Kinetics of dodecanoic acid adsorption from caustic solution by activated carbon.

PubMed

Pendleton, Phillip; Wu, Sophie Hua

2003-10-15

This study examines the influences of adsorbent porosity and surface chemistry and of carbon dosage on dodecanoic acid adsorption kinetics from aqueous and 2 M NaOH solutions as batch adsorption processes. Both adsorbents are steam-activated carbons prepared from either coconut or coal precursors. Prior to use the adsorbents were washed in deionized water or 2 M NaOH. Mass transfer coefficients and effective overall diffusion coefficients indicate a minor contribution from adsorbent porosity. In contrast, high surface oxygen content impedes transport to and into the adsorbent structure. Carbon dosage shows a proportional increase in transport coefficients with increasing mass; these coefficients are constant when normalized per unit mass. Neither water nor NaOH treatment of the adsorbents has a significant influence on dodecanoic acid adsorption kinetics. Molecular and Knudsen diffusion coefficients are defined to demonstrate that the overall effective diffusion coefficient values and the diffusion process are controlled by surface diffusion.

Relating the variation of secondary structure of gelatin at fish oil-water interface to adsorption kinetics, dynamic interfacial tension and emulsion stability.

PubMed

Liu, Huihua; Wang, Bo; Barrow, Colin J; Adhikari, Benu

2014-01-15

The objectives of this study were to quantify the relationship between secondary structure of gelatin and its adsorption at the fish-oil/water interface and to quantify the implication of the adsorption on the dynamic interfacial tension (DST) and emulsion stability. The surface hydrophobicity of the gelatin solutions decreased when the pH increased from 4.0 to 6.0, while opposite tend was observed in the viscosity of the solution. The DST values decreased as the pH increased from 4.0 to 6.0, indicating that higher positive charges (measured trough zeta potential) in the gelatin solution tended to result in higher DST values. The adsorption kinetics of the gelatin solution was examined through the calculated diffusion coefficients (Deff). The addition of acid promoted the random coil and β-turn structures at the expense of α-helical structure. The addition of NaOH decreased the β-turn and increased the α-helix and random coil. The decrease in the random coil and triple helix structures in the gelatin solution resulted into increased Deff values. The highest diffusion coefficients, the highest emulsion stability and the lowest amount of random coil and triple helix structures were observed at pH=4.8. The lowest amount of random coil and triple helix structures in the interfacial protein layer correlated with the highest stability of the emulsion (highest ESI value). The lower amount of random coil and triple helix structures allowed higher coverage of the oil-water interface by relatively highly ordered secondary structure of gelatin. Copyright © 2013 Elsevier Ltd. All rights reserved.

Role of oxygen functional groups for structure and dynamics of interfacial water on low rank coal surface: a molecular dynamics simulation

NASA Astrophysics Data System (ADS)

You, Xiaofang; Wei, Hengbin; Zhu, Xianchang; Lyu, Xianjun; Li, Lin

2018-07-01

Molecular dynamics simulations were employed to study the effects of oxygen functional groups for structure and dynamics properties of interfacial water molecules on the subbituminous coal surface. Because of complex composition and structure, the graphite surface modified by hydroxyl, carboxyl and carbonyl groups was used to represent the surface model of subbituminous coal according to XPS results, and the composing proportion for hydroxyl, carbonyl and carboxyl is 25:3:5. The hydration energy with -386.28 kJ/mol means that the adsorption process between water and coal surface is spontaneous. Density profiles for oxygen atoms and hydrogen atoms indicate that the coal surface properties affect the structural and dynamic characteristics of the interfacial water molecules. The interfacial water exhibits much more ordering than bulk water. The results of radial distribution functions, mean square displacement and local self-diffusion coefficient for water molecule related to three oxygen moieties confirmed that the water molecules prefer to absorb with carboxylic groups, and adsorption of water molecules at the hydroxyl and carbonyl is similar.

Simulation and Experimental Study of Metal Organic Frameworks Used in Adsorption Cooling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jenks, Jeromy J.; Motkuri, Radha K.; TeGrotenhuis, Ward

2016-10-11

Metal-organic frameworks (MOFs) have recently attracted enormous interest over the past few years in energy storage and gas separation, yet there have been few reports for adsorption cooling applications. Adsorption cooling technology is an established alternative to mechanical vapor compression refrigeration systems and is an excellent alternative in industrial environments where waste heat is available. We explored the use of MOFs that have very high mass loading and relatively low heats of adsorption, with certain combinations of refrigerants to demonstrate a new type of highly efficient adsorption chiller. Computational fluid dynamics combined with a system level lumped-parameter model have beenmore » used to project size and performance for chillers with a cooling capacity ranging from a few kW to several thousand kW. These systems rely on stacked micro/mini-scale architectures to enhance heat and mass transfer. Recent computational studies of an adsorption chiller based on MOFs suggests that a thermally-driven coefficient of performance greater than one may be possible, which would represent a fundamental breakthrough in performance of adsorption chiller technology. Presented herein are computational and experimental results for hydrophyilic and fluorophilic MOFs.« less

Surface imprinting on nano-TiO2 as sacrificial material for the preparation of hollow chlorogenic acid imprinted polymer and its recognition behavior

NASA Astrophysics Data System (ADS)

Li, Hui; Li, Gui; Li, Zhiping; Lu, Cuimei; Li, Yanan; Tan, Xianzhou

2013-01-01

Surface imprinting chlorogenic acid (CGA) on nano-TiO2 particles as sacrificial support material was successfully performed by using 4-vinylpyridine (4-VP) as functional monomer to obtain a hollow CGA-imprinted polymer (H-MIP1). Fourier transmission infrared spectrometry (FTIR) and scanning electron microscopy (SEM) were utilized for structurally characterizing the polymers obtained and adsorption dynamics and thermodynamic behavior investigated according to different models. Binding selectivity, adsorption capacity and the reusability for this H-MIP1 were also evaluated. This hollow CGA imprinted polymer shows rapid binding dynamics and higher binding capability toward the template molecules. The pseudo first-order kinetic model was shown best to describe the binding process of CGA on the H-MIP1 and Langmuir isotherm model best to fit the experimental adsorption isotherm data. Through adsorption isotherms at different temperatures, thermodynamic parameter values were obtained. Selectivity coefficients for the H-MIP1 toward the template were 2.209, 3.213, 1.746 and 2.353 relative to CA, VA, PCA and GA, respectively. This H-MIP1 was also indicated with a good imprint effect and a high capability to capture CGA from methanol extract of Eucommia ulmoides (E. ulmoides) leaves. Additionally, a good reusability for this imprinted polymer was exhibited during repeated adsorption-desorption use.

Colloidal Particle Adsorption at Water-Water Interfaces with Ultralow Interfacial Tension

NASA Astrophysics Data System (ADS)

Keal, Louis; Colosqui, Carlos E.; Tromp, R. Hans; Monteux, Cécile

2018-05-01

Using fluorescence confocal microscopy we study the adsorption of single latex microparticles at a water-water interface between demixing aqueous solutions of polymers, generally known as a water-in-water emulsion. Similar microparticles at the interface between molecular liquids have exhibited an extremely slow relaxation preventing the observation of expected equilibrium states. This phenomenon has been attributed to "long-lived" metastable states caused by significant energy barriers Δ F ˜γ Ad≫kBT induced by high interfacial tension (γ ˜10-2 N /m ) and nanoscale surface defects with characteristic areas Ad≃10 - 30 nm2 . For the studied water-water interface with ultralow surface tension (γ ˜10-4 N /m ) we are able to characterize the entire adsorption process and observe equilibrium states prescribed by a single equilibrium contact angle independent of the particle size. Notably, we observe crossovers from fast initial dynamics to slower kinetic regimes analytically predicted for large surface defects (Ad≃500 nm2). Moreover, particle trajectories reveal a position-independent damping coefficient that is unexpected given the large viscosity contrast between phases. These observations are attributed to the remarkably diffuse nature of the water-water interface and the adsorption and entanglement of polymer chains in the semidilute solutions. This work offers some first insights on the adsorption dynamics or kinetics of microparticles at water-water interfaces in biocolloidal systems.

Dissociation coefficients of protein adsorption to nanoparticles as quantitative metrics for description of the protein corona: A comparison of experimental techniques and methodological relevance.

PubMed

Hühn, Jonas; Fedeli, Chiara; Zhang, Qian; Masood, Atif; Del Pino, Pablo; Khashab, Niveen M; Papini, Emanuele; Parak, Wolfgang J

2016-06-01

Protein adsorption to nanoparticles is described as a chemical reaction in which proteins attach to binding sites on the nanoparticle surface. This process is defined by a dissociation coefficient, which tells how many proteins are adsorbed per nanoparticle in dependence of the protein concentration. Different techniques to experimentally determine dissociation coefficients of protein adsorption to nanoparticles are reviewed. Results of more than 130 experiments in which dissociation coefficients have been determined are compared. Data show that different methods, nanoparticle systems, and proteins can lead to significantly different dissociation coefficients. However, we observed a clear tendency of smaller dissociation coefficients upon less negative towards more positive zeta potentials of the nanoparticles. The zeta potential thus is a key parameter influencing protein adsorption to the surface of nanoparticles. Our analysis highlights the importance of the characterization of the parameters governing protein-nanoparticle interaction for quantitative evaluation and objective literature comparison. Copyright © 2015 Elsevier Ltd. All rights reserved.

Experimental and theoretical studies of the effect of temperature on supercritical CO2 adsorption on illite

NASA Astrophysics Data System (ADS)

Joewondo, N.; Zhang, Y.; Prasad, M.

2016-12-01

Sequestration of carbon dioxide in shale has been a subject of interest as the result of the technological advancement in gas shale production. The process involves injection of CO2 to enhance methane recovery and storing CO2 in depleted shale reservoir at elevated pressures. To better understand both shale production and carbon storage one must study the physical phenomena acting at different scales that control the in situ fluid flow. Shale rocks are complex systems with heterogeneous structures and compositions. Pore structures of these systems are in nanometer scales and have significant gas storage capacity and surface area. Adsorption is prominent in nanometer sized pores due to the high attraction between gas molecules and the surface of the pores. Recent studies attempt to find correlation between storage capacity and the rock composition, particularly the clay content. This study, however, focuses on the study of supercritical adsorption of CO2 on pure clay sample. We have built an in-house manometric experimental setup that can be used to study both the equilibrium and kinetics of adsorption. The experiment is conducted at isothermal condition. The study of equilibrium of adsorption gives insight on the storage capacity of these systems, and the study of the kinetics of adsorption is essential in understanding the resistance to fluid transport. The diffusion coefficient, which can be estimated from the dynamic experimental results, is a parameter which quantify diffusion mobility, and is affected by many factors including pressure and temperature. The first part of this paper briefly discusses the study of both equilibrium and kinetics of the CO2 adsorption on illite. Both static and dynamic measurements on the system are compared to theoretical models available in the literature to estimate the storage capacity and the diffusion time constants. The main part of the paper discusses the effect of varying temperature on the static and dynamic experimental results.

Vapor-phase interactions and diffusion of organic solvents in the unsaturated zone

USGS Publications Warehouse

Roy, W.R.; Griffin, R.A.

1990-01-01

This article presents an analysis of the interactions and static movement of 37 organic solvents as vapors through the unsaturated soil zone. The physicochemical interactions of the organic vapors with unsaturated soil materials were emphasized with focus on diffusive, and adsorptive interactions. Fick's Law and porous media diffusion coefficients for most of the solvent vapors were either compiled or estimated; coefficients were not available for some of the fluorinated solvents. The adsorption of some of the solvent vapors by silica was concluded to be due to hydrogen bond formation with surface silanol groups. Heats of adsorption data for different adsorbents were also compiled. There were very few data on the adsorption of these solvent vapors by soils, but it appears that the magnitude of adsorption of nonpolar solvents is reduced as the relative humidity of the vapor-solid system is increased. Consequently, the interaction of the vapors may then separated into two processes; (1) gas-water partitioning described by Henry's Law constants, and (2) solid-water adsorption coefficients which may be estimated from liquid-solid partition coefficients (Kd values). ?? 1990 Springer-Verlag New York Inc.

Research and Development of Methods for Estimating Physicochemical Properties of Organic Compounds of Environmental Concern

DTIC Science & Technology

1979-02-01

coefficient (at equilibrium) when hysteresis is apparent. 6. Coefficient n in Freundlich equation for 1/n soil or sediment adsorption isotherms ýX - KC . 7...Biodegradation Chemical structures cal clasaes (e.g., Diffusion Correlations phenols). General Diffusion coefficients Equations terms for organic...OF THE FATE AND TRANSPORT OF ORGANIC CHEMICALS Adsorption coefficients: K, n* from Freundlich equation + Desorption coefficients: K’*, n’* from

Selective sulfur dioxide adsorption on crystal defect sites on an isoreticular metal organic framework series

PubMed Central

Rodríguez-Albelo, L. Marleny; López-Maya, Elena; Hamad, Said; Ruiz-Salvador, A. Rabdel; Calero, Sofia; Navarro, Jorge A.R.

2017-01-01

The widespread emissions of toxic gases from fossil fuel combustion represent major welfare risks. Here we report the improvement of the selective sulfur dioxide capture from flue gas emissions of isoreticular nickel pyrazolate metal organic frameworks through the sequential introduction of missing-linker defects and extra-framework barium cations. The results and feasibility of the defect pore engineering carried out are quantified through a combination of dynamic adsorption experiments, X-ray diffraction, electron microscopy and density functional theory calculations. The increased sulfur dioxide adsorption capacities and energies as well as the sulfur dioxide/carbon dioxide partition coefficients values of defective materials compared to original non-defective ones are related to the missing linkers enhanced pore accessibility and to the specificity of sulfur dioxide interactions with crystal defect sites. The selective sulfur dioxide adsorption on defects indicates the potential of fine-tuning the functional properties of metal organic frameworks through the deliberate creation of defects. PMID:28198376

Mesoscopic Simulations of Adsorption and Association of PEO-PPO-PEO Triblock Copolymers on a Hydrophobic Surface: From Mushroom Hemisphere to Rectangle Brush.

PubMed

Song, Xianyu; Zhao, Shuangliang; Fang, Shenwen; Ma, Yongzhang; Duan, Ming

2016-11-08

The dissipative particle dynamics (DPD) method is used to investigate the adsorption behavior of PEO-PPO-PEO triblock copolymers at the liquid/solid interface. The effect of molecular architecture on the self-assembled monolayer adsorption of PEO-PPO-PEO triblock copolymers on hydrophobic surfaces is elucidated by the adsorption process, film properties, and adsorption morphologies. The adsorption thicknesses on hydrophobic surfaces and the diffusion coefficient as well as the aggregation number of Pluronic copolymers in aqueous solution observed in our simulations agree well with previous experimental and numerical observations. The radial distribution function revealed that the ability of self-assembly on hydrophobic surfaces is P123 > P84 > L64 > P105 > F127, which increased with the EO ratio of the Pluronic copolymers. Moreover, the shape parameter and the degree of anisotropy increase with increasing molecular weight and mole ratio of PO of the Pluronic copolymers. Depending on the conformation of different Pluronic copolymers, the morphology transition of three regimes on hydrophobic surfaces is present: mushroom or hemisphere, progressively semiellipsoid, and rectangle brush regimes induced by decreasing molecular weight and mole ratio of EO of Pluronic copolymers.

Properties of the water to boron nitride interaction: From zero to two dimensions with benchmark accuracy.

PubMed

Al-Hamdani, Yasmine S; Rossi, Mariana; Alfè, Dario; Tsatsoulis, Theodoros; Ramberger, Benjamin; Brandenburg, Jan Gerit; Zen, Andrea; Kresse, Georg; Grüneis, Andreas; Tkatchenko, Alexandre; Michaelides, Angelos

2017-07-28

Molecular adsorption on surfaces plays an important part in catalysis, corrosion, desalination, and various other processes that are relevant to industry and in nature. As a complement to experiments, accurate adsorption energies can be obtained using various sophisticated electronic structure methods that can now be applied to periodic systems. The adsorption energy of water on boron nitride substrates, going from zero to 2-dimensional periodicity, is particularly interesting as it calls for an accurate treatment of polarizable electrostatics and dispersion interactions, as well as posing a practical challenge to experiments and electronic structure methods. Here, we present reference adsorption energies, static polarizabilities, and dynamic polarizabilities, for water on BN substrates of varying size and dimension. Adsorption energies are computed with coupled cluster theory, fixed-node quantum Monte Carlo (FNQMC), the random phase approximation, and second order Møller-Plesset theory. These wavefunction based correlated methods are found to agree in molecular as well as periodic systems. The best estimate of the water/h-BN adsorption energy is -107±7 meV from FNQMC. In addition, the water adsorption energy on the BN substrates could be expected to grow monotonically with the size of the substrate due to increased dispersion interactions, but interestingly, this is not the case here. This peculiar finding is explained using the static polarizabilities and molecular dispersion coefficients of the systems, as computed from time-dependent density functional theory (DFT). Dynamic as well as static polarizabilities are found to be highly anisotropic in these systems. In addition, the many-body dispersion method in DFT emerges as a particularly useful estimation of finite size effects for other expensive, many-body wavefunction based methods.

Understanding interactions in the adsorption of gaseous organic compounds to indoor materials.

PubMed

Ongwandee, Maneerat; Chatsuvan, Thabtim; Suksawas Na Ayudhya, Wichitsawat; Morris, John

2017-02-01

We studied adsorption of organic compounds to a wide range of indoor materials, including plastics, gypsum board, carpet, and many others, under various relative humidity conditions by applying a conceptual model of the free energy of interfacial interactions of both van der Waals and Lewis acid-base (e-donor/acceptor) types. Data used for the analyses were partitioning coefficients of adsorbates between surface and gas phase obtained from three sources: our sorption experiments and two other published studies. Target organic compounds included apolars, monopolars, and bipolars. We established correlations of partitioning coefficients of adsorbates for a considered surface with the corresponding hexadecane/air partitioning coefficients of the adsorbates which are used as representative of a van der Waals descriptor instead of vapor pressure. The logarithmic adsorption coefficients of the apolars and weak bases, e.g., aliphatics and aromatics, to indoor materials linearly correlates well with the logarithmic hexadecane/air partitioning coefficients regardless of the surface polarity. The surface polarity in terms of e-donor/acceptor interactions becomes important for adsorption of the strong bases and bipolars, e.g., amines, phenols, and alcohols, to unpainted gypsum board. Under dry or humid conditions, the adsorption to flat plastic materials still linearly correlates well with the van der Waals interactions of the adsorbates, but no correlations were observed for the adsorption to fleecy or plush materials, e.g., carpet. Adsorption of highly bipolar compounds, e.g., phenol and isopropanol, is strongly affected by humidity, attributed to Lewis acid-base interactions with modified surfaces.

Characterization of metal adsorption kinetic properties in batch and fixed-bed reactors.

PubMed

Chen, J Paul; Wang, Lin

2004-01-01

Copper adsorption kinetic properties in batch and fixed-bed reactors were studied in this paper. The isothermal adsorption experiments showed that the copper adsorption capacity of a granular activated carbon (Filtrasorb 200) increased when ionic strength was higher. The presence of EDTA diminished the adsorption. An intraparticle diffusion model and a fixed-bed model were successfully used to describe the batch kinetic and fixed-bed operation behaviors. The kinetics became faster when the solution pH was not controlled, implying that the surface precipitation caused some metal uptake. The external mass transfer coefficient, the diffusivity and the dispersion coefficient were obtained from the modeling. It was found that both external mass transfer and dispersion coefficients increased when the flow rate was higher. Finally effects of kinetic parameters on simulation of fixed-bed operation were conducted.

A procedure to find thermodynamic equilibrium constants for CO2 and CH4 adsorption on activated carbon.

PubMed

Trinh, T T; van Erp, T S; Bedeaux, D; Kjelstrup, S; Grande, C A

2015-03-28

Thermodynamic equilibrium for adsorption means that the chemical potential of gas and adsorbed phase are equal. A precise knowledge of the chemical potential is, however, often lacking, because the activity coefficient of the adsorbate is not known. Adsorption isotherms are therefore commonly fitted to ideal models such as the Langmuir, Sips or Henry models. We propose here a new procedure to find the activity coefficient and the equilibrium constant for adsorption which uses the thermodynamic factor. Instead of fitting the data to a model, we calculate the thermodynamic factor and use this to find first the activity coefficient. We show, using published molecular simulation data, how this procedure gives the thermodynamic equilibrium constant and enthalpies of adsorption for CO2(g) on graphite. We also use published experimental data to find similar thermodynamic properties of CO2(g) and of CH4(g) adsorbed on activated carbon. The procedure gives a higher accuracy in the determination of enthalpies of adsorption than ideal models do.

Impact of soil properties on selected pharmaceuticals adsorption in soils

NASA Astrophysics Data System (ADS)

Kodesova, Radka; Kocarek, Martin; Klement, Ales; Fer, Miroslav; Golovko, Oksana; Grabic, Roman; Jaksik, Ondrej

2014-05-01

The presence of human and veterinary pharmaceuticals in the environment has been recognized as a potential threat. Pharmaceuticals may contaminate soils and consequently surface and groundwater. Study was therefore focused on the evaluation of selected pharmaceuticals adsorption in soils, as one of the parameters, which are necessary to know when assessing contaminant transport in soils. The goals of this study were: (1) to select representative soils of the Czech Republic and to measure soil physical and chemical properties; (2) to measure adsorption isotherms of selected pharmaceuticals; (3) to evaluate impact of soil properties on pharmaceutical adsorptions and to propose pedotransfer rules for estimating adsorption coefficients from the measured soil properties. Batch sorption tests were performed for 6 selected pharmaceuticals (beta blockers Atenolol and Metoprolol, anticonvulsant Carbamazepin, and antibiotics Clarithromycin, Trimetoprim and Sulfamethoxazol) and 13 representative soils (soil samples from surface horizons of 11 different soil types and 2 substrates). The Freundlich equations were used to describe adsorption isotherms. The simple correlations between measured physical and chemical soil properties (soil particle density, soil texture, oxidable organic carbon content, CaCO3 content, pH_H2O, pH_KCl, exchangeable acidity, cation exchange capacity, hydrolytic acidity, basic cation saturation, sorption complex saturation, salinity), and the Freundlich adsorption coefficients were assessed using Pearson correlation coefficient. Then multiple-linear regressions were applied to predict the Freundlich adsorption coefficients from measured soil properties. The largest adsorption was measured for Clarithromycin (average value of 227.1) and decreased as follows: Trimetoprim (22.5), Metoprolol (9.0), Atenolol (6.6), Carbamazepin (2.7), Sulfamethoxazol (1.9). Absorption coefficients for Atenolol and Metoprolol closely correlated (R=0.85), and both were also related to absorption coefficients of Carbamazepin (R=0.67 and 0.68). Positive correlation was found between Trimetoprim absorption coefficients and Atenolol, Metoprolol or Carbamazepin absorption coefficients. The negative relationship was found between absorption coefficients of Sulfomethoxazol and Clarithromycin (R=-0.80). Sulfamethoxazol absorption coefficient was negatively related to pH_H2O, pH_KCL or sorption complex saturation and positively to the hydrolytic acidity or exchangeable acidity. Trimetoprim absorption coefficient was positively related to the oxidable organic carbon content, cation exchange capacity, basic cation saturation or silt content and negatively to particle density or sand content. Clarithromycin absorption coefficient was positively related to pH_H2O, pH_KCL, CaCO3 content, basic cation saturation or sorption complex saturation and negatively to hydrolytic acidity or exchangeable acidity. Atenolol and Metoprolol absorption coefficients were positively related to the oxidable organic carbon content, cation exchange capacity, basic cation saturation, salinity, clay content or silt content, and negatively to the particle density or sand content. Finally Carbamazepin absorption coefficient was positively related to the oxidable organic carbon content, cation exchange capacity or basic cation saturation, and negatively to the particle density or sand content. Evaluated pedotransfer rules for different pharmaceuticals included different sets of soil properties. Absorption coefficients could be predicted from: the hydrolytic acidity (Sulfamethoxazol), the oxidable organic carbon content (Trimetoprim and Carbamazepin), the oxidable organic carbon content, hydrolytic acidity and cation exchange capacity (Clarithromycin), the basic cation saturation (Atenolol and Metoprolol). Acknowledgement: Authors acknowledge the financial support of the Czech Science Foundation (Project No. 13-12477S).

Kinetics of Cd(ii) adsorption and desorption on ferrihydrite: experiments and modeling.

PubMed

Liang, Yuzhen; Tian, Lei; Lu, Yang; Peng, Lanfang; Wang, Pei; Lin, Jingyi; Cheng, Tao; Dang, Zhi; Shi, Zhenqing

2018-05-15

The kinetics of Cd(ii) adsorption/desorption on ferrihydrite is an important process affecting the fate, transport, and bioavailability of Cd(ii) in the environment, which was rarely systematically studied and understood at quantitative levels. In this work, a combination of stirred-flow kinetic experiments, batch adsorption equilibrium experiments, high-resolution transmission electron microscopy (HR-TEM), and mechanistic kinetic modeling were used to study the kinetic behaviors of Cd(ii) adsorption/desorption on ferrihydrite. HR-TEM images showed the open, loose, and sponge-like structure of ferrihydrite. The batch adsorption equilibrium experiments revealed that higher pH and initial metal concentration increased Cd(ii) adsorption on ferrihydrite. The stirred-flow kinetic results demonstrated the increased adsorption rate and capacity as a result of the increased pH, influent concentration, and ferrihydrite concentration. The mechanistic kinetic model successfully described the kinetic behaviors of Cd(ii) during the adsorption and desorption stages under various chemistry conditions. The model calculations showed that the adsorption rate coefficients varied as a function of solution chemistry, and the relative contributions of the weak and strong ferrihydrite sites for Cd(ii) binding varied with time at different pH and initial metal concentrations. Our model is able to quantitatively assess the contributions of each individual ferrihydrite binding site to the overall Cd(ii) adsorption/desorption kinetics. This study provided insights into the dynamic behavior of Cd(ii) and a predictive modeling tool for Cd(ii) adsorption/desorption kinetics when ferrihydrite is present, which may be helpful for the risk assessment and management of Cd contaminated sites.

Adsorption and solvation of ethanol at the water liquid-vapor interface: a molecular dynamics study

NASA Technical Reports Server (NTRS)

Wilson, M. A.; Pohorille, A.

1997-01-01

The free energy profiles of methanol and ethanol at the water liquid-vapor interface at 310K were calculated using molecular dynamics computer simulations. Both alcohols exhibit a pronounced free energy minimum at the interface and, therefore, have positive adsorption at this interface. The surface excess was computed from the Gibbs adsorption isotherm and was found to be in good agreement with experimental results. Neither compound exhibits a free energy barrier between the bulk and the surface adsorbed state. Scattering calculations of ethanol molecules from a gas phase thermal distribution indicate that the mass accommodation coefficient is 0.98, and the molecules become thermalized within 10 ps of striking the interface. It was determined that the formation of the solvation structure around the ethanol molecule at the interface is not the rate-determining step in its uptake into water droplets. The motion of an ethanol molecule in a water lamella was followed for 30 ns. The time evolution of the probability distribution of finding an ethanol molecule that was initially located at the interface is very well described by the diffusion equation on the free energy surface.

Interpretation and estimation for dynamic mobility of chlorpyrifos in soils containing different organic matters.

PubMed

Hwang, Jeong-In; Lee, Sung-Eun; Kim, Jang-Eok

2015-12-01

The adsorption and removal behaviors of the organophosphate insecticide chlorpyrifos in two soils (AS and GW soils) with different organic matter contents were investigated to predict the dynamic residues in the soil environment. The adsorption test showed that the chlorpyrifos adsorptive power for the AS soil containing high organic matter content was greater than that for the GW soil. The extent of the time-dependent removal of chlorpyrifos in the tested soils was not significantly different except at 90 days after the treatment. The availability of a chemical-specific residue model developed in this study was statistically assessed to estimate the chlorpyrifos residue in soil solutions that could be absorbed into plants. The values modeled using the soil experimental data were satisfactory, having a mean deviation of 32% from the measured data. The correlation between the modeled and measured data was acceptable, with mean coefficients of correlation (R(2)) of 0.89. Furthermore, the average of the residual error was low at 0.43, which corresponded to a mean factor of -1.9. The developed model could be used as a critical tool to predict the subsequent plant uptake of chlorpyrifos.

Selective adsorption of Pb(II), Cd(II), and Ni(II) ions from aqueous solution using chitosan-MAA nanoparticles.

PubMed

Heidari, Aghdas; Younesi, Habibollah; Mehraban, Zahra; Heikkinen, Harri

2013-10-01

Chitosan-MAA nanoparticles (CS-MAA) with an average size of 10-70 nm were prepared by polymerizing chitosan with methacrylic acid in aqueous solution. The physicochemical properties of nanoparticles were investigated using Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), dynamic light scattering (DLS) and nuclear magnetic resonance (NMR). The adsorption of Pb(II), Cd(II) and Ni(II) from aqueous solution on CS-MAA was studied in a batch system. The effects of the solution pH, initial metal concentration, contact time, and dosage of the adsorbent on the adsorption process were examined. The experimental data were analyzed using the pseudo-second-order kinetic equations and the Langmuir, Freundlich and Redlish-Peterson isotherms. The maximum adsorption capacity was 11.30, 1.84, and 0.87 mg/g for Pb(II), Cd(II) and Ni(II) ions, respectively, obtained by the Langmuir isotherm. However, the adsorption isotherm was better explained by the Freundlich rather than by the Langmuir model, as the high correlation coefficients (R(2)>0.99) were obtained at a higher confidence level. Copyright © 2013 Elsevier B.V. All rights reserved.

Effects of Motility and Adsorption Rate Coefficient on Transport of Bacteria through Saturated Porous Media

PubMed Central

Camper, Anne K.; Hayes, Jason T.; Sturman, Paul J.; Jones, Warren L.; Cunningham, Alfred B.

1993-01-01

Three strains of Pseudomonas fluorescens with different motility rates and adsorption rate coefficients were injected into porous-medium reactors packed with l-mm-diameter glass spheres. Cell breakthrough, time to peak concentration, tailing, and cell recovery were measured at three interstitial pore velocities (higher than, lower than, and much lower than the maximal bacterial motility rate). All experiments were done with distilled water to reduce the effects of growth and chemotaxis. Contrary to expectations, motility did not result in either early breakthrough or early time to peak concentration at flow velocities below the motility rate. Bacterial size exclusion effects were shown to affect breakthrough curve shape at the very low flow velocity, but no such effect was seen at the higher flow velocity. The tendency of bacteria to adsorb to porous-medium surfaces, as measured by adsorption rate coefficients, profoundly influenced transport characteristics. Cell recoveries were shown to be correlated with the ratio of advective to adsorptive transport in the reactors. Adsorption rate coefficients were found to be better predictors of microbial transport phenomena than individual characteristics, such as size, motility, or porous-medium hydrodynamics. PMID:16349075

Capacitance of Nanoporous Carbon-Based Supercapacitors Is a Trade-Off between the Concentration and the Separability of the Ions.

PubMed

Burt, Ryan; Breitsprecher, Konrad; Daffos, Barbara; Taberna, Pierre-Louis; Simon, Patrice; Birkett, Greg; Zhao, X S; Holm, Christian; Salanne, Mathieu

2016-10-06

Nanoporous carbon-based supercapacitors store electricity through adsorption of ions from the electrolyte at the surface of the electrodes. Room temperature ionic liquids, which show the largest ion concentrations among organic liquid electrolytes, should in principle yield larger capacitances. Here, we show by using electrochemical measurements that the capacitance is not significantly affected when switching from a pure ionic liquid to a conventional organic electrolyte using the same ionic species. By performing additional molecular dynamics simulations, we interpret this result as an increasing difficulty of separating ions of opposite charges when they are more concentrated, that is, in the absence of a solvent that screens the Coulombic interactions. The charging mechanism consistently changes with ion concentration, switching from counterion adsorption in the diluted organic electrolyte to ion exchange in the pure ionic liquid. Contrarily to the capacitance, in-pore diffusion coefficients largely depend on the composition, with a noticeable slowing of the dynamics in the pure ionic liquid.

Dynamic release of gentamicin sulfate (GS) from alginate dialdehyde (AD)-crosslinked casein (CAS) films for antimicrobial applications

PubMed Central

Bajpai, S. K.; Shah, Farhan Ferooz; Bajpai, M.

2017-01-01

Abstract In the present work, antibiotic drug gentamicin sulfate (GS) has been loaded into alginate dialdehyde-crosslinked casein (CAS) films for wound dressing applications. The films have been characterized by Fourier transform infrared spectroscopy, X-ray diffraction analysis and scanning electron microscopy. The dynamic release of model drug GS has been investigated in the physiological fluid at 37 °C. The drug release data has been interpreted in the terms of various kinetic models such as Power function model, first order model and Schott model. The release data was found to be well fitted by Schott model. The various diffusion coefficients are also evaluated. The adsorption of model therapeutic protein BSA on the film has been investigated. The maximum adsorption is found to be 5.7 mg/cm2.The films were tested for their antibacterial and anti-fungal action. Finally, the in vivo wound healing study was carried out on Albino wistar rats. PMID:29491776

Temperature effect on affinity chromatography of two lectins from the seeds of Ricinus communis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hsu, H.W.; Davis, D.S.; Wei, C.H.

1976-06-01

Specific adsorption capacity of Sepharose 4B in affinity chromatography for two purified galactose-binding lectins, designated as III/sub L/ and III/sub H/, from the seed of Ricinus communis (castor bean) was measured from 7 to 24/sup 0/C. The adsorption coefficients for these two protein fractions as a function of temperature were also obtained. It was found that there is a characteristic transition of adsorption coefficient at 18/sup 0/C for both lectins. Adsorption coefficients between Sepharose 4B and these two lectins were also expressed in terms of ..delta..G, ..delta..H, and ..delta..S. It is suggested that the difference in the temperature dependence ofmore » the binding energy of these two lectins may be used for their separation at selected temperature.« less

Adsorption-desorption and degradation of insecticides clothianidin and thiamethoxam in agricultural soils.

PubMed

Li, Yang; Su, Peidong; Li, Yadong; Wen, Kejun; Bi, Guihong; Cox, Michael

2018-09-01

Studied were the adsorption-desorption and degradation of two widely used neonicotinoid insecticides clothianidin and thiamethoxam in three different agricultural soils in the state of Mississippi. The adsorptions of both the neonicotinoids fit a linear isotherm model. In different soils at different depths with different moisture contents, the adsorption distribution coefficients of clothianidin and thiamethoxam were found to be 0.62 to 1.94 and 0.59-2.03 L kg -1 , respectively. These distribution coefficients showed strong positive correlations with organic carbon content and pH of the soils. The desorptions of clothianidin and thiamethoxam also followed a linear isotherm, but were irreversible in respect to their adsorption isotherms. The desorption distribution coefficients ranged from 0.14 to 0.62 L kg -1 , increased with the decrease of organic carbon content. The degradations of clothianidin and thiamethoxam in the soils were found to be slow with half-lives ranged from 90 to 280 and 65 to 170 d for clothianidin and thiamethoxam respectively. The degradation rates increased with the increase of the organic carbon content in the soils. The moisture content in the soils had a positive effect on the degradation rates. The Groundwater Ubiquity Scores calculated from the adsorption distribution coefficient, organic content, and half-life suggest that clothianidin and thiamethoxam have moderate to high potential to leach to groundwater. Copyright © 2018 Elsevier Ltd. All rights reserved.

