby proposed was verified with experimental breakthrough curves of Cu(II) - Ni(II) - Zn(II) systems using as biosorbent the acidified residue of alginate extraction (RAE) from Sargassum filipendula. The applied model allowed to consistently predict the concentration of the three heavy metals competing for the active sites of the adsorbent material through all the column extension. Due to the relative complexity of the mathematical model, the discretization to transform the system of partial differential equations into a system of ordinary differential equations and the utilization of fictional points for the convergence and stability of the numerical solution were described in detail. All the mathematical development is presented in a generic way, thus, helping other researchers to apply the analysis methodology proposed in this study. By analyzing the breakthrough curves, competitive adsorption was observed for the heavy metals Cu(II) - Ni(II) - Zn(II) in the biosorbent used in the experiments. This is highlighted by the occurrence of outlet concentrations of Ni(II) and Zn(II) above the feed concentrations. The observed affinity order of the metallic ions with the acidified biosorbent RAE is Cu(II) > Zn(II) > Ni(II).

Multiscale modeling of ammonia adsorption on zinc sulfate-doped activated carbon: Sensitivity analysis, parameter identification, and model validation

In this study four models are developed and validated to describe the dynamic adsorption of ammonia on zinc sulfate-doped activated carbon, ranging from simple single-scale to complex multiscale models. They are based on equations for mass balance, thermodynamics, hydrodynamics, and adsorption kinetics. Since the values of the parameters are needed for the implementation of the models, the doped activated carbon is characterized and ammonia isotherms measurements are performed at three different temperatures, i.e., 288, 303, and 313 K. A method based on parameter sensitivity analysis is used to evaluate the estimability of the unknown parameters of the Toth isotherm equation. Experimental breakthrough curves were then measured at various ammonia concentrations and gas flow rates. These curves were used to determine the overall mass transfer and axial dispersion coefficients, as well as the effective and intracrystalline diffusion, involved in the model equations. The models were implemented and solved using Comsol Multiphysics®. The study showed that the adsorption process was limited by the diffusion of ammonia and adsorption on the zinc sulfate crystal. The models were validated using breakthrough curves different from those used for parameter identification. The agreement between model predictions and measurements was evaluated using performance indices and confirmed by a Kolmogorov-Smirnov statistical test.

Laboratory Studies on the Influence of Ionic Strength on Particle Transport Behavior in a Saturated Porous Medium

An experimental study has been undertaken to investigate the effect of flow velocity and ionic strength on the transport of suspended particles (SP) and their deposition in a saturated porous medium. The SP injections were carried out using a laboratory column filled with sand and a pulse injection method. Ionic strengths varying between 0 and 600 mM (NaCl) have prospected. Two velocities were tested: 0.15 and 0.30 cm/s. Selected polydisperse particles diameters ranging from 0.27 to 5 μm and a median diameter (dp50) equal to 2.25 μm were used. An analytical solution of the convection–dispersion equation with first-order deposition kinetics was used to describe the experimental breakthrough curves and to identify the transport parameters. The results show that the increase of ionic strength promotes the retention of the SP in the porous medium. In addition, retention is more important when the flow velocity is low. The deposition kinetics coefficient increases with increasing ionic strength and flow velocity.

Transport and removal of stormwater vehicle-related mobile organic contaminants in geomedia-amended sand columns

Green infrastructure drainage systems are innovative treatment units that capture and treat stormwater. Unfortunately, highly polar contaminants remain challenging to remove in conventional biofilters. To overcome treatment limitations, we assessed the transport and removal of stormwater vehicle-related organic contaminants with persistent, mobile, and toxic (in short: PMTs) properties, such as 1H-benzotriazole, NN'-diphenylguanidine, and hexamethoxymethylmelamine (PMT precursor), using batch experiments and continuous-flow sand columns amended with pyrogenic carbonaceous materials, like granulated activated carbon (GAC) or wheat-straw derived biochar. Our results indicated that all investigated contaminants were subjected to nonequilibrium interactions in sand-only and geomedia-amended columns, with kinetic effects upon transport. Experimental breakthrough curves could be well described by a one-site kinetic transport model assuming saturation of sorption sites, which we inferred could occur due to dissolved organic matter fouling. Furthermore, from both batch and column experiments, we found that GAC could remove contaminants significantly better than biochar with higher sorption capacity and faster sorption kinetics. Hexamethoxymethylmelamine, with the lowest organic carbon-water partition coefficient (KOC) and largest molecular volume among target chemicals, exhibited the lowest affinity in both carbonaceous adsorbents based on estimated sorption parameters. Results suggest that sorption of investigated PMTs was likely driven by steric and hydrophobic effects, and coulombic and other weak intermolecular forces (e.g., London–van der Waals, H-bonding). Results from extrapolating our data to a 1-m depth geomedia-amended sand filter suggested that GAC and biochar could enhance the removal of organic contaminants in biofilters and last for more than one decade. Overall, our work is the first to study treatment alternatives for NN'-diphenylguanidine and hexamethoxymethylmelamine, and contributes to better PMT contaminant removal strategies in environmental applications.

Phosphonium based anion exchange resin for enrichment of phenolic acids

The aim of this work is to investigate the efficiency of a phosphonium-based strong anion exchange sorbent for the extraction of some selected phenolic acids. The material was synthesized through chloromethylation of a porous poly(styrene-divinylbenzene) substrate with high degree of crosslinking, followed by quaternarization with tributyl phosphine. The parameters affecting the solid phase extraction of five phenolic acids, namely chlorogenic acid, caffeic acid, dihydroxybenzoic acid, ferulic acid and rosmarinic acid were optimized. The sample pH and the type, volume and concentration of the eluting solutions were investigated. The analysis of the phenolic acids after extraction was performed using HPLC with diode array detection. Limit of detection, limit of quantitation, linear range, correlation coefficient and reproducibility for the determination of the phenolic acids were estimated. The retention of the phenolic acids on the developed phase was studied using breakthrough analysis. The experimental breakthrough curves were fitted by Boltzmann's function, and the regression parameters were utilized for the determination of the breakthrough parameters. The results obtained using the developed phase were compared with those obtained by the commercially available Oasis MAX sorbent. The proposed approach was successfully applied for the extraction and pre-concentration of rosmarinic acid from rosemary leaf (Rosmarini folium) alcoholic extract.