Desorption Of Contaminants Research Articles

Aspects of Reduced Performance of Proton-Exchange-Membrane Water Electrolysis Via Continuum Modeling

Proton-exchange-membrane water electrolysis (PEMWE) is a technology, where hydrogen is electrochemically produced from water. Efficient industrial-scale production of hydrogen via PEMWE is contingent upon developing systems that are sufficiently resilient to operate under non-ideal operating conditions. Mathematical models can provide insight into the underlying physical mechanisms and inform the development of mitigating strategies. In the current work, a cell-level non-isothermal continuum model that is based on concentrated-solution theory that accounts for multiple ionic mobile species in the membrane and ionomer, energy transport, and fluid flow through porous media, was used to investigate two challenges to PEMWE becoming a viable technology, specifically contamination and hydrogen crossover. In cationic contamination, dissolved salts in the reactant water supplant protons in the membrane and ionomer and significantly increase the applied potentials required for operation. Hydrogen crossover is a concern especially in low-current operational modes, which can arise due to PEMWE powered by variable and cyclical renewable energy sources and can result in the production of combustible gas mixtures.For cation-contaminated cells, simulation results suggest that the uptake of the contaminant cation increased as a function of current density until local conditions in the cathode catalyst layer (cCL) allowed the contaminant desorption to occur. The model suggests that the increased cell potential is primarily due to proton activity losses in the hydrogen evolution reaction within the cCL and that ionic conductivity losses are insufficient to cause the performance losses observed experimentally. Agreement with experimental data lends the model as a possible method or predictive models for PEMWE cell recovery methods. Observations of hydrogen crossover simulations suggest several aspects of hydrogen crossover, which include that localized pressures within the catalyst layers can enhance crossover, bubble-nucleation kinetics limit the exhaust of product gases, and convective fluxes due to electroomostic drag are negligible. An improved understanding of the crossover mechanisms can inform the development of low-crossover designs and mitigation strategies. Figure 1

Hydrogen-Assisted Thermal Treatment of Electrode Materials for Electrochemical Double-Layer Capacitors.

The capacitance of electrode materials used in electrochemical double-layer capacitors (EDLCs) is currently limited by several factors, including inaccessible isolated micropores in high-surface area carbons, the finite density of states resulting in a quantum capacitance in series to Helmholtz double-layer capacitance, and the presence of surface impurities, such as functional groups and adsorbed species. To unlock the full potential of EDLC active materials and corresponding electrodes, several post-production treatments are commonly proposed to improve their capacitance and, thus, the energy density of the corresponding devices. In this work, we report a systematic study of the effect of a prototypical treatment, namely H2-assisted thermal treatment, on the chemical, structural, and thermal properties of activated carbon and corresponding electrodes. By combining multiple characterization techniques, we clarify the actual origins of the improvement of the performance (e.g., > +35% energy density for the investigated power densities in the 0.5-45 kW kg-1 range) of the EDLCs based on treated electrodes compared to the case based on the pristine electrodes. Contrary to previous works supporting a questionable graphitization of the activated carbon at temperatures <1000 °C, we found that a "surface graphitization" of the activated carbon, detected by spectroscopic analysis, is mainly associated with the desorption of surface contaminants. The elimination of surface impurities, including adsorbed species, improves the surface capacitance of the activated carbon (CsurfAC) by +37.1 and +36.3% at specific currents of 1 and 10 A g-1, respectively. Despite the presence of slight densification of the activated carbon upon the thermal treatment, the latter still improves the cell gravimetric capacitance normalized on the mass of the activated carbon only (CgAC), e.g., + 28% at 1 A g-1. Besides, our holistic approach identifies the change in the active material and binder contents as a concomitant cause of the increase of cell gravimetric capacitance (Cg), accounting for the mass of all of the electrode materials measured for treated electrodes compared to pristine ones. Overall, this study provides new insights into the relationship between the modifications of the electrode materials induced by H2-assisted thermal treatments and the performance of the resulting EDLCs.