Determination of semicarbazide in fish by molecularly imprinted stir bar sorptive extraction coupled with high performance liquid chromatography.

PubMed

Tang, Tang; Wei, Fangdi; Wang, Xu; Ma, Yujie; Song, Yueyue; Ma, Yunsu; Song, Quan; Xu, Guanhong; Cen, Yao; Hu, Qin

2018-02-15

A novel molecularly imprinted stir bar (MI-SB) for sorptive extraction of semicarbazide (SEM) was prepared in present paper. The coating of the stir bar was characterized by scanning electron microscopy, Fourier-transform infrared spectroscopy, dynamic adsorption and static adsorption tests. The saturated adsorption of MI-SB was about 4 times over that of non-imprinted stir bar (NI-SB). The selectivity of MI-SB for SEM was much better than NI-SB. A method to determine SEM was established by coupling MI-SB sorptive extraction with HPLC-UV. The liner range was 1-100ng/mL for SEM with a correlation coefficient of 0.9985. The limit of detection was about 0.59ng/mL, which was below the minimum required performance limit of SEM in meat products regulated by European Union. The method was applied to the determination of SEM in fish samples with satisfactory results. Copyright © 2018 Elsevier B.V. All rights reserved.

Predicting adsorption isotherms for aqueous organic micropollutants from activated carbon and pollutant properties.

PubMed

Li, Lei; Quinlivan, Patricia A; Knappe, Detlef R U

2005-05-01

A method based on the Polanyi-Dubinin-Manes (PDM) model is presented to predict adsorption isotherms of aqueous organic contaminants on activated carbons. It was assumed that trace organic compound adsorption from aqueous solution is primarily controlled by nonspecific dispersive interactions while water adsorption is controlled by specific interactions with oxygen-containing functional groups on the activated carbon surface. Coefficients describing the affinity of water for the activated carbon surface were derived from aqueous-phase methyl tertiary-butyl ether (MTBE) and trichloroethene (TCE) adsorption isotherm data that were collected with 12 well-characterized activated carbons. Over the range of oxygen contents covered by the adsorbents (approximately 0.8-10 mmol O/g dry, ash-free activated carbon), a linear relationship between water affinity coefficients and adsorbent oxygen content was obtained. Incorporating water affinity coefficients calculated from the developed relationship into the PDM model, isotherm predictions resulted that agreed well with experimental data for three adsorbents and two adsorbates [tetrachloroethene (PCE), cis-1,2-dichloroethene (DCE)] that were not used to calibrate the model.

To Identify the Important Soil Properties Affecting Dinoseb Adsorption with Statistical Analysis

PubMed Central

Guan, Yiqing; Wei, Jianhui; Zhang, Danrong; Zu, Mingjuan; Zhang, Liru

2013-01-01

Investigating the influences of soil characteristic factors on dinoseb adsorption parameter with different statistical methods would be valuable to explicitly figure out the extent of these influences. The correlation coefficients and the direct, indirect effects of soil characteristic factors on dinoseb adsorption parameter were analyzed through bivariate correlation analysis, and path analysis. With stepwise regression analysis the factors which had little influence on the adsorption parameter were excluded. Results indicate that pH and CEC had moderate relationship and lower direct effect on dinoseb adsorption parameter due to the multicollinearity with other soil factors, and organic carbon and clay contents were found to be the most significant soil factors which affect the dinoseb adsorption process. A regression is thereby set up to explore the relationship between the dinoseb adsorption parameter and the two soil factors: the soil organic carbon and clay contents. A 92% of the variation of dinoseb sorption coefficient could be attributed to the variation of the soil organic carbon and clay contents. PMID:23737715

Parameterization of an interfacial force field for accurate representation of peptide adsorption free energy on high-density polyethylene

PubMed Central

Abramyan, Tigran M.; Snyder, James A.; Yancey, Jeremy A.; Thyparambil, Aby A.; Wei, Yang; Stuart, Steven J.; Latour, Robert A.

2015-01-01

Interfacial force field (IFF) parameters for use with the CHARMM force field have been developed for interactions between peptides and high-density polyethylene (HDPE). Parameterization of the IFF was performed to achieve agreement between experimental and calculated adsorption free energies of small TGTG–X–GTGT host–guest peptides (T = threonine, G = glycine, and X = variable amino-acid residue) on HDPE, with ±0.5 kcal/mol agreement. This IFF parameter set consists of tuned nonbonded parameters (i.e., partial charges and Lennard–Jones parameters) for use with an in-house-modified CHARMM molecular dynamic program that enables the use of an independent set of force field parameters to control molecular behavior at a solid–liquid interface. The R correlation coefficient between the simulated and experimental peptide adsorption free energies increased from 0.00 for the standard CHARMM force field parameters to 0.88 for the tuned IFF parameters. Subsequent studies are planned to apply the tuned IFF parameter set for the simulation of protein adsorption behavior on an HDPE surface for comparison with experimental values of adsorbed protein orientation and conformation. PMID:25818122

Using natural Chinese zeolite to remove ammonium from rainfall runoff following urea fertilization of a paddy rice field.

PubMed

Wang, Xiao-Ling; Qiao, Bin; Li, Song-Min; Li, Jian-Sheng

2016-03-01

The potential of natural Chinese zeolite to remove ammonium from rainfall runoff following urea applications to a paddy rice field is assessed in this study. Laboratory batch kinetic and isotherm experiments were carried out first to investigate the ammonium adsorption capacity of the natural zeolite. Field experiments using zeolite adsorption barriers installed at drain outlets in a paddy rice field were also carried out during natural rainfall events to evaluate the barrier's dynamic removal capacity of ammonium. The results demonstrate that the adsorption kinetics are accurately described by the Elovich model, with a coefficient of determination (R (2)) ranging from 0.9705 to 0.9709, whereas the adsorption isotherm results indicate that the Langmuir-Freundlich model provides the best fit (R (2) = 0.992) for the equilibrium data. The field experiments show that both the flow rate and the barrier volume are important controls on ammonium removal from rainfall runoff. A low flow rate leads to a higher ammonium removal efficiency at the beginning of the tests, while a high flow rate leads to a higher quantity of ammonium adsorbed over the entire runoff process.

Batch and fixed-bed adsorption of tartrazine azo-dye onto activated carbon prepared from apricot stones

NASA Astrophysics Data System (ADS)

Albroomi, H. I.; Elsayed, M. A.; Baraka, A.; Abdelmaged, M. A.

2017-07-01

This work describes the potential of utilizing prepared activated carbon from apricot stones as an efficient adsorbent material for tartrazine (TZ) azo-dye removal in a batch and dynamic adsorption system. The results revealed that activated carbons with well-developed surface area (774 m2/g) and pore volume (1.26 cm3/g) can be manufactured from apricot stones by H3PO4 activation. In batch experiments, effects of the parameters such as initial dye concentration and temperature on the removal of the dye were studied. Equilibrium was achieved in 120 min. Adsorption capacity was found to be dependent on the initial concentration of dye solution, and maximum adsorption was found to be 76 mg/g at 100 mg/L of TZ. The adsorption capacity at equilibrium ( q e) increased from 22.6 to 76 mg/g with an increase in the initial dye concentrations from 25 to 100 mg/L. The thermodynamic parameters such as change in free energy (Δ G 0), enthalpy (Δ H 0) and entropy (Δ S 0) were determined and the positive value of (Δ H) 78.1 (K J mol-1) revealed that adsorption efficiency increased with an increase in the process temperature. In fixed-bed column experiments, the effect of selected operating parameters such as bed depth, flow rate and initial dye concentration on the adsorption capacity was evaluated. Increase in bed height of adsorption columns leads to an extension of breakthrough point as well as the exhaustion time of adsorbent. However, the maximum adsorption capacities decrease with increases of flow rate. The breakthrough data fitted well to bed depth service time and Thomas models with high coefficient of determination, R 2 ≥ 94.

Mechanisms for the adsorption of substituted nitrobenzenes by smectite clays.

PubMed

Boyd, S A; Sheng, G; Teppen, B J; Johnston, C T

2001-11-01

To more fully understand the potential for transport of nitroaromatic compounds in soils and subsoils,the adsorption of a series of para- and meta-substituted nitrobenzenes (SNBs) by K-smectite clay was measured. Adsorption isotherms were fit to the Freundlich equation, and the resultant Freundlich adsorption coefficients (log(Kf) were positively correlated with the Hammett substituent constant (r2 = 0.80). This relationship and a positive reaction constant (p = 1.15) indicate that the adsorption reaction is favored by electron-withdrawing substituents. These results are consistent with an electron donor (smectite)-acceptor (substituted nitrobenzene) mechanism offered previously. However, quantum calculations did not reveal any systematic relationship between the Hammett constant and the electron density on the aromatic ring, which would explain a donor-acceptor relationship. Rather, electron density donated by a second substituent on nitrobenzene appears to be appropriated by the nitro group leaving ring electron density unchanged. Fourier transform infrared spectroscopy revealed shifts in the -NO2 vibrational modes of 1,3,5-trinitrobenzene (TNB) upon adsorption to K+-smectite that were consistent with the complexation of K+ by -NO2 groups. Such TNB vibrational shifts were not observed for SWy-1 saturated with more strongly hydrated cations (i.e., Na+, Mg2+, Ca2+, and Ba2+). The simultaneous interaction of multiple -NO2 groups with exchangeable K+ was indicated by molecular dynamic simulations. Adsorption of SNBs by smectite clays appears to result from the additive interactions of -NO2 groups and secondary substituents with interlayer K+ ions. Adsorption occurs to a greater or lesser extent depending on the abilities of substituents to complex additional interlayer cations and the water solubilities of SNBs. We conclude that the adsorption trends of SNBs on K-SAz-1 can be explained without recourse to hypothetical electron donor-acceptor complexes.

Characterization and evaluation of the novel agarose-nickel composite matrix for possible use in expanded bed adsorption of bio-products.

PubMed

Rezvani, Azita; Jahanshahi, Mohsen; Najafpour, Ghasem D

2014-02-28

Agarose-nickel (Ag-Ni) composite matrix was evaluated for its use in expanded bed adsorption (EBA). Bovine serum albumin (BSA) and lysozyme were used as model proteins in batch and column adsorption studies. Accordingly, Reactive Green 19 (RG19) dye-ligand was covalently immobilized onto the support matrix to prepare affinity adsorbent for protein adsorption. Results were then compared with data obtained from Streamline commercial matrix. In batch experiments RG19 derivatives of Ag-Ni (RG19-Ag-Ni) exhibited high adsorption rate; and also a higher binding capacity of BSA (31.4mg/ml adsorbent) was observed for Ag-Ni compared to the commercial adsorbent. More than 70% of the adsorption capacity was achieved within 30min which is a reasonable contact time for EBA operations. The equilibrium adsorption data well agreed with Langmuir isotherm model. The expanded bed adsorption studies showed a reasonable breakthrough behavior at high flow rates and a higher dynamic binding capacity (DBC) was obtained for novel matrix in compare to streamline at the same fluid velocity. DBC at 10% breakthrough reached 66% of the saturated adsorption capacity at the high flow velocity of 450cm/h which indicates the favorable column efficiency. Additionally, two different Ag-Ni size fractions (75-150 and 150-300μm) were examined to investigate the expanded bed performance dependency on the adsorbent particle size with respect to the hydrodynamic stability and adsorption properties using lysozyme as model protein. Interestingly, the small ones showed less axial dispersion coefficient (<1.0×10(-5)m(2)/s) which resulted in higher bed stability in high fluid viscosities. Overall, the adsorption experiments results demonstrated that small size fraction of Ag-Ni matrices acts more effectively for expanded bed adsorption of bio-molecules. Copyright © 2014 Elsevier B.V. All rights reserved.

Determination of adsorption parameters in numerical simulation for polymer flooding

NASA Astrophysics Data System (ADS)

Bao, Pengyu; Li, Aifen; Luo, Shuai; Dang, Xu

2018-02-01

A study on the determination of adsorption parameters for polymer flooding simulation was carried out. The study mainly includes polymer static adsorption and dynamic adsorption. The law of adsorption amount changing with polymer concentration and core permeability was presented, and the one-dimensional numerical model of CMG was established under the support of a large number of experimental data. The adsorption laws of adsorption experiments were applied to the one-dimensional numerical model to compare the influence of two adsorption laws on the historical matching results. The results show that the static adsorption and dynamic adsorption abide by different rules, and differ greatly in adsorption. If the static adsorption results were directly applied to the numerical model, the difficulty of the historical matching will increase. Therefore, dynamic adsorption tests in the porous medium are necessary before the process of parameter adjustment in order to achieve the ideal history matching result.

Molecular Simulations of Adsorption and Diffusion in Silicalite.

NASA Astrophysics Data System (ADS)

Snurr, Randall Quentin

The adsorption and diffusion of hydrocarbons in the zeolite silicalite have been studied using molecular simulations. The simulations use an atomistic description of zeolite/sorbate interactions and are based on principles of statistical mechanics. Emphasis was placed on developing new simulation techniques to allow complex systems relevant to industrial applications in catalysis and separations processes to be studied. Adsorption isotherms and heats of sorption for methane in silicalite were calculated from grand canonical Monte Carlo (GCMC) simulations and also from molecular dynamics (MD) simulations accompanied by Widom test particle insertions. Good agreement with experimental data from the literature was found. The adsorption thermodynamics of aromatic species in silicalite at low loading was predicted by direct evaluation of the configurational integrals. Good agreement with experiment was obtained for the Henry's constants and the heats of adsorption. Molecules were predicted to be localized in the channel intersections at low loading. At higher loading, conventional GCMC simulations were found to be infeasible. Several variations of the GCMC technique were developed incorporating biased insertion moves. These new techniques are much more efficient than conventional GCMC and allow for the prediction of adsorption isotherms of tightly-fitting aromatic molecules in silicalite. Our simulations when combined with experimental evidence of a phase change in the zeolite structure at intermediate loading provide an explanation of the characteristic steps seen in the experimental isotherms. A hierarchical atomistic/lattice model for studying these systems was also developed. The hierarchical model is more than an order of magnitude more efficient computationally than direct atomistic simulation. Diffusion of benzene in silicalite was studied using transition-state theory (TST). Such an approach overcomes the time-scale limitations of using MD simulations for studying sorbate dynamics. Predicted diffusion coefficients were found to be too low compared to experiment. This was attributed to the assumption of a rigid zeolite structure in the calculations and the use of a harmonic approximation for calculating the TST rate constants. Details of sorbate motion were also investigated.

Experimental investigation of cephapirin adsorption to quartz filter sands and dune sands

NASA Astrophysics Data System (ADS)

Peterson, Jonathan W.; O'Meara, Theresa A.; Seymour, Michael D.

2008-08-01

Batch experiments were performed to investigate cephapirin (a widely used veterinary antibiotic) adsorption on various size sands of low total organic carbon content (0.08-0.36 wt%). In the aqueous concentration range investigated (11-112 μmol/L cephapirin), adsorption to nearly pure quartz filter sands (0.50-3.35 mm diameter) is low. Isotherms are S-shaped and most display a region of minimum adsorption, where decreased adsorption occurs with increasing solution concentration, followed by increased adsorption at higher concentrations. Cephapirin adsorption to quartz-rich, feldspar-bearing dune sands (0.06-0.35 mm diameter), and the smallest quartz filter sand investigated (0.43-0.50 mm), can be described by linear sorption isotherms over the range of concentrations investigated. Distribution coefficients ( K d) range from 0.94 to 3.45 L/kg. No systematic relationship exists between grain size and amount of adsorption for any of the sands investigated. Cephapirin adsorption is positively correlated to the feldspar ratio (K-feldspar/(albite + Ca-plagioclase). Feldspar-ratio normalization of distribution coefficients was more effective than organic carbon normalization at reducing variability of K d values in the dune sands investigated.

Load-dependent surface diffusion model for analyzing the kinetics of protein adsorption onto mesoporous materials.

PubMed

Marbán, Gregorio; Ramírez-Montoya, Luis A; García, Héctor; Menéndez, J Ángel; Arenillas, Ana; Montes-Morán, Miguel A

2018-02-01

The adsorption of cytochrome c in water onto organic and carbon xerogels with narrow pore size distributions has been studied by carrying out transient and equilibrium batch adsorption experiments. It was found that equilibrium adsorption exhibits a quasi-Langmuirian behavior (a g coefficient in the Redlich-Peterson isotherms of over 0.95) involving the formation of a monolayer of cyt c with a depth of ∼4nm on the surface of all xerogels for a packing density of the protein inside the pores of 0.29gcm -3 . A load-dependent surface diffusion model (LDSDM) has been developed and numerically solved to fit the experimental kinetic adsorption curves. The results of the LDSDM show better fittings than the standard homogeneous surface diffusion model. The value of the external mass transfer coefficient obtained by numerical optimization confirms that the process is controlled by the intraparticle surface diffusion of cyt c. The surface diffusion coefficients decrease with increasing protein load down to zero for the maximum possible load. The decrease is steeper in the case of the xerogels with the smallest average pore diameter (∼15nm), the limit at which the zero-load diffusion coefficient of cyt c also begins to be negatively affected by interactions with the opposite wall of the pore. Copyright © 2017 Elsevier Inc. All rights reserved.

Adsorption mechanisms of the nonequilibrium incorporation of admixtures in a growing crystal

NASA Astrophysics Data System (ADS)

Franke, V. D.; Punin, Yu. O.; Smetannikova, O. G.; Kenunen, D. S.

2007-12-01

The nonequilibrium partition of components between a crystal and solution is mainly controlled by impurity adsorption on the surface of the growing crystal. The specificity of adsorption on the faces of various simple forms leads to the sectorial zoning of crystals. This effect was studied experimentally for several crystallizing systems with different impurities, including isomorphous, 2d-isomorphous, and nonisomorphous, readily adsorbed impurities. In all systems, the sectorial selectivity of impurity incorporation into host crystals has been detected with partition coefficients many times higher than in the case of equilibrium partition. Specific capture of impurities by certain faces is accompanied by inhibition of their growth and modification of habit. The decrease in nonequilibrium partition coefficients with degree of oversaturation provides entrapment of impurities in the growing crystals. Thereby, the adsorption mechanism works in much the same mode for impurities of quite different nature. The behavior of partition coefficient differs drastically from impurity capturing by diffusion mechanism.

Thermophysical property and pore structure evolution in stressed and non-stressed neutron irradiated IG-110 nuclear graphite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Snead, Lance; Contescu, Christian I.; Byun, Thak Sang

2016-08-01

The nuclear graphite, IG-110, was irradiated with and without a compressive load of 5 MPa at ~400 *C up to 9.3E25 n/m2 (E > 0.1 MeV). Following irradiation physical properties were studied to compare the effect of graphite irradiation on microstructure developed under compression and in stress-free conditions. Properties included: dimensional change, thermal conductivity, dynamic modulus, and CTE. The effect of stress on open internal porosity was determined through nitrogen adsorption. The IG-110 graphite experienced irradiation-induced creep that is differentiated from irradiation-induced swelling. Irradiation under stress resulted in somewhat greater thermal conductivity and coefficient of thermal expansion. While a significantmore » increase in dynamic modulus occurs, no differentiation between materials irradiated with and without compressive stress was observed. Nitrogen adsorption analysis suggests a difference in pore evolution in the 0.3e40 nm range for graphite irradiated with and without stress, but this evolution is seen to be a small contributor to the overall dimensional change.« less

Thermophysical property and pore structure evolution in stressed and non-stressed neutron irradiated IG-110 nuclear graphite

DOE PAGES

Snead, Lance L.; Contescu, C. I.; Byun, T. S.; ...

2016-04-23

The nuclear graphite, IG-110, was irradiated with and without a compressive load of 5 MPa at ~400 C up to 9.3x10 25 n/m 2 (E>0.1 MeV.) Following irradiation physical properties were studied to compare the effect of graphite irradiation on microstructure developed under compression and in stress-free condition. Properties included: dimensional change, thermal conductivity, dynamic modulus, and CTE. The effect of stress on open internal porosity was determined through nitrogen adsorption. The IG-110 graphite experienced irradiation-induced creep that is differentiated from irradiation-induced swelling. Irradiation under stress resulted in somewhat greater thermal conductivity and coefficient of thermal expansion. While a significantmore » increase in dynamic modulus occurs, no differentiation between materials irradiated with and without compressive stress was observed. Nitrogen adsorption analysis suggests a difference in pore evolution in the 0.3-40 nm range for graphite irradiated with and without stress, but this evolution is seen to be a small contributor to the overall dimensional change.« less

Effect of aggregate structure on VOC gas adsorption onto volcanic ash soil.

PubMed

Hamamoto, Shoichiro; Seki, Katsutoshi; Miyazaki, Tsuyoshi

2009-07-15

The understanding of the gaseous adsorption process and the parameters of volatile organic compounds such as organic solvents or fuels onto soils is very important in the analysis of the transport or fate of these chemicals in soils. Batch adsorption experiments with six different treatments were conducted to determine the adsorption of isohexane, a gaseous aliphatic, onto volcanic ash soil (Tachikawa loam). The measured gas adsorption coefficient for samples of Tachikawa loam used in the first three treatments, Control, AD (aggregate destroyed), and AD-OMR (aggregate destroyed and organic matter removed), implied that the aggregate structure of volcanic ash soil as well as organic matter strongly enhanced gas adsorption under the dry condition, whereas under the wet condition, the aggregate structure played an important role in gas adsorption regardless of the insolubility of isohexane. In the gas adsorption experiments for the last three treatments, soils were sieved in different sizes of mesh and were separated into three different aggregate or particle size fractions (2.0-1.0mm, 1.0-0.5mm, and less than 0.5mm). Tachikawa loam with a larger size fraction showed higher gas adsorption coefficient, suggesting the higher contributions of macroaggregates to isohexane gas adsorption under dry and wet conditions.

Experiments in water-macrophyte systems to uncover the dynamics of pesticide mitigation processes in vegetated surface waters/streams.

PubMed

Stang, Christoph; Bakanov, Nikita; Schulz, Ralf

2016-01-01

Knowledge on the dynamics and the durability of the processes governing the mitigation of pesticide loads by aquatic vegetation in vegetated streams, which are characterized by dynamic discharge regimes and short chemical residence times, is scarce. In a static long-term experiment (48 h), the dissipation of five pesticides from the aqueous phase followed a biphasic pattern in the presence of aquatic macrophytes. A dynamic concentration decrease driven by sorption to the macrophytes ranged from 8.3 to 60.4% for isoproturon and bifenox, respectively, within the first 2 h of exposure. While the aqueous concentrations of imidacloprid, isoproturon, and tebufenozide remained constant thereafter, the continuous but decelerated concentration decrease of difenoconazole and bifenox in the water-macrophyte systems used here was assumed to be attributed to macrophyte-induced degradation processes. In addition, a semi-static short-term experiment was conducted, where macrophytes were transferred to uncontaminated medium after 2 h of exposure to simulate a transient pesticide peak. In the first part of the experiment, adsorption to macrophytes resulted in partitioning coefficients (logK D_Adsorp) ranging from 0.2 for imidacloprid to 2.2 for bifenox. One hour after the macrophytes were transferred to the uncontaminated medium, desorption of the compounds from the macrophytes resulted in a new phase equilibrium and K D_Desorp values of 1.46 for difenoconazole and 1.95 for bifenox were determined. A correlation analysis revealed the best match between the compound affinity to adsorb to macrophytes (expressed as K D_Adsorp) and their soil organic carbon-water partitioning coefficient (K OC) compared to their octanol-water partitioning coefficient (K OW) or a mathematically derived partitioning coefficient.

Adsorption of organic chemicals in soils.

PubMed Central

Calvet, R

1989-01-01

This paper presents a review on adsorption of organic chemicals on soils sediments and their constituents. The first part of this review deals with adsorption from gas and liquid phases and gives a discussion on the physical meaning of the shape of adsorption isotherms. Results show that no general rules can be proposed to describe univocally the relation between the shape of isotherms and the nature of adsorbate-adsorbent system. Kinetics of adsorption is discussed through the description of various models. Theoretical developments exist both for the thermodynamics and the kinetics of adsorption, but there is a strong need for experimental results. Possible adsorption mechanisms are ion exchange, interaction with metallic cations, hydrogen bonds, charge transfers, and London-van der Waals dispersion forces/hydrophobic effect. However, direct proofs of a given mechanism are rare. Several factors influence adsorption behavior. Electronic structure of adsorbed molecules, properties of adsorbents, and characteristics of the liquid phase are discussed in relation to adsorption. Such properties as water solubility, organic carbon content of adsorbing materials, and the composition of the liquid phase are particularly important. Evaluation of adsorption can be obtained through either laboratory measurements or use of several correlations. Adsorption measurements must be interpreted, taking into account treatment of adsorbent materials, experimental conditions, and secondary phenomena such as degradations. Correlations between adsorption coefficients and water-octanol partition coefficient or water solubility are numerous. They may be useful tools for prediction purposes. Relations with transport, bioavailability, and degradation are described. PMID:2695323

Adsorption Behavior of Heat Modified Soybean Oil via Boundary Lubrication Coefficient of Friction Measurements

USDA-ARS?s Scientific Manuscript database

The frictional behaviors of soybean oil and heat modified soybean oils with different Gardner scale viscosities as additives in hexadecane have been examined in a boundary lubrication test regime (steel contacts) using Langmuir adsorption model. The free energy of adsorption (delta-Gads) of various...

Permeability and kinetic coefficients for mesoscale BCF surface step dynamics: Discrete two-dimensional deposition-diffusion equation analysis

DOE PAGES

Zhao, Renjie; Evans, James W.; Oliveira, Tiago J.

2016-04-08

Here, a discrete version of deposition-diffusion equations appropriate for description of step flow on a vicinal surface is analyzed for a two-dimensional grid of adsorption sites representing the stepped surface and explicitly incorporating kinks along the step edges. Model energetics and kinetics appropriately account for binding of adatoms at steps and kinks, distinct terrace and edge diffusion rates, and possible additional barriers for attachment to steps. Analysis of adatom attachment fluxes as well as limiting values of adatom densities at step edges for nonuniform deposition scenarios allows determination of both permeability and kinetic coefficients. Behavior of these quantities is assessedmore » as a function of key system parameters including kink density, step attachment barriers, and the step edge diffusion rate.« less

Permeability and kinetic coefficients for mesoscale BCF surface step dynamics: Discrete two-dimensional deposition-diffusion equation analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Renjie; Evans, James W.; Oliveira, Tiago J.

Here, a discrete version of deposition-diffusion equations appropriate for description of step flow on a vicinal surface is analyzed for a two-dimensional grid of adsorption sites representing the stepped surface and explicitly incorporating kinks along the step edges. Model energetics and kinetics appropriately account for binding of adatoms at steps and kinks, distinct terrace and edge diffusion rates, and possible additional barriers for attachment to steps. Analysis of adatom attachment fluxes as well as limiting values of adatom densities at step edges for nonuniform deposition scenarios allows determination of both permeability and kinetic coefficients. Behavior of these quantities is assessedmore » as a function of key system parameters including kink density, step attachment barriers, and the step edge diffusion rate.« less

A CONTINUUM HARD-SPHERE MODEL OF PROTEIN ADSORPTION

PubMed Central

Finch, Craig; Clarke, Thomas; Hickman, James J.

2012-01-01

Protein adsorption plays a significant role in biological phenomena such as cell-surface interactions and the coagulation of blood. Two-dimensional random sequential adsorption (RSA) models are widely used to model the adsorption of proteins on solid surfaces. Continuum equations have been developed so that the results of RSA simulations can be used to predict the kinetics of adsorption. Recently, Brownian dynamics simulations have become popular for modeling protein adsorption. In this work a continuum model was developed to allow the results from a Brownian dynamics simulation to be used as the boundary condition in a computational fluid dynamics (CFD) simulation. Brownian dynamics simulations were used to model the diffusive transport of hard-sphere particles in a liquid and the adsorption of the particles onto a solid surface. The configuration of the adsorbed particles was analyzed to quantify the chemical potential near the surface, which was found to be a function of the distance from the surface and the fractional surface coverage. The near-surface chemical potential was used to derive a continuum model of adsorption that incorporates the results from the Brownian dynamics simulations. The equations of the continuum model were discretized and coupled to a CFD simulation of diffusive transport to the surface. The kinetics of adsorption predicted by the continuum model closely matched the results from the Brownian dynamics simulation. This new model allows the results from mesoscale simulations to be incorporated into micro- or macro-scale CFD transport simulations of protein adsorption in practical devices. PMID:23729843

Modeling growth kinetics of thin films made by atomic layer deposition in lateral high-aspect-ratio structures

NASA Astrophysics Data System (ADS)

Ylilammi, Markku; Ylivaara, Oili M. E.; Puurunen, Riikka L.

2018-05-01

The conformality of thin films grown by atomic layer deposition (ALD) is studied using all-silicon test structures with long narrow lateral channels. A diffusion model, developed in this work, is used for studying the propagation of ALD growth in narrow channels. The diffusion model takes into account the gas transportation at low pressures, the dynamic Langmuir adsorption model for the film growth and the effect of channel narrowing due to film growth. The film growth is calculated by solving the diffusion equation with surface reactions. An efficient analytic approximate solution of the diffusion equation is developed for fitting the model to the measured thickness profile. The fitting gives the equilibrium constant of adsorption and the sticking coefficient. This model and Gordon's plug flow model are compared. The simulations predict the experimental measurement results quite well for Al2O3 and TiO2 ALD processes.

CO2 Fluxes Monitoring at the Level of Field Agroecosystem in Moscow Region of Russia

NASA Astrophysics Data System (ADS)

Meshalkina, Joulia; Mazirov, Ilya; Samardzic, Miljan; Yaroslavtsev, Alexis; Valentini, Riccardo; Vasenev, Ivan

2014-05-01

The Central Russia is still one of the less GHG-investigated European areas especially in case of agroecosystem-level carbon dioxide fluxes monitoring by eddy covariance method. The eddy covariance technique is a statistical method to measure and calculate vertical turbulent fluxes within atmospheric boundary layers. The major assumption of the metod is that measurements at a point can represent an entire upwind area. Eddy covariance researches, which could be considered as repeated for the same area, are very rare. The research has been carried out on the Precision Farming Experimental Field of the Russian Timiryazev State Agricultural University (Moscow, Russia) in 2013 under the support of RF Government grant No. 11.G34.31.0079. Arable derno-podzoluvisls have around 1 The results have shown high daily and seasonal dynamic of agroecosystem CO2 emission. Sowing activates soil microbiological activity and the average soil CO2 emission and adsorption are rising at the same time. CO2 streams are intensified after crop emerging from values of 3 to 7 μmol/s-m2 for emission, and from values of 5 to 20 μmol/s-m2 for adsorption. Stabilization of the flow has come at achieving plants height of 10-12 cm. The vegetation period is characterized by high average soil CO2 emission and adsorption at the same time, but the adsorption is significantly higher. The resulted CO2 absorption during the day is approximately 2-5 times higher than emissions at night. For example, in mid-June, the absorption value was about 0.45 mol/m2 during the day-time, and the emission value was about 0.1 mol/m2 at night. After harvesting CO2 emission is becoming essentially higher than adsorption. Autumn and winter data are fluctuate around zero, but for some periods a small predominance of CO2 emissions over the absorption may be observed. The daily dynamics of CO2 emissions depends on the air temperature with the correlation coefficient changes between 0.4 and 0.8. Crop stage, agrotechnological operation and soil moisture has stronger influence on the seasonal dynamics of soil and agroecosystem CO2 emissions. Obtained unique for Russian agriculture data are very useful for land-use practices environmental assessment, for soil organic carbon dynamics analysis and agroecological evaluation, and for food C-footprint calculation. Their system analysis together with the nearest forest eddy covariance stations helps us to understand better the land-use change impact on the GHG fluxes dynamics and ecosystem services.

Malachite Green Adsorption by Spent Coffee Grounds

NASA Astrophysics Data System (ADS)

Syamimie Atirah Mat, Siti; Zati Hanani Syed Zuber, Sharifah; Rahim, Siti Kartini Enche Ab; Sohaimi, Khairunissa Syairah Ahmad; Halim, Noor Amirah Abdul; Fauziah Zainudin, Nor; Aida Yusoff, Nor; Munirah Rohaizad, Nor; Hidayah Ishak, Noor; Anuar, Adilah; Sarip, Mohd Sharizan Md

2018-03-01

In this work, the ability of spent coffee grounds (SCG) as a low-cost adsorbent to remove malachite green (MG) from aqueous solutions was studied. Batch adsorption tests were carried out to observe the effect of various experimental parameters such as contact time, initial concentration of malachite green and adsorbent dosage on the removal of dye. The results obtained show that the percentage of dye removal will decreased with the increased of initial concentration of dye in the range of 50 mg/L to 250 mg/L. Besides, percentage removal of dye was also found to be increased as the contact time increased until it reached equilibrium condition. The results also showed that the adsorbent dosage in range of 0.2 g to 1.0 g is proportional to the percentage removal of malachite green dye. Study on the kinetic adsorption and isotherm adsorption has also been investigated. The adsorption isotherm data were described by Langmuir isotherm with high-correlation coefficients while the experimental data showed the pseudo-second-order kinetics model was the best model for the adsorption of MG by SCG with the coefficients of correlation R2 > 0.9978.

Effect of the porous structure of activated carbon on the adsorption kinetics of gold(I) cyanide complex

NASA Astrophysics Data System (ADS)

Ibragimova, P. I.; Grebennikov, S. F.; Gur'yanov, V. V.; Fedyukevich, V. A.; Vorob'ev-Desyatovskii, N. V.

2014-06-01

The effect the porous structure of activated carbons obtained from furfural and coconut shells has on the kinetics of [Au(CN)2]- ion adsorption is studied. Effective diffusion coefficients for [Au(CN)2]- anions in transport and adsorbing pores and mass transfer coefficients in a transport system of the pores and in microporous zones are calculated using the statistical moments of the kinetic curve.

Adsorption of organophosphorus pesticides in tropical soils: The case of karst landscape of northwestern Yucatan.

PubMed

Alfonso, Lorenzo-Flores; Germán, Giácoman Vallejos; María Del Carmen, Ponce Caballero; Hossein, Ghoveisi

2017-01-01

This article discusses the adsorption of four organophosphorus pesticides-diazinon, dimethoate, methyl parathion, and sulfotep-in soil samples from four sites-Komchén, Xcanatún, Chablekal and Mocochá- in the northwest of Yucatan, Mexico. These pesticides have been detected in groundwater at concentrations greater than 5 (μg/L) during recent monitoring campaigns in the study area. In this region, groundwater contamination is exacerbated by its karst aquifer, which is susceptible to contamination and is considered very vulnerable. The experimental work was carried out using the batch equilibrium technique. Pesticide analyses by solid-phase extraction and gas chromatography were performed. The equilibrium adsorption data were analyzed by Henry, Langmuir and Freundlich models. The results indicate that the Freundlich model provides the best correlation of the experimental data. Freundlich adsorption coefficients K f were in the range of 1.62-2.35 for sulfotep, 2.43 to 3.25 for dimethoate, from 5.54 to 9.27 for methyl parathion, and 3.22 to 5.17 for diazinon. Freundlich adsorption coefficients were normalized to the content of organic carbon in the soil to estimate the sorption coefficient of organic carbon (K OC ). K OC values were in the range of 9.45-71.80, indicated that four pesticides have low adsorption on the four studied soils, which represents a high risk of contamination to the aquifer. Copyright © 2016 Elsevier Ltd. All rights reserved.

Characterization of adsorption and degradation of diuron in carbonatic and noncarbonatic soils.

PubMed

Kasozi, Gabriel N; Nkedi-Kizza, Peter; Agyin-Birikorang, Sampson; Zimmerman, Andrew R

2010-01-27

The adsorption and degradation of the pesticide diuron in carbonatic and noncarbonatic soils were investigated to better understand the fate and transport of diuron in the environment. Batch adsorption experiments yielded isotherms that were well-described by the linear model. Adsorption coefficients normalized to soil organic carbon content (K(oc)) were lowest for carbonatic soils, averaging 259 +/- 48 (95% CI), 558 +/- 109, 973 +/- 156, and 2090 +/- 1054 for carbonatic soils, Histosols, Oxisols, and Spodosols, respectively. In addition, marl-carbonatic soils had much lower K(oc) values (197 +/- 27) than nonmarl-carbonatic soils. Diuron degradation data fit a first-order reaction kinetics model, yielding half-lives in soils ranging from 40 to 267 days. There was no significant difference between the average diuron degradation rate coefficients of each of the soil groups studied. Given the low adsorption capacity of carbonatic soils, it may be advisable to lower herbicide application rates in agricultural regions with carbonatic soils such as southern Florida to protect aquatic ecosystems and water quality.

Adsorption coefficients for TNT on soil and clay minerals

NASA Astrophysics Data System (ADS)

Rivera, Rosángela; Pabón, Julissa; Pérez, Omarie; Muñoz, Miguel A.; Mina, Nairmen

2007-04-01

To understand the fate and transport mechanisms of TNT from buried landmines is it essential to determine the adsorption process of TNT on soil and clay minerals. In this research, soil samples from horizons Ap and A from Jobos Series at Isabela, Puerto Rico were studied. The clay fractions were separated from the other soil components by centrifugation. Using the hydrometer method the particle size distribution for the soil horizons was obtained. Physical and chemical characterization studies such as cation exchange capacity (CEC), surface area, percent of organic matter and pH were performed for the soil and clay samples. A complete mineralogical characterization of clay fractions using X-ray diffraction analysis reveals the presence of kaolinite, goethite, hematite, gibbsite and quartz. In order to obtain adsorption coefficients (K d values) for the TNT-soil and TNT-clay interactions high performance liquid chromatography (HPLC) was used. The adsorption process for TNT-soil was described by the Langmuir model. A higher adsorption was observed in the Ap horizon. The Freundlich model described the adsorption process for TNT-clay interactions. The affinity and relative adsorption capacity of the clay for TNT were higher in the A horizon. These results suggest that adsorption by soil organic matter predominates over adsorption on clay minerals when significant soil organic matter content is present. It was found that, properties like cation exchange capacity and surface area are important factors in the adsorption of clayey soils.

Adsorption of n-butane on graphene/Ru(0001)—A molecular beam scattering study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sivapragasam, Nilushni; Nayakasinghe, Mindika T.; Burghaus, Uwe, E-mail: uwe.burghaus@ndsu.edu

2016-07-15

Adsorption kinetics/dynamics of n-butane on graphene, physical vapor deposited on Ru(0001) (hereafter G/Ru), and bare Ru(0001) (hereafter Ru) are discussed. The chemical activity of the supported-graphene as well as the support was probed by thermal desorption spectroscopy (adsorption kinetics). In addition and to the best of our knowledge, for the first time, molecular beam scattering data of larger molecules were collected for graphene (probing the adsorption dynamics). Furthermore, samples were inspected by x-ray photoelectron spectroscopy and Auger electron spectroscopy. At the measuring conditions used here, n-butane adsorption kinetics/dynamics are molecular and nonactivated. Binding energies of butane on Ru and G/Rumore » are indistinguishable within experimental uncertainty. Thus, G/Ru is “kinetically transparent.” Initial adsorption probabilities, S{sub 0}, of n-butane decrease with increasing impact energy (0.76–1.72 eV) and are adsorption temperature independent for both Ru and G/Ru, again consistent with molecular adsorption. Also, S{sub 0} of Ru and G/Ru are indistinguishable within experimental uncertainty. Thus, G/Ru is “dynamically transparent.” Coverage dependent adsorption probabilities indicate precursor effects for graphene/Ru.« less

Selectivity and self-diffusion of CO2 and H2 in a mixture on a graphite surface

PubMed Central

Trinh, Thuat T.; Vlugt, Thijs J. H.; Hägg, May-Britt; Bedeaux, Dick; Kjelstrup, Signe

2013-01-01

We performed classical molecular dynamics (MD) simulations to understand the mechanism of adsorption from a gas mixture of CO2 and H2 (mole fraction of CO2 = 0.30) and diffusion along a graphite surface, with the aim to help enrich industrial off-gases in CO2, separating out H2. The temperature of the system in the simulation covered typical industrial conditions for off-gas treatment (250–550 K). The interaction energy of single molecules CO2 or H2 on graphite surface was calculated with classical force fields (FFs) and with Density Functional Theory (DFT). The results were in good agreement. The binding energy of CO2 on graphite surface is three times larger than that of H2. At lower temperatures, the selectivity of CO2 over H2 is five times larger than at higher temperatures. The position of the dividing surface was used to explain how the adsorption varies with pore size. In the temperature range studied, the self-diffusion coefficient of CO2 is always smaller than of H2. The temperature variation of the selectivities and the self-diffusion coefficient imply that the carbon molecular sieve membrane can be used for gas enrichment of CO2. PMID:24790965

Adsorption and transport of methane in biochars derived from waste wood.

PubMed

Sadasivam, Bala Yamini; Reddy, Krishna R

2015-09-01

Mitigation of landfill gas (LFG) is among the critical aspects considered in the design of a landfill cover in order to prevent atmospheric pollution and control global warming. In general, landfill cover soils can partially remove methane (CH4) through microbial oxidation carried out by methanotrophic bacteria present within them. The oxidizing capacity of these landfill cover soils may be improved by adding organic materials, such as biochar, which increase adsorption and promote subsequent or simultaneous oxidation of CH4. In this study, seven wood-derived biochars and granular activated carbon (GAC) were characterized for their CH4 adsorption capacity by conducting batch and small-scale column studies. The effects of influential factors, such as exposed CH4 concentration, moisture content and temperature on CH4 adsorption onto biochars, were determined. The CH4 transport was modeled using a 1-D advection-dispersion equation that accounted for sorption. The effects of LFG inflow rates and moisture content on the combined adsorption and transport properties of biochars were determined. The maximum CH4 adsorption capacity of GAC (3.21mol/kg) was significantly higher than that of the biochars (0.05-0.9mol/kg). The CH4 gas dispersion coefficients for all of the biochars ranged from 1×10(-3) to 3×10(-3)m(2)s(-1). The presence of moisture significantly suppressed the extent of methane adsorption onto the biochars and caused the methane to break through within shorter periods of time. Overall, certain biochar types have a high potential to enhance CH4 adsorption and transport properties when used as a cover material in landfills. However, field-scale studies need to be conducted in order to evaluate the performance of biochar-based cover system under a more dynamic field condition that captures the effect of seasonal and temporal changes. Copyright © 2015 Elsevier Ltd. All rights reserved.

Adsorption of antibiotics on microplastics.

PubMed

Li, Jia; Zhang, Kaina; Zhang, Hua

2018-06-01

Microplastics and antibiotics are two classes of emerging contaminants with proposed negative impacts to aqueous ecosystems. Adsorption of antibiotics on microplastics may result in their long-range transport and may cause compound combination effects. In this study, we investigated the adsorption of 5 antibiotics [sulfadiazine (SDZ), amoxicillin (AMX), tetracycline (TC), ciprofloxacin (CIP), and trimethoprim (TMP)] on 5 types of microplastics [polyethylene (PE), polystyrene (PS), polypropylene (PP), polyamide (PA), and polyvinyl chloride (PVC)] in the freshwater and seawater systems. Scanning Electron Microscope (SEM) and X-ray diffractometer (XRD) analysis revealed that microplastics have different surface characterizes and various degrees of crystalline. Adsorption isotherms demonstrated that PA had the strongest adsorption capacity for antibiotics with distribution coefficient (K d ) values ranged from 7.36 ± 0.257 to 756 ± 48.0 L kg -1 in the freshwater system, which can be attributed to its porous structure and hydrogen bonding. Relatively low adsorption capacity was observed on other four microplastics. The adsorption amounts of 5 antibiotics on PS, PE, PP, and PVC decreased in the order of CIP > AMX > TMP > SDZ > TC with K f correlated positively with octanol-water partition coefficients (Log K ow ). Comparing to freshwater system, adsorption capacity in seawater decreased significantly and no adsorption was observed for CIP and AMX. Our results indicated that commonly observed polyamide particles can serve as a carrier of antibiotics in the aquatic environment. Copyright © 2018 Elsevier Ltd. All rights reserved.

The Interactions Between Three Typical PPCPs and LDH

PubMed Central

Li, Erwei; Liao, Libing; Lv, Guocheng; Li, Zhaohui; Yang, Chengxue; Lu, Yanan

2018-01-01

With a layered structure, layered double hydroxide (LDH) has potential applications in remediation of anionic contaminants, which has been a hot topic for recent years. In this study, a Cl type Mg-Al hydrotalcite (Cl-LDH) was prepared by a co-precipitation method. The adsorption process of three pharmaceuticals and personal care products (PPCPs) [tetracycline (TC), diclofenac sodium (DF), chloramphenicol (CAP)] by Cl-LDH was investigated by X-ray diffraction (XRD), Zeta potential, dynamic light scattering (DLS), BET, Fourier transform infrared (FTIR) spectroscopy, and molecular dynamics simulation. The results showed that the adsorption equilibrium of TC and DF could be reached in 120 min, and the maximum adsorption capacity of the TC and DF were 1.85 and 0.95 mmol/g, respectively. The isothermal adsorption model of TC was fitted with the Freundlich adsorption model, and the isothermal adsorption model of DF was fitted with the Langmuir adsorption model. The adsorption dynamics of TC and DF followed the pseudo-second-order model. The adsorption mechanisms of the three PPCPs into Cl-LDH were different based on the experimental results and molecular dynamics simulation. The TC adsorption on Cl-LDH was accompanied by the electrostatic interactions between the negative charge of TC and the positive charge of Cl-LDH. The uptake of DF was attributed to anion exchange and electrostatic interaction. Cl-LDH does not adsorb CAP due to no electrostatic interaction. The molecular dynamic simulation further confirmed different configurations of three selected PPCPs, which were ultimately responsible for the uptake of PPCPs on Cl-LDH. PMID:29556493

Competitive adsorption of heavy metals onto sesame straw biochar in aqueous solutions.

PubMed

Park, Jong-Hwan; Ok, Yong Sik; Kim, Seong-Heon; Cho, Ju-Sik; Heo, Jong-Soo; Delaune, Ronald D; Seo, Dong-Cheol

2016-01-01

Objective of this research was to evaluate adsorption of heavy metals in mono and multimetal forms onto sesame straw biochar (SSB). Competitive sorption of metals by SSB has never been reported previously. The maximum adsorption capacities (mgg(-1)) of metals by SSB were in the order of Pb (102)≫Cd (86)≫Cr (65)>Cu (55)≫Zn (34) in the monometal adsorption isotherm and Pb (88)≫Cu (40)≫Cr (21)>Zn (7)⩾Cd (5) in the multimetal adsorption isotherm. Based on data obtained from the distribution coefficients, Freundlich and Langmuir adsorption models, and three-dimensional simulation, multimetal adsorption behaviors differed from monometal adsorption due to competition. Especially, during multimetal adsorption, Cd was easily exchanged and substituted by other metals. Further competitive adsorption studies are necessary in order to accurately estimate the heavy metal adsorption capacity of biochar in natural environments. Copyright © 2015 Elsevier Ltd. All rights reserved.

Certification of the European Reference Soil Set (IRMM-443--EUROSOILS). Part II. Soil-pH in suspensions of water and CaCl2.

PubMed

Gawlik, B M; Lamberty, A; Pauwels, J; Blum, W E H; Mentler, A; Bussian, B; Eklo, O; Fox, K; Kördel, W; Hennecke, D; Maurer, T; Perrin-Ganier, C; Romero-Taboada, E; Szabo, G; Muntau, H

2003-08-01

IRMM-443 re-groups a set of six European Reference Soils (EUROSOILS), which had been certified for their adsorption coefficients for atrazine, 2,4-D and lindane (Certification of the European Reference Soil Set (IRMM-443-EUROSOILS)-Part I. Adsorption coefficients for atrazine, 2,4-D and lindane. Sci Total Environ, in press). The certification of these parameters was complemented by an additional certification of pH in suspension as well by the determination of indicative values for total nitrogen, organic and total carbon content. While Part I explained the principles of the value assignment process and discussed their application to the adsorption coefficients, Part II presents the certified values for pH as well as the indicative values for N(tot), C(tot) and C(org). In addition, the assessment of uncertainty components for stability and homogeneity, which have been included in the final uncertainty budget, is discussed.

A novel method for the determination of adsorption partition coefficients of minor gases in a shale sample by headspace gas chromatography.

PubMed

Zhang, Chun-Yun; Hu, Hui-Chao; Chai, Xin-Sheng; Pan, Lei; Xiao, Xian-Ming

2013-10-04

A novel method has been developed for the determination of adsorption partition coefficient (Kd) of minor gases in shale. The method uses samples of two different sizes (masses) of the same material, from which the partition coefficient of the gas can be determined from two independent headspace gas chromatographic (HS-GC) measurements. The equilibrium for the model gas (ethane) was achieved in 5h at 120°C. The method also involves establishing an equation based on the Kd at higher equilibrium temperature, from which the Kd at lower temperature can be calculated. Although the HS-GC method requires some time and effort, it is simpler and quicker than the isothermal adsorption method that is in widespread use today. As a result, the method is simple and practical and can be a valuable tool for shale gas-related research and applications. Copyright © 2013 Elsevier B.V. All rights reserved.

Computer simulations of adsorption and diffusion for binary mixtures of methane and hydrogen in titanosilicates.

PubMed

Mitchell, Martha C; Gallo, Marco; Nenoff, Tina M

2004-07-22

Equilibrium molecular dynamics (MD) simulations of equimolar mixtures of hydrogen and methane were performed in three different titanosilicates: naturally occurring zorite and two synthetic titanosilicates, ETS-4 and ETS-10. In addition, single-component MD simulations and adsorption isotherms generated using grand canonical Monte Carlo simulations were performed to support the mixture simulations. The goal of this study was to determine the best membrane material to carry out hydrogen/methane separations. ETS-10 has a three-dimensional pore network. ETS-4 and zorite have two-dimensional pore networks. The simulations carried out in this study show that the increased porosity of ETS-10 results in self-diffusion coefficients for both hydrogen and methane that are higher in ETS-10 than in either ETS-4 or zorite. Methane only showed appreciable displacement in ETS-10. The ability of the methane molecules to move in all three directions in ETS-10 was demonstrated by the high degree of isotropy shown in the values of the x, y, and z components of the self-diffusion coefficient for methane in ETS-10. From our simulations we conclude that ETS-10 would be better suited for fast industrial separations of hydrogen and methane. However, the separation would not result in a pure hydrogen stream. In contrast, ETS-4 and zorite would act as true molecular sieves for separations of hydrogen and methane, as the methane would not move through membranes made of these materials. This was indicated by the near-zero self-diffusion coefficient of methane in ETS-4 and zorite.

Computer simulations of adsorption and diffusion for binary mixtures of methane and hydrogen in titanosilicates

NASA Astrophysics Data System (ADS)

Mitchell, Martha C.; Gallo, Marco; Nenoff, Tina M.

2004-07-01

Equilibrium molecular dynamics (MD) simulations of equimolar mixtures of hydrogen and methane were performed in three different titanosilicates: naturally occurring zorite and two synthetic titanosilicates, ETS-4 and ETS-10. In addition, single-component MD simulations and adsorption isotherms generated using grand canonical Monte Carlo simulations were performed to support the mixture simulations. The goal of this study was to determine the best membrane material to carry out hydrogen/methane separations. ETS-10 has a three-dimensional pore network. ETS-4 and zorite have two-dimensional pore networks. The simulations carried out in this study show that the increased porosity of ETS-10 results in self-diffusion coefficients for both hydrogen and methane that are higher in ETS-10 than in either ETS-4 or zorite. Methane only showed appreciable displacement in ETS-10. The ability of the methane molecules to move in all three directions in ETS-10 was demonstrated by the high degree of isotropy shown in the values of the x, y, and z components of the self-diffusion coefficient for methane in ETS-10. From our simulations we conclude that ETS-10 would be better suited for fast industrial separations of hydrogen and methane. However, the separation would not result in a pure hydrogen stream. In contrast, ETS-4 and zorite would act as true molecular sieves for separations of hydrogen and methane, as the methane would not move through membranes made of these materials. This was indicated by the near-zero self-diffusion coefficient of methane in ETS-4 and zorite.

Molecular dynamic simulations of selective self-diffusion of CH4/CO2/H2O/N2 in coal

NASA Astrophysics Data System (ADS)

Song, Y.; Jiang, B.; Li, F. L.

2017-06-01

The self-diffusion coefficients (D) of CH4/CO2/H2O/N2 at a relatively broad range of temperatures(298.15∼ 458.15K)and pressures (1∼6MPa) under the NPT, NPH, NVE, and NVT ensembles were obtained after the calculations of molecular mechanics(MM), annealing kinetics(AK), giant canonical Monte Carlo(GCMC), and molecular dynamics (MD) based on Wiser bituminous coal model (WM). The Ds of the adsorbates at the saturated adsorption configurations are D CH4418K. The average swelling ratios manifest as H2O (14.7∼35.18%)>CO2 (13.38∼32.25%)>CH4 (15.35∼23.71%)> N2 (11.47∼22.14%) (NPH, 1∼6MPa). There exits differences in D, swelling ratios and E among various ensembles, indicating that the selection of ensembles has an important influence on the MD calculations for self-diffusion coefficients.

The interactions between three typical PPCPs and LDH

NASA Astrophysics Data System (ADS)

Li, Erwei; Liao, Libing; Lv, Guocheng; Li, Zhaohui; Yang, Chengxue; Lu, Yanan

2018-03-01

With a positively charged layered structure, layered double hydroxide has potential applications in remediation of anionic contaminants, which has been a hot topic for recent years. In this study, a Cl type Mg-Al hydrotalcite (Cl-LDH) was prepared by a co-precipitation method. The adsorption process of three pharmaceuticals and personal care products (PPCPs) (tetracycline (TC), diclofenac sodium (DF), chloramphenicol (CAP)) by Cl-LDH was investigated by X-ray diffraction (XRD), Zeta potential, dynamic light scattering (DLS), BET, FT-IR spectroscopy and molecular dynamics simulation. The results showed that the adsorption equilibrium of TC and DF could be reached in 120 min, and the maximum adsorption capacity of the Cl-LDH for TC and DF were 1.85 mmol/g and 0.95 mmol/g, respectively. The adsorption isothermal of TC was fitted with the Freundlich adsorption model, and the adsorption isothermal of DF was fitted with the Langmuir adsorption model. The adsorption dynamics of TC and DF followed the pseudo-second-order model. The adsorption mechanisms of the three PPCPs onto Cl-LDH were different based on the experimental results and molecular dynamics simulation. The TC adsorption on Cl-LDH was mainly driven by the electrostatic interactions between the negative charge of TC and the positive charge of Cl-LDH. The uptake of anionic DF was attributed both to ion exchange of DF for Cl- and the electrostatic interaction between the negatively charged DF and the positively charged structure layer of Cl-LDH. Cl-LDH does not adsorb the neutral CAP due to no electrostatic interaction. The molecular dynamic simulation further confirmed different configurations of the three selected PPCPs in the interlayer of Cl-LDH, which were responsible for the different uptake process of PPCPs on Cl-LDH.

Chitosan/nanohydroxyapatite composite based scallop shells as an efficient adsorbent for mercuric ions: Static and dynamic adsorption studies.

PubMed

Hassan, Asaad F; Hrdina, Radim

2018-04-01

Chitosan/nanohydroxyapatite composites based on scallop shells (CP12, CP14 and CP21) were prepared with different chitosan: nanohydroxyapatite ratios (1:2, 1:4 and 2:1, respectively). Nanohydroxyapatite (P), chitosan(C) and their composites were characterized by means of TGA, XRD, N 2 adsorption/desorption analysis, SEM, Zeta potential and FTIR. The BET surface area ranged between 189 and 512 m 2 /g. Static adsorption of Hg +2 was tested for the effect of adsorbent dosage, pH, time and initial Hg +2 concentrations indicating that maximum static adsorption capacity was confirmed by CP12 (111.6 mg/g). Static adsorption well fitted with Langmuir adsorption isotherm and Pseudo-second order kinetic models. CP12 was selected for dynamic adsorption of Hg +2 considering the effect of bed height, flow rate and the effect of Hg +2 concentrations. Maximum dynamic adsorption capacity was confirmed at bed height of 3 cm, 2.0 mL/min flow rate and 300 mg/L as Hg +2 concentration with breakthrough time (t b ) and exhaustion time (t e ) of 9 and 21 h. Yoon-Nelson and Thomas models best described the experimental Hg +2 breakthrough curve model. After static adsorption, EDTA solution confirmed the maximum desorption efficiency. The validity of CP12 was tested through three cycles of column dynamic adsorption-desorption. Copyright © 2017 Elsevier B.V. All rights reserved.

Fixed-bed column studies of total organic carbon removal from industrial wastewater by use of diatomite decorated with polyethylenimine-functionalized pyroxene nanoparticles.

PubMed

Hethnawi, Afif; Manasrah, Abdallah D; Vitale, Gerardo; Nassar, Nashaat N

2018-03-01

In this study, a fixed-bed column adsorption process was employed to remove organic pollutants from a real industrial wastewater effluent using polyethylenimine-functionalized pyroxene nanoparticles (PEI-PY) embedded into Diatomite at very low mass percentage. Various dynamic parameters (e.g., inlet concentration, inlet flow rate, bed height, and PEI-nanoparticle concentration in Diatomite, (%nps)) were investigated to determine the breakthrough behavior. The obtained breakthrough curves were fit with a convection-dispersion model to determine the characteristic parameters based on mass transfer phenomena. The axial dispersion coefficient (D L ) and group of dimensionless numbers; including Renold number (Re), Schmidt number (Sc), and Sherwood number (Sh) were all determined and correlated by Wilson-Geankoplis correlation that was used to estimate the external film diffusion coefficients (Kc) at 0.0015 < Re<55. Copyright © 2017 Elsevier Inc. All rights reserved.

Degree of time dependency of kinetic coefficient as a function of adsorbate concentration; new insights from adsorption of tetracycline onto monodispersed starch-stabilized magnetic nanocomposite.

PubMed

Okoli, Chukwunonso P; Ofomaja, Augustine E

2018-07-15

The realization that the observed kinetic coefficient (k obs ) varies with time in most real-time adsorption system, as against the constant value conceived in the most widely-applied adsorption kinetic models, have attracted much attention in recent time. Understanding the factors that control the extent/degree of time dependency (otherwise known as fractal-like kinetics), is therefore central in taking manipulative advantage of this phenomenon in critical adsorption applications. This study therefore deployed non-fractal-like and fractal-like kinetic approach to study the adsorption of tetracycline on monodispersed starch-stabilized magnetite nanocomposite (MSM). MSM was synthesized by in-situ coprecipitation of magnetite in the presence of starch, and successfully characterized with classical solid-state techniques. Isotherm studies indicated that MSM has heterogenous surface adsorption sites. Equilibrium and kinetic data indicated the existence of π-cation interaction as the underlying mechanism, while pH study revealed that tetracycline was adsorbed in its zwitterion form. Though the non-fractal kinetic models exhibited some level of relevance in explaining the tetracycline adsorption interactions, the best fitting of the fractal-like pseudo second order model to the adsorption kinetic data, indicated that the real-time adsorption kinetics occurred in fractal-like manner. The study also revealed that the degree of time dependency of k obs had negative correlation with the initial tetracycline concentration. Apart from developing a low-cost strategy for addressing tetracycline water pollution, the result of this study serves a positive step towards gaining manipulative control of adsorption mechanism in potential application of MSM for targeted drug delivery and controlled release of tetracycline antibiotics. Copyright © 2018 Elsevier Ltd. All rights reserved.

Competitive adsorption of ibuprofen and amoxicillin mixtures from aqueous solution on activated carbons.

PubMed

Mansouri, Hayet; Carmona, Rocio J; Gomis-Berenguer, Alicia; Souissi-Najar, Souad; Ouederni, Abdelmottaleb; Ania, Conchi O

2015-07-01

This work investigates the competitive adsorption under dynamic and equilibrium conditions of ibuprofen (IBU) and amoxicillin (AMX), two widely consumed pharmaceuticals, on nanoporous carbons of different characteristics. Batch adsorption experiments of pure components in water and their binary mixtures were carried out to measure both adsorption equilibrium and kinetics, and dynamic tests were performed to validate the simultaneous removal of the mixtures in breakthrough experiments. The equilibrium adsorption capacities evaluated from pure component solutions were higher than those measured in dynamic conditions, and were found to depend on the porous features of the adsorbent and the nature of the specific/dispersive interactions that are controlled by the solution pH, density of surface change on the carbon and ionization of the pollutant. A marked roll-up effect was observed for AMX retention on the hydrophobic carbons, not seen for the functionalized adsorbent likely due to the lower affinity of amoxicillin towards the carbon adsorbent. Dynamic adsorption of binary mixtures from wastewater of high salinity and alkalinity showed a slight increase in IBU uptake and a reduced adsorption of AMX, demonstrating the feasibility of the simultaneous removal of both compounds from complex water matrices. Copyright © 2014 Elsevier Inc. All rights reserved.

Adsorption/Desorption Transition of Recombinant Human Neurotrophin 4: Physicochemical Characterization.

PubMed

Dąbkowska, Maria; Adamczak, Małgorzata; Barbasz, Jakub; Cieśla, Michał; Machaliński, Bogusław

2017-09-26

Bulk physicochemical properties of neurotrophin 4 (NT-4) in electrolyte solutions and its adsorption/desorption on/from mica surfaces have been studied using dynamic light scattering (DLS), microelectrophoresis, a solution depletion technique (enzyme-linked immunosorbent assay, ELISA), and AFM imaging. Our study presents a determination of the diffusion coefficient, hydrodynamic diameters, electrophoretic mobility, and isoelectric point of the NT-4 under various ionic strength and pH conditions. The size of the NT-4 homodimer for an ionic strength of 0.015 M was substantially independent of pH and equal to 5.1 nm. It has been found that the number of electrokinetic charges per NT-4 molecule was equal to zero for all studied ionic strengths at pH 8.1, which was identified as the isoelectric point (iep). The protein adsorption/desorption on/from mica surfaces was examined as a function of ionic strength and pH. The kinetics of neurotrophin adsorption/desorption were evaluated at pH 3.5, 7.4, and 11 by direct AFM imaging and the ELISA technique. A monotonic increase in the maximum coverage of adsorbed NT-4 molecules with ionic strength (up to 5.5 mg/m 2 ) was observed at pH 3.5. These results were interpreted in terms of the theoretical model postulating an irreversible adsorption of the protein governed by the random sequential adsorption (RSA). Our measurements revealed a significant role of ionic strength, pH, and electrolyte composition in the lateral electrostatic interactions among differently charged NT-4 molecules. The transition between adsorption/desorption processes is found for the region of high pH and low surface concentration of adsorbed neurotrophin molecules at constant ionic strength. Additionally, results presented in this work show that the adsorption behavior of neurotrophin molecules may be governed by intrasolvent electrostatic interactions yielding an aggregation process. Understanding polyvalent neurotrophin interactions may have an impact on the reversibility/irreversibility of adsorption, and hence they might be useful for obtaining well-ordered protein layers, targeting the future development of drug delivery systems for treating neurodegenerative diseases.

Helium Adsorption on Carbon Nanotube Bundles with Different Diameters:. Molecular Dynamics Simulation

NASA Astrophysics Data System (ADS)

Majidi, R.; Karami, A. R.

2013-05-01

We have used molecular dynamics simulation to study helium adsorption capacity of carbon nanotube bundles with different diameters. Homogeneous carbon nanotube bundles of (8,8), (9,9), (10,10), (11,11), and (12,12) single walled carbon nanotubes have been considered. The results indicate that the exohedral adsorption coverage does not depend on the diameter of carbon nanotubes, while the endohedral adsorption coverage is increased by increasing the diameter.

Sorption of polycyclic aromatic hydrocarbons to polystyrene nanoplastic.

PubMed

Liu, Lijing; Fokkink, Remco; Koelmans, Albert A

2016-07-01

Microplastic has become an emerging contaminant of global concern. Bulk plastic can degrade to form smaller particles down to the nanoscale (<100 nm), which are referred to as nanoplastics. Because of their high surface area, nanoplastic may bind hydrophobic chemicals very effectively, increasing their hazard when such nanoplastics are taken up by biota. The present study reports distribution coefficients for sorption of polycyclic aromatic hydrocarbons (PAHs) to 70 nm polystyrene in freshwater, and PAH adsorption isotherms spanning environmentally realistic aqueous concentrations of 10(-5)  μg/L to 1 μg/L. Nanopolystyrene aggregate state was assessed using dynamic light scattering. The adsorption isotherms were nonlinear, and the distribution coefficients at the lower ends of the isotherms were very high, with values up to 10(9) L/kg. The high and nonlinear sorption was explained from π-π interactions between the planar PAHs and the surface of the aromatic polymer polystyrene and was higher than for micrometer-sized polystyrene. Reduction of nanopolystyrene aggregate sizes had no significant effect on sorption, which suggests that the PAHs could reach the sorption sites on the pristine nanoparticles regardless of the aggregation state. Pre-extraction of the nanopolystyrene with C18 polydimethylsiloxane decreased sorption of PAHs, which could be explained by removal of the most hydrophobic fraction of the nanopolystyrene. Environ Toxicol Chem 2016;35:1650-1655. © 2015 SETAC. © 2015 SETAC.

Adsorption of basic dyes on granular activated carbon and natural zeolite.

PubMed

Meshko, V; Markovska, L; Mincheva, M; Rodrigues, A E

2001-10-01

The adsorption of basic dyes from aqueous solution onto granular activated carbon and natural zeolite has been studied using an agitated batch adsorber. The influence of agitation, initial dye concentration and adsorbent mass has been studied. The parameters of Langmuir and Freundlich adsorption isotherms have been determined using the adsorption data. Homogeneous diffusion model (solid diffusion) combined with external mass transfer resistance is proposed for the kinetic investigation. The dependence of solid diffusion coefficient on initial concentration and mass adsorbent is represented by the simple empirical equations.

Carbon Dioxide Adsorption on a 5A Zeolite Designed for CO2 Removal in Spacecraft Cabins

NASA Technical Reports Server (NTRS)

Mulloth, Lila M.; Finn, John E.

1998-01-01

Carbon dioxide adsorption data were obtained for a 5A zeolite manufactured by AlliedSignal Inc. (Des Plaines, Illinois). The material is planned for use in the Carbon Dioxide Removal Assembly (CDRA) for U.S. elements of the International Space Station. The family of adsorption isotherms covers a temperature range of O to 250 C, and a pressure range of 0.001 to 800 torr. Coefficients of the Toth equation are fit to the data. Isosteric heats of adsorption are derived from the equilibrium loading data.

Irrigation model of bleached Kraft mill wastewater through volcanic soil as a pollutants attenuation process.

PubMed

Navia, R; Inostroza, X; Diez, M C; Lorber, K E

2006-05-01

An irrigation process through volcanic soil columns was evaluated for bleached Kraft mill effluent pollutants retention. The system was designed to remove color and phenolic compounds and a simple kinetic model for determining the global mass transfer coefficient and the adsorption rate constant was used. The results clearly indicate that the global mass transfer coefficient values (K(c)a) and the adsorption rate constants are higher for the irrigation processes onto acidified soil. This means that the pretreatment of washing the volcanic soil with an acid solution has a positive effect on the adsorption rate for both pollutant groups. The enhanced adsorption capacity is partially explained by the activation of the metal oxides present in the soil matrix during the acid washing process. Increasing the flow rate from 1.5 to 2.5 ml/min yielded higher (K(c)a) values and adsorption rate constants for both pollutant groups. For instance, regarding color adsorption onto acidified soil, there is an increment of 43% in the (K(c)a) value for the experiment with a flow rate of 2.5 ml/min. Increasing the porosity of the column from 0.55 to 0.59, yielded a decrease in the (K(c)a) values for color and phenolic compounds adsorption processes. Onto natural soil for example, these decreases reached 21% and 24%, respectively. Therefore, the (K(c)a) value is dependent on both the liquid-phase velocity (external resistance) and the soil fraction in the column (internal resistance); making forced convection and diffusion to be the main transport mechanisms involved in the adsorption process. Analyzing the adsorption rate constants (K(c)a)/m, phenolic compounds and color adsorption rates onto acidified soil of 2.25 x 10(-6) and 2.62 x 10(-6) l/mg min were achieved for experiment 1. These adsorption rates are comparable with other adsorption systems and adsorbent materials.

PREDICTING THE ADSORPTION CAPACITY OF ACTIVATED CARBON FOR ORGANIC CONTAMINANTS FROM ADSORBENT AND ADSORBATE PROPERTIES

EPA Science Inventory

A quantitative structure-property relationship (QSPR) was developed and combined with the Polanyi-Dubinin-Manes model to predict adsorption isotherms of emerging contaminants on activated carbons with a wide range of physico-chemical properties. Affinity coefficients (β_l

Investigation into adsorption and photocatalytic degradation of gaseous benzene in an annular fluidized bed photocatalytic reactor.

PubMed

Geng, Qijin; Tang, Shankang; Wang, Lintong; Zhang, Yunchen

2015-01-01

The adsorption and photocatalytic degradation of gaseous benzene were investigated considering the operating variables and kinetic mechanism using nano-titania agglomerates in an annular fluidized bed photocatalytic reactor (AFBPR) designed. The special adsorption equilibrium constant, adsorption active sites, and apparent reaction rate coefficient of benzene were determined by linear regression analysis at various gas velocities and relative humidities (RH). Based on a series of photocatalytic degradation kinetic equations, the influences of operating variables on degradation efficiency, apparent reaction rate coefficient and half-life were explored. The findings indicated that the operating variables have obviously influenced the adsorption/photocatalytic degradation and corresponding kinetic parameters. In the photocatalytic degradation process, the relationship between photocatalytic degradation efficiency and RH indicated that water molecules have a dual-function which was related to the structure characteristics of benzene. The optimal operating conditions for photocatalytic degradation of gaseous benzene in AFBPR were determined as the fluidization number at 1.9 and RH required related to benzene concentration. This investigation highlights the importance of controlling RH and benzene concentration in order to obtain the desired synergy effect in photocatalytic degradation processes.

Statistical inference in single molecule measurements of protein adsorption

NASA Astrophysics Data System (ADS)

Armstrong, Megan J.; Tsitkov, Stanislav; Hess, Henry

2018-02-01

Significant effort has been invested into understanding the dynamics of protein adsorption on surfaces, in particular to predict protein behavior at the specialized surfaces of biomedical technologies like hydrogels, nanoparticles, and biosensors. Recently, the application of fluorescent single molecule imaging to this field has permitted the tracking of individual proteins and their stochastic contribution to the aggregate dynamics of adsorption. However, the interpretation of these results is complicated by (1) the finite time available to observe effectively infinite adsorption timescales and (2) the contribution of photobleaching kinetics to adsorption kinetics. Here, we perform a protein adsorption simulation to introduce specific survival analysis methods that overcome the first complication. Additionally, we collect single molecule residence time data from the adsorption of fibrinogen to glass and use survival analysis to distinguish photobleaching kinetics from protein adsorption kinetics.