Electrode plasma formation and melt in Z -pinch accelerators

Recent studies of power flow and particle transport in multi-MA pulsed-power accelerators demonstrate that electrode plasmas may reduce accelerator efficiency by shunting current upstream from the load [Bennett et al., Phys. Rev. Accel. Beams 24, 060401 (2021)]. The detailed generation and evolution of these electrode plasmas are examined here using fully relativistic, Monte Carlo particle-in-cell (PIC) and magnetohydrodynamic (MHD) simulations over a range of peak currents (8--48 MA). The PIC calculations, informed by vacuum science, describe the electrode surface breakdown and particle transport prior to electrode melt. The MHD calculations show the bulk electrode evolution during melt. The physical description provided by this combined study begins with the rising local magnetic field that increases the local electrode surface temperature. This initiates the thermal desorption of contaminants from the electrode surface, with contributions from atoms outgassing from the bulk metal. The contaminants rapidly ionize forming a ${10}^{15}--{10}^{18}\text{ }\text{ }{\mathrm{cm}}^{\ensuremath{-}3}$ plasma that is effectively resistive while weakly collisional because it is created within, and rapidly penetrated by, a strong magnetic field ($&gt;30\text{ }\text{ }\mathrm{T}$). Prior to melting, the density of this surface plasma is limited by the concentration of absorbed contaminants in the bulk ($\ensuremath{\sim}{10}^{19}\text{ }\text{ }{\mathrm{cm}}^{\ensuremath{-}3}$ for hydrogen), its diffusion, and ionization. Eventually, the melting electrodes form a conducting plasma (${10}^{21}--{10}^{23}\text{ }\text{ }{\mathrm{cm}}^{\ensuremath{-}3}$) that experiences $\mathbf{j}\ifmmode\times\else\texttimes\fi{}\mathbf{B}$ compression and a typical decaying magnetic diffusion profile. This physical sequence ignores the transport of collisional plasmas of ${10}^{19}\text{ }\text{ }{\mathrm{cm}}^{\ensuremath{-}3}$ which may arise from electrode defects and associated instabilities. Nonetheless, this picture of plasma formation and melt may be extrapolated to higher-energy pulsed-power systems.

Ultra-Short Pulse Laser Cleaning of Contaminated Pleistocene Bone: A Comprehensive Study on the Influence of Pulse Duration and Wavelength

The impact of wavelength and pulse duration in laser cleaning of hard blackish contaminants crust from archaeologically significant Pleistocene bone is investigated in this research. The objective is to determine the practical cleaning procedures and identify adequate laser parameters for cleaning archaeological bone from Sima de los Huesos (Spain) based on conservation and restoration perspectives. Bone surface cleaning was performed utilizing two Q-switched Nd:YAG lasers: sub-nanosecond pulsed lasers with emission wavelengths at 355 nm and 1064 nm, respectively, and a Yb:KGW femtosecond pulsed laser with an emission wavelength in the third harmonic at 343 nm. In all experiments, the laser beam scanning mode was applied to measure cleaning efficiency in removing contaminants and degradation products while assessing the underlying substrate surface damage. Several properties, including wavelength-dependent absorption, pulse repetition rate, and thermal properties of the material, are analyzed when evaluating the ability of these lasers to boost the cleaning efficiency of the deteriorated bone surface. Bone surface morphology and composition were studied and compared before and after laser irradiation, using Optical Microscopy, Scanning Electron Microscopy with Energy Dispersive X-ray Spectrometry (SEM-EDS), Fourier Transform Infrared Spectroscopy (FTIR), and X-ray Photoelectron Spectroscopy (XPS) characterization methods. The results indicate that 238-femtosecond UV laser irradiation with 2.37 TWcm−2 is significantly safer and more efficient toward surface contaminant desorption than sub-nanosecond laser irradiation. The results herein presented suggest that these types of fs lasers may be considered for realistic laser conservation of valuable historic and archaeological museum artifacts.

Thermal desorption mechanism of n-dodecane on unsaturated clay: Experimental study and molecular dynamics simulation

Thermal desorption technology can effectively remediate fuels-contaminated clayey soil. However, the microscopic mechanism for the contaminant desorption on clay is still unclear, especially with the existence of water on clay surfaces. In this study, a combination method including TGA experiments, multi-phase and multi-component kinetic models, and MD simulation was proposed to reveal the thermal desorption mechanism of n-dodecane in unsaturated clay. Results showed that the thermal desorption behavior of the free nonaqueous phase liquid (NAPL) and the adsorbed phase of n-dodecane or water could be identified by the multi-phase and multi-component kinetic models based on the desorption process rate obtained by thermogravimetric analysis (TGA) experiments. The activation energy of the NAPL phase (49–69.9 kJ/mol) was lower than the adsorbed phase (90 kJ/mol). The activation energy of the NAPL phase had the same linear relationship with its mass on kaolinite and montmorillonite, while adsorbed phase only existed on the kaolinite surface. MD simulation showed that water demonstrated competitive adsorption with n-dodecane on montmorillonite surfaces and prevented the formation of the adsorbed phase while having little influence on the n-dodecane adsorption on kaolinite surface, which agrees well with the kinetic analysis of the TGA experiments. With the combination of macroscopic experimental analysis and microscopic molecular simulation, it can be concluded that the mass of the NAPL phase limited the desorption behavior, while the interaction between the clay mineral surface and n-dodecane was the key factor that dominated the thermal desorption behavior of the adsorbed phase. The presented results provide new insight into the desorption mechanism of hydrocarbon on clay minerals, which is of significance for the design of thermal desorption remediation.

Ultrashort pulsed Femtosecond UV laser for selective cleaning of significant Cretaceous flints

This work reports on studies aimed to evaluate the utilization of ultrashort 238 fs (fs) pulsed UV laser emission at 343 nm for eliminating colored crusts and surface deposits on significant Cretaceous flint surfaces, in an attempt to safeguard its aesthetic appearance and archaeological value. The results indicate that fs UV lasers may be an ideal, non-contact tool for selective surface cleaning of sensitive archaeological artefacts, since they enable contaminant desorption while avoiding photothermal damage.

Effect of soil pH on thermally enhanced desorption of m-xylene by zero-valent iron particles under an electromagnetic field.

This study, for the first time, evaluates a novel method for the desorption of contaminants from soil that uses the heat generated by zero-valent iron (ZVI) under low-frequency electromagnetic fields (EMF), and elucidates the specific effects of soil pH upon the process. It was found that the temperature of soil mixed with ZVI could reach up to ∼60°C within 20min under the applied EMF, and after 60min the residual fraction of m-xylene in soil decreased by 86.4% compared to no-ZVI soil. The most efficient desorption of m-xylene occurred at a soil of pH 5. Desorption was related to the net heating capacity of the ZVI particles, which was defined by pH-dependent formation of surface corrosion products. The preservation of metal iron and formation of Fe(II) species was favored for heat generation. Soil pH also affected m-xylene retention and the local thermal conduction from ZVI to m-xylene by regulating the surface properties of fulvic acid and ZVI. This study provides valuable information regarding the impact of pH on the thermal desorption of soil contaminants by ZVI coupled with EMF and illustrates the potential of the method in the remediation of contaminated sites.

Sorption and Desorption of Tire Rubber and Roadway-Derived Organic Contaminants in Soils and a Representative Engineered Geomedium

Sorption and Desorption of Tire Rubber and Roadway-Derived Organic Contaminants in Soils and a Representative Engineered Geomedium

Groundwater flow numerical model to evaluate the water mass balance and flow patterns in Groundwater Circulation Wells (GCW) with varying aquifer parameters

Groundwater Circulation Wells (GCW) can be an effective in-situ remediation option allowing high mass recovery of contaminants in cases where contamination hotspots are located in saturated soil having low hydraulic conductivity. Traditional treatment options such as Pump&amp;Treat, Air Sparging (AS)/Soil Vapor Extraction (SVE) and Multi Phase Extraction (MPE) typically require long operation times and significant costs for long-term plume management. GCWs induce meaningful changes in the groundwater flow introducing vertical flows both downward and upward, generating a “circulation cell”, which facilitates contaminant desorption from the soil. This study aims to understand the effects of a GCW on an aquifer in terms of both groundwater flow directions and water balance. A groundwater numerical model was built using MODFLOW-2005 to simulate the effect of the hydraulic parameters of the aquifer on the hydraulic circulation pattern of the GCW. The use of particle tracking simulated by MODPATH 7 showed the circulation cells and the impact on groundwater directions induced by different configurations of hydraulic parameters. The water flowing into the cell comes from both the injection well and the surrounding aquifer and the model shows how the hydraulic parameters of the aquifer, in particular the horizontal and vertical hydraulic conductivity, have a paramount influence in determining the shape and dimension of the circulation cell. A water mass balance analysis was carried out. It allowed to predict the groundwater flows exchanges between the GCW system and the surrounding aquifer, and to verify the sensitivity of the water budget to specific aquifer parameters. The results of this study are useful for further understanding the hydraulics of a GCW remediation system in order to support the design and to predict its performance.

Coupling surfactants with ISCO for remediating of NAPLs: Recent progress and application challenges.

Non-aqueous phase liquids (NAPLs) pose a serious risk to the soil-groundwater environment. Coupling surfactants with in situ chemical oxidation (ISCO) technology is a promising strategy, which is attributed to the enhanced desorption and solubilization efficiency of NAPL contaminants. However, the complex interactions among surfactants, oxidation systems, and NAPL contaminants have not been fully revealed. This review provides a comprehensive overview on the development of surfactant-coupled ISCO technology focusing on the effects of surfactants on oxidation systems and NAPLs degradation behavior. Specifically, we discussed the compatibility between surfactants and oxidation systems, including the non-productive consumption of oxidants by surfactants, the role of surfactants in catalytic oxidation systems, and the loss of surfactants solubilization capacity during oxidation process. The effect of surfactants on the degradation behavior of NAPL contaminants is then thoroughly summarized in terms of degradation kinetics, byproducts and degradation mechanisms. This review demonstrates that it is crucial to minimize the negative effects of surfactants on NAPL contaminants oxidation process by fully understanding the interaction between surfactants and oxidation systems, which would promote the successful implementation of surfactant-coupled ISCO technology in remediation of NAPLs-contaminated sites.

Interactions between microplastics and benthic biofilms in fluvial ecosystems: Knowledge gaps and future trends

Plastics, especially microplastics (<5 mm in length), are anthropogenic polymer particles that have been detected in almost all environments. Microplastics are extremely persistent pollutants and act as long-lasting reactive surfaces for additives, organic matter, and toxic substances. Biofilms are microbial assemblages that act as a sink for particulate matter, including microplastics. They are ubiquitous in freshwater ecosystems and provide key services that promote biodiversity and help sustain ecosystem function. Here, we provide a conceptual framework to describe the transient storage of microplastics in fluvial biofilm and develop hypotheses to help explain how microplastics and biofilms interact in fluvial ecosystems. We identify lines of future research that need to be addressed to better manage microplastics and biofilms, including how the sorption and desorption of environmental contaminants in microplastics affect biofilms and how microbial exchange between microplastics and the biofilm matrix affects biofilm characteristics like antibiotic resistance, speciation, biodiversity, species composition, and function. We also address the uptake mechanisms of microplastics by consumers and their propagation through the food web.

Opportunities and critical issues related to the use of amendments as sustainable remediation techniques

This study aims to analyse the opportunities and critical issues related to the use of amendments as remediation techniques. The performance of amendments (Aerobic Bioremediation, In Situ Chemical Oxidation and Surfactants) was compared with the performance of other groundwater remediation technologies (Air Sparging, Pump&amp;Treat, Multi-Phase Extraction, Pump&amp;Reinjection, Monitoring Natural Attenuation) based on a dataset of 180 contaminated sites. The considered factors are: effectiveness of the remediation; cost to remediate; operational time; environmental sustainability. The occurrence and types of amendment-related issues analyzed were studied on the 40 sites where the amendments had been applied. Issues occurred in 20% of the 40 analyzed cases and consisted of: a) partial or total occlusion of the monitoring wells and by-product formation, for example heavy metals (5%); b) uncontrolled increase in contaminant concentrations and potential downstream migration (8%); c) byproduct formation without well obstruction (7%). For each critical event, a detailed analysis was conducted to understand the processes (pH-Eh equilibria, contaminant desorption, hydraulic conductivity reduction), to highlight the design and procedural gaps (surplus of amendment, injection method selection, contaminant removal by purge). However, it has been observed that the issues can be avoided or mitigated with an accurate design, pilot tests performance, with the application of delivery and monitoring protocols, and at least with a prompt response adopting a corrective action plan, if necessary. The use of amendments turns out to be an effective solution: in 64% of the analyzed sites, it led to a significative reduction of the contamination within one year from the application. The cost is about one third if compared to the average of the other technologies. The operational time is about half the average operational time of the other technologies. Based on the results of sustainability analysis, amendments technologies reduce the production of waste, energy and water consumption, and they minimize air emissions. Considering the sustainability in its broadest sense (environmental, economic, and temporal), it is possible to state that the remediation by amendments is the most sustainable and would meet the interest of all the stakeholders.

Enhanced Electrodesorption Performance via Cathode Potential Extension during Capacitive Deionization

Complete desorption of contaminants from electrode materials is required for the efficient utilization and long service life of capacitive deionization (CDI) but remains a major challenge. The electrodesorption capacity of CDI in the conventional electrode configuration is limited by the narrow electrochemical stability window of water, which lowers the operating potential to approximately 1.2 V. Here, we report a graphite anode–titanium cathode electrode configuration that extends the cathode potential to −1.7 V and provides an excellent (100%) electrodesorption performance, which is maintained after five cycles. The improvement of the cathode potential depends on the redox property of the electrode. The stronger the oxidizability of the anode and reducibility of the cathode, the wider the cathode potential. The complete desorption potential of SO42− predicted by theoretical electrochemistry was the foundation for optimizing the electrode configuration. The desorption efficiency of Cl− depended on the ionic strength and was negligibly affected by circulating velocities above 112 mL min−1. This work can direct the design optimizations of CDI devices, especially for reactors undergoing chemisorption during the electrosorption process.

Influence of ionic strength and surfactant concentration on the alkane contaminant desorption in solution: A molecular dynamics simulation

The cleaning of the optical and mechanical components in a high-power laser system is essential for the cleaning control of the high-power laser system. Many factors affect the cleaning efficiency of the solution cleaning. Ion concentration, surfactant concentration and molecular weight of organic molecules are three key factors. In this article, equilibrium and nonequilibrium molecular dynamics simulations are performed to investigate the interfacial interaction among fluid, substrate and oil droplets and the dynamic desorption process of the oil droplet. As the increase of ion concentration, the contact angle of the oil droplet decreases, and the height of the oil droplet decreases slightly. Higher ion concentrations make the oil droplet more hydrophobic because of the reduction in hydrogen bonds between oil droplets and water and the reduction in residual time. In water flow simulation, high ion concentration is not beneficial to the desorption of oil droplets. Pure water flooding is not effective as brine flooding, which is related to water flow velocity. High surfactant concentration is beneficial to the desorption of oil droplets without water flow. Alkane molecule with larger molecular weight is difficult to detach from the solid surface, since the higher interaction energy between alkane molecule and substrate.

Desorption of micropollutant from superfine and normal powdered activated carbon in submerged-membrane system due to influent concentration change in the presence of natural organic matter: Experiments and two-component branched-pore kinetic model

Submerged-membrane hybrid systems (SMHSs) that combine membrane filtration with powdered activated carbon (PAC) take advantage of PAC's ability to adsorb and remove contaminants dissolved in water. However, the risk of contaminant desorption due to temporal changes in the influent concentration of the contaminant has not been thoroughly explored. In this study, we used a SMHS with conventionally-sized PAC or superfine PAC (SPAC) to remove 2-methylisoborneol (MIB), a representative micropollutant, from water containing natural organic matter (NOM), with the goal of elucidating adsorption–desorption phenomena in the SMHS. We found that 20–40% of the MIB that adsorbed on PAC and SPAC while the influent was contaminated with MIB (6 h, contamination period) desorbed to the liquid phase within 6 h from the time that the MIB-containing influent was replaced by MIB-free influent (no-contamination period). The percentage of desorption during the no-contamination period increased with increasing MIB breakthrough concentration during the contamination period. These findings indicate that the PAC/SPAC in the SMHS should be replaced while the breakthrough concentration is low, not only to keep a high removal rate but also to decrease the desorption risk. SPAC is fast in removal by adsorption, but it is also fast in release by desorption. SPAC (median diameter: 0.94 µm) showed almost the same adsorption-desorption kinetics as PAC (12.1 µm) of a double dose. A two-component branched-pore diffusion model combined with an IAST (ideal adsorbed solution theory)–Freundlich isotherm was used to describe and analyze the adsorption–desorption of MIB. The diffusivity of MIB molecules in the pores of the activated carbon particles decreased markedly in a short period of time. This decrease, which was attributed to fouling of the activated carbon in the SMHS by coagulant-treated water containing NOM, not only reduced the rate of MIB removal during the contamination period but also hindered the rate of MIB desorption during the no-contamination period and thus prevented the effluent MIB concentration from becoming high. On the other hand, coagulation did not change the concentration of NOM that competes with MIB for adsorption sites.

Degradation of Adsorbed Bisphenol A by Soluble Mn(III).

Bisphenol A (BPA), a high production volume chemical and potential endocrine disruptor, is found to be associated with sediments and soils due to its hydrophobicity (log KOW of 3.42). We used superfine powdered activated carbon (SPAC) with a particle size of 1.38 ± 0.03 μm as a BPA sorbent and assessed degradation of BPA by oxidized manganese (Mn) species. SPAC strongly sorbed BPA, and desorption required organic solvents. No degradation of adsorbed BPA (278.7 ± 0.6 mg BPA g-1 SPAC) was observed with synthetic, solid α-MnO2 with a particle size of 15.41 ± 1.35 μm; however, 89% mass reduction occurred following the addition of 0.5 mM soluble Mn(III). Small-angle neutron scattering data suggested that both adsorption and degradation of BPA occurred in SPAC pores. The findings demonstrate that Mn(III) mediates oxidative transformation of dissolved and adsorbed BPA, the latter observation challenging the paradigm that contaminant desorption and diffusion out of pore structures are required steps for degradation. Soluble Mn(III) is abundant near oxic-anoxic interfaces, and the observation that adsorbed BPA is susceptible to degradation has implications for predicting, and possibly managing, the fate and longevity of BPA in environmental systems.

Microplastics and nanoplastics barely enhance contaminant mobility in agricultural soils

Farmland soils are prone to contamination with micro- and nanoplastics through a variety of agricultural practices. Concerns are recurrently raised that micro- and nanoplastics act as vector for organic contaminants to deeper soil layers and endanger groundwater resources. Whether and to what extent micro- and nanoplastics facilitate the transport of organic contaminants in soil remains unclear. Here we calculated the ratio between transport and desorption time scales using two diffusion models for micro- and nanoplastics between 100 nm and 1 mm. To identify micro- and nanoplastics bound contaminant transport we evaluated diffusion and partitioning coefficients of prominent agrochemicals and additives and of frequently used polymers e.g., polyethylene and tire material. Our findings suggest that the desorption of most organic contaminants is too fast for micro- and nanoplastics to act as transport facilitators in soil. Contaminant transport enabled by microplastics was found to be relevant only for very hydrophobic contaminants (logKow >5) under preferential flow conditions. While micro- and nanoplastics might be a source of potentially harmful contaminants in farmland soils this study suggests that they do not considerably enhance contaminant mobility.

Investigation on desorption of petroleum hydrocarbon contaminants by active and passive particle self-rotation

Particle self-rotation is a common phenomenon in the natural environment and industrial fluids. The particle surface renewal and centrifugation caused by particle self-rotation are the inherent mechanisms that enhance the desorption of pollutants. In this paper, a motor and rotary shear flow field are used to drive the self-rotation of the porous media Maifan stone particles and soil particles, respectively. An experimental device for active and passive particle self-rotation control is established to determine the driving parameters that influence the relationship between the diesel desorption efficiency of particles and particle self-rotation. Active self-rotation increased the diesel desorption efficiency of Maifan stone particles by approximately 65.1%. Alternating active and passive self-rotation, self-rotation speed, and temperature were positively correlated with diesel desorption efficiency. Passive particle self-rotation in the rotating shear flow field achieves balanced desorption efficiency in a single pass through the hydrocyclone. The desorption efficiency of underflow particles is approximately 50% higher than that of overflow particles. The experimental results show that both active and passive self-rotation can improve the diesel desorption of particles and suggest the possibility of reducing the amount of surfactant used.

Desorption Studies for Methylene Blue Dye Removal by Kaolinite

In wastewater treatment, the reusability of an adsorbent strongly relies on the feasibility of contaminant desorption from the spent adsorbent. This research aims to investigate the Methylene Blue (MB) release from the spent kaolinite clay mineral against a variety of desorbing eluent in an aqueous solution. Malaysia’s kaolinite was characterised using Scanning Electron Microscopy (SEM), surface area analysis, and Fourier Transform Infrared (FTIR) Spectroscopy. The MB desorption was performed using eluents of distilled water, solutions of HCl, NaOH, and NaCl (0.01 M and 0.1 M), and ethanol: water mixtures (30:70, 50:50, and 70:30 v/v ratios). It was found that the MB desorption only occurs in 0.1 M NaOH (pH 12.7). A 4.2% MB desorption was recorded in 1 hour and was increased to 19.5% within 24 hours desorption time. The pH change measurement also reveals the favorability for highly alkaline conditions for MB desorption. The overall finding indicates that the MB retention towards kaolinite is strong, and its adsorption occurs via electrostatic and hydrophobic interaction, as suggested by the FTIR analysis. Kaolinite is a good scavenger for removing the MB dye from contaminated water but requires a strong eluent in the desorption process for its future reusability process.

Integrating Thermal Analysis and Reaction Modeling for Rational Design of Pyrolytic Processes to Remediate Soils Contaminated with Heavy Crude Oil.

We developed a novel methodology that combines thermo-analytical measurements and mathematical methods to inform the reliable pyrolytic treatment of specific soil/contaminant systems. Our approach improves upon current "black-box" design methods that may overestimate the required treatment intensity and hinder cost efficacy. We used thermogravimetry and evolved gas analysis to characterize the complex network of soil mineral transformations, contaminant desorption, and pyrolytic reactions occurring when contaminated soils are heated in an anoxic atmosphere. The kinetics of these reactions were quantified using a distributed activation energy (DAE) approach with six pseudocomponents and used in a mathematical model for continuous-flow reactors to predict the removal of hydrocarbon contaminants without other fitting parameters. This model was tested with pilot-scale data from pyrolytic treatment of soils contaminated with crude oil and found to be a good predictor of the total petroleum hydrocarbon (TPH) removal for temperatures between 370 and 470 °C and residence times from 15 to 60 min. The light hydrocarbon fraction desorbed quickly, and over 99.7% removal was achieved at 420 °C and 15 min residence time. However, 95% removal of the heavy hydrocarbon fraction, which is a good proxy for polyaromatic hydrocarbons (PAHs), required 470 °C with 15 min residence time. This model can be employed to select operating conditions (e.g., reactor size, treatment time, and temperature) to reliably achieve remediation objectives for specific hydrocarbon/soil mixtures without inflating energy requirements, which would lower operating costs and decrease the process carbon footprint on a system-specific basis.