Predictive beyond-mean-field rate equations for multisite lattice–gas models of catalytic surface reactions: CO oxidation on Pd(100)

DOE PAGES

Liu, Da -Jiang; Zahariev, Federico; Gordon, Mark S.; ...

2016-11-29

Tailored multisite lattice–gas (msLG) models are developed for CO oxidation on Pd(100) at low-pressures. These models include multiple adsorption site types and superlattice adlayer ordering due to short-range exclusion for highly mobile reactant adspecies. However, they are simplified to neglect longer-range weaker adspecies interactions, so that the key energetic parameters are the CO desorption barrier and the reaction barrier. We discuss existing density functional theory results for these energies and present additional analysis for CO adsorption. After also including an appropriate nontrivial specification of the dynamics of adsorption onto mixed reactant adlayers, we develop rate equations for the reaction kinetics.more » Our formulation goes beyond traditional mean-field (MF) Langmuirian treatments by accounting for multiple adsorption sites and for the strong spatial correlations associated with superlattice ordering. Specifically, we utilize factorization approximations based on appropriate site motifs, and also Padé resummation of exact low-coverage expansions for sticking coefficients. Our beyond-MF rate equations are successful in accurately predicting key aspects of reactive steady-state behavior, and thus expand the utility of rate equation formulations in surface chemistry. This is confirmed by comparison with precise kinetic Monte Carlo simulation results. Furthermore, we not only assess bistability and criticality observed for CO oxidation but also find more complex multistability associated with symmetry-breaking transitions in high-coverage CO adlayers.« less

Cs-137 immobilization in C-S-H gel nanopores.

PubMed

Duque-Redondo, Eduardo; Kazuo, Yamada; López-Arbeloa, Iñigo; Manzano, Hegoi

2018-04-04

Cementation is a widespread technique to immobilize nuclear waste due to the low leachability of cementitious materials. The capacity of calcium silicate hydrate (C-S-H), the main component of cement, to retain radionuclide Cs has been empirically studied at the macroscale, yet the specific molecular scale mechanisms that govern the retention have not been determined. In this work, we employed molecular dynamics simulations to investigate the adsorption and diffusivity of Cs into a C-S-H gel nanopore. From the simulations, it was possible to distinguish three types of Cs adsorption configurations on the C-S-H: an inner-sphere surface site where Cs is strongly bound, an outer-sphere surface site where Cs is loosely bound, and Cs free in the nanopore. For each configuration, we determined the sorption energy, and the diffusion coefficients, up to two orders of magnitude lower than in bulk water due to the effect of nanoconfinement in the worst case scenario. It has also proved that Cs cannot displace the intrinsic Ca from the C-S-H surface, and we calculated the binding strength and the residence time of the cations in the surface adsorption sites. Finally, we quantified the average number of adsorption sites per nm2 of the C-S-H surface. All these results are the first insights into Cs retention in cement at the molecular scale and will be useful to build macroscopic diffusion models and devise cement formulations to improve radionuclide Cs retention from spent nuclear fuel.

Effects of sorbents in sorption of agrochemical

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jayasundera, T.; Jayasundera, S.

1996-10-01

Sorption to soil materials is a key process controlling the fate of agrochemicals in the environment. Batch experiments were performed to determine sorption coefficients of metolachlor, alachlor and linuron onto clays, natural organic matter (NOM) coated-clays, and organic sorbents. Our results indicate that the partition coefficient K{sub d} is a function of both sorbent and sorbate properties. The carbon referenced sorption coefficient (K{sub oc}) decreased with increasing polarity of the organic sorbent. Adsorption isotherms onto clays and NOM coated-clays conformed to a Freunlich equation. Studies indicate that at low NOM surface coverage, interactions between NOM and clay surfaces could reducemore » the surface affinity for agrochemical adsorption. Our results suggest that sorption cannot be simply defined as {open_quotes}adsorption{close_quotes} or {open_quotes}partitioning{close_quotes}, but rather there is a continuum of possible interactions. The more polar the solute, the more likely it is that interactions other than hydrophobic will contribute to sorption, causing the currently used K{sub oc}-K{sub ow} correlations to fail.« less

Determination of solid-liquid partition coefficients (Kd) for the herbicides isoproturon and trifluralin in five UK agricultural soils.

PubMed

Cooke, Cindy M; Shaw, George; Collins, Chris D

2004-12-01

Isoproturon and trifluralin are herbicides of contrasting chemical characters and modes of action. Standard batch sorption procedures were carried out to investigate the individual sorption behaviour of 14C-isoproturon and 14C-trifluralin in five agricultural soils (1.8-4.2% OC), and the soil solid-liquid partition coefficients (Kd values) were determined. Trifluralin exhibited strong partitioning to the soil solid phase (Kd range 106-294) and low desorption potential, thus should not pose a threat to sensitive waters via leaching, although particle erosion and preferential flow pathways may facilitate transport. For isoproturon, soil adsorption was low (Kd range 1.96-5.75) and desorption was high, suggesting a high leaching potential, consistent with isoproturon being the most frequently found pesticide in UK surface waters. Soil partitioning was directly related to soil organic carbon (OC) content. Accumulation isotherms were modelled using a dual-phase adsorption model to estimate adsorption and desorption rate coefficients. Associations between herbicides and soil humic substances were also shown using gel filtration chromatography.

Kafirin adsorption on ion-exchange resins: isotherm and kinetic studies.

PubMed

Kumar, Prashant; Lau, Pei Wen; Kale, Sandeep; Johnson, Stuart; Pareek, Vishnu; Utikar, Ranjeet; Lali, Arvind

2014-08-22

Kafirin is a natural, hydrophobic and celiac safe prolamin protein obtained from sorghum seeds. Today kafirin is found to be useful in designing delayed delivery systems and coatings of pharmaceuticals and nutraceuticals where its purity is important and this can be obtained by adsorptive chromatography. This study is the first scientific insight into the isotherm and kinetic studies of kafirin adsorption on anion- and cation-exchange resins for practical applications in preparative scale chromatography. Adsorption isotherms of kafirin were determined for five anion- and two cation-exchange resins in batch systems. Isotherm parameters such as maximum binding capacity and dissociation constant were determined from Langmuir isotherm, and adsorptive capacity and affinity constant from Freundlich isotherm. Langmuir isotherm was found to fit the adsorption equilibrium data well. Batch uptake kinetics for kafirin adsorption on these resins was also carried out and critical parameters including the diffusion coefficient, film mass transfer coefficient, and Biot number for film-pore diffusion model were calculated. Both the isotherm and the kinetic parameters were considered for selection of appropriate resin for kafirin purification. UNOsphere Q (78.26 mg/ml) and Toyopearl SP-650M (57.4 mg/ml) were found to offer better kafirin binding capacities and interaction strength with excellent uptake kinetics under moderate operating conditions. With these adsorbents, film diffusion resistance was found to be major governing factor for adsorption (Bi<10 and δ<1). Based on designer objective function, UNOsphere Q was found be best adsorbent for binding of kafirin. The data presented is valuable for designing large scale preparative adsorptive chromatographic kafirin purification systems. Copyright © 2014 Elsevier B.V. All rights reserved.

Batch soil adsorption and column transport studies of 2,4-dinitroanisole (DNAN) in soils

NASA Astrophysics Data System (ADS)

Arthur, Jennifer D.; Mark, Noah W.; Taylor, Susan; Šimunek, J.; Brusseau, M. L.; Dontsova, Katerina M.

2017-04-01

The explosive 2,4,6-trinitrotoluene (TNT) is currently a main ingredient in munitions; however the compound has failed to meet the new sensitivity requirements. The replacement compound being tested is 2,4-dinitroanisole (DNAN). DNAN is less sensitive to shock, high temperatures, and has good detonation characteristics. However, DNAN is more soluble than TNT, which can influence transport and fate behavior and thus bioavailability and human exposure potential. The objective of this study was to investigate the environmental fate and transport of DNAN in soil, with specific focus on sorption processes. Batch and column experiments were conducted using soils collected from military installations located across the United States. The soils were characterized for pH, electrical conductivity, specific surface area, cation exchange capacity, and organic carbon content. In the batch rate studies, change in DNAN concentration with time was evaluated using the first order equation, while adsorption isotherms were fitted using linear and Freundlich equations. Solution mass-loss rate coefficients ranged between 0.0002 h- 1 and 0.0068 h- 1. DNAN was strongly adsorbed by soils with linear adsorption coefficients ranging between 0.6 and 6.3 L g- 1, and Freundlich coefficients between 1.3 and 34 mg1 - n Ln kg- 1. Both linear and Freundlich adsorption coefficients were positively correlated with the amount of organic carbon and cation exchange capacity of the soil, indicating that similar to TNT, organic matter and clay minerals may influence adsorption of DNAN. The results of the miscible-displacement column experiments confirmed the impact of sorption on retardation of DNAN during transport. It was also shown that under flow conditions DNAN transforms readily with formation of amino transformation products, 2-ANAN and 4-ANAN. The magnitudes of retardation and transformation observed in this study result in significant attenuation potential for DNAN, which would be anticipated to contribute to a reduced risk for contamination of ground water from soil residues.

Batch soil adsorption and column transport studies of 2,4-dinitroanisole (DNAN) in soils.

PubMed

Arthur, Jennifer D; Mark, Noah W; Taylor, Susan; Šimunek, J; Brusseau, M L; Dontsova, Katerina M

2017-04-01

The explosive 2,4,6-trinitrotoluene (TNT) is currently a main ingredient in munitions; however the compound has failed to meet the new sensitivity requirements. The replacement compound being tested is 2,4-dinitroanisole (DNAN). DNAN is less sensitive to shock, high temperatures, and has good detonation characteristics. However, DNAN is more soluble than TNT, which can influence transport and fate behavior and thus bioavailability and human exposure potential. The objective of this study was to investigate the environmental fate and transport of DNAN in soil, with specific focus on sorption processes. Batch and column experiments were conducted using soils collected from military installations located across the United States. The soils were characterized for pH, electrical conductivity, specific surface area, cation exchange capacity, and organic carbon content. In the batch rate studies, change in DNAN concentration with time was evaluated using the first order equation, while adsorption isotherms were fitted using linear and Freundlich equations. Solution mass-loss rate coefficients ranged between 0.0002h -1 and 0.0068h -1 . DNAN was strongly adsorbed by soils with linear adsorption coefficients ranging between 0.6 and 6.3Lg -1 , and Freundlich coefficients between 1.3 and 34mg 1 - n L n kg -1 . Both linear and Freundlich adsorption coefficients were positively correlated with the amount of organic carbon and cation exchange capacity of the soil, indicating that similar to TNT, organic matter and clay minerals may influence adsorption of DNAN. The results of the miscible-displacement column experiments confirmed the impact of sorption on retardation of DNAN during transport. It was also shown that under flow conditions DNAN transforms readily with formation of amino transformation products, 2-ANAN and 4-ANAN. The magnitudes of retardation and transformation observed in this study result in significant attenuation potential for DNAN, which would be anticipated to contribute to a reduced risk for contamination of ground water from soil residues. Copyright © 2017 Elsevier B.V. All rights reserved.

PREDICTING THE ADSORPTION CAPACITY OF ACTIVATED CARBON FOR EMERGING ORGANIC CONTAMINANTS FROM FUNDAMENTAL ADSORBENT AND ADSORBATE PROPERTIES - PRESENTATION

EPA Science Inventory

A quantitative structure-property relationship (QSPR) was developed and combined with the Polanyi-Dubinin-Manes model to predict adsorption isotherms of emerging contaminants on activated carbons with a wide range of physico-chemical properties. Affinity coefficients (β_l

Concurrent Solution and Adsorption of Hydrocarbons in Gas Chromatographic Columns Packed with Different Loadings of 3-Methylsydnone on Chromosorb P

PubMed

Castells; Romero; Nardillo

1997-08-01

Thermodynamic properties of solution in 3-methylsydnone (3MS) and of adsorption at the nitrogen/3MS interface were gas chromatographically measured for a group of fifteen hydrocarbons at infinite dilution conditions. Retention volumes were measured at five temperatures within the range 37-52°C in six columns containing different loadings of 3MS on Chromosorb P AW. Partition and adsorption coefficients were calculated and from their temperature dependence the corresponding enthalpies were obtained, although with considerable error; infinite dilution activity coefficients of the hydrocarbons in the bulk and in the surface phases demonstrated a strong correlation. Bulk activity coefficients in 3MS were very much smaller than those previously measured for the same solutes in formamide (FA) and in ethyleneglycol (EG), and were also smaller than what could be predicted on account of 3MS cohesive energy density as estimated from the quotient sigma/v1/3 (sigma, surface tension; v, molar volume). There was not such a large difference between the surface activity coefficients in the three solvents; furthermore, the quotients (surface activity coefficient/bulk activity coefficient) for a given solute in 3MS were twice as large as in FA and about three times larger than in EG. These results make evident the difficulties inherent in the prediction of surface phase properties from those in the bulk and cast doubts on the pertinency of employing the surface tension to compare cohesive energy densities of polar solvents with important chemical differences.

Electronic theoretical study of the influences of O adsorption on the electronic structure and optical properties of graphene

NASA Astrophysics Data System (ADS)

Shuang, Zhou; Guili, Liu; Dazhi, Fan

2017-02-01

The electronic structure and optical properties of adsorbing O atoms on graphene with different O coverage are researched using the density functional theory based upon the first-principle study to obtain further insight into properties of graphene. The adsorption energies, band structures, the density of states, light absorption coefficient and reflectivity of each system are calculated theoretically after optimizing structures of each system with different O coverage. Our calculations show that adsorption of O atoms on graphene increases the bond length of C-C which adjacent to the O atoms. When the O coverage is 9.4%, the adsorption energy (3.91 eV) is the maximum, which only increases about 1.6% higher than that of 3.1% O coverage. We find that adsorbed O atoms on pristine graphene opens up indirect gap of about 0.493-0.952 eV. Adsorbing O atoms make pristine graphene from metal into a semiconductor. When the O coverage is 9.4%, the band gap (0.952 eV) is the maximum. Comparing with pristine graphene, we find the density of states at Fermi level of O atoms adsorbing on graphene with different coverage are significantly increased. We also find that light absorption coefficient and reflectivity peaks are significantly reduced, and the larger the coverage, the smaller the absorption coefficient and reflectivity peaks are. And the blue shift phenomenon appears.

Synthesis and characterization of Silica/polyvinyl imidazole/H2PO4-core-shell nanoparticles as recyclable adsorbent for efficient scavenging of Sm(III) and Dy(III) from water.

PubMed

Ettehadi Gargari, Jafar; Sid Kalal, Hossein; Shakeri, Alireza; Khanchi, Alireza

2017-11-01

In this study, we used Silica/polyvinyl imidazole core-shell nanoparticles impregnated with sodium dihydrogen phosphate (SiO 2 /PVI/H 2 PO 4 - NPs) for adsorption of samarium and dysprosium ions from aqueous solutions. The effects of the pH, adsorbent dose, contact time, and initial concentration of the adsorbate on the Core-shell nanoparticles adsorption capacity have been studied. The pH value for maximum removal of Sm (III) and Dy (III) on the core-shell nanoparticles surface were found to be 4. The saturated capacity of SiO 2 /PVI/H 2 PO 4 - NPs was up to 160mg.g -1 and 150mg.g -1 at 25°C for Sm (III) and Dy (III) ions respectively. The obtained uptake data were analyzed by the Langmuir and Freundlich equations using a linearized correlation coefficient at room temperature. The Freundlich isotherm was found to fit well with the equilibrium data. The adsorption kinetics could be modeled by a pseudo-second-order rate expression. Thermodynamic investigation revealed the adsorption process of the studied ions is entropy driven. Furthermore, the performance of regeneration and reutilization were studied. The adsorbed Sm (III) and Dy (III) can be desorbed by 0.5mol/L HCl, with the desorption percentage of 90% for Sm (III) and Dy (III). After five adsorption-desorption cycles, the adsorption capacity shows a slight decrease (about 15%), implying that the SiO 2 /PVI/H 2 PO 4 - NPs can be used as an effective adsorbent for the removal and recovery of Sm(III) and Dy(III) from aqueous solution. The colloid stability of the SiO 2 /PVI/H 2 PO 4 - NPs was investigated by dynamic light scattering measurements. The SiO 2 /PVI/H 2 PO 4 - NPs are stable in adsorption media after five adsorption - desorption cycles. The high stability of SiO 2 /PVI/H 2 PO 4 - NPs can be attributed to steric stabilization by polyvinyl imidazole adsorbed on SiO 2 nanoparticle surfaces. Copyright © 2017 Elsevier Inc. All rights reserved.

Predictive Simulation of Gas Adsorption in Fixed-Beds and Limitations due to the Ill-Posed Danckwerts Boundary Condition

NASA Technical Reports Server (NTRS)

Knox, James Clinton

2016-01-01

The 1-D axially dispersed plug flow model is a mathematical model widely used for the simulation of adsorption processes. Lumped mass transfer coefficients such as the Glueckauf linear driving force (LDF) term and the axial dispersion coefficient are generally obtained by fitting simulation results to the experimental breakthrough test data. An approach is introduced where these parameters, along with the only free parameter in the energy balance equations, are individually fit to specific test data that isolates the appropriate physics. It is shown that with this approach this model provides excellent simulation results for the C02 on zeolite SA sorbent/sorbate system; however, for the H20 on zeolite SA system, non-physical deviations from constant pattern behavior occur when fitting dispersive experimental results with a large axial dispersion coefficient. A method has also been developed that determines a priori what values of the LDF and axial dispersion terms will result in non-physical simulation results for a specific sorbent/sorbate system when using the one-dimensional axially dispersed plug flow model. A relationship between the steepness of the adsorption equilibrium isotherm as indicated by the distribution factor, the magnitude of the axial dispersion and mass transfer coefficient, and the resulting non-physical behavior is derived. This relationship is intended to provide a guide for avoiding non-physical behavior by limiting the magnitude of the axial dispersion term on the basis of the mass transfer coefficient and distribution factor.

Adsorption and Retardation of PFASs in Soil

NASA Astrophysics Data System (ADS)

Chen, W.; Yan, N.; Fu, X.; Carroll, K. C.; Holguin, F. O. O.; Brusseau, M. L.

2017-12-01

Per- and poly-fluorinated alkyl substances (PFASs) are emerging contaminants of concern that are present in the subsurface at numerous military and industrial facilities. Knowledge of the retention behavior of these compounds in the subsurface environment is critical for effective risk characterization and remediation. The objective of this research is to investigate the role of adsorption at the air-water interface on PFAS retention in vadose-zone systems. Surface tensions were measured for select PFAS to determine interfacial adsorption coefficients. Column experiments were conducted to characterize retardation and transport under saturated and unsaturated flow conditions. The impact of soil properties and groundwater constituents on surface tension, solid-phase adsorption, and interfacial adsorption was investigated.

Reactive multi-particle collision dynamics with reactive boundary conditions

NASA Astrophysics Data System (ADS)

Sayyidmousavi, Alireza; Rohlf, Katrin

2018-07-01

In the present study, an off-lattice particle-based method called the reactive multi-particle collision (RMPC) dynamics is extended to model reaction-diffusion systems with reactive boundary conditions in which the a priori diffusion coefficient of the particles needs to be maintained throughout the simulation. To this end, the authors have made use of the so-called bath particles whose purpose is only to ensure proper diffusion of the main particles in the system. In order to model partial adsorption by a reactive boundary in the RMPC, the probability of a particle being adsorbed, once it hits the boundary, is calculated by drawing an analogy between the RMPC and Brownian Dynamics. The main advantages of the RMPC compared to other molecular based methods are less computational cost as well as conservation of mass, energy and momentum in the collision and free streaming steps. The proposed approach is tested on three reaction-diffusion systems and very good agreement with the solutions to their corresponding partial differential equations is observed.

Nature of Interactions between PEO-PPO-PEO Triblock Copolymers and Lipid Membranes: (I) The Effect of Polymer Hydrophobicity on Its Ability to Protect Liposomes from Peroxidation

PubMed Central

Wang, Jia-Yu; Marks, Jeremy; Lee, Ka Yee C.

2013-01-01

PEO-PPO-PEO triblock copolymers have opposing effects on lipid membrane integrity- they can behave either as membrane sealants or as membrane permeabilizers. To gain insights into their biomembrane activities, the fundamental interactions between a series of PEO-based polymers and phospholipid vesicles were investigated. Specifically, the effect of copolymer hydrophobicity on its ability to prevent liposomes from peroxidation was evaluated, and partitioning free energy and coefficient involved in the interactions were derived. Our results show that the high degree of hydrophilicity is a key feature of the copolymers that can effectively protect liposomes from peroxidation and the protective effect of the copolymers stems from their adsorption at the membrane surface without penetrating into the bilayer core. The origin of this protective effect induced by polymer absorption is attributed to the retardation of membrane hydration dynamics, which is further illustrated in the accompany study on dynamic nuclear polarization (DNP)-derived hydration dynamics1. PMID:22808900

Characterisation under static and dynamic conditions of commercial activated carbons for their use in wastewater plants

NASA Astrophysics Data System (ADS)

Sabio, E.; Zamora, F.; González, J. F.; García, C. M. González; Román, S.; Al-Kassir, A.

2006-06-01

The use of activated carbon for removing organic contaminants in fixed beds is increasing. This is a dynamic process in which the kinetics plays an important role. The aim of this paper is to get more insight into adsorption of p-nitrophenol (PNP) in activated carbon under equilibrium and dynamic conditions. Five commercial activated carbons were studied. The analysis carried out were PNP adsorption isotherms in aqueous solution at 20 °C, N 2 at 77 K isotherms, FT-IR and PNP adsorption under dynamic conditions. The results indicate that the external porous affinity toward the organic contaminants determines in large extent the adsorbents behaviour under dynamic conditions.

Linearised and non-linearised isotherm models optimization analysis by error functions and statistical means

PubMed Central

2014-01-01

In adsorption study, to describe sorption process and evaluation of best-fitting isotherm model is a key analysis to investigate the theoretical hypothesis. Hence, numerous statistically analysis have been extensively used to estimate validity of the experimental equilibrium adsorption values with the predicted equilibrium values. Several statistical error analysis were carried out. In the present study, the following statistical analysis were carried out to evaluate the adsorption isotherm model fitness, like the Pearson correlation, the coefficient of determination and the Chi-square test, have been used. The ANOVA test was carried out for evaluating significance of various error functions and also coefficient of dispersion were evaluated for linearised and non-linearised models. The adsorption of phenol onto natural soil (Local name Kalathur soil) was carried out, in batch mode at 30 ± 20 C. For estimating the isotherm parameters, to get a holistic view of the analysis the models were compared between linear and non-linear isotherm models. The result reveled that, among above mentioned error functions and statistical functions were designed to determine the best fitting isotherm. PMID:25018878

Heavy metal adsorption changes of EAF steel slag after phosphorus adsorption.

PubMed

Song, Guanling; Cao, Lijing; Chen, Xiao; Hou, Wenhua; Wang, Qunhui

2012-01-01

A kind of electric arc furnace (EAF) steel slag was phosphated, and its isothermal and dynamic adsorptions of copper, cadmium, and lead ions were measured to determine if heavy metal adsorption changes after phosphorus adsorption. The surface area increased greatly after the slag was phosphated. Isothermal adsorption experiments showed that the theoretical Q(max) of the EAF steel slag on Cu(2+), Cd(2+), and Pb(2+) improved 59, 50, and 89% respectively after it was phosphated. Dynamic adsorption results showed that the greatest adsorption capacities of unit volume of Cu(2+), Cd(2+), and Pb(2+) were 2.2, 1.8, and 1.8 times that of the column packed with original EAF steel slag when the column was packed with phosphate EAF steel slag at the same heavy metal ion concentration. The breakthrough time, the exhaustion time and elution efficiency of the column also increased when the column was packed with phosphated EAF steel slag compared with that packed with original EAF steel slag. Phosphorus adsorption could further improve the heavy metal ion adsorption of the EAF steel slag.

[Toluene, Benzene and Acetone Adsorption by Activated Carbon Coated with PDMS].

PubMed

Liu, Han-bing; Jiang, Xin; Wang, Xin; Yang, Bing; Xue, Nan-dong; Zhang, Shi-lei

2016-04-15

To improve the adsorption selectivity of volatile organic compounds ( VOCs) , activated carbon ( AC) was modified by polydimethylsiloxane (PDMS) and characterized by BET analysis and Boehm titration. Dynamic adsorption column experiments were conducted and Yoon-Neslon(Y-N) model was used to identify adsorption effect for toluene, beuzene and acetone on AC when relative humidity was 0%, 50% and 90%, respectively. The results showed that the BET area, micropore volume and surface functional groups decreased with the PDMS modification, and surface hydrophobicity of the modified AC was enhanced leading to a lower water adsorption capacity. The results of dynamic adsorption showed that the adsorption kinetics and capacity of Bare-AC decreased with the increase of relative humidity, and the adsorption capacities of PDMS coated AC were 1.86 times (toluene) and 1.92 times (benzene) higher than those of Bare-AC, while a significant improvement of adsorption capacity for acetone was not observed. These findings suggest that polarity of molecule can be an important influencing factor for adsorption on hydrophobic surface developed by PDMS.

Nylon 6 electrospun nanofibers mat as effective sorbent for the removal of estrogens: kinetic and thermodynamic studies

PubMed Central

2014-01-01

Nylon 6 electrospun nanofibers mat was prepared via electrospinning for the removal of three estrogens, namely, diethylstilbestrol (DES), dienestrol (DS), and hexestrol (HEX) from aqueous solution. Static adsorption as well as the dynamic adsorption was evaluated by means of batch and dynamic disk flow mode, respectively. The kinetic study indicated that the adsorption of the target compounds could be well fitted by the pseudo-second-order equation, suggesting the intra-particle/membrane diffusion process as the rate-limiting step of the adsorption process. The adsorption equilibrium data were all fitted well to the Freundlich isotherm models, with a maximum adsorption capacity values in the range of 97.71 to 208.95 mg/g, which can be compared to or moderately higher than other sorbents published in the literatures. The dynamic disk mode studies indicated that the mean removal yields of three model estrogens were over 95% with a notable smaller amount of adsorbent (4 mg). Thermodynamic study revealed that the adsorption process was exothermic and spontaneous in nature. Desorption results showed that the adsorption capacity can remain up to 80% after seven times usage. It was suggested that Nylon 6 electrospun nanofibers mat has great potential as a novel effective sorbent material for estrogens removal. PMID:25114645

Kinetics of adsorption of dyes from aqueous solution using activated carbon prepared from waste apricot.

PubMed

Onal, Yunus

2006-10-11

Adsorbent (WA11Zn5) has been prepared from waste apricot by chemical activation with ZnCl(2). Pore properties of the activated carbon such as BET surface area, pore volume, pore size distribution, and pore diameter were characterized by N(2) adsorption and DFT plus software. Adsorption of three dyes, namely, Methylene Blue (MB), Malachite Green (MG), Crystal Violet (CV), onto activated carbon in aqueous solution was studied in a batch system with respect to contact time, temperature. The kinetics of adsorption of MB, MG and CV have been discussed using six kinetic models, i.e., the pseudo-first-order model, the pseudo-second-order model, the Elovich equation, the intraparticle diffusion model, the Bangham equation, the modified Freundlich equation. Kinetic parameters and correlation coefficients were determined. It was shown that the second-order kinetic equation could describe the adsorption kinetics for three dyes. The dyes uptake process was found to be controlled by external mass transfer at earlier stages (before 5 min) and by intraparticle diffusion at later stages (after 5 min). Thermodynamic parameters, such as DeltaG, DeltaH and DeltaS, have been calculated by using the thermodynamic equilibrium coefficient obtained at different temperatures and concentrations. The thermodynamics of dyes-WA11Zn5 system indicates endothermic process.

Adsorption of dissolved Reactive red dye from aqueous phase onto activated carbon prepared from agricultural waste.

PubMed

Senthilkumaar, S; Kalaamani, P; Porkodi, K; Varadarajan, P R; Subburaam, C V

2006-09-01

The adsorption of Reactive red dye (RR) onto Coconut tree flower carbon (CFC) and Jute fibre carbon (JFC) from aqueous solution was investigated. Adsorption studies were carried out at different initial dye concentrations, initial solution pH and adsorbent doses. The kinetic studies were also conducted; the adsorption of Reactive red onto CFC and JFC followed pseudosecond-order rate equation. The effective diffusion coefficient was evaluated to establish the film diffusion mechanism. Quantitative removal of Reactive red dye was achieved at strongly acidic conditions for both the carbons studied. The adsorption isotherm data were fitted well to Langmuir isotherm and the adsorption capacity were found to be 181.9 and 200 mg/g for CFC and JFC, respectively. The overall rate of dye adsorption appeared to be controlled by chemisorption, in this case in accordance with poor desorption studies.

Adsorption and leaching behaviour of bispyribac-sodium in soils.

PubMed

Singh, Neera; Singh, S B

2015-01-01

Adsorption-desorption of the herbicide bispyribac-sodium was studied in four Indian soil types. Bispyribac-sodium was poorly adsorbed in the four soils and adsorption decreased with an increase in the herbicide concentration in solution. Freundlich adsorption coefficient (Kf) values for bispyribac-sodium ranged between 0.37 and 0.87. Slope (1/n) values varied from 0.2 to 0.31 suggesting that bispyribac-sodium adsorption was highly dependent on its initial concentration in solution. Bispyribac-sodium adsorption showed a positive correlation with soil pH (r = 0.809) and clay content (r = 0.699) while no correlation was observed with the organic carbon (r = 0.063) content. Sorbed herbicide was completely desorbed during a single desorption step suggesting that the herbicide was bound by weak adsorptive forces. Leaching studies of herbicide in soil 1 packed column indicated complete loss of soil applied herbicide under a simulated rainfall equivalent to 162 mm.

Evaluation of BTEX and phenol removal from aqueous solution by multi-solute adsorption onto smectite organoclay.

PubMed

Carvalho, M N; da Motta, M; Benachour, M; Sales, D C S; Abreu, C A M

2012-11-15

The removal process of BTEX and phenol was evaluated. The smectite organoclay for single-solute system reached removal was evaluated by adsorption on smectite organoclay adsorbent by kinetic and equilibrium efficiencies between 55 and 90% while was reached between 30 and 90% for multi-solute system at 297 K and pH 9. The Langmuir-Freundlich model was used to fit the experimental data with correlation coefficient between 0.98 and 0.99 providing kinetic and equilibrium parameter values. Phenol and ethylbenzene presented high maximum adsorbed amount, 8.28 and 6.67 mg/g, respectively, compared to the other compounds for single-solute. Toluene and p-xylene presented high values of adsorption constant which indicates a high adsorption affinity of compounds to organoclay surface and high binding energy of adsorption. Phenol presented low kinetic adsorption constant value indicating slow rate of adsorption. Copyright © 2012 Elsevier B.V. All rights reserved.

Variable Lysozyme Transport Dynamics on Oxidatively Functionalized Polystyrene Films.

PubMed

Moringo, Nicholas A; Shen, Hao; Tauzin, Lawrence J; Wang, Wenxiao; Bishop, Logan D C; Landes, Christy F

2017-10-17

Tuning protein adsorption dynamics at polymeric interfaces is of great interest to many biomedical and material applications. Functionalization of polymer surfaces is a common method to introduce application-specific surface chemistries to a polymer interface. In this work, single-molecule fluorescence microscopy is utilized to determine the adsorption dynamics of lysozyme, a well-studied antibacterial protein, at the interface of polystyrene oxidized via UV exposure and oxygen plasma and functionalized by ligand grafting to produce varying degrees of surface hydrophilicity, surface roughness, and induced oxygen content. Single-molecule tracking indicates lysozyme loading capacities, and surface mobility at the polymer interface is hindered as a result of all functionalization techniques. Adsorption dynamics of lysozyme depend on the extent and the specificity of the oxygen functionalities introduced to the polystyrene surface. Hindered adsorption and mobility are dominated by hydrophobic effects attributed to water hydration layer formation at the functionalized polystyrene surfaces.

Counterion adsorption theory of dilute polyelectrolyte solutions: Apparent molecular weight, second virial coefficient, and intermolecular structure factor

PubMed Central

Muthukumar, M.

2012-01-01

Polyelectrolyte chains are well known to be strongly correlated even in extremely dilute solutions in the absence of additional strong electrolytes. Such correlations result in severe difficulties in interpreting light scattering measurements in the determination of the molecular weight, radius of gyration, and the second virial coefficient of charged macromolecules at lower ionic strengths from added strong electrolytes. By accounting for charge-regularization of the polyelectrolyte by the counterions, we present a theory of the apparent molecular weight, second virial coefficient, and the intermolecular structure factor in dilute polyelectrolyte solutions in terms of concentrations of the polymer and the added strong electrolyte. The counterion adsorption of the polyelectrolyte chains to differing levels at different concentrations of the strong electrolyte can lead to even an order of magnitude discrepancy in the molecular weight inferred from light scattering measurements. Based on counterion-mediated charge regularization, the second virial coefficient of the polyelectrolyte and the interchain structure factor are derived self-consistently. The effect of the interchain correlations, dominating at lower salt concentrations, on the inference of the radius of gyration and on molecular weight is derived. Conditions for the onset of nonmonotonic scattering wave vector dependence of scattered intensity upon lowering the electrolyte concentration and interpretation of the apparent radius of gyration are derived in terms of the counterion adsorption mechanism. PMID:22830728

Insulin adsorption on crystalline SiO2: Comparison between polar and nonpolar surfaces using accelerated molecular-dynamics simulations

NASA Astrophysics Data System (ADS)

Nejad, Marjan A.; Mücksch, Christian; Urbassek, Herbert M.

2017-02-01

Adsorption of insulin on polar and nonpolar surfaces of crystalline SiO2 (cristobalite and α -quartz) is studied using molecular dynamics simulation. Acceleration techniques are used in order to sample adsorption phase space efficiently and to identify realistic adsorption conformations. We find major differences between the polar and nonpolar surfaces. Electrostatic interactions govern the adsorption on polar surfaces and can be described by the alignment of the protein dipole with the surface dipole; hence spreading of the protein on the surface is irrelevant. On nonpolar surfaces, on the other hand, van-der-Waals interaction dominates, inducing surface spreading of the protein.

UNDERSTANDING VARIATION IN PARTITION COEFFICIENT KD, VALUES, VOLUME III: AMERICIUM, ARSENIC, CURIUM, IODINE, NEPTUNIUM, RADIUM, AND TECHNETIUM

EPA Science Inventory

This report describes the conceptualization, measurement, and use of the partition (or distribution) coefficient, Kd, parameter, and the geochemical aqueous solution and sorbent properties that are most important in controlling adsorption/retardation behavior of selected contamin...

A Comprehensive Study of Hydrogen Adsorbing to Amorphous Water ice: Defining Adsorption in Classical Molecular Dynamics

NASA Astrophysics Data System (ADS)

Dupuy, John L.; Lewis, Steven P.; Stancil, P. C.

2016-11-01

Gas-grain and gas-phase reactions dominate the formation of molecules in the interstellar medium (ISM). Gas-grain reactions require a substrate (e.g., a dust or ice grain) on which the reaction is able to occur. The formation of molecular hydrogen (H2) in the ISM is the prototypical example of a gas-grain reaction. In these reactions, an atom of hydrogen will strike a surface, stick to it, and diffuse across it. When it encounters another adsorbed hydrogen atom, the two can react to form molecular hydrogen and then be ejected from the surface by the energy released in the reaction. We perform in-depth classical molecular dynamics simulations of hydrogen atoms interacting with an amorphous water-ice surface. This study focuses on the first step in the formation process; the sticking of the hydrogen atom to the substrate. We find that careful attention must be paid in dealing with the ambiguities in defining a sticking event. The technical definition of a sticking event will affect the computed sticking probabilities and coefficients. Here, using our new definition of a sticking event, we report sticking probabilities and sticking coefficients for nine different incident kinetic energies of hydrogen atoms [5-400 K] across seven different temperatures of dust grains [10-70 K]. We find that probabilities and coefficients vary both as a function of grain temperature and incident kinetic energy over the range of 0.99-0.22.

Protein adsorption to poly(ethylenimine)-modified Sepharose FF: V. Complicated effects of counterions.

PubMed

Liu, Na; Yu, Linling; Sun, Yan

2015-07-24

In the previous studies on protein adsorption to poly(ethylenimine) (PEI)-grafted Sepharose FF resins, a critical ionic capacity (600mmol/L) of PEI-Sepharose resins was found for the adsorption of bovine serum albumin (BSA), above which both protein capacity and uptake rate increased drastically. In this work, the influence of counterions on the PEI-Sepharose resin with an ionic capacity of 683mmol/L (FF-PEI-L680) was investigated with sodium salts of SCN(-), Cl(-), HPO4(2-) and SO4(2-). Linear gradient elution, batch adsorption and breakthrough experiments showed that counterion preference, effective pore diffusion coefficient (De) and dynamic binding capacity (DBC) values increased in the order of SCN(-), Cl(-), HPO4(2-) and SO4(2-), while static adsorption capacity decreased in this order. It is considered that higher counterion preference of the ion exchange groups resulted in lower protein binding strength and adsorption capacity, while the De value increased due to the enhanced "chain delivery" effect (a kind of surface diffusion). Besides, the DBC value was mainly dependent on De value. In particular, SO4(2-) was the most favorable counterion for the PEI-Sepharose resin, which gave rise to the highest De value (De/D0=1.17, D0 is protein diffusivity in free solution) and DBC value (118mg/mL at a residence time of 2min). Moreover, the effects of counterions on BSA adsorption to DEAE Sepharose FF and Q Sepharose FF, which were non-grafted resins, were also studied for comparisons. It was found that the counterion preferences of the two non-grafted resins were different from each other and also different from that of FF-PEI-L680. The different counterion preferences were attributed to the differences in the ion-exchange ligand chemistries. In addition, the De values for DEAE Sepharose FF and Q Sepharose FF kept unchanged. The low counterion sensitivity of De values could be interpreted as the lack of "chain delivery" effect for the non-grafted resins. The results indicate that protein adsorption and chromatographic performance with PEI-Sepharose can be improved by proper counterions. For the four counterions tested, SO4(2-) was the most favorable for providing the best adsorption and elution outcomes with FF-PEI-L680. Copyright © 2015 Elsevier B.V. All rights reserved.

Fixed-bed adsorption of reactive azo dye onto granular activated carbon prepared from waste.

PubMed

Ahmad, A A; Hameed, B H

2010-03-15

In this work, the adsorption potential of bamboo waste based granular activated carbon (BGAC) to remove C.I. Reactive Black (RB5) from aqueous solution was investigated using fixed-bed adsorption column. The effects of inlet RB5 concentration (50-200mg/L), feed flow rate (10-30 mL/min) and activated carbon bed height (40-80 mm) on the breakthrough characteristics of the adsorption system were determined. The highest bed capacity of 39.02 mg/g was obtained using 100mg/L inlet dye concentration, 80 mm bed height and 10 mL/min flow rate. The adsorption data were fitted to three well-established fixed-bed adsorption models namely, Adam's-Bohart, Thomas and Yoon-Nelson models. The results fitted well to the Thomas and Yoon-Nelson models with coefficients of correlation R(2)>or=0.93 at different conditions. The BGAC was shown to be suitable adsorbent for adsorption of RB5 using fixed-bed adsorption column. (c) 2009 Elsevier B.V. All rights reserved.

Adsorption of cadmium(II) on waste biomaterial.

PubMed

Baláž, M; Bujňáková, Z; Baláž, P; Zorkovská, A; Danková, Z; Briančin, J

2015-09-15

Significant increase of the adsorption ability of the eggshell biomaterial toward cadmium was observed upon milling, as is evidenced by the value of maximum monolayer adsorption capacity of 329mgg(-1), which is markedly higher than in the case of most "green" sorbents. The main driving force of the adsorption was proven to be the presence of aragonite phase as a consequence of phase transformation from calcite occurring during milling. Cadmium is adsorbed in a non-reversible way, as documented by different techniques (desorption tests, XRD and EDX measurements). The optimum pH for cadmium adsorption was 7. The adsorption process was accompanied by the increase of the value of specific surface area. The course of adsorption has been described by Langmuir, Freundlich and Dubinin-Radushkevich isotherms. The adsorption kinetics was evaluated using three models, among which the best correlation coefficients and the best normalized standard deviation values were achieved for the pseudo-second order model and the intraparticle diffusion model, respectively. Copyright © 2015 Elsevier Inc. All rights reserved.

Linear free energy relationships for the adsorption of volatile organic compounds onto multiwalled carbon nanotubes at different relative humidities: comparison with organoclays and activated carbon.

PubMed

Li, Mei-Syue; Wang, Reuben; Fu Kuo, Dave Ta; Shih, Yang-Hsin

2017-03-22

Accurate prediction of the sorption coefficients of volatile organic compounds (VOCs) on carbon nanotubes (CNTs) is of major importance for developing an effective VOC removal process and risk assessment of released nanomaterial-carrying contaminants. The linear free energy relationship (LFER) approach was applied to investigate the adsorption mechanisms of VOCs on multiwalled CNTs (MWCNTs). The gas-solid partition coefficients (log K d ) of 17 VOCs were determined at 0%, 55%, and 90% relative humidity (RH). The cavity/dispersion interaction is generally the most influential adsorption mechanism for all RH cases. The hydrogen-accepting interactions declined but with constant hydrogen-donating interactions during the increase of RH, suggesting that the acidity of VOC was important in forming sorptive interaction with the MWCNT surface. Moreover, the comparison of log K d of VOCs on MWCNTs and other sorbents revealed that the sorption performance of MWCNTs is much more stable over a wider range of RHs due to better site availability and site quality. Furthermore, for all 6 adsorbents in all RHs, the positive contribution of hydrogen bonding ability was found as compared to the negative one found for sorbents completely in water, indicating that the hydrogen-bond donor and acceptor on the sorbent surface contribute to the sorption in the gas phase. In conclusion, the LFER-derived coefficients can be useful in predicting the performance of VOC adsorption on adsorbents and in facilitating the design of efficient VOC removal systems.

Removal of xenobiotics from effluent discharge by adsorption on zeolite and expanded clay: an alternative to activated carbon?

PubMed

Tahar, A; Choubert, J M; Miège, C; Esperanza, M; Le Menach, K; Budzinski, H; Wisniewski, C; Coquery, M

2014-04-01

Xenobiotics such as pesticides and pharmaceuticals are an increasingly large problem in aquatic environments. A fixed-bed adsorption filter, used as tertiary stage of sewage treatment, could be a solution to decrease xenobiotics concentrations in wastewater treatment plants (WWTPs) effluent. The adsorption efficiency of two mineral adsorbent materials (expanded clay (EC) and zeolite (ZE)), both seen as a possible alternative to activated carbon (AC), was evaluated in batch tests. Experiments involving secondary treated domestic wastewater spiked with a cocktail of ten xenobiotics (eight pharmaceuticals and two pesticides) known to be poorly eliminated in conventional biological process were carried out. Removal efficiencies and partitions coefficients were calculated for two levels of initial xenobiotic concentration, i.e, concentrations lower to 10 μg/L and concentrations ranged from 100 to 1,000 μg/L. While AC was the most efficient adsorbent material, both alternative adsorbent materials showed good adsorption efficiencies for all ten xenobiotics (from 50 to 100 % depending on the xenobiotic/adsorbent material pair). For all the targeted xenobiotics, at lower concentrations, EC presented the best adsorption potential with higher partition coefficients, confirming the results in terms of removal efficiencies. Nevertheless, Zeolite presents virtually the same adsorption potential for both high and low xenobiotics concentrations to be treated. According to this first batch investigation, ZE and EC could be used as alternative absorbent materials to AC in WWTP.

Elucidation of the naproxen sodium adsorption onto activated carbon prepared from waste apricot: kinetic, equilibrium and thermodynamic characterization.

PubMed

Onal, Y; Akmil-Başar, C; Sarici-Ozdemir, C

2007-09-30

In this study, activated carbon (WA11Zn5) was prepared from waste apricot, which is waste in apricot plants in Malatya, by chemical activation with ZnCl(2). BET surface area of activated carbon is determined as 1060 m(2)/g. The ability of WA11Zn5, to remove naproxen sodium from effluent solutions by adsorption has been studied. Equilibrium isotherms for the adsorption of naproxen sodium on activated carbon were measured experimentally. Results were analyzed by the Langmiur, Freundlich equation using linearized correlation coefficient at 298 K. The characteristic parameters for each isotherm have been determined. Langmiur equation is found to best represent the equilibrium data for naproxen sodium-WA11Zn5 systems. The monolayer adsorption capacity of WA11Zn5 for naproxen sodium was found to be 106.38 mg/g at 298 K. The process was favorable and spontaneous. The kinetics of adsorption of naproxen sodium have been discussed using three kinetic models, i.e., the pseudo first-order model, the pseudo second-order model, the intraparticle diffusion model. Kinetic parameters and correlation coefficients were determined. It was shown that the pseudo second-order kinetic equation could describe the adsorption kinetics for naproxen sodium onto WA11Zn5. The thermodynamic parameters, such as DeltaG degrees , DeltaS degrees and DeltaH degrees, were calculated. The thermodynamics of naproxen sodium-WA11Zn5 system indicates endothermic process.

[Adsorption characteristics of acetone and butanone onto honeycomb ZSM-5 molecular sieve].

PubMed

Du, Juan; Luan, Zhi-Qiang; Xie, Qiang; Ye, Ping-Wei; Li, Kai; Wang, Xi-Qin

2013-12-01

Adsorption capacity of acetone and acetone-butanone mixture onto honeycomb ZSM-5 molecular sieve was measured in this paper, and the influences of relative humidity, initial adsorbate concentration and airflow velocity on the adsorption process were investigated. Besides, adsorption performance parameters were calculated by Wheeler's equation. The results showed that relative humidity had no obvious influence on the acetone adsorption performance, which suggests that this material has good hydrophobic ability; in the low concentration range, the dynamic saturated adsorption capacity of acetone increased with the increase of initial concentration, but in the occasion of high concentration of acetone gas (more than 9 mg x L(-1)), the dynamic saturated adsorption capacity maintained at a certain level and did not vary with the increase of initial concentration; the increase of air flow velocity resulted in significant increase of acetone adsorption rate constant, at the same time the critical layer thickness of the adsorbent bed also increased significantly. In the cases of acetone-butanone mixture, the adsorption capacity of butanone onto ZSM-5 was clearly higher than that of acetone.

Novel three-stage kinetic model for aqueous benzene adsorption on activated carbon.

PubMed

Choi, Jae-Woo; Choi, Nag-Choul; Lee, Soon-Jae; Kim, Dong-Ju

2007-10-15

We propose a novel kinetic model for adsorption of aqueous benzene onto both granular activated carbon (GAC) and powdered activated carbon (PAC). The model is based on mass conservation of benzene coupled with three-stage adsorption: (1) the first portion for an instantaneous stage or external surface adsorption, (2) the second portion for a gradual stage with rate-limiting intraparticle diffusion, and (3) the third portion for a constant stage in which the aqueous phase no longer interacts with activated carbon. An analytical solution of the kinetic model was validated with the kinetic data obtained from aqueous benzene adsorption onto GAC and PAC in batch experiments with two different solution concentrations (C(0)=300 mg L(-1), 600 mg L(-1)). Experimental results revealed that benzene adsorption for the two concentrations followed three distinct stages for PAC but two stages for GAC. The analytical solution could successfully describe the kinetic adsorption of aqueous benzene in the batch reaction system, showing a fast instantaneous adsorption followed by a slow rate-limiting adsorption and a final long constant adsorption. Use of the two-stage model gave incorrect values of adsorption coefficients in the analytical solution due to inability to describe the third stage.

Effect of hydrophobicity of pharmaceuticals and personal care products for adsorption on activated carbon: Adsorption isotherms, kinetics and mechanism.

PubMed

Kaur, Harkirat; Bansiwal, Amit; Hippargi, Girivyankatesh; Pophali, Girish R

2017-09-11

Adsorption of three pharmaceuticals and personal care products (PPCPs), namely caffeine, ibuprofen and triclosan on commercial powdered activated carbon was examined in aqueous medium. The contaminants were chosen based on their diverse log K ow (octanol-water partition coefficient) viz. - 0.07 for caffeine, 3.97 for ibuprofen and 4.76 for triclosan to examine the role of hydrophobicity on adsorption process. The adsorbent characterisation was achieved using BET surface area, SEM, pore size distribution studies and FTIR. Influence of mass of PAC, contact time, solution pH and initial concentration on adsorption capacity of PAC was studied. Adsorption isotherms and kinetics were applied to establish the mechanism of adsorption. The kinetics followed pseudo-second order with physisorption occurring through particle diffusion. The Freundlich model fitted best among the isotherm models. The adsorption capacity increased in the order CFN < IBU < TCS which correlates with increasing hydrophobicity (log K ow ), molecular weight and decreasing water solubility, respectively. We conclude that micro-pollutant hydrophobicity contributes towards adsorption on activated carbon.

Adsorption and bioadsorption of granular activated carbon (GAC) for dissolved organic carbon (DOC) removal in wastewater.

PubMed

Xing, W; Ngo, H H; Kim, S H; Guo, W S; Hagare, P

2008-12-01

In this study, the performances of GAC adsorption and GAC bioadsorption in terms of dissolved organic carbon (DOC) removal were investigated with synthetic biologically treated sewage effluent (BTSE), synthetic primary treated sewage effluent (PTSE), real BTSE and real PTSE. The main aims of this study are to verify and compare the efficiency of DOC removal by GAC (adsorption) and acclimatized GAC (bioadsorption). The results indicated that the performance of bioadsorption was significantly better than that of adsorption in all cases, showing the practical use of biological granular activated carbon (BGAC) in filtration process. The most significance was observed at a real PTSE with a GAC dose of 5g/L, having 54% and 96% of DOC removal by adsorption and bioadsorption, respectively. In addition, it was found that GAC adsorption equilibrium was successfully predicted by a hybrid Langmuir-Freundlich model whilst integrated linear driving force approximation (LDFA)+hybrid isotherm model could describe well the adsorption kinetics. Both adsorption isotherm and kinetic coefficients determined by these models will be useful to model the adsorption/bioadsorption process in DOC removal of BGAC filtration system.

A flexible metal–organic framework: Guest molecules controlled dynamic gas adsorption

DOE PAGES

Mahurin, Shannon Mark; Li, Man -Rong; Wang, Hailong; ...

2015-04-13

A flexible metal–organic framework (MOF) of [Zn 3(btca) 2(OH) 2]·(guest) n (H 2btca = 1,2,3-benzotriazole-5-carboxylic acid) that exhibits guest molecule-controlled dynamic gas adsorption is reported in which carbon dioxide molecules rather than N 2, He, and Ar induce a structural transition with a corresponding appearance of additional steps in the isotherms. Physical insights into the dynamic adsorption behaviors of flexible compound 1 were detected by gas adsorption at different temperatures and different pressures and confirmed by Fourier transform infrared spectroscopy and molecular simulations. Interestingly, by taking advantage of the flexible nature inherent to the framework, this MOF material enables highlymore » selective adsorption of CO 2/N 2, CO 2/Ar, and CO 2/He of 36.3, 32.6, and 35.9, respectively, at 298 K. Furthermore, this class of flexible MOFs has potential applications for controlled release, molecular sensing, noble gas separation, smart membranes, and nanotechnological devices.« less

PREDICTING SOIL SORPTION COEFFICIENTS OF ORGANIC CHEMICALS USING A NEURAL NETWORK MODEL

EPA Science Inventory

The soil/sediment adsorption partition coefficient normalized to organic carbon (K_oc) is extensively used to assess the fate of organic chemicals in hazardous waste sites. Several attempts have been made to estimate the value of K_oc from chemical structure ...

Simulation of methylene blue adsorption by salts-treated beech sawdust in batch and fixed-bed systems.

PubMed

Batzias, F A; Sidiras, D K

2007-10-01

Batch and column kinetics of methylene blue adsorption on calcium chloride, zinc chloride, magnesium chloride and sodium chloride treated beech sawdust were simulated, using untreated beech sawdust as control, in order to explore its potential use as a low-cost adsorbent for wastewater dye removal. The adsorption capacity, estimated according to Freundlich's model, the Langmuir constant K(L) and the adsorption capacity coefficient values, determined using the Bohart and Adams' bed depth service model indicate that salts treatment enhanced the adsorption properties of the original material. Since sawdust is an industrial waste/byproduct and the salts used can be recovered as spent liquids from various chemical operations, this process of adsorbent upgrading/modification might be considered to take place within an 'Industrial Ecology' framework.

Linear solvation energy relationship for the adsorption of synthetic organic compounds on single-walled carbon nanotubes in water.

PubMed

Ding, H; Chen, C; Zhang, X

2016-01-01

The linear solvation energy relationship (LSER) was applied to predict the adsorption coefficient (K) of synthetic organic compounds (SOCs) on single-walled carbon nanotubes (SWCNTs). A total of 40 log K values were used to develop and validate the LSER model. The adsorption data for 34 SOCs were collected from 13 published articles and the other six were obtained in our experiment. The optimal model composed of four descriptors was developed by a stepwise multiple linear regression (MLR) method. The adjusted r(2) (r(2)adj) and root mean square error (RMSE) were 0.84 and 0.49, respectively, indicating good fitness. The leave-one-out cross-validation Q(2) ([Formula: see text]) was 0.79, suggesting the robustness of the model was satisfactory. The external Q(2) ([Formula: see text]) and RMSE (RMSEext) were 0.72 and 0.50, respectively, showing the model's strong predictive ability. Hydrogen bond donating interaction (bB) and cavity formation and dispersion interactions (vV) stood out as the two most influential factors controlling the adsorption of SOCs onto SWCNTs. The equilibrium concentration would affect the fitness and predictive ability of the model, while the coefficients varied slightly.

Colloid-Facilitated Transport of 137Cs in Fracture-Fill Material. Experiments and Modeling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dittrich, Timothy M.; Reimus, Paul William

2015-10-29

In this study, we demonstrate how a combination of batch sorption/desorption experiments and column transport experiments were used to effectively parameterize a model describing the colloid-facilitated transport of Cs in the Grimsel granodiorite/FFM system. Cs partition coefficient estimates onto both the colloids and the stationary media obtained from the batch experiments were used as initial estimates of partition coefficients in the column experiments, and then the column experiment results were used to obtain refined estimates of the number of different sorption sites and the adsorption and desorption rate constants of the sites. The desorption portion of the column breakthrough curvesmore » highlighted the importance of accounting for adsorption-desorption hysteresis (or a very nonlinear adsorption isotherm) of the Cs on the FFM in the model, and this portion of the breakthrough curves also dictated that there be at least two different types of sorption sites on the FFM. In the end, the two-site model parameters estimated from the column experiments provided excellent matches to the batch adsorption/desorption data, which provided a measure of assurance in the validity of the model.« less

Molecular surface area based predictive models for the adsorption and diffusion of disperse dyes in polylactic acid matrix.

PubMed

Xu, Suxin; Chen, Jiangang; Wang, Bijia; Yang, Yiqi

2015-11-15

Two predictive models were presented for the adsorption affinities and diffusion coefficients of disperse dyes in polylactic acid matrix. Quantitative structure-sorption behavior relationship would not only provide insights into sorption process, but also enable rational engineering for desired properties. The thermodynamic and kinetic parameters for three disperse dyes were measured. The predictive model for adsorption affinity was based on two linear relationships derived by interpreting the experimental measurements with molecular structural parameters and compensation effect: ΔH° vs. dye size and ΔS° vs. ΔH°. Similarly, the predictive model for diffusion coefficient was based on two derived linear relationships: activation energy of diffusion vs. dye size and logarithm of pre-exponential factor vs. activation energy of diffusion. The only required parameters for both models are temperature and solvent accessible surface area of the dye molecule. These two predictive models were validated by testing the adsorption and diffusion properties of new disperse dyes. The models offer fairly good predictive ability. The linkage between structural parameter of disperse dyes and sorption behaviors might be generalized and extended to other similar polymer-penetrant systems. Copyright © 2015 Elsevier Inc. All rights reserved.

Design and development of low pressure evaporator/condenser unit for water-based adsorption type climate control systems

NASA Astrophysics Data System (ADS)

Venkataramanan, Arjun; Rios Perez, Carlos A.; Hidrovo, Carlos H.

2016-11-01

Electric vehicles (EVs) are the future of clean transportation and driving range is one of the important parameters which dictates its marketability. In order to increase driving range, electrical battery energy consumption should be minimized. Vapor-compression refrigeration systems currently employed in EVs for climate control consume a significant fraction of the battery charge. Thus, by replacing this traditional heating ventilation and air-conditioning system with an adsorption based climate control system one can have the capability of increasing the drive range of EVs.The Advanced Thermo-adsorptive Battery (ATB) for climate control is a water-based adsorption type refrigeration cycle. An essential component of the ATB is a low pressure evaporator/condenser unit (ECU) which facilitates both the evaporation and condensation processes. The thermal design of the ECU relies predominantly on the accurate prediction of evaporation/boiling heat transfer coefficients since the standard correlations for predicting boiling heat transfer coefficients have large uncertainty at the low operating pressures of the ATB. This work describes the design and development of a low pressure ECU as well as the thermal performance of the actual ECU prototype.

Adsorption-Coupled Diffusion of Gold Nanoclusters within a Large-Pore Protein Crystal Scaffold.

PubMed

Hartje, Luke F; Munsky, Brian; Ni, Thomas W; Ackerson, Christopher J; Snow, Christopher D

2017-08-17

Large-pore protein crystals (LPCs) are ordered biologically derived nanoporous materials exhibiting pore diameters greater than 8 nm. These substantial pores distinguish LPCs from typical nanoporous scaffolds, enabling engineered LPC materials to readily uptake, immobilize, and release macromolecular guests. In this study, macromolecular transport within an LPC environment was experimentally and computationally investigated by studying adsorption-coupled diffusion of Au 25 (glutathione) 18 nanoclusters within a cross-linked LPC scaffold via time-lapse confocal microscopy, bulk equilibrium adsorption, and hindered diffusion simulation. Equilibrium adsorption data is congruent with a Langmuir adsorption model, exhibiting strong binding behavior between nanoclusters and the scaffold. The standard Gibbs free energy of binding is equivalent to -37.2 kJ/mol, and the maximum binding capacity of 1.25 × 10 3 mg/g corresponds to approximately 29 nanoclusters per LPC unit cell. The hindered diffusion model showed good agreement with experimental data, revealing a pore diffusion coefficient of 3.7 × 10 -7 cm 2 /s under low nanocluster concentration. Furthermore, the model was sufficient to determine adsorption and desorption kinetic values for k a and k d equal to 13 cm 3 /mol·s and 1.7 × 10 -7 s -1 , respectively. At higher nanocluster concentrations, the simulated pore diffusion coefficient could be reduced by 3 orders of magnitude to 3.4 × 10 -10 cm 2 /s due to the effects of pore occlusion. This study demonstrates a strategy to analyze adsorption-coupled diffusion data to better understand complex transport of fluorescent macromolecules into LPCs. This approach fits the observable fluorescence data to the key molecular details and will benefit downstream efforts to engineer LPC-based nanoporous materials.

Longitudinal dispersion coefficient depending on superficial velocity of hydrogen isotopes flowing in column packed with zeolite pellets at 77.4 K

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kotoh, K.; Graduate School of Engineering, Kyushu University, Nishi-ku, Fukuoka; Kubo, K.

2015-03-15

Authors have been developing a cryogenic pressure swing adsorption system for hydrogen isotope separation. In the problem of its design and operation, it is necessary to predict the concentration profiles developing in packed beds of adsorbent pellets. The profiling is affected by the longitudinal dispersion of gas flowing in packed beds, in addition to the mass transfer resistance in porous media of adsorbent pellets. In this work, an equation is derived for estimating the packed-bed dispersion coefficient of hydrogen isotopes, by analyzing the breakthrough curves of trace D{sub 2} or HD replacing H{sub 2} adsorbed in synthetic zeolite particles packedmore » columns at the liquefied nitrogen temperature 77.4 K. Since specialized for hydrogen isotopes, this equation can be considered to estimate the dispersion coefficients more reliable for the cryogenic hydrogen isotope adsorption process, than the existing equations. (authors)« less

On the enrichment of hydrophobic organic compounds in fog droplets

NASA Astrophysics Data System (ADS)

Valsaraj, K. T.; Thoma, G. J.; Reible, D. D.; Thibodeaux, L. J.

The unusual degree of enrichment of hydrophobic organics in fogwater droplets reported by several investigators can be interpreted as a result of (a) the effects of temperature correction on the reported enrichment factors, (b) the effects of colloidal organic matter (both filterable and non-filterable) in fog water and (c) the effects of the large air-water interfacial adsorption of neutral hydrophobic organics on the tiny fog droplets. The enrichment factor was directly correlated to the hydrophobicity (or the activity coefficient in water) of the compounds, as indicated by their octanol-water partition constants. Compounds with large octanol-water partition coefficients (high activity coefficients in water) showed the largest enrichment. Available experimental data on the adsorption of hydrophobic compounds at the air-water interface and on colloidal organic carbon were used to show that the large specific air-water interfacial areas of fog droplets contribute significantly to the enrichment factor.

Chromatography, solid-phase extraction, and capillary electrochromatography with MIPs.

PubMed

Tóth, Blanka; Horvai, George

2012-01-01

Most analytical applications of molecularly imprinted polymers are based on their selective adsorption properties towards the template or its analogs. In chromatography, solid phase extraction and electrochromatography this adsorption is a dynamic process. The dynamic process combined with the nonlinear adsorption isotherm of the polymers and other factors results in complications which have limited the success of imprinted polymers. This chapter explains these problems and shows many examples of successful applications overcoming or avoiding the problems.

Effect of pH on the adsorption of dodecylamine on montmorillonite: Insights from experiments and molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Peng, Chenliang; Min, Fanfei; Liu, Lingyun

2017-12-01

The hydrophobic aggregation in cationic surfactant suspension is an effective method to enhance the dewatering of clay-rich tailing. The solution pH can affect the adsorption behavior of cationic surfactant on clay mineral. The effect of pH on the adsorption of dodecylamine (DDA) on montmorillonite was investigated by the sedimentation test and the characterization of flocs images, contact angle, adsorption quantity, and fourier transform infrared (FTIR) spectroscopy, as well as molecular dynamics (MD) simulation. It was found that DDA ions were adsorbed on montmorillonite basal surfaces mainly by physical adsorption, including the electrostatic attraction and hydrogen bonding. A certain number of neutral DDA molecules can favor the adsorption of DDA. At pH around 8, the effect of hydrophobic modification was the best because DDA molecules and ions form compact and well-organized monolayer. The MD simulation results were in good agreement with that of contact angle, adsorption quantity and FTIR.

Measurement of the absorption coefficient using the sound-intensity technique

NASA Technical Reports Server (NTRS)

Atwal, M.; Bernhard, R.

1984-01-01

The possibility of using the sound intensity technique to measure the absorption coefficient of a material is investigated. This technique measures the absorption coefficient by measuring the intensity incident on the sample and the net intensity reflected by the sample. Results obtained by this technique are compared with the standard techniques of measuring the change in the reverberation time and the standing wave ratio in a tube, thereby, calculating the random incident and the normal incident adsorption coefficient.

The Evaluation of Foam Performance and Flooding Efficiency

NASA Astrophysics Data System (ADS)

Keliang, Wang; Yuhao, Chen; Gang, Wang; Gen, Li

2017-12-01

ROSS-Miles and spinning drop interfacial tensionmeter are used to select suitable foam system through foam composite index (FCI) and interfacial tension (IT). The selected foam system are taken to conduct further test. The further tests are evaluating the foam system resistance to adsorption with multi-round core flooding dynamic adsorption test and evaluating the performance of foam system with four kinds of different transport distance, quantitatively analyzing the foam system effective distance after dynamic adsorption. The result shows that the foaming ability and the mobilizing ability of the foam system decrease with the increase of the round of dynamic adsorption. As the transport distance increases, the foaming ability and the mobilizing ability of the foam system decrease. This result further reveals the flooding characteristics of nitrogen foam flooding, which provides a reference for the implementation of nitrogen foam flooding technology.

Adsorption behavior of acetone solvent at the HMX crystal faces: A molecular dynamics study.

PubMed

Liu, Yingzhe; Yu, Tao; Lai, Weipeng; Ma, Yiding; Kang, Ying; Ge, Zhongxue

2017-06-01

Molecular dynamics simulations have been performed to understand the adsorption behavior of acetone (AC) solvent at the three surfaces of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctan (HMX) crystal, i.e. (011), (110), and (020) faces. The simulation results show that the structural features and electrostatic potentials of crystal faces are determined by the HMX molecular packing, inducing distinct mass density distribution, dipole orientation, and diffusion of solvent molecules in the interfacial regions. The solvent adsorption is mainly governed by the van der Waals forces, and the crystal-solvent interaction energies among three systems are ranked as (020)≈(110)>(011). The adsorption sites for solvent incorporation at the crystal surface were found and visualized with the aid of occupancy analysis. A uniform arrangement of adsorption sites is observed at the rough (020) surface as a result of ordered adsorption motif. Copyright © 2017 Elsevier Inc. All rights reserved.

Thermodynamic study of quercetin and rutin mixtures with alcohols

NASA Astrophysics Data System (ADS)

Szymczyk, Katarzyna; Taraba, Anna

2018-04-01

The paper presents interactions between quercetin (3,3‧,4‧,5,7-pentahydroxyflavone) and its glycoside, rutin with short chain alcohols, methanol, ethanol and 1-propanol studied by the surface tension measurements. An attempt was made to investigate the effect of flavonoid and alcohol concentrations as well as temperature on the thermodynamic parameters of alcohols adsorption at the water-air interface that is the standard free enthalpy, enthalpy and entropy of adsorption as well as the infinite dilution activity coefficient. The obtained results show that the mixtures of quercetin with methanol and rutin with ethanol are characterized by the best adsorption properties but all studied systems become less structured after adsorption.

Dynamic technique for measuring adsorption in a gas chromatograph

NASA Technical Reports Server (NTRS)

Deuel, C. L.; Hultgren, N. W.; Mobert, M. L.

1973-01-01

Gas-chromatographic procedure, together with mathematical analysis of adsorption isotherm, allows relative surface areas and adsorptive powers for trace concentrations to be determined in a few minutes. Technique may be used to evaluate relative surface areas of different adsorbates, expressed as volume of adsorbent/gram of adsorbate, and to evaluate their relative adsorptive power.

Highly porous activated carbon based adsorption cooling system employing difluoromethane and a mixture of pentafluoroethane and difluoromethane

NASA Astrophysics Data System (ADS)

Askalany, Ahmed A.; Saha, Bidyut B.

2017-01-01

This paper presents a simulation for a low-grade thermally powered two-beds adsorption cooling system employing HFC-32 and a mixture of HFC-32 and HFC-125 (HFC-410a) with activated carbon of type Maxsorb III. The present simulation model adopts experimentally measured adsorption isotherms, adsorption kinetics and isosteric heat of adsorption data. Effect of operating conditions (mass flow rate of hot water, driving heat source temperature and evaporator temperature) on the system performance has been studied in detail. The simulation results showed that the system could be powered by low-grade heat source temperature (below 85 °C). AC/HFC-32 and AC/HFC-410a adsorption cooling cycles achieved close specific cooling power and coefficient of performance values of 0.15 kW/kg and 0.3, respectively at a regeneration temperature of 90 °C along with evaporator temperature of 10 °C. The investigated semi continuous adsorption cooling system could produce a cooling power of 9 kW.

Sizable dynamics in small pores: CO2 location and motion in the α-Mg formate metal-organic framework.

PubMed

Lu, Yuanjun; Lucier, Bryan E G; Zhang, Yue; Ren, Pengju; Zheng, Anmin; Huang, Yining

2017-02-22

Metal-organic frameworks (MOFs) are promising materials for carbon dioxide (CO 2 ) adsorption and storage; however, many details regarding CO 2 dynamics and specific adsorption site locations within MOFs remain unknown, restricting the practical uses of MOFs for CO 2 capture. The intriguing α-magnesium formate (α-Mg 3 (HCOO) 6 ) MOF can adsorb CO 2 and features a small pore size. Using an intertwined approach of 13 C solid-state NMR (SSNMR) spectroscopy, 1 H- 13 C cross-polarization SSNMR, and computational molecular dynamics (MD) simulations, new physical insights and a rich variety of information have been uncovered regarding CO 2 adsorption in this MOF, including the surprising suggestion that CO 2 motion is restricted at elevated temperatures. Guest CO 2 molecules undergo a combined localized rotational wobbling and non-localized twofold jumping between adsorption sites. MD simulations and SSNMR experiments accurately locate the CO 2 adsorption sites; the mechanism behind CO 2 adsorption is the distant interaction between the hydrogen atom of the MOF formate linker and a guest CO 2 oxygen atom, which are ca. 3.2 Å apart.

Different Effects of NSF and PCE Superplasticizer on Adsorption, Dynamic Yield Stress and Thixotropy of Cement Pastes

PubMed Central

2018-01-01

This study compares the differences and similarities of two types of superplasticizers—NSF (Naphthalene Sulfonate Formaldehyde) and PCE (PolyCarboxylate Ester)—in fresh cement paste systems, in terms of adsorption, dynamic yield stress, and thixotropic index. Results show that with either NSF or PCE addition, the more superplasticizer is added, the more it is adsorbed and the more it remains in the interstitial pore solution. The dynamic yield stress and thixotropic index also decrease with increasing addition the amount of either superplasticizer. However, NSF is less efficient in decreasing the dynamic yield stress than PCE. More importantly, the decreasing patterns of dynamic yield stress and thixotropic index are different with NSF and PCE additions; this is tied to the adsorption and dispersing mechanisms of these two types of superplasticizers. PMID:29710782

Competitive adsorption of textile dyes using peat: adsorption equilibrium and kinetic studies in monosolute and bisolute systems.

PubMed

Sepulveda, L; Troncoso, F; Contreras, E; Palma, C

2008-09-01

The purpose of this study is to investigate the adsorption by peat of four reactive textile dyes with the following commercial names: Yellow CIBA WR 200% (Y), Dark Blue CIBA WR (DB), Navy CIBA WB (N), and Red CIBA WB 150% (R), used in a cotton-polyester fabric finishing plant. The decolorization levels obtained varied between 5% and 30%, and the most significant variables were pH and ionic strength. Equilibrium studies were carried out at pH 2.8 and temperature of 25 degrees C. Maximum adsorption capacities were between 15 and 20 mg g(-1). Experimental data were fitted to the models of Langmuir. The equilibrium studies for bisolute systems were DB-R and Y-N mixtures. The Langmuir extended model indicated that there is competition for adsorption sites and without interaction between dyes. The results of the kinetic adsorption studies on monosolute and bisolute systems were fitted to the film-pore diffusion, variable diffusivity and quasi-stationary models. They showed that the diffusivity coefficients obtained varied between 2.0 x 10(-8) and 8.5 x 10(-8) cm2s(-1) when the variable diffusivity mass transfer model (VDM) was used and effective diffusion coefficient was fitted between 3.3 x 10(-7) and 56.0 x 10(-7) cm2s(-1) for the film-pore diffusion model (FPDM). The root of average of squares relative error obtained varied between 0.8% and 47.0% for the VDM and FPDM models, respectively.

Pesticide adsorption in relation to soil properties and soil type distribution in regional scale.

PubMed

Kodešová, Radka; Kočárek, Martin; Kodeš, Vít; Drábek, Ondřej; Kozák, Josef; Hejtmánková, Kateřina

2011-02-15

Study was focused on the evaluation of pesticide adsorption in soils, as one of the parameters, which are necessary to know when assessing possible groundwater contamination caused by pesticides commonly used in agriculture. Batch sorption tests were performed for 11 selected pesticides and 13 representative soils. The Freundlich equations were used to describe adsorption isotherms. Multiple-linear regressions were used to predict the Freundlich adsorption coefficients from measured soil properties. Resulting functions and a soil map of the Czech Republic were used to generate maps of the coefficient distribution. The multiple linear regressions showed that the K(F) coefficient depended on: (a) combination of OM (organic matter content), pH(KCl) and CEC (cation exchange capacity), or OM, SCS (sorption complex saturation) and salinity (terbuthylazine), (b) combination of OM and pH(KCl), or OM, SCS and salinity (prometryne), (c) combination of OM and pH(KCl), or OM and ρ(z) (metribuzin), (d) combination of OM, CEC and clay content, or clay content, CEC and salinity (hexazinone), (e) combination of OM and pH(KCl), or OM and SCS (metolachlor), (f) OM or combination of OM and CaCO(3) (chlorotoluron), (g) OM (azoxystrobin), (h) combination of OM and pH(KCl) (trifluralin), (i) combination of OM and clay content (fipronil), (j) combination of OM and pH(KCl), or OM, pH(KCl) and CaCO(3) (thiacloprid), (k) combination of OM, pH(KCl) and CEC, or sand content, pH(KCl) and salinity (chlormequat chloride). Copyright © 2010 Elsevier B.V. All rights reserved.

Adsorption of an anionic dye on a novel low-cost mesoporous adsorbent: kinetic, thermodynamic and isotherm studies

NASA Astrophysics Data System (ADS)

Msaad, Asmaa; Belbahloul, Mounir; Zouhri, Abdeljalil

2018-05-01

Our activated carbon was prepared successfully using phosphoric acid as an activated agent. The activated carbon was characterized by Scanning Electron Micrograph (SEM), Brunauer-Emmett- Teller (BET), Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD). The aim of our study is to evaluate the adsorption capacity of Methyl Orange (MO) on Ziziphus lotus activated carbon. Adsorption isotherms were studied according to Langmuir and Freundlich Model, and adsorption kinetics according to pseudo-first and second-order. Results show that the maximum adsorption was reached in the first 10min at ambient temperature with a yield of 96.31%. The Langmuir isotherm shows a correlation coefficient of 99.4 % higher than Freundlich model and the adsorption kinetic model follow a pseudo-second-order with a maximum adsorption capacity of 769.23 mg/g. FTIR and X-Ray spectroscopy indicate that our activated carbon has an amorphous structure with the presence of functional groups, where BET analysis revealed a high surface area of 553 mg/g, which facilitate the adsorption process

Dynamic Determination of Some Optical and Electrical Properties of Galena Natural Mineral: Potassium Ethyl Xanthate Solution Interface

NASA Astrophysics Data System (ADS)

Todoran, D.; Todoran, R.; Anitas, E. M.; Szakacs, Zs.

2017-12-01

This paper presents results concerning optical and electrical properties of galena natural mineral and of the interface layer formed between it and the potassium ethyl xanthate solution. The applied experimental method was differential optical reflectance spectroscopy over the UV-Vis/NIR spectral domain. Computations were made using the Kramers-Kronig formalism. Spectral dependencies of the electron loss functions, determined from the reflectance data obtained from the polished mineral surface, display van Hove singularities, leading to the determination of its valence band gap and electron plasma energy. Time dependent measurement of the spectral dispersion of the relative reflectance of the film formed at the interface, using the same computational formalism, leads to the dynamical determination of the spectral variation of its optical and electrical properties. We computed behaviors of the dielectric constant (dielectric permittivity), the dielectric loss function, refractive index and extinction coefficient, effective valence number and of the electron loss functions. The measurements tend to stabilize when the dynamic adsorption-desorption equilibrium is reached at the interface level.

Removal of pharmaceutical pollutants from synthetic wastewater using chemically modified biomass of green alga Scenedesmus obliquus.

PubMed

Ali, Mohamed E M; Abd El-Aty, Azza M; Badawy, Mohamed I; Ali, Rizka K

2018-04-30

Pharmaceutical compounds are considered emerging environmental pollutants that have a potential harmful impact on environment and human health. In this study, the biomass of alga (Scenedesmus obliquus) was modified using alkaline solution, and used for the biosorption of tramadol (TRAM) and other pharmaceuticals. The adsorption kinetics and isotherms were investigated. The obtained results reveal high adsorption capacity of tramadol over modified algal biomass (MAB) after 45min with removal percentage of 91%. Pseudo-second order model was well fitted with the experimental data with correlation coefficient (0.999). Biosorption of tramadol on modified algal biomass proceeds with Freundlich isotherm model with correlation coefficient (0.942) that emphasized uptake of TRAM by MAB is driven by chemisorption. FTIR spectra of MAB before and after the adsorption were analyzed; some IR bands were detected with slight shift and low intensity suggesting their involving in adsorption. The tramadol biosorption by MAB is a chemical process as confirmed by Dubinin-Radushkevich. The adsorption of pharmaceutical over MAB is mainly preceded by hydrophilic interactions between amino and carbonyl groups in pharmaceutical molecules and hydroxyl and carbonyl functional groups on surface of biosorbent. It was emphasized by disappearance O-H and C-O from biomass IR spectra after adsorption. In matrix of pharmaceutical, the recorded adsorption capacities for CEFA, PARA, IBU, TRAM and CIP are 68, 58, 42, 42 and 39mg/g over MAB at natural pH and MAB dose of 0.5g/L. Furthermore, oxygen uptake by bacteria was applied for estimate the toxicity of pharmaceutical. The recorded result concluded the efficient reusability of modified algal biomass for biosorption of pharmaceuticals, as well only the adsorption efficiency decreased by 4.5% after three runs. Subsequently, the modified algal biomass is a promising reusable adsorbent for decontamination of wastewater from pharmaceuticals. Copyright © 2018 Elsevier Inc. All rights reserved.

Removal of Congo Red from Aqueous Solution by Anion Exchange Membrane (EBTAC): Adsorption Kinetics and Themodynamics.

PubMed

Khan, Muhammad Imran; Akhtar, Shahbaz; Zafar, Shagufta; Shaheen, Aqeela; Khan, Muhammad Ali; Luque, Rafael; Rehman, Aziz Ur

2015-07-08

The adsorption behavior of anionic dye congo red (CR) from aqueous solutions using an anion exchange membrane (EBTAC) has been investigated at room temperature. The effect of several factors including contact time, membrane dosage, ionic strength and temperature were studied. Kinetic models, namely pseudo-first-order and pseudo-second-order, liquid film diffusion and Elovich models as well as Bangham and modified freundlich Equations, were employed to evaluate the experimental results. Parameters such as adsorption capacities, rate constant and related correlation coefficients for every model were calculated and discussed. The adsorption of CR on anion exchange membranes followed pseudo-second-order Kinetics. Thermodynamic parameters, namely changes in Gibbs free energy ( ∆G° ), enthalpy ( ∆H° ) and entropy ( ∆S° ) were calculated for the adsorption of congo red, indicating an exothermic process.

Removal of Congo Red from Aqueous Solution by Anion Exchange Membrane (EBTAC): Adsorption Kinetics and Themodynamics

PubMed Central

Khan, Muhammad Imran; Akhtar, Shahbaz; Zafar, Shagufta; Shaheen, Aqeela; Khan, Muhammad Ali; Luque, Rafael; ur Rehman, Aziz

2015-01-01

The adsorption behavior of anionic dye congo red (CR) from aqueous solutions using an anion exchange membrane (EBTAC) has been investigated at room temperature. The effect of several factors including contact time, membrane dosage, ionic strength and temperature were studied. Kinetic models, namely pseudo-first-order and pseudo-second-order, liquid film diffusion and Elovich models as well as Bangham and modified freundlich Equations, were employed to evaluate the experimental results. Parameters such as adsorption capacities, rate constant and related correlation coefficients for every model were calculated and discussed. The adsorption of CR on anion exchange membranes followed pseudo-second-order Kinetics. Thermodynamic parameters, namely changes in Gibbs free energy (∆G°), enthalpy (∆H°) and entropy (∆S°) were calculated for the adsorption of congo red, indicating an exothermic process. PMID:28793430

The adsorption and reaction of adenine nucleotides on montmorillonite

NASA Technical Reports Server (NTRS)

Ferris, James P.; Hagan, William J., Jr.

1986-01-01

The binding of AMP to Zn(2+)-montmorillonite is investigated in the presence of salts and Good's zwitterion buffers, PIPES and MES. The initial concentrations of nucleotide and the percent adsorbtion are used to calculate the adsorption isotherms, and the Langmuir adsorption equation is used for the analysis of data. The adsorption coefficient was found to be three times greater in the presence of 0.2 M PIPES than in its absence. In addition, basal spacings measured by X-ray diffraction were increased by the buffer. These results are interpreted in terms of a model in which the adsorption of AMP is mediated by a Zn(2+) complex of PIPES in different orientations in the interlamellar region of the montmorillonite. Mixed ligand complexes of this type are reminiscent of the complexes observed between metal ions and biological molecules in living systems.

An exploration of the relationship between adsorption and bioavailability of pesticides in soil to earthworm.

PubMed

Yu, Yun Long; Wu, Xiao Mao; Li, Shao Nan; Fang, Hua; Zhan, Hai Yan; Yu, Jing Quan

2006-06-01

A study was conducted to determine the adsorption/desorption of butachlor, myclobutanil and chlorpyrifos on five soils using a batch equilibration technique and to study the relationship between bioavailability to Allolobophora caliginosa and the adsorption/desorption of these three pesticides. The results showed that the adsorption/desorption processes of the tested compounds were mainly controlled by soil organic matter content (OM) and octanol/water-partitioning coefficient (K(ow)), and that the bioavailability of the pesticides was dependent on characteristics of pesticides, properties of soils, and uptake routes of earthworms. Bioconcentration of butachlor and myclobutanil was negatively correlated with Freundlich adsorption constant K(af) and K(df). However, only a slightly positive correlation between bioconcentration and K(af) and K(df) was observed for chlorpyrifos due to its high affinity onto soil.

Removal of dieldrin from aqueous solution by a novel triolein-embedded composite adsorbent.

PubMed

Ru, Jia; Liu, Huijuan; Qu, Jiuhui; Wang, Aimin; Dai, Ruihua

2007-03-06

In this study, a novel triolein-embedded activated carbon composite adsorbent (CA-T) was prepared and applied for the adsorption and removal of dieldrin from aqueous systems. Experiments were carried out to investigate the adsorption behavior of dieldrin on CA-T, including adsorption isotherms, adsorption kinetics, the influence of initial concentration, temperature, shaking speed, pH and the addition of humic acid (HA) on adsorption. The adsorption isotherms accorded with Freundlich equation. Three kinetics models, including pseudo-first-order, pseudo-second-order and intraparticle diffusion models, were used to fit the experimental data. By comparing the correlation coefficients, it was found that both pseudo-second-order and intraparticle diffusion models were used to well describe the adsorption of dieldrin on CA-T. The addition of HA had little effect on dieldrin adsorption by CA-T. Results indicated that CA-T appeared to be a promising adsorbent for removing lipophilic dieldrin in trace amount, which was advantageous over pure granular activated carbon (GAC). The adsorption rate increased with increasing shaking speed, initial concentration and temperature, and remained almost unchanged in the pH range of 4-8. Thermodynamic calculations indicated that the adsorption reaction was spontaneous with a high affinity and the adsorption was an endothermic reaction.

Study on the Adsorption Phenomenon in Shale with the Combination of Molecular Dynamic Simulation and Fractal Analysis

NASA Astrophysics Data System (ADS)

Zhang, Liehui; Li, Jianchao; Jia, Du; Zhao, Yulong; Xie, Chunyu; Tao, Zhengwu

As one of the key status of gas in shale reservoir, adsorption gas accounts for considerable percentage of total gas amount. Due to the complexity and nanostructure of shale gas reservoir, it is very challenging to represent adsorption gas through traditional methods. However, the integration of the fractal theory and molecular dynamics (MD) simulation may provide a new perspective of understanding such nanostructure and the micro-phenomenon happening in it. The key purpose of this paper is to investigate the adsorption phenomenon in shale kerogen. By using MD simulation and grand canonical Monte Carlo (GCMC) algorithm, the adsorption of methane in 2, 5 and 10nm slit-like pores is simulated for different temperature and pressure status. According to the results, the average gas density in smaller pores is higher than that in bigger pores, and multilayer adsorption presents on some areas of pore surfaces. Then, the simulation results are analyzed using the multilayer fractal adsorption model. The analysis indicates that the number of adsorption layer increases with pressure increase: four-layer adsorption presents in 10nm pores while three-layer adsorption shows up in 2nm and 5nm pores due to pore volume limit. Fractal dimension of pore wall surface generated in this study is in the range of 2.31-2.63. Moreover, high temperature could decrease the adsorption behavior in reservoir condition.

Measurements of Submicron Particle Adsorption and Particle Film Elasticity at Oil-Water Interfaces.

PubMed

Manga, Mohamed S; Hunter, Timothy N; Cayre, Olivier J; York, David W; Reichert, Matthew D; Anna, Shelly L; Walker, Lynn M; Williams, Richard A; Biggs, Simon R

2016-05-03

The influence of particle adsorption on liquid/liquid interfacial tension is not well understood, and much previous research has suggested conflicting behaviors. In this paper we investigate the surface activity and adsorption kinetics of charge stabilized and pH-responsive polymer stabilized colloids at oil/water interfaces using two tensiometry techniques: (i) pendant drop and (ii) microtensiometer. We found, using both techniques, that charge stabilized particles had little or no influence on the (dynamic) interfacial tension, although dense silica particles affected the "apparent" measured tension in the pendent drop, due to gravity driven elongation of the droplet profile. Nevertheless, this apparent change additionally allowed the study of adsorption kinetics, which was related qualitatively between particle systems by estimated diffusion coefficients. Significant and real interfacial tension responses were measured using ∼53 nm core-shell latex particles with a pH-responsive polymer stabilizer of poly(methyl methacrylate)-b-poly(2-(dimethylamino)ethyl methacrylate) (pMMA-b-pDMAEMA) diblock copolymer. At pH 2, where the polymer is strongly charged, behavior was similar to that of the bare charge-stabilized particles, showing little change in the interfacial tension. At pH 10, where the polymer is discharged and poorly soluble in water, a significant decrease in the measured interfacial tension commensurate with strong adsorption at the oil-water interface was seen, which was similar in magnitude to the surface activity of the free polymer. These results were both confirmed through droplet profile and microtensiometry experiments. Dilational elasticity measurements were also performed by oscillation of the droplet; again, changes in interfacial tension with droplet oscillation were only seen with the responsive particles at pH 10. Frequency sweeps were performed to ascertain the dilational elasticity modulus, with measured values being significantly higher than previously reported for nanoparticle and surfactant systems, and similar in magnitude to protein stabilized droplets.

Batch versus column modes for the adsorption of radioactive metal onto rice husk waste: conditions optimization through response surface methodology.

PubMed

Kausar, Abida; Bhatti, Haq Nawaz; Iqbal, Munawar; Ashraf, Aisha

2017-09-01

Batch and column adsorption modes were compared for the adsorption of U(VI) ions using rice husk waste biomass (RHWB). Response surface methodology was employed for the optimization of process variables, i.e., (pH (A), adsorbent dose (B), initial ion concentration (C)) in batch mode. The B, C and C 2 affected the U(VI) adsorption significantly in batch mode. The developed quadratic model was found to be validated on the basis of regression coefficient as well as analysis of variance. The predicted and actual values were found to be correlated well, with negligible residual value, and B, C and C 2 were significant terms. The column study was performed considering bed height, flow rate and initial metal ion concentration, and adsorption efficiency was evaluated through breakthrough curves and bed depth service time and Thomas models. Adsorption was found to be dependent on bed height and initial U(VI) ion concentration, and flow rate decreased the adsorption capacity. Thomas models fitted well to the U(VI) adsorption onto RHWB. Results revealed that RHWB has potential to remove U(VI) ions and batch adsorption was found to be efficient versus column mode.

Efficient removal of chromate and arsenate from individual and mixed system by malachite nanoparticles.

PubMed

Saikia, Jiban; Saha, Bedabrata; Das, Gopal

2011-02-15

Malachite nanoparticles of 100-150 nm have been efficiently and for the first time used as an adsorbent for the removal of toxic arsenate and chromate. We report a high adsorption capacity for chromate and arsenate on malachite nanoparticle from both individual and mixed solution in pH ∼4-5. However, the adsorption efficiency decreases with the increase of solution pH. Batch studies revealed that initial pH, temperature, malachite nanoparticles dose and initial concentration of chromate and arsenate were important parameters for the adsorption process. Thermodynamic analysis showed that adsorption of chromate and arsenate on malachite nanoparticles is endothermic and spontaneous. The adsorption of these anions has also been investigated quantitatively with the help of adsorption kinetics, isotherm, and selectivity coefficient (K) analysis. The adsorption data for both chromate and arsenate were fitted well in Langmuir isotherm and preferentially followed the second order kinetics. The binding affinity of chromate is found to be slightly higher than arsenate in a competitive adsorption process which leads to the comparatively higher adsorption of chromate on malachite nanoparticles surface. Copyright © 2010 Elsevier B.V. All rights reserved.

Replica-exchange molecular dynamics simulation of basic fibroblast growth factor adsorption on hydroxyapatite.

PubMed

Liao, Chenyi; Zhou, Jian

2014-06-05

The adsorption of basic fibroblast growth factor (bFGF) on the hydroxyapatite (001) surface was investigated by a combination of replica-exchange molecular dynamics (REMD) and conventional molecular dynamics (CMD) methods. In CMD, the protein cannot readily cross the surface water layer, whereas in REMD, the protein can cross the adsorption barrier from the surface water layer and go through weak, medium, then strong adsorption states with three energetically preferred configurations: heparin-binding-up (HP-up), heparin-binding-middle (HP-middle), and heparin-binding-down (HP-down). The HP-middle orientation, with the strongest adsorption energy (-1149 ± 40 kJ·mol(-1)), has the largest adsorption population (52.1-52.6%) and exhibits the largest conformational charge (RMSD of 0.26 ± 0.01 nm) among the three orientations. The HP-down and HP-up orientations, with smaller adsorption energies of -1022 ± 55 and -894 ± 70 kJ·mol(-1), respectively, have smaller adsorption populations of 27.4-27.7% and 19.7-20.5% and present smaller RMSD values of 0.21 ± 0.01 and 0.19 ± 0.01 nm, respectively. The convergent distribution indicates that nearly half of the population (in the HP-middle orientation) will support both FGF/FGFR and DGR-integrin signaling and another half (in the HP-up and HP-down orientations) will support DGR-integrin signaling. The major population (~80%) has the protein dipole directed outward. In the strong adsorption state, there are usually 2 to 3 basic residues that form the anchoring interactions of 210-332 kJ·mol(-1) per residue or that are accompanied by an acidic residue with an adsorption energy of ~207 kJ·mol(-1). Together, the major bound residues form a triangle or a quadrilateral on the surface and stabilize the adsorption geometrically, which indicates topologic matching between the protein and HAP surfaces.

Intensify dodecylamine adsorption on magnesite and dolomite surfaces by monohydric alcohols

NASA Astrophysics Data System (ADS)

Zhang, Hao; Liu, Wengang; Han, Cong; Wei, Dezhou

2018-06-01

The flotation of magnesite and dolomite were investigated with the presence of single dodecylamine (DDA) and combined mixtures of DDA and monohydric alcohols, respectively. The adsorption behavior of DDA, butanol, hexanol and octanol on the surface of the two minerals were shown by molecular dynamics simulation, and the results were corresponding with the analysis of zeta potential, measurements of the contact angle and adsorption. Flotation results indicated that part of DDA could be replaced by the three alcohols (butanol, hexanol, octanol) to get better flotation results. Molecular dynamics simulation and the results of zeta potential and contact angle measurements indicated that adsorption of DDA on mineral surfaces could be strengthened by monohydric alcohols.

Determination of the effects of water adsorption on the sensitivity and detonation performance of the explosive JOB-9003 by molecular dynamics simulation.

PubMed

Hang, GuiYun; Yu, WenLi; Wang, Tao; Li, Zhen

2016-11-01

In order to determine the adsorption mechanism of water on the crystal surfaces of the explosive JOB-9003 and the effect of this adsorption on the sensitivity and detonation performance of this explosive, a model of the crystal of JOB-9003 was created in the software package Materials Studio (MS). The adsorption process was simulated, and molecular dynamics simulation was performed with the COMPASS force field in the NPT ensemble to calculate the sensitivity and detonation performance of the explosive. The results show that the maximum trigger bond length decreases whereas the interaction energy of the trigger bond and the cohesive energy density increase after adsorption, indicating that the sensitivity of JOB-9003 decreases. The results for the detonation performance show that the detonation pressure, detonation velocity, and detonation heat decrease upon the adsorption of water, thus illustrating that the detonation performance of JOB-9003 is degraded. In summary, the adsorption of water has a positive effect on the sensitivity and safety of the explosive JOB-9003 but a negative effect on its detonation performance.

Peptide adsorption on the hydrophobic surface: A free energy perspective

NASA Astrophysics Data System (ADS)

Sheng, Yuebiao; Wang, Wei; Chen, P.

2011-05-01

Protein adsorption is a very attractive topic which relates to many novel applications in biomaterials, biotechnology and nanotechnology. Ionic complementary peptides are a group of novel nano-biomaterials with many biomedical applications. In this work, molecular dynamics simulations of the ionic-complementary peptide EAK16-II on a hydrophobic graphite surface were performed under neutral, acidic and basic solution conditions. Adsorption free energy contour maps were obtained by analyzing the dynamical trajectories. Hydrophobic interactions were found to govern the adsorption of the first peptide molecule, and both hydrophobic and electrostatic interactions contributed to the adsorption of the second peptide molecule. Especially under acidic and basic solution conditions, interplay existed among chain-chain hydrophobic, chain-surface hydrophobic and chain-chain electrostatic interactions during the adsorption of the second peptide molecule. Non-charged residues were found to lie on the graphite surface, while charged residue side-chains oriented towards the solution after the peptide deposited on the surface. These results provide a basis for understanding peptide adsorption on the hydrophobic surface under different solution conditions, which is useful for novel applications such as bioactive implant devices and drug delivery material design.

Promoting the Adsorption of Metal Ions on Kaolinite by Defect Sites: A Molecular Dynamics Study

PubMed Central

Li, Xiong; Li, Hang; Yang, Gang

2015-01-01

Defect sites exist abundantly in minerals and play a crucial role for a variety of important processes. Here molecular dynamics simulations are used to comprehensively investigate the adsorption behaviors, stabilities and mechanisms of metal ions on defective minerals, considering different ionic concentrations, defect sizes and contents. Outer-sphere adsorbed Pb2+ ions predominate for all models (regular and defective), while inner-sphere Na+ ions, which exist sporadically only at concentrated solutions for regular models, govern the adsorption for all defective models. Adsorption quantities and stabilities of metal ions on kaolinite are fundamentally promoted by defect sites, thus explaining the experimental observations. Defect sites improve the stabilities of both inner- and outer-sphere adsorption, and (quasi) inner-sphere Pb2+ ions emerge only at defect sites that reinforce the interactions. Adsorption configurations are greatly altered by defect sites but respond weakly by changing defect sizes or contents. Both adsorption quantities and stabilities are enhanced by increasing defect sizes or contents, while ionic concentrations mainly affect adsorption quantities. We also find that adsorption of metal ions and anions can be promoted by each other and proceeds in a collaborative mechanism. Results thus obtained are beneficial to comprehend related processes for all types of minerals. PMID:26403873

Molecular dynamics simulations of collagen adsorption onto grooved rutile surface: the effects of groove width.

PubMed

Chen, Mingjun; Zheng, Ting; Wu, Chunya; Xing, Cheng

2014-09-01

The early adsorption stages of collagen onto nano-grooved rutile surface without hydroxylation were studied using molecular dynamics and steered MD simulations. On the basis of plane rutile (110), two kinds of models have been adopted: single groove and parallel grooves along [1-11] crystal orientation with various width dimensions. Initially, collagens were parallel or perpendicular to the groove orientation, respectively, in order to investigate the influence of groove width on collagen adsorption. The simulation result suggests that surface grooves could exert a strong effect on collagen adsorption: when collagen was parallel to the groove direction, adsorption was favored if the groove width matched well with the dimension of collagen. However, adsorption strength may decrease as the groove width expanded. As for the condition of collagen perpendicular to the groove orientation, collagen was difficult to bend and insert into grooves in the free adsorption procedure. But the steered MD simulation results reveal that more energy was consumed for collagen to insert into narrower grooves which may be interpreted as strong barrier for adsorption. We believe that adsorption will be favored if appropriate dimension match between dimension of collagen and the groove width was approached. Copyright © 2014 Elsevier B.V. All rights reserved.

Adsorption of pharmaceuticals onto trimethylsilylated mesoporous SBA-15.

PubMed

Bui, Tung Xuan; Pham, Viet Hung; Le, Son Thanh; Choi, Heechul

2013-06-15

The adsorption of a complex mixture of 12 selected pharmaceuticals to trimethylsilylated mesoporous SBA-15 (TMS-SBA-15) has been investigated by batch adsorption experiments. The adsorption of pharmaceuticals to TMS-SBA-15 was highly dependent on the solution pH and pharmaceutical properties (i.e., hydrophobicity (logKow) and acidity (pKa)). Good log-log linear relationships between the adsorption (Kd) and pH-dependent octanol-water coefficients (Kow(pH)) were then established among the neutral, anionic, and cationic compounds, suggesting hydrophobic interaction as a primary driving force in the adsorption. In addition, the neutral species of each compound accounted for a major contribution to the overall compound adsorption onto TMS-SBA-15. The adsorption kinetics of pharmaceuticals was evaluated by the nonlinear first-order and pseudo-second-order models. The first-order model gave a better fit for five pharmaceuticals with lower adsorption capacity, whereas the pseudo-second-order model fitted better for seven pharmaceuticals having higher adsorption capacity. In the same group of properties, pharmaceuticals having higher adsorption capacity exhibited faster adsorption rates. The rate-limiting steps for adsorption of pharmaceuticals onto TMS-SBA-15 are boundary layer diffusion and intraparticle diffusion including diffusion in mesopores and micropores. In addition, the adsorption of pharmaceuticals to TMS-SBA-15 was not influenced by the change of initial pharmaceutical concentration (10-100μgL(-1)) and the presence of natural organic matter. Copyright © 2013 Elsevier B.V. All rights reserved.

Wettability modification of Wender lignite by adsorption of dodecyl poly ethoxylated surfactants with different degree of ethoxylation: A molecular dynamics simulation study.

PubMed

Zhang, Lei; Li, Bao; Xia, Yangchao; Liu, Shengyu

2017-09-01

Lignite is an important and useful fossil fuel in the world and the strong hydrophilicity of it limits its applications. Surfactant adsorption on lignite is an effective way to make it hydrophobic. In this work, aiming to examine the effect of the degree of ethoxylation on the adsorption behavior of dodecyl poly ethoxylated surfactants on lignite and the wettability modification of modified lignite by surfactant adsorption, different combined systems formed by surfactants, water and a model surface of Wender lignite have been studied using molecular dynamics simulation. The adsorption configurations vary with the degree of ethoxylation. At the same adsorption amounts, increasing the degree of ethoxylation can make the adsorption layer more compactness and bring stronger adsorption strength. The results of binding energy and its components show that the adsorption of alkyl polyoxyethylene ethers surfactant on lignite is physically adsorbed rather than electrostatically or chemisorbed. Meanwhile, van der Waals interaction plays a dominant role in the adsorption. The addition of surfactant could reduce the possibility of the interaction between water and lignite. Compared to the original lignite, the interaction between them is weakened after surfactant adsorption in water/surfactant/lignite system, thus strengthening the hydrophobicity of lignite. Similar to the adsorption strength, hydrophobicity of modified lignite increases with the increase of the degree of ethoxylation. The lignite surface properties are changed due to surfactant adsorption by analyzing the compositions of interaction energy and the change of hydrogen bonds. Copyright © 2017 Elsevier Inc. All rights reserved.

Statistical mechanical model of gas adsorption in porous crystals with dynamic moieties

PubMed Central

Braun, Efrem; Carraro, Carlo; Smit, Berend

2017-01-01

Some nanoporous, crystalline materials possess dynamic constituents, for example, rotatable moieties. These moieties can undergo a conformation change in response to the adsorption of guest molecules, which qualitatively impacts adsorption behavior. We pose and solve a statistical mechanical model of gas adsorption in a porous crystal whose cages share a common ligand that can adopt two distinct rotational conformations. Guest molecules incentivize the ligands to adopt a different rotational configuration than maintained in the empty host. Our model captures inflections, steps, and hysteresis that can arise in the adsorption isotherm as a signature of the rotating ligands. The insights disclosed by our simple model contribute a more intimate understanding of the response and consequence of rotating ligands integrated into porous materials to harness them for gas storage and separations, chemical sensing, drug delivery, catalysis, and nanoscale devices. Particularly, our model reveals design strategies to exploit these moving constituents and engineer improved adsorbents with intrinsic thermal management for pressure-swing adsorption processes. PMID:28049851

Statistical mechanical model of gas adsorption in porous crystals with dynamic moieties.

PubMed

Simon, Cory M; Braun, Efrem; Carraro, Carlo; Smit, Berend

2017-01-17

Some nanoporous, crystalline materials possess dynamic constituents, for example, rotatable moieties. These moieties can undergo a conformation change in response to the adsorption of guest molecules, which qualitatively impacts adsorption behavior. We pose and solve a statistical mechanical model of gas adsorption in a porous crystal whose cages share a common ligand that can adopt two distinct rotational conformations. Guest molecules incentivize the ligands to adopt a different rotational configuration than maintained in the empty host. Our model captures inflections, steps, and hysteresis that can arise in the adsorption isotherm as a signature of the rotating ligands. The insights disclosed by our simple model contribute a more intimate understanding of the response and consequence of rotating ligands integrated into porous materials to harness them for gas storage and separations, chemical sensing, drug delivery, catalysis, and nanoscale devices. Particularly, our model reveals design strategies to exploit these moving constituents and engineer improved adsorbents with intrinsic thermal management for pressure-swing adsorption processes.

Ac electroosmotic flows above coplanar electrodes

NASA Astrophysics Data System (ADS)

Kweon Suh, Yong

2009-03-01

Interactive numerical method has been proposed to calculate the ac electroosmotic flows above a pair of coplanar electrodes. The thin electrical triple layer (ETL) has been modeled by an asymptotic theory developed by the authors. The model corresponds to a simple dynamic equation for the surface charge density representing the integrated charge over the inner layer. Interactive calculation of the dynamic equation and the Laplace equation for several periods of ac frequency then yielded steady-state distribution of potential and the potential drop across the Stern and inner layers. The Smoluchowski's slip velocity was then determined from those two set of data and used as the boundary condition for the calculation of the Stokes' flow above the electrodes. We have shown that our solutions compared well with the experimental data reported in the literature. We investigated the effect of various parameters on the slip velocity distribution, such as the ac frequency, the electrode length, the effective Stern-layer thickness and the adsorption coefficients.

Adsorption of bentazon on CAT and CARBOPAL activated carbon: Experimental and computational study

NASA Astrophysics Data System (ADS)

Spaltro, Agustín; Simonetti, Sandra; Torrellas, Silvia Alvarez; Rodriguez, Juan Garcia; Ruiz, Danila; Juan, Alfredo; Allegretti, Patricia

2018-03-01

Removal of the bentazon by adsorption on two different types of activated carbon was investigated under various experimental conditions.Kinetics of adsorption is followed and the adsorption isotherms of the pesticide are determined. The effects of the changes in pH, ionic strength and temperature are analyzed. Computational simulation was employed to analyze the geometry and the energy of pesticide absorption on activated carbon. Concentration of bentazon decreases while increase all the variables, from the same initial concentration. Experimental data for equilibrium was analyzed by three models: Langmuir, Freundlich and Guggenheim-Anderson-de Boer isotherms. Pseudo-first and pseudo-second-order kinetics are tested with the experimental data, and pseudo-second-order kinetics was the best for the adsorption of bentazon by CAT and CARBOPAL with coefficients of correlation R2 = 0.9996 and R2 = 0.9993, respectively. The results indicated that both CAT and CARBOPAL are very effective for the adsorption of bentazon from aqueous solutions, but CAT carbon has the greater capacity.

Citric acid modified kenaf core fibres for removal of methylene blue from aqueous solution.

PubMed

Sajab, Mohd Shaiful; Chia, Chin Hua; Zakaria, Sarani; Jani, Saad Mohd; Ayob, Mohd Khan; Chee, Kah Leong; Khiew, Poi Sim; Chiu, Wee Siong

2011-08-01

Chemically modified kenaf core fibres were prepared via esterification in the presence of citric acid (CA). The adsorption kinetics and isotherm studies were carried out under different conditions to examine the adsorption efficiency of CA-treated kenaf core fibres towards methylene blue (MB). The adsorption capacity of the kenaf core fibres increased significantly after the citric acid treatment. The values of the correlation coefficients indicated that the Langmuir isotherm fitted the experimental data better than the Freundlich isotherm. The maximum adsorption capacity of the CA-treated kenaf core fibres was found to be 131.6mg/g at 60°C. Kinetic models, pseudo-first-order, pseudo-second-order and intraparticle diffusion, were employed to describe the adsorption mechanism. The kinetic data were found to fit pseudo-second-order model equation as compared to pseudo-first-order model. The adsorption of MB onto the CA-treated kenaf core fibres was spontaneous and endothermic. Copyright © 2011 Elsevier Ltd. All rights reserved.

Adsorptive performance of coal-based magnetic activated carbon for cyclic volatile methylsiloxanes from landfill leachate.

PubMed

Zhang, Chunhui; Jiang, Shan; Zhang, Wenwen

2018-02-01

Bituminous coal-based magnetic activated carbon (MAC) was prepared, characterized, and used successfully for removal of cyclic volatile methylsiloxanes (cVMSs) from treated landfill leachate. Batch adsorption studies were performed at different adsorption dosages and contact times. With adsorptive dosage of 0.75 g/L and contact time of 60 min, the removal efficiencies achieved by MAC for octamethylcyclotetrasiloxane (D 4 ), decamethylcyclopentasiloxane (D 5 ), and dodecamethylcyclohexasiloxane (D 6 ) are 100, 82.8, and 71.4%, respectively. The specific magnetization coefficients of MAC before and after adsorption are 4.6 × 10 -7 and 5.2 × 10 -7  m 3 /kg, between 1.26 × 10 -7 and 3.8 × 10 -5  m 3 /kg, which suggests that MAC can be recycled by the high-intensity magnetic separators.

BN-C Hybrid Nanoribbons as Gas Sensors

NASA Astrophysics Data System (ADS)

Darvishi Gilan, Mahdi; Chegel, Raad

2018-02-01

The effects of carbon monoxide (CO) and ammonia (NH3) molecules adsorption on the various composites of boron nitride and graphene BN-C hybrid nanoribbons are investigated using the non-equilibrium Green's function (NEGF) technique based on density functional theory (DFT). The effects of adsorption with possible random configurations on the average of the density of states (DOS), transmission coefficient, and the current-voltage ( I- V) characteristics are calculated. The results indicate that, by embedding armchair graphene nanoribbon (AGNR) with boron nitride nanoribbon (BNNR), the various electronic properties can be observed after gas molecule adsorption. The electronic structure and gap of hybrids system is modified due to gas adsorption, and the systems act like the n-type semiconductor by NH3 molecule adsorption. The hybrid structures due to their tunable band gap are better candidates for gas detecting compared to the pristine BNNRs and AGNRs.

Adsorption of acetanilide herbicides on soil and its components. II. Adsorption and catalytic hydrolysis of diethatyl-ethyl on saturated Na(+)-, K(+)-, Ca(2+)-, and Mg(2+)-montmorillonite.

PubMed

Liu, W P; Fang, Z; Liu, H J; Yang, W C

2001-04-01

Adsorption and catalytic hydrolysis of the herbicide diethatyl-ethyl [N-chloroacetyl-N-(2,6-diethylphenyl)glycine ethyl ester] on homoionic Na(+)-, K(+)-, Ca(2+)-, and Mg(2+)-montmorillonite clays were investigated in water solution. The Freundlich adsorption coefficient, Ki, got from isotherms on clay followed the order of Na+ approximately K+ > Mg2+ approximately Ca2+. Analysis of FT-IR spectra of diethatyl-ethyl adsorbed on clay suggests probable bonding at the carboxyl and amide carbonyl groups of the herbicide. The rate of herbicide hydrolysis in homoionic clay suspensions followed the same order as that for adsorption, indicating that adsorption may have preceded and thus caused hydrolysis. Preliminary product identification showed that hydrolysis occurred via nucleophilic substitution at the carboxyl carbon, causing the cleavage of the ester bond and formation of diethatyl and its dechlorinated derivative, and at the amide carbon, yielding an ethyl ester derivative and its acid. These pathways also suggest that hydrolysis of diethatyl-ethyl was catalyzed by adsorption on the clay surface.

Single, competitive, and dynamic adsorption on activated carbon of compounds used as plasticizers and herbicides.

PubMed

Abdel daiem, Mahmoud M; Rivera-Utrilla, José; Sánchez-Polo, Manuel; Ocampo-Pérez, Raúl

2015-12-15

The main aim of this study was to investigate the single, competitive, and dynamic adsorption of phthalic acid (PA), bisphenol A (BPA), diphenolic acid (DPA), 2,4-dichlorophenoxy-acetic acid (2,4-D), and 4-chloro-2-methylphenoxyacetic acid (MCPA) on two activated carbons with different chemical natures and similar textural characteristics. The adsorption mechanism was also elucidated by analyzing the influence of solution pH and ionic strength. The activated carbons demonstrated high adsorption capacity to remove all micropollutants due to the presence of active sites on their surfaces, which increase dispersive interactions between the activated carbon graphene layers and the aromatic ring of pollutants. The adsorption capacity of the activated carbons increased in the order: DPA

Adsorption of insulin peptide on charged single-walled carbon nanotubes: significant role of ordered water molecules.

PubMed

Shen, Jia-Wei; Wu, Tao; Wang, Qi; Kang, Yu; Chen, Xin

2009-06-02

Ordered hydration shells: The more ordered hydration shells outside the charged CNT surfaces prevent more compact adsorption of the peptide in the charged CNT systems [picture: see text], but peptide binding strengths on the charged CNT surfaces are stronger due to the electrostatic interaction.Studies of adsorption dynamics and stability for peptides/proteins on single-walled carbon nanotubes (SWNTs) are of great importance for a better understanding of the properties and nature of nanotube-based biosystems. Herein, the dynamics and mechanism of the adsorption of the insulin chain B peptide on different charged SWNTs are investigated by explicit solvent molecular dynamics simulations. The results show that all types of surfaces effectively attract the model peptide. Water molecules play a significant role in peptide adsorption on the surfaces of charged carbon nanotubes (CNTs). Compared to peptide adsorption on neutral CNT surfaces, the more ordered hydration shells outside the tube prevent more compact adsorption of the peptide in charged CNT systems. This shield effect leads to a smaller conformational change and van der Waals interaction between the peptide and surfaces, but peptide binding strengths on charged CNT surfaces are stronger than those on the neutral CNT surface due to the strong electrostatic interaction. The result of these simulations implies the possibility of improving the binding strength of peptides/proteins on CNT surfaces, as well as keeping the integrity of the peptide/protein conformation in peptide/protein-CNT complexes by charging the CNTs.

Adsorption and desorption performance of benzene over hierarchically structured carbon-silica aerogel composites.

PubMed

Dou, Baojuan; Li, Jinjun; Wang, Yufei; Wang, Hailin; Ma, Chunyan; Hao, Zhengping

2011-11-30

Hierarchically structured carbon-silica aerogel (CSA) composites were synthesized from cheap water glass precursors and granulated activated carbon via a post-synthesis surface modification with trimethylchlorosilane (TMCS) and a low-cost ambient pressure drying procedure. The resultant CSA composites possess micro/mesoporous structure and hydrophobic surface. The adsorption and desorption performance of benzene on carbon-silica aerogel composite (CSA-2) under static and dynamic conditions were investigated, comparing with pure silica aerogel (CSA-0) and microporous activated carbon (AC). It was found that CSA-2 has high affinity towards aromatic molecules and fast adsorption kinetics. Excellent performance of dynamic adsorption and desorption observed on CSA-2 is related to its higher adsorption capacity than CSA-0 and less mass transfer resistance than AC, arising from the well-developed microporosity and open foam mesostructure in the CSA composites. Copyright © 2011 Elsevier B.V. All rights reserved.

Application of Statistical Thermodynamics To Predict the Adsorption Properties of Polypeptides in Reversed-Phase HPLC.

PubMed

Tarasova, Irina A; Goloborodko, Anton A; Perlova, Tatyana Y; Pridatchenko, Marina L; Gorshkov, Alexander V; Evreinov, Victor V; Ivanov, Alexander R; Gorshkov, Mikhail V

2015-07-07

The theory of critical chromatography for biomacromolecules (BioLCCC) describes polypeptide retention in reversed-phase HPLC using the basic principles of statistical thermodynamics. However, whether this theory correctly depicts a variety of empirical observations and laws introduced for peptide chromatography over the last decades remains to be determined. In this study, by comparing theoretical results with experimental data, we demonstrate that the BioLCCC: (1) fits the empirical dependence of the polypeptide retention on the amino acid sequence length with R(2) > 0.99 and allows in silico determination of the linear regression coefficients of the log-length correction in the additive model for arbitrary sequences and lengths and (2) predicts the distribution coefficients of polypeptides with an accuracy from 0.98 to 0.99 R(2). The latter enables direct calculation of the retention factors for given solvent compositions and modeling of the migration dynamics of polypeptides separated under isocratic or gradient conditions. The obtained results demonstrate that the suggested theory correctly relates the main aspects of polypeptide separation in reversed-phase HPLC.

Evaluation of nonequilibrium boundary conditions for hypersonic rarefied gas flows

NASA Astrophysics Data System (ADS)

Le, N. T. P.; Greenshields, Ch. J.; Reese, J. M.

2012-01-01

A new Computational Fluid Dynamics (CFD) solver for high-speed viscous §ows in the OpenFOAM code is validated against published experimental data and Direct Simulation Monte Carlo (DSMC) results. The laminar §at plate and circular cylinder cases are studied for Mach numbers, Ma, ranging from 6 to 12.7, and with argon and nitrogen as working gases. Simulation results for the laminar §at plate cases show that the combination of accommodation coefficient values σu = 0.7 and σT = 1.0 in the Maxwell/Smoluchowski conditions, and the coefficient values A1 = 1.5 and A2 = 1.0 in the second-order velocity slip condition, give best agreement with experimental data of surface pressure. The values σu = 0.7 and σT = 1.0 also give good agreement with DSMC data of surface pressure at the stagnation point in the circular cylinder case at Kn = 0.25. The Langmuir surface adsorption condition is also tested for the laminar §at plate case, but initial results were not as good as the Maxwell/Smoluchowski boundary conditions.

Surface area of montmorillonite from the dynamic sorption of nitrogen and carbon dioxide

USGS Publications Warehouse

Thomas, Josephus; Bohor, Bruce F.

1968-01-01

Surface area determinations were made on a montmorillonite with various cations emplaced on the exchangeable sites, utilizing nitrogen and carbon dioxide as adsorbates at 77°K and 195°K, respectively, in a dynamic system. From the fraction of a Mississippi montmorillonite less than about 1 μ in size, samples were prepared by replacing the original exchangeable cations with Li+, Na+, K+, Rb+, Cs+, Mg++, Ca++, Ba++, and NH4+, forming a series of homoionic montmorillonite species.Surface areas from 3-point B.E.T. plots (half-hour adsorption points), with nitrogen as the adsorbate, ranged from 61 m2/g for Li-montmorillonite to 138 m2/g for Cs-montmorillonite, thus reflecting a certain degree of nitrogen penetration between layers. Complete penetration should theoretically result in a surface area of over 300 m2/g for this clay with a nitrogen monolayer between each pair of platelets. The experimental data indicate that the extent of penetration is time-dependent and is also a function of the interlayer forces as governed by the size and charge of the replaceable cation. This finding negates the generally accepted concept that nitrogen at 77°K does not penetrate the layers and provides a measure only of the external surface of expandable clay minerals.A further measure of the variation of interlayer forces is provided by the adsorption of carbon dioxide at 195°K. Surface area values ranged from 99 m2/g for Li-montmorillonite to 315 m2/g for Csmontmorillonite. Although the carbon dioxide molecule is larger than the nitrogen molecule, its greater penetration apparently is a result of its being kinetically more energetic (with a larger diffusion coefficient) at its higher adsorption temperature. Similar differences have been found with both adsorbates in the study of microporous substances, such as coal, where activated diffusion is of considerable significance.

Ab initio molecular dynamics determination of competitive O₂ vs. N₂ adsorption at open metal sites of M₂(dobdc).

PubMed

Parkes, Marie V; Greathouse, Jeffery A; Hart, David B; Gallis, Dorina F Sava; Nenoff, Tina M

2016-04-28

The separation of oxygen from nitrogen using metal-organic frameworks (MOFs) is of great interest for potential pressure-swing adsorption processes for the generation of purified O2 on industrial scales. This study uses ab initio molecular dynamics (AIMD) simulations to examine for the first time the pure-gas and competitive gas adsorption of O2 and N2 in the M2(dobdc) (M = Cr, Mn, Fe) MOF series with coordinatively unsaturated metal centers. Effects of metal, temperature, and gas composition are explored. This unique application of AIMD allows us to study in detail the adsorption/desorption processes and to visualize the process of multiple guests competitively binding to coordinatively unsaturated metal sites of a MOF.

Liquid/vapor-induced reversible dynamic structural transformation of a three-dimensional Cu-based MOF to a one-dimensional MOF showing gate adsorption.

PubMed

Kondo, Atsushi; Suzuki, Takayuki; Kotani, Ryosuke; Maeda, Kazuyuki

2017-05-23

A new 3D metal-organic framework (MOF), in which 2D layers are interlaced to form a 3D architecture, was synthesized by a reaction of Cu(BF 4 ) 2 and 1,3-bis(4-pyridyl)propane (bpp) in a water/1-hexanol solvent system, and the crystal structure of the MOF was successfully solved. The MOF is reversibly transformed to a 1D chain MOF, which shows gate adsorption properties. The dynamic transformation gives crystal size reduction resulting in a slight change in CO 2 adsorption isotherms. The 1D MOF shows selective adsorption/separation properties on benzene and its analogues with similar sizes and shapes (benzene, toluene, and cyclohexane).

Adsorption of lead on multi-walled carbon nanotubes with different outer diameters and oxygen contents: kinetics, isotherms and thermodynamics.

PubMed

Yu, Fei; Wu, Yanqing; Ma, Jie; Zhang, Chi

2013-01-01

The effects of different outer diameters and surface oxygen contents on the adsorption of heavy metals onto six types of multi-walled carbon nanotubes (MWCNTs) were investigated in an aqueous solution and lead was chosen as a model metal ion. The results indicated that the percentage removal and adsorption capacity of lead remarkably increased with decreasing outer diameter due to larger specific surface area (SSA). The SSA-normalized maximum adsorption capacity (qmSSA) and SSA-normalized adsorption coefficient (Kd/SSA) were strongly positively correlated with surface oxygen content, implying that lead adsorption onto MWCNTs significantly increases with the rise of oxygen content and decreases with decreasing SSA. The calculated thermodynamic parameters indicated that adsorption of lead on MWCNTs was endothermic and spontaneous. When the oxygen content of MWCNTs increased from 2.0% to 5.9%, the standard free energy (deltaG0) became more negative, which implied that the oxygenated functional groups increased the adsorption affinity of MWCNTs for lead. Through calculation of enthalpy (deltaH0), deltaG0 and free energy of adsorption (Ea), lead adsorption onto MWCNTs was recognized as a chemisorption process. The chemical interaction between lead and the phenolic groups of MWCNTs could be one of the main adsorption mechanisms due to highly positive correlations between the phenolic groups and Kd/SSA or qm/SSA.

Combined Homogeneous Surface Diffusion Model - Design of experiments approach to optimize dye adsorption considering both equilibrium and kinetic aspects.

PubMed

Muthukkumaran, A; Aravamudan, K

2017-12-15

Adsorption, a popular technique for removing azo dyes from aqueous streams, is influenced by several factors such as pH, initial dye concentration, temperature and adsorbent dosage. Any strategy that seeks to identify optimal conditions involving these factors, should take into account both kinetic and equilibrium aspects since they influence rate and extent of removal by adsorption. Hence rigorous kinetics and accurate equilibrium models are required. In this work, the experimental investigations pertaining to adsorption of acid orange 10 dye (AO10) on activated carbon were carried out using Central Composite Design (CCD) strategy. The significant factors that affected adsorption were identified to be solution temperature, solution pH, adsorbent dosage and initial solution concentration. Thermodynamic analysis showed the endothermic nature of the dye adsorption process. The kinetics of adsorption has been rigorously modeled using the Homogeneous Surface Diffusion Model (HSDM) after incorporating the non-linear Freundlich adsorption isotherm. Optimization was performed for kinetic parameters (color removal time and surface diffusion coefficient) as well as the equilibrium affected response viz. percentage removal. Finally, the optimum conditions predicted were experimentally validated. Copyright © 2017 Elsevier Ltd. All rights reserved.

Hierarchical porous membrane via electrospinning PIM-1 for micropollutants removal

NASA Astrophysics Data System (ADS)

Pan, Ying; Zhang, Lijie; Li, Zhaojing; Ma, Liujia; Zhang, Yufeng; Wang, Jun; Meng, Jianqiang

2018-06-01

Ideal adsorbents are featured by both high adsorption capacity and high adsorption rate. Current adsorptive membranes enjoy good mass transfer performance but have limited sorption capacity. Microporous organic polymer has superiorities of small pore size and high surface area which is conductive to high adsorption capacity, but usually suffers from high mass transfer resistance. In this work, the polymer of intrinsic microporosity PIM-1 was fabricated into microfiber membranes by electrospinning for carbendazim and phenol adsorption. The PIM-1 and its electrospun membranes were characterized by 1H NMR, GPC, ATR-FTIR, FESEM, TG and BET measurements. The electrospun PIM-1 membrane was demonstrated to have hierarchical porous structure with high surface area. The equilibrium adsorption capacity for carbendazim and phenol was 0.084 mmol/g and 0.804 mmol/g, respectively. The adsorption isotherm fits well with Langmuir model and the adsorption kinetic can be described by film diffusion and chemical reaction model. The membrane can retain 95% of its initial capacity after cycling 10 times. Both the sorption capacity and kinetic coefficients are high when comparing with other sorbents for either carbendazim or phenol, demonstrating that the electrospun PIM-1 is a good adsorbent.

Adsorption equilibrium and kinetics of Immunoglobulin G on a mixed-mode adsorbent in batch and packed bed configuration.

PubMed

Gomes, Pedro Ferreira; Loureiro, José Miguel; Rodrigues, Alírio E

2017-11-17

It is commonly accepted that efficient protein separation and purification to the desired level of purity is one bottleneck in pharmaceutical industries. MabDirect MM is a new type of mixed mode adsorbent, especially designed to operate in expanded bed adsorption (EBA) mode. In this study, equilibrium and kinetics experiments were carried out for the adsorption of Human Immunoglobulin G (hIgG) protein on this new adsorbent. The effects of ionic strength and pH are assessed. Langmuir isotherms parameters are obtained along with the estimation of the effective pore diffusion coefficient (D pe ) by fitting the batch adsorption kinetics experiments with the pore diffusion model. The maximum adsorption of the IgG protein on the MabDirect MM adsorbent, 149.7±7.1mg·g dry -1 , was observed from a pH 5.0 buffer solution without salt addition. Adding salt to the buffer solution, and/or increasing pH, decreases the adsorption capacity which is 4.7±0.4mg·g dry -1 for pH 7.0 with 0.4M NaCl in solution. Regarding the D pe estimation, a value of 15.4×10 -6 cm 2 ·min -1 was obtained for a pH 5.0 solution without salt. Increasing the salt concentration and/or the pH value will decrease the effective pore diffusion, the lowest D pe (0.16×10 -6 cm 2 ·min -1 ) value being observed for an IgG solution at pH 7.0 with 0.4M NaCl. Fixed bed experiments were conducted with the purpose to validate the equilibrium and kinetic parameters obtained in batch. For a feed concentration of 0.5 g·L -1 of IgG in pH 5.0 buffer solution with 0.4M NaCl, a dynamic binding capacity at 10% of breakthrough of 5.3mg·g wet -1 (15.4mg IgG ·mL resin -1 ) was obtained, representing 62% of the saturation capacity. As far as the authors know, this study is the first one concerning the adsorption of hIgG on this type of mixed mode chromatography adsorbent. Copyright © 2017 Elsevier B.V. All rights reserved.

Elaboration of chitosan/activated carbon composites for the removal of organic micropollutants from waters.

PubMed

Venault, A; Vachoud, L; Pochat, C; Bouyer, D; Faur, C

2008-12-01

Composite hydrogels were prepared by a wet-casting process by blending a biopolymer, chitosan, with activated carbon (AC) for use in water treatment. Adsorption properties of the composite gels for an organic micro-pollutant (phenol) which may be encountered in wastewaters was studied with an experimental design approach as a function of: - the concentration of raw materials and thus the AC weight within the chitosan matrix. - the accessibility of AC in the polymeric matrix, which is assumed to be related to the coating and thus to the pH of the immersion bath. ESEM observations showed that at a higher pH of gelation (pH = 14), AC particles were entrapped at the surface of the polymer matrix because of a faster gelation kinetic than at a lower pH (13.3). Adsorption kinetic tests showed that phenol adsorption occurred according to two mechanisms. During the first step, phenol molecules were adsorbed by the AC particles located at the surface. The second step corresponded to a slow diffusion through chitosan chains leading to an adsorption by AC particles entrapped within the polymeric matrix coupled to an adsorption on to the chitosan. A mass transfer model was used to describe this two-step adsorption phenomenon. However, due to a heterogeneous coating of AC by chitosan, this phenomenon was not supported by experimental design results: the initial kinetic coefficients were associated with a high experimental error which didn't allow for an analysis of the influence of elaboration parameters on kinetic coefficients. Regardling equilibrium adsorption properties, it was shown that composite gels were good adsorbents for phenol with removal ranging from 94% to 98% corresponding to adsorption capacities from 30 to 41 mg g(-1). The pH of the immersion bath had no influence on equilibrium adsorption properties, contrary to the AC weight within the chitosan matrix which wasdemonstrated to influence significantly adsorption capacities. Because carbon particles may improve mechanical properties, mechanical tests were carried out on the composite gels. For a total amount of dried matter in the compositekept constant, the increase in chitosan content led to an increase in the mechanical properties, because of an increase in thenumber of interactions between chitosan chains. The influence of sonication during the stirring step, leading to a better homogenisation of AC particules within the polymer matrix, was also examined.

Behavior of human immunoglobulin G adsorption onto immobilized Cu(II) affinity hollow-fiber membranes.

PubMed

Borsoi-Ribeiro, Mariana; Bresolin, Igor Tadeu Lazzarotto; Vijayalakshmi, Mookambeswaran; Bueno, Sônia Maria Alves

2013-10-01

Iminodiacetic acid (IDA) and tris(2-aminoethyl)amine (TREN) chelating ligands were immobilized on poly(ethylene vinyl alcohol) (PEVA) hollow-fiber membranes after activation with epichlorohydrin or butanediol diglycidyl ether (bisoxirane). The affinity membranes complexed with Cu(II) were evaluated for adsorption of human immunoglobulin G (IgG). The effects of matrix activation and buffer system on adsorption of IgG were studied. Isotherms of batch IgG adsorption onto finely cut membranes showed that neither of the chelates, IDA-Cu(II) or TREN-Cu(II), had a Langmuirean behavior with negative cooperativity for IgG binding. A comparison of equilibrium and dynamic maximum capacities showed that the dynamic capacity for a mini-cartridge in a cross-flow filtration mode (52.5 and 298.4 mg g(-1) dry weight for PEVA-TREN-Cu(II) and PEVA-IDA-Cu(II), respectively) was somewhat higher than the equilibrium capacity (9.2 and 73.3 mg g(-1) dry weight for PEVA-TREN-Cu(II) and PEVA-IDA-Cu(II), respectively). When mini-cartridges were used, the dynamic adsorption capacity of IDA-Cu(II) was the same for both mini-cartridge and agarose gel. Copyright © 2013 John Wiley & Sons, Ltd.

Design theory and performance of cryogenic molecular adsorption refrigeration systems

NASA Technical Reports Server (NTRS)

Hartwig, W. H.; Woltman, A. W.; Masson, J. P.

1978-01-01

Closed-cycle operation of molecular adsorption refrigeration systems (MARS) has been demonstrated by using thermally cycled zeolites to adsorb and desorb various gases under pressures of 20-60 atm. This paper develops three aspects of the design theory: the physical theory of molecular adsorption of small molecules such as A, N2, N2O and NH3, the design relations for closed-cycle flow for three or more compressors, and the coefficient of performance. This work is intended to demonstrate nonmechanical gas compression for various cryogenic gases than can compete with mechanical systems with a different mix of advantages and disadvantages.

Adsorption of polycyclic aromatic hydrocarbons by graphene and graphene oxide nanosheets.

PubMed

Wang, Jun; Chen, Zaiming; Chen, Baoliang

2014-05-06

The adsorption of naphthalene, phenanthrene, and pyrene onto graphene (GNS) and graphene oxide (GO) nanosheets was investigated to probe the potential adsorptive sites and molecular mechanisms. The microstructure and morphology of GNS and GO were characterized by elemental analysis, XPS, FTIR, Raman, SEM, and TEM. Graphene displayed high affinity to the polycyclic aromatic hydrocarbons (PAHs), whereas GO adsorption was significantly reduced after oxygen-containing groups were attached to GNS surfaces. An unexpected peak was found in the curve of adsorption coefficients (Kd) with the PAH equilibrium concentrations. The hydrophobic properties and molecular sizes of the PAHs affected the adsorption of G and GO. The high affinities of the PAHs to GNS are dominated by π-π interactions to the flat surface and the sieving effect of the powerful groove regions formed by wrinkles on GNS surfaces. In contrast, the adsorptive sites of GO changed to the carboxyl groups attaching to the edges of GO because the groove regions disappeared and the polar nanosheet surfaces limited the π-π interactions. The TEM and SEM images initially revealed that after loading with PAH, the conformation and aggregation of GNS and GO nanosheets dramatically changed, which explained the observations that the potential adsorption sites of GNS and GO were unusually altered during the adsorption process.

Adsorption of cadmium by biochar produced from pyrolysis of corn stalk in aqueous solution.

PubMed

Ma, Fengfeng; Zhao, Baowei; Diao, Jingru

2016-09-01

The purpose of this work is to investigate adsorption characteristic of corn stalk (CS) biochar for removal of cadmium ions (Cd 2+ ) from aqueous solution. Batch adsorption experiments were carried out to evaluate the effects of pH value of solution, adsorbent particle size, adsorbent dosage, and ionic strength of solution on the adsorption of Cd 2+ onto biochar that was pyrolytically produced from CS at 300 °C. The results showed that the initial pH value of solution played an important role in adsorption. The adsorptive amount of Cd 2+ onto the biochar decreased with increasing the adsorbent dosage, adsorbent particle size, and ionic strength, while it increased with increasing the initial pH value of solution and temperature. Cd 2+ was removed efficiently and quickly from aqueous solutions by the biochar with a maximum capacity of 33.94 mg/g. The adsorption process was well described by the pseudo-second-order kinetic model with the correlation coefficients greater than 0.986. The adsorption isotherm could be well fitted by the Langmuir model. The thermodynamic studies showed that the adsorption of Cd 2+ onto the biochar was a spontaneous and exothermic process. The results indicate that CS biochar can be considered as an efficient adsorbent.

A comparative study of fibrinogen adsorption onto metal oxide thin films

NASA Astrophysics Data System (ADS)

Silva-Bermudez, P.; Muhl, S.; Rodil, S. E.

2013-10-01

One of the first events occurring upon foreign material-biological medium contact is the adsorption of proteins, which evolution greatly determines the cells response to the material. Protein-surface interactions are a complex phenomenon driven by the physicochemical properties of the surface, protein(s) and liquid medium involve in the interaction. In this article the adsorption of fibrinogen (Fbg) onto Ta2O5, Nb2O5, TiO2 and ZrO2 thin films is reported. The adsorption kinetics and characteristics of the adsorbed fibrinogen layer were studied in situ using dynamic and spectroscopic ellipsometry. The films wettability, surface energy (γLW/AB) and roughness were characterized aiming to elucidate their correlations with Fbg adsorption. The adsorption rate changed accordingly to the film; the fastest adsorption rate and highest Fbg surface mass concentration (Γ) was observed on ZrO2. The hydrophobic/hydrophilic character of the oxide highly influenced Fbg adsorption. On Ta2O5, Nb2O5 and TiO2, which were either hydrophilic or in the breaking-point between hydrophilicity and hydrophobicity, Γ was correlated to the polar component of γLW/AB and roughness of the surface. On ZrO2, clearly hydrophobic, Γ increased significantly off the correlation observed for the other films. The results indicated different adsorption dynamics and orientations of the Fbg molecules dependent on the surface hydrophobic/hydrophilic character.

COMPARISON OF THE OCTANOL-AIR PARTITION COEFFICIENT AND LIQUID-PHASE VAPOR PRESSURE AS DESCRIPTORS FOR PARTICLE/GAS PARTITIONING USING LABORATORY AND FIELD DATA FOR PCBS AND PCNS

EPA Science Inventory

The conventional Junge-Pankow adsorption model uses the sub-cooled liquid vapor pressure (pLo) as a correlation parameter for gas/particle interactions. An alternative is the octanol-air partition coefficient (Koa) absorption model. Log-log plots of the particle-gas partition c...

Adsorption of sodium dodecylbenzenesulfonate on activated carbons: effects of solution chemistry and presence of bacteria.

PubMed

Bautista-Toledo, M I; Méndez-Díaz, J D; Sánchez-Polo, M; Rivera-Utrilla, J; Ferro-García, M A

2008-01-01

The objective of the present investigation was to determine the effectiveness of activated carbon in removing sodium dodecylbenzenesulfonate (SDBS) and to analyze the chemical and textural characteristics of the activated carbons that are involved in the adsorption process. Studies were also performed on the influence of operational variables (pH, ionic strength, and presence of microorganisms) and on the kinetics and interactions involved in the adsorption of this pollutant on activated carbon. The kinetics study of SDBS adsorption revealed no problems in its diffusion on any of the activated carbons studied, and Weisz-Prater coefficient (C WP) values were considerably lower than unity for all activated carbons studied. SDBS adsorption isotherms on these activated carbons showed that: (i) adsorption capacity of activated carbons was very high (260-470 mg/g) and increased with larger surface area; and (ii) dispersive interactions between SDBS and carbon surface were largely responsible for the adsorption of this pollutant. SDBS adsorption was not significantly affected by the solution pH, indicating that electrostatic adsorbent-adsorbate interactions do not play an important role in this process. The presence of electrolytes (NaCl) in the medium favors SDBS adsorption, accelerating the process and increasing adsorption capacity. Under the working conditions used, SDBS is not degraded by bacteria; however, the presence of bacteria during the process accelerates and increases SDBS adsorption on the activated carbon. Microorganism adsorption on the activated carbon surface increases its hydrophobicity, explaining the results observed.

Influence of surface morphology on adsorption of potassium stearate molecules on diamond-like carbon substrate: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Guo, Shusen; Cao, Yongzhi; Sun, Tao; Zhang, Junjie; Gu, Le; Zhang, Chuanwei; Xu, Zhiqiang

2018-05-01

Molecular dynamics (MD) simulations were used to provide insights into the influence of nano-scale surface morphology on adsorptive behavior of Potassium stearate molecules on diamond-like carbon (DLC) substrates. Particular focus was given to explain that how the distinctive geometric properties of different surface morphologies affect the equilibrium structures and substrate-molecules interactions of monolayers, which was achieved through adsorptive analysis methods including adsorptive process, density profile, density distribution and surface potential energy. Analysis on surface potential energy demonstrated that the adsorptivity of amorphous smooth substrate is uniformly distributed over the surface, while DLC substrates with different surface morphologies appear to be more potentially corrugated, which improves the adsorptivity significantly. Because of the large distance of molecules from carbon atoms located at the square groove bottom, substrate-molecules interactions vanish significantly, and thus potassium stearate molecules cannot penetrate completely into the square groove. It can be observed that the equilibrium substrate-molecules interactions of triangle groove and semi-circle groove are much more powerful than that of square groove due to geometrically advantageous properties. These findings provided key information of optimally design of solid substrates with controllable adsorptivity.

Adsorption characteristics of 210Pb, 210Po and 7Be onto micro-particle surfaces and the effects of macromolecular organic compounds

NASA Astrophysics Data System (ADS)

Yang, Weifeng; Guo, Laodong; Chuang, Chia-Ying; Schumann, Dorothea; Ayranov, Marin; Santschi, Peter H.

2013-04-01

210Po, 210Pb and Be isotopes (e.g. 7Be and 10Be) have long been used as proxies of particle/sediment dynamics, carbon cycling, and oceanographic investigations of coupled processes. However, adsorption characteristics and interactions between these nuclides and particle surfaces remain poorly understood. Laboratory studies have been conducted to examine the adsorption of 210Po, 210Pb and 7Be onto micro-particles, including marine suspended particulate matter, kaolinite, Al2O3, SiO2, CaCO3, Fe2O3, MnO2, and chitin in natural seawater (<1 kDa), and the role of macromolecular organic compounds (MOCs), including humic acids (HA), acid polysaccharides (APS) and proteins (BSA) in regulating the adsorption process. In the absence of MOCs, the partition coefficients (Kd, reported in log Kd) range from 3.02 to 5.19 for 210Po, from 3.22 to 6.29 for 210Pb, and from 3.57 to 4.65 for 7Be. Ferric and manganese oxides are the strongest sorbents of 210Po and 210Pb, comparing with SiO2 and CaCO3. In the presence of the protein BSA, both SiO2 and CaCO3 preferentially adsorb 210Po over 210Pb, whereas the opposite effect was observed in the presence of acid polysaccharides, indicating that proteins could enhance the adsorption of 210Po and acid polysaccharides enhance the adsorption of 210Pb. The log Kd values of both 210Po and 210Pb in the presence of MOCs become similar (log Kd at ˜4.0) for all lithogenic and biogenic particles, suggesting that their adsorption is likely controlled by specific natural organic compounds associated with particle surfaces. For 7Be, the highest and lowest log Kd value was measured, in general, on SiO2 and CaCO3, respectively, consistent with field observations. Nevertheless, the log Kd values of 7Be varied little between particle types regardless of the presence or absence of MOCs, suggesting that the adsorption of Be on particle surfaces is less affected by particle composition or MOCs. These results indicate that 7Be and 10Be could quantitatively track the bulk particles and their fluxes in marine environments while both 210Po and 210Pb could be quantitative proxies for the bulk organic carbon, although 210Po and 210Pb could be fractionated by specific organic compounds during their sorption or scavenging on particle surfaces.

Enantiospecific adsorption of propranolol enantiomers on naturally chiral copper surface: A molecular dynamics simulation investigation

NASA Astrophysics Data System (ADS)

Sedghamiz, Tahereh; Bahrami, Maryam; Ghatee, Mohammad Hadi

2017-04-01

Adsorption of propranolol enantiomers on naturally chiral copper (Cu(3,1,17)S) and achiral copper (Cu(100)) surfaces were studied by molecular dynamics simulation to unravel the features of adsorbate-adsorbent enantioselectivity. Adsorption of S- and R-propranolol on Cu(3,1,17)S terraces (with 100 plane) leads mainly to endo- and exo-conformers, respectively. Simulated pair correlation function (g(r)) and mean square displacement (MSD) were analyzed to identify adsorption sites of enantiomers on Cu(3,1,17)S substrate surface, and their simulated binding energies were used to access the adsorption strength. According to (g(r)), R-propranolol adsorbs via naphtyl group while S-propranolol mainly adsorbs through chain group. R-enantiomer binds more tightly to the chiral substrate surface than S-enantiomer as indicated by a higher simulated binding energy by 2.74 kJ mol-1 per molecule. The difference in binding energies of propranolol enantiomers on naturally chiral Cu(3,1,17)S is almost six times larger than on the achiral Cu(100) surface, which substantiates the appreciably strong specific enantioselective adsorption on the former surface.

Arsenic Adsorption Equilibrium Concentration and Adsorption Rate of Activated Carbon Coated with Ferric-Aluminum Hydroxides

NASA Astrophysics Data System (ADS)

Zhang, M.; Sugita, H.; Oguma, T.; Hara, J.; Takahashi, S.

2015-12-01

In some areas of developing countries, ground or well water contaminated with arsenic has been reluctantly used as drinking water. It is highly desirable that effective and inexpensive arsenic removal agents should be developed and provided to reduce the potential health risk. Previous studies demonstrated that activated carbon coated with ferric-aluminum hydroxides (Fe-Al-C) has high adsorptive potential for removal of arsenic. In this study, a series of experiments using Fe-Al-C were carried to discuss adsorption equilibrium time, adsorption equilibrium concentration and adsorption rate of arsenic for Fe-Al-C. Fe-Al-C used in this study was provided by Astec Co., Ltd. Powder reagent of disodium hydrogen arsenate heptahydrate was dissolved into ion-exchanged water. The solution was then further diluted with ion-exchanged water to be 1 and 10 mg/L as arsenic concentration. The pH of the solution was adjusted to be around 7 by adding HCl and/or NaOH. The solution was used as artificial arsenic contaminated water in two types of experiments (arsenic adsorption equilibrium and arsenic adsorption rate tests). The results of the arsenic equilibrium tests were showed that a time period of about 3 days to reach apparent adsorption equilibrium for arsenic. The apparent adsorption equilibrium concentration and adsorbed amount of arsenic on Fe-Al-C adsorbent could be estimated by application of various adsorption isotherms, but the distribution coefficient of arsenic between solid and liquid varies with experimental conditions such as initial concentration of arsenic and addition concentration of adsorbent. An adsorption rate equation that takes into account the reduction in the number of effective adsorption sites on the adsorbent caused by the arsenic adsorption reaction was derived based on the data obtained from the arsenic adsorption rate tests.

The effect of natural organic matter on the adsorption of mercury to bacterial cells

NASA Astrophysics Data System (ADS)

Dunham-Cheatham, Sarrah; Mishra, Bhoopesh; Myneni, Satish; Fein, Jeremy B.

2015-02-01

We investigated the ability of non-metabolizing Bacillus subtilis, Shewanella oneidensis MR-1, and Geobacter sulfurreducens bacterial species to adsorb mercury in the absence and presence of Suwanee River fulvic acid (FA). Bulk adsorption and X-ray absorption spectroscopy (XAS) experiments were conducted at three pH conditions, and the results indicate that the presence of FA decreases the extent of Hg adsorption to biomass under all of the pH conditions studied. Hg XAS results show that the presence of FA does not alter the binding environment of Hg adsorbed onto the biomass regardless of pH or FA concentration, indicating that ternary bacteria-Hg-FA complexes do not form to an appreciable extent under the experimental conditions, and that Hg binding on the bacteria is dominated by sulfhydryl binding. We used the experimental results to calculate apparent partition coefficients, Kd, for Hg under each experimental condition. The calculations yield similar coefficients for Hg onto each of the bacterial species studies, suggesting there is no significant difference in Hg partitioning between the three bacterial species. The calculations also indicate similar coefficients for Hg-bacteria and Hg-FA complexes. S XAS measurements confirm the presence of sulfhydryl sites on both the FA and bacterial cells, and demonstrate the presence of a wide range of S moieties on the FA in contrast to the bacterial biomass, whose S sites are dominated by thiols. Our results suggest that although FA can compete with bacterial binding sites for aqueous Hg, because of the relatively similar partition coefficients for the types of sorbents, the competition is not dominated by either bacteria or FA unless the concentration of one type of site greatly exceeds that of the other.

Adsorption of hydrophobic organic compounds onto a hydrophobic carbonaceous geosorbent in the presence of surfactants.

PubMed

Wang, Peng; Keller, Arturo A

2008-06-01

The adsorption of hydrophobic organic compounds (HOCs; atrazine and diuron) onto lampblack was studied in the presence of nonionic, cationic, and anionic surfactants (Triton(R) X-100), benzalkonium chloride [BC], and linear alkylbenzene sulfonate [LAS]) to determine the effect of the surfactant on HOC adsorption onto a hydrophobic carbonaceous geosorbent. Linear alkylbenzene sulfonate showed an adsorption capacity higher than that of BC but similar to that of Triton X-100, implying the charge property of a surfactant is not a useful indicator for predicting the surfactant's adsorption onto a hydrophobic medium. The results also indicated that the octanol-water partition coefficient (K(OW)) of a surfactant is not a good predictor of that surfactant's sorption onto a hydrophobic medium. Under subsaturation adsorption conditions (i.e., before sorption saturation is reached), surfactant adsorption reduced HOC adsorption to a significant extent, with the reduction in HOC adsorption increasing monotonically with the amount of surfactant adsorbed. Among the three surfactants, Triton X-100 was the most effective in reducing HOC adsorption, whereas BC and LAS showed similar effectiveness in this regard. Under the same amount of the surfactant sorbed, the reduction in atrazine adsorption was consistently greater than that for diuron because of atrazine's lower hydrophobicity. No significant difference was observed in the amount of the HOC adsorbed under different adsorption sequences. Our results showed that the presence of surfactant can significantly decrease HOC adsorption onto hydrophobic environmental media and, thus, is important in predicting HOC fate and transport in the environment.

Functionally ecological assessment of C dominant pools and fluxes in field agroecosystems with sod-podzoluvosols at the Central Region of Russia

NASA Astrophysics Data System (ADS)

Mazirov, Ilya; Vizirskaya, Mariya; Epikhina, Anna; Vasenev, Ivan; Valentini, Riccardo; Meshalkina, Julia

2014-05-01

The Global Change problem has obvious interaction with greenhouse gases (GHG) emission. The principal GHG is carbon dioxide. There is a lot of data on its fluxes but the Central Region of Russia is still one of less investigated area especially in case of agroecosystem carbon dioxide fluxes monitoring by chambers and eddy covariance methods combined application. Our research has been at the representative key plots of cultivated sod-podzoluvosols located at the Precision Farming Experimental Field of the Russian Timiryazev State Agricultural University (Moscow) in 2012-2013 in frame of RF Government grant 11.G34.31.0079 and RFBR grant 11-04-01376 activities. The research include the detailed soil cover patterns morphogenetic investigation, soil C pools dynamic analysis, soil CO2 flux decade-based monitoring by method of exposition chambers with IRGA (infra red gas analyzer) and agroecosystem CO2 flux seasonal monitoring by two eddy covariance stations in frame of 4 ha experimental plot. There were two crop versions (barley and grass mixture), and in case of chamber analysis - also two agrotecnology versions (traditional and no-till ones) with soil temperature and moisture analysis too. The results have shown high daily and seasonal dynamic of soil and agroecosystem CO2 emission. The beginning of vegetation period (until plant height of 10-12 cm) is characterized by high average soil CO2 emission and adsorption at the same time. The adsorption is significantly higher. The resulted CO2 absorption during the day is approximately two times higher than emissions at night. After harvesting CO2 emission is becoming essentially higher than adsorption. In 2012 data have shown for barley the small predominance of CO2 emissions over the absorption. The daily dynamics of soil CO2 emissions depends on the air temperature dynamics with the correlation coefficient changes from 0.86 at the beginning of the season to 0.52 and 0.38 at the middle and at the end of one. Soil moisture has stronger influence on the seasonal dynamics of soil and agroecosystem CO2 emissions. The crop factor input is stronger that the agro technology one. According to the obtained results it is especially important to carry out the soil CO2 emission measurement at the same time period during the day (the best one is between 11 and 15) due to high changes in CO2 emission during the 24 hours period - especially at the beginning of the summer. At the end of the season the influence of the temperature daily dynamics is becoming not so significant for CO2 emission monitoring.

Influence of Structural Heterogeneity on Diffusion of CH4 and CO2 in Silicon Carbide-Derived Nanoporous Carbon

PubMed Central

2015-01-01

We investigate the influence of structural heterogeneity on the transport properties of simple gases in a Hybrid Reverse Monte Carlo (HRMC) constructed model of silicon carbide-derived carbon (SiC-DC). The energy landscape of the system is determined based on free energy analysis of the atomistic model. The overall energy barriers of the system for different gases are computed along with important properties, such as Henry constant and differential enthalpy of adsorption at infinite dilution, and indicate hydrophobicity of the SiC-DC structure and its affinity for CO2 and CH4 adsorption. We also study the effect of molecular geometry, pore structure and energy heterogeneity considering different hopping scenarios for diffusion of CO2 and CH4 through ultramicropores using the Nudged Elastic Band (NEB) method. It is shown that the energy barrier of a hopping molecule is very sensitive to the shape of the pore entry. We provide evidence for the influence of structural heterogeneity on self-diffusivity of methane and carbon dioxide using molecular dynamics simulation, based on a maximum in the variation of self-diffusivity with loading. A comparison of the MD simulation results with self-diffusivities from quasi-elastic neutron scattering (QENS) measurements and, with macroscopic uptake-based low-density transport coefficients, reveals the existence of internal barriers not captured in MD simulation and QENS experiments. Nevertheless, the simulation and macroscopic uptake-based diffusion coefficients agree within a factor of 2–3, indicating that our HRMC model structure captures most of the important energy barriers affecting the transport of CH4 in the nanostructure of SiC-DC. PMID:24932319

Influence of Structural Heterogeneity on Diffusion of CH4 and CO2 in Silicon Carbide-Derived Nanoporous Carbon.

PubMed

Farmahini, Amir H; Shahtalebi, Ali; Jobic, Hervé; Bhatia, Suresh K

2014-06-05

We investigate the influence of structural heterogeneity on the transport properties of simple gases in a Hybrid Reverse Monte Carlo (HRMC) constructed model of silicon carbide-derived carbon (SiC-DC). The energy landscape of the system is determined based on free energy analysis of the atomistic model. The overall energy barriers of the system for different gases are computed along with important properties, such as Henry constant and differential enthalpy of adsorption at infinite dilution, and indicate hydrophobicity of the SiC-DC structure and its affinity for CO 2 and CH 4 adsorption. We also study the effect of molecular geometry, pore structure and energy heterogeneity considering different hopping scenarios for diffusion of CO 2 and CH 4 through ultramicropores using the Nudged Elastic Band (NEB) method. It is shown that the energy barrier of a hopping molecule is very sensitive to the shape of the pore entry. We provide evidence for the influence of structural heterogeneity on self-diffusivity of methane and carbon dioxide using molecular dynamics simulation, based on a maximum in the variation of self-diffusivity with loading. A comparison of the MD simulation results with self-diffusivities from quasi-elastic neutron scattering (QENS) measurements and, with macroscopic uptake-based low-density transport coefficients, reveals the existence of internal barriers not captured in MD simulation and QENS experiments. Nevertheless, the simulation and macroscopic uptake-based diffusion coefficients agree within a factor of 2-3, indicating that our HRMC model structure captures most of the important energy barriers affecting the transport of CH 4 in the nanostructure of SiC-DC.

Ammonium Removal from Aqueous Solutions by Clinoptilolite: Determination of Isotherm and Thermodynamic Parameters and Comparison of Kinetics by the Double Exponential Model and Conventional Kinetic Models

PubMed Central

Tosun, İsmail

2012-01-01

The adsorption isotherm, the adsorption kinetics, and the thermodynamic parameters of ammonium removal from aqueous solution by using clinoptilolite in aqueous solution was investigated in this study. Experimental data obtained from batch equilibrium tests have been analyzed by four two-parameter (Freundlich, Langmuir, Tempkin and Dubinin-Radushkevich (D-R)) and four three-parameter (Redlich-Peterson (R-P), Sips, Toth and Khan) isotherm models. D-R and R-P isotherms were the models that best fitted to experimental data over the other two- and three-parameter models applied. The adsorption energy (E) from the D-R isotherm was found to be approximately 7 kJ/mol for the ammonium-clinoptilolite system, thereby indicating that ammonium is adsorbed on clinoptilolite by physisorption. Kinetic parameters were determined by analyzing the nth-order kinetic model, the modified second-order model and the double exponential model, and each model resulted in a coefficient of determination (R2) of above 0.989 with an average relative error lower than 5%. A Double Exponential Model (DEM) showed that the adsorption process develops in two stages as rapid and slow phase. Changes in standard free energy (∆G°), enthalpy (∆H°) and entropy (∆S°) of ammonium-clinoptilolite system were estimated by using the thermodynamic equilibrium coefficients. PMID:22690177

A comparative study of sorption of chromium (III) onto chitin and chitosan

NASA Astrophysics Data System (ADS)

Singh, Pooja; Nagendran, R.

2016-06-01

Heavy metals have always been the most hazardous components in the wastewater of industries like electroplating, automobiles, mining facilities and fertilizer manufacturers. Treatment of heavy metal laden wastewater requires expensive operational and maintenance systems. Food processing industries create a huge amount of shell waste which is sold to poultry farms in powdered form but the quantity thus used is still not comparable to the left over waste. The shell contains chitin which acts as an adsorbent for the heavy metals and can be used to treat heavy metal wastewater. The paper presents a study on the use of chitin and its processed product, chitosan, to remove chromium. Shake flask experiment was conducted to compare the adsorptive capacity of chitin and chitosan for chromium removal from simulated solution and isotherm studies were carried out. The studies showed that the chitosan was a better adsorbent than chitin. Both chitin and chitosan gave best adsorption results at pH 3. Chitin exhibited maximum chromium removal of 49.98 % in 20 min, whereas chitosan showed 50 % removal efficiency at a contact time of 20 min showing higher adsorptive capacity for chromium than chitin. The Langmiur and Freundlich isotherm studies showed very good adsorption capacity and monolayer interaction according to the regression coefficient 0.973 for chitosan and 0.915 for chitin. The regression coefficient for Freundlich isotherm was 0.894 and 0.831 for chitosan and chitin, respectively.

Breakthrough behavior of granular ferric hydroxide (GFH) fixed-bed adsorption filters: modeling and experimental approaches.

PubMed

Sperlich, Alexander; Werner, Arne; Genz, Arne; Amy, Gary; Worch, Eckhard; Jekel, Martin

2005-03-01

Breakthrough curves (BTC) for the adsorption of arsenate and salicylic acid onto granulated ferric hydroxide (GFH) in fixed-bed adsorbers were experimentally determined and modeled using the homogeneous surface diffusion model (HSDM). The input parameters for the HSDM, the Freundlich isotherm constants and mass transfer coefficients for film and surface diffusion, were experimentally determined. The BTC for salicylic acid revealed a shape typical for trace organic compound adsorption onto activated carbon, and model results agreed well with the experimental curves. Unlike salicylic acid, arsenate BTCs showed a non-ideal shape with a leveling off at c/c0 approximately 0.6. Model results based on the experimentally derived parameters over-predicted the point of arsenic breakthrough for all simulated curves, lab-scale or full-scale, and were unable to catch the shape of the curve. The use of a much lower surface diffusion coefficient D(S) for modeling led to an improved fit of the later stages of the BTC shape, pointing on a time-dependent D(S). The mechanism for this time dependence is still unknown. Surface precipitation was discussed as one possible removal mechanism for arsenate besides pure adsorption interfering the determination of Freundlich constants and D(S). Rapid small-scale column tests (RSSCT) proved to be a powerful experimental alternative to the modeling procedure for arsenic.

Ammonium removal from aqueous solutions by clinoptilolite: determination of isotherm and thermodynamic parameters and comparison of kinetics by the double exponential model and conventional kinetic models.

PubMed

Tosun, Ismail

2012-03-01

The adsorption isotherm, the adsorption kinetics, and the thermodynamic parameters of ammonium removal from aqueous solution by using clinoptilolite in aqueous solution was investigated in this study. Experimental data obtained from batch equilibrium tests have been analyzed by four two-parameter (Freundlich, Langmuir, Tempkin and Dubinin-Radushkevich (D-R)) and four three-parameter (Redlich-Peterson (R-P), Sips, Toth and Khan) isotherm models. D-R and R-P isotherms were the models that best fitted to experimental data over the other two- and three-parameter models applied. The adsorption energy (E) from the D-R isotherm was found to be approximately 7 kJ/mol for the ammonium-clinoptilolite system, thereby indicating that ammonium is adsorbed on clinoptilolite by physisorption. Kinetic parameters were determined by analyzing the nth-order kinetic model, the modified second-order model and the double exponential model, and each model resulted in a coefficient of determination (R(2)) of above 0.989 with an average relative error lower than 5%. A Double Exponential Model (DEM) showed that the adsorption process develops in two stages as rapid and slow phase. Changes in standard free energy (∆G°), enthalpy (∆H°) and entropy (∆S°) of ammonium-clinoptilolite system were estimated by using the thermodynamic equilibrium coefficients.

The Adsorption of Cd(II) on Manganese Oxide Investigated by Batch and Modeling Techniques.

PubMed

Huang, Xiaoming; Chen, Tianhu; Zou, Xuehua; Zhu, Mulan; Chen, Dong; Pan, Min

2017-09-28

Manganese (Mn) oxide is a ubiquitous metal oxide in sub-environments. The adsorption of Cd(II) on Mn oxide as function of adsorption time, pH, ionic strength, temperature, and initial Cd(II) concentration was investigated by batch techniques. The adsorption kinetics showed that the adsorption of Cd(II) on Mn oxide can be satisfactorily simulated by pseudo-second-order kinetic model with high correlation coefficients (R² > 0.999). The adsorption of Cd(II) on Mn oxide significantly decreased with increasing ionic strength at pH < 5.0, whereas Cd(II) adsorption was independent of ionic strength at pH > 6.0, which indicated that outer-sphere and inner-sphere surface complexation dominated the adsorption of Cd(II) on Mn oxide at pH < 5.0 and pH > 6.0, respectively. The maximum adsorption capacity of Mn oxide for Cd(II) calculated from Langmuir model was 104.17 mg/g at pH 6.0 and 298 K. The thermodynamic parameters showed that the adsorption of Cd(II) on Mn oxide was an endothermic and spontaneous process. According to the results of surface complexation modeling, the adsorption of Cd(II) on Mn oxide can be satisfactorily simulated by ion exchange sites (X₂Cd) at low pH and inner-sphere surface complexation sites (SOCd⁺ and (SO)₂CdOH - species) at high pH conditions. The finding presented herein plays an important role in understanding the fate and transport of heavy metals at the water-mineral interface.

Adsorption of Rh(III) complexes from chloride solutions obtained by leaching chlorinated spent automotive catalysts on ion-exchange resin Diaion WA21J.

PubMed

Shen, Shaobo; Pan, Tonglin; Liu, Xinqiang; Yuan, Lei; Wang, Jinchao; Zhang, Yongjian; Guo, Zhanchen

2010-07-15

It was found that Rh, Pd and Pt contained in the spent ceramic automotive catalysts could be effectively extracted by dry chlorination with chlorine. In order to concentrate Rh(III) ions contained in the chloride solutions obtained, thermodynamic and kinetics studies for adsorption of Rh(III) complexes from the chloride solutions on an anionic exchange resin Diaion WA21J were carried out. Rh, Pd, Pt, Al, Fe, Si, Zn and Pb from the chloride solution could be adsorbed on the resin. The distribution coefficients (K(d)) of Rh(III) decreased with the increase in initial Rh(III) concentration or in adsorption temperature. The isothermal adsorption of Rh(III) was found to fit Langmuir, Freundlich and Dubinin-Kaganer-Radushkevich models under the adsorption conditions. The maximum monolayer adsorption capacities Q(max) based on Langmuir adsorption isotherms were 6.39, 6.61 and 5.81 mg/g for temperatures 18, 28 and 40 degrees C, respectively. The apparent adsorption energy of Rh was about -7.6 kJ/mol and thus Rh(III) adsorption was a physical type. The experimental data obtained could be better simulated by pseudo-first-order kinetic model and the activation energy obtained was 6.54 J/mol. The adsorption rate of Rh(III) was controlled by intraparticle diffusion in most of time of adsorption process. 2010 Elsevier B.V. All rights reserved.

Time and temperature dependent adsorption-desorption behaviour of pretilachlor in soil.

PubMed

Kaur, Paawan; Kaur, Pervinder

2018-06-04

Understanding and quantifying the adsorption-desorption behaviour of herbicide in soil is imperative for predicting their fate and transport in the environment. In the present study, the effect of time and temperature on the adsorption-desorption behaviour of pretilachlor in soils was investigated using batch equilibration technique. The adsorption-desorption kinetics of pretilachlor in soils was two step process and was well described by pseudo-second-order kinetic model. Freundlich model accurately predicted the sorption behaviour of pretilachlor. The adsorption-desorption of pretilachlor varied significantly with the concentration, temperature and properties of soil viz. organic matter and clay content. All the studied soils had non-linear slopes (n < 1) and degree of nonlinearity increased with increase in clay, organic matter content and temperature (p < 0.05). Desorption of pretilachlor was hysteretic in studied soils and hysteresis coefficient varied from 0.023 to 0.275. Thermodynamic analysis showed that pretilachlor adsorption onto soils was a feasible, spontaneous and endothermic process which becomes more favourable at high temperature. It could be inferred that the adsorption of pretilachlor on soils was physical in nature. Copyright © 2018 Elsevier Inc. All rights reserved.

Adsorption and co-adsorption of diclofenac and Cu(II) on calcareous soils.

PubMed

Graouer-Bacart, Mareen; Sayen, Stéphanie; Guillon, Emmanuel

2016-02-01

Pharmaceuticals are emerging contaminants and their presence in different compartments of the environment has been detected in many countries. In this study, laboratory batch experiments were conducted to characterize the adsorption of diclofenac, a widely used non-steroidal anti-inflammatory drug, on six calcareous soils. The adsorption of diclofenac was relatively low, which may lead to a risk of groundwater contamination and plant uptake. A correlation between the soil-water distribution coefficient Kd and soil characteristics has been highlighted. Indeed, diclofenac adsorption as a function of soil organic matter content (% OM) and Rt=% CaCO3/% OM was successfully described through a simple empirical model, indicating the importance of considering the inhibiting effect of CaCO3 on OM retention properties for a better assessment of diclofenac fate in the specific case of calcareous soils. The simultaneous co-adsorption of diclofenac and copper - a ubiquitous pollutant in the environment - at the water/soil interface, was also investigated. It appeared quite unexpectedly that copper did not have a significant influence on diclofenac retention. Copyright © 2015 Elsevier Inc. All rights reserved.

[Adsorption of phenol chemicals by surfactant-modified zeolites].

PubMed

Xie, Jie; Wang, Zhe; Wu, De-Yi; Li, Chun-Jie

2012-12-01

Two kinds of zeolites were prepared from fly ash and modified by surfactant subsequently. Surfactant-modified zeolites were studied for adsorption of phenol chemicals (phenol, p-chlorphenol, bisphenol A). It showed that the adsorption affinity of zeolite to phenol chemicals was significantly improved after surfactant modification. The adsorption isotherms of phenol chemicals were well fitted by the Langmuir isotherm. For the two surfactant-surfactant modified zeolites, the maximum adsorption amounts of phenol, p-chlorphenol, and bisphenol A calculated from the Langmuir equation were 37.7, 52.36, 90.9 mg x g(-1) and 10.7, 22.83, 56.8 mg x g(-1), respectively. When pH values of solutions were higher than the pK(a) values of phenol chemicals, the removal efficiencies were getting higher with the increase of pH values. The octanol/water partition coefficient (K(ow)) was also found to be an important factor affecting adsorption of phenol chemicals by the modified zeolites. Higher K(ow) value, which means the greater hydrophobicity of the chemicals, resulted in a higher removal.

Adsorptive removal of catalyst poisons from coal gas for methanol synthesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhatt, B.L.; Golden, T.C.; Hsiung, T.H.

1991-12-01

As an integral part of the liquid-phase methanol (LPMEOH) process development program, the present study evaluated adsorptive schemes to remove traces of catalyst poisons such as iron carbonyl, carbonyl sulfide, and hydrogen sulfide from coal gas on a pilot scale. Tests were conducted with coal gas from the Cool Water gasification plant at Daggett, California. Iron carbonyl, carbonyl sulfide, and hydrogen sulfide were effectively removed from the coal gas. The adsorption capacities of Linde H-Y zeolite and Calgon BPL carbon for Fe(CO){sub 5} compared well with previous bench-scale results at similar CO{sub 2} partial pressure. Adsorption of COS by Calgonmore » FCA carbon appeared to be chemical and nonregenerable by thermal treatment in nitrogen. A Cu/Zn catalyst removed H{sub 2}S very effectively. With the adsorption system on-line, a methanol catalyst showed stable activity during 120 h operation, demonstrating the feasibility of adsorptive removal of trace catalyst poisons from the synthesis gas. Mass transfer coefficients were estimated for Fe(CO){sub 5} and COS removal which can be directly used for design and scale up.« less

Preparation and adsorption behavior of berberine hydrochloride imprinted polymers by using silica gel as sacrificed support material

NASA Astrophysics Data System (ADS)

Li, Hui; Li, Yuzhuo; Li, Zhiping; Peng, Xiyang; Li, Yanan; Li, Gui; Tan, Xianzhou; Chen, Gongxi

2012-03-01

Preparation of berberine hydrochloride (B-Cl) imprinted polymers (MIPs) based on surface imprinting technique with silica gel as sacrificial support material was performed successfully by using B-Cl as template, methacrylic acid (MAA) and ethylene glycol dimethacrylate (EGDMA) as functional monomer and cross-linker, respectively. The prepared polymers were characterized by Fourier transmission infrared spectrometry (FTIR) and scanning electron microscopy (SEM). Adsorption behavior of the MIPs for the template and its structural analogues was investigated. Sites distribution on the surface of MIPs was explored by using different isotherm adsorption models and thermodynamic parameters for the adsorption of B-Cl on the MIPs determined. Sample application and reusability for the MIPs was also evaluated. Results indicated the strong adsorption and high selectivity of the MIPs for B-Cl. Saturated adsorption capacity reached 27.2 μmol g-1 and the selectivity coefficient of the MIPs for B-Cl relative to jatrorrhizine hydrochloride (J-Cl) and palmatine palmatus hydrochloride (P-Cl) are 3.70 and 6.03, respectively. In addition, the MIPs were shown with good reusability and selectively retention ability in sample application.

[Adsorption of the TiO2 @ yeast composite microspheres for adsorbing Fluorescent Whitening Agent-VBL in fixed bed].

PubMed

Wu, Fei; Zhang, Kai-Qiang; Bai, Bo; Wang, Hong-Lun; Suo, You-Rui

2015-02-01

In this work, the adsorption potential of TiO2@ yeast composite microspheres to remove Fluorescent Whitening Agent-VBL (FWA-VBL) from aqueous solution was investigated using fixed-bed adsorption column. The effects of pH(2.0-8.0), bed height (1-3 cm), inlet concentration (20-80 mg x L(-1)) and feed flow rate (5-11 mL x min(-1)) on the breakthrough characteristics of the adsorption system were determined. The results showed that the highest bed capacity of 223.80 mg x g(-1) was obtained under the condition of pH 2.0, 80 mg x L(-1) inlet dye concentration, 1.0 cm bed height and 5 mL x min(-1) flow rate. The adsorption data were fitted to three well-established fixed-bed adsorption models, namely, BDST model, Thomas model and Yoon-Nelson model. The results fitted well to the three models with coefficients of correlation R2 > 0.980 in different conditions. The TiO2 @ yeast composite microspheres have desired regeneration ability and could be reused for four times.

Competitive adsorption of furfural and phenolic compounds onto activated carbon in fixed bed column.

PubMed

Sulaymon, Abbas H; Ahmed, Kawther W

2008-01-15

For a multicomponent competitive adsorption of furfural and phenolic compounds, a mathematical model was builtto describe the mass transfer kinetics in a fixed bed column with activated carbon. The effects of competitive adsorption equilibrium constant, axial dispersion, external mass transfer, and intraparticle diffusion resistance on the breakthrough curve were studied for weakly adsorbed compound (furfural) and strongly adsorbed compounds (parachlorophenol and phenol). Experiments were carried out to remove the furfural and phenolic compound from aqueous solution. The equilibrium data and intraparticle diffusion coefficients obtained from separate experiments in a batch adsorber, by fitting the experimental data with theoretical model. The results show that the mathematical model includes external mass transfer and pore diffusion using nonlinear isotherms and provides a good description of the adsorption process for furfural and phenolic compounds in a fixed bed adsorber.

Periodic protein adsorption at the gold/biotin aqueous solution interface: evidence of kinetics with time delay

NASA Astrophysics Data System (ADS)

Neff, H.; Laborde, H. M.; Lima, A. M. N.

2016-11-01

An oscillatory molecular adsorption pattern of the protein neutravidin from aqueous solution onto gold, in presence of a pre-deposited self assembled mono-molecular biotin film, is reported. Real time surface Plasmon resonance sensing was utilized for evaluation of the adsorption kinetics. Two different fractions were identified: in the initial phase, protein molecules attach irreversibly onto the Biotin ligands beneath towards the jamming limit, forming a neutravidin-biotin fraction. Afterwards, the growth rate exhibits distinct, albeit damped adsorption-desorption oscillations over an extended time span, assigned to a quasi reversibly bound fraction. These findings agree with, and firstly confirm a previously published model, proposing macro-molecular adsorption with time delay. The non-linear dynamic model is applicable to and also resembles non-damped oscillatory binding features of the hetero-catalytic oxidation of carbon monoxide molecules on platinum in the gas phase. An associated surface residence time can be linked to the dynamics and time scale required for self-organization.

Dynamic filtration and static adsorption of lead ions in aqueous solution by use of blended polysulfone membranes with nano size MCM-41 particles coated by polyaniline.

PubMed

Toosi, Mohammad Reza; Emami, Mohammad Reza Sarmasti; Hajian, Sudeh

2018-05-11

MCM-41 mesopore was prepared by hydrothermal method and used for synthesis of polyaniline/MCM-41 nanocomposite via in situ polymerization. The nanocomposite was blended with polysulfone to prepare mixed matrix membrane in different content of nanocomposite by phase inversion method. Structural and surface properties of the samples were characterized by SEM, XRD, FTIR, AFM, TGA, BET, and zeta potential measurements. Effect of the nanocomposite content on the hydrophilicity, porosity, and permeability of the membrane was determined. Membrane performance was evaluated for removal of lead ions in dynamic filtration and static adsorption. The membranes were found as effective adsorptive filters for removal of lead ions via interactions between active sites of nanocomposite in membrane structure and lead ions during filtration. Results of batch experiments proved adsorptive mechanism of membranes for removal of lead ions with the maximum adsorption capacity of 19.6 mg/g.

Adsorption of sunset yellow FCF from aqueous solution by chitosan-modified diatomite.

PubMed

Zhang, Y Z; Li, J; Li, W J; Li, Y

2015-01-01

Sunset yellow (SY) FCF is a hazardous azo dye pollutant found in food processing effluent. This study investigates the use of diatomaceous earth with chitosan (DE@C) as a modified adsorbent for the removal of SY from wastewater. Fourier transform infrared spectroscopy results indicate the importance of functional groups during the adsorption of SY. The obtained N2 adsorption-desorption isotherm values accord well with IUPAC type II. Our calculations determined a surface area of 69.68 m2 g(-1) for DE@C and an average pore diameter of 4.85 nm. Using response surface methodology, optimized conditions of process variables for dye adsorption were achieved. For the adsorption of SY onto DE@C, this study establishes mathematical models for the optimization of pH, contact time and initial dye concentration. Contact time plays a greater role in the adsorption process than either pH or initial dye concentration. According to the adjusted correlation coefficient (adj-R2>0.97), the models used here are suitable for illustration of the adsorption process. Theoretical experimental conditions included a pH of 2.40, initial dye concentration of 113 mg L(-1) and 30.37 minutes of contact time. Experimental values for the adsorption rate (92.54%) were close to the values predicted by the models (95.29%).

Adsorption mechanism of 2,4-dichlorophenoxyacetic acid onto nitric-acid-modified activated carbon fiber.

PubMed

Li, Qun; Sun, Jie; Ren, Tianhao; Guo, Lin; Yang, Zhilin; Yang, Qi; Chen, Hai

2018-04-01

Adsorption by carbon materials is one of the relatively fast methods in present research, which is widely used in emergency events. Activated carbon fiber (ACF) modified by nitric acid (N-ACF) was studied in this research to determine the adsorption performance for 2,4-dichlorophenoxyacetic acid (2,4-D). Subsequently, influence factors, adsorption isotherm models, kinetics and thermodynamic were investigated in a batch system to realize this adsorption. Experimental results showed that ACF modified by 0.1M nitric acid had a better removal ability than 2,4-D. Removal rate of 2,4-D by N-ACF was greatly influenced by pH with the optimum pH at 2. The superiority of the Langmuir isotherm model in describing the adsorption equilibrium was revealed by correlation coefficients R2 (R 2  ≥ 0.997). Furthermore, adsorption kinetics was well described by pseudo-second-order model. The results of thermodynamic showed that adsorption was a spontaneous, endothermic process with randomness increasing. Additionally, surface structure properties of adsorbent were characterized by Scanning electron microscopy, Fourier transform infrared spectroscopy, Specific surface area analysis of Brunauer, Emmett and Teller and Boehm's titration. It turned out that the micropore structure and functional groups on N-ACF all can contribute to the removal of 2,4-D.

Adsorption characteristics of Copper (Ⅱ), Zinc (Ⅱ) and Mercury (Ⅱ) by four kinds of immobilized fungi residues.

PubMed

Li, Xia; Zhang, Dan; Sheng, Fei; Qing, Hui

2018-01-01

This study investigated the adsorption characteristics of Copper (Ⅱ), Zinc (Ⅱ) and Mercury (Ⅱ) by immobilized Flammulina velutipes, Auricularia polytricha, Pleurotus eryngii and Pleurotus ostreatus residues. Lagergren model, elovich and intraparticle diffusion model were used to present the adsorption kinetics, and it was proved that Langmuir isotherm model and pseudo-second order kinetics are the best suitable model with high correlation coefficient to characterize the adsorption process of Copper (Ⅱ), Zinc (Ⅱ) and Mercury (Ⅱ). The results showed that adsorption process finished in 120min at pH 6.0. The adsorption rate of Cu 2+ , Zn 2+ and Hg 2+ were reached to 53.8-84.1% of total in the initial 60min, and finished in 120min. Ion exchange and complexation of F. velutipes were the main mechanisms for adsorption of metal ions by characterizations of Scanning electron microscopy (SEM) and Fourier transform infrared (FTIR). In addition the functional group of cell walls such as hydroxyl, amide, carbonyl, phosphoric played a critical role in ions adsorption of edible mushroom residues. Cu 2+ , Zn 2+ and Hg 2+ in wastewater could be efficiently removed by F. velutipes residue with removal ratio of 73.11%, 66.67% and 69.35%, respectively. Copyright © 2017 Elsevier Inc. All rights reserved.

The influence of iron oxide nanoparticles upon the adsorption of organic matter on magnetic powdered activated carbon.

PubMed

Lompe, Kim Maren; Menard, David; Barbeau, Benoit

2017-10-15

Combining powdered activated carbon (PAC) with magnetic iron oxides has been proposed in the past to produce adsorbents for natural organic matter (NOM) removal that can be easily separated using a magnetic field. However, the trade-off between the iron oxides' benefits and the reduced carbon content, porosity, and surface area has not yet been investigated systematically. We produced 3 magnetic powdered activated carbons (MPAC) with mass fractions of 10%, 38% and 54% maghemite nanoparticles and compared them to bare PAC and pure nanoparticles with respect to NOM adsorption kinetics and isotherms. While adsorption kinetics were not influenced by the presence of the iron oxide nanoparticles (IONP), as shown by calculated diffusion coefficients from the homogeneous surface diffusion model, nanoparticles reduced the adsorption capacity of NOM due to their lower adsorption capacity. Although the nanoparticles added mesoporosity to the composite materials they blocked intrinsic PAC mesopores at mass fractions >38% as measured by N 2 -adsorption isotherms. Below this mass fraction, the adsorption capacity was mainly dependent on the carbon content in MPAC and mesopore blocking was negligible. If NOM adsorption with MPAC is desired, a highly mesoporous PAC and a low IONP mass fraction should be chosen during MPAC synthesis. Copyright © 2017 Elsevier Ltd. All rights reserved.

Determination of gas-liquid partition coefficients of several organic solutes in trihexyl(tetradecyl)phosphonium bromide using capillary gas chromatography columns.

PubMed

Ronco, Nicolás R; Menestrina, Fiorella; Romero, Lílian M; Castells, Cecilia B

2017-06-09

In this paper, we report gas-liquid partition constants for thirty-five volatile organic solutes in the room temperature ionic liquid trihexyl(tetradecyl)phosphonium bromide measured by gas-liquid chromatography using capillary columns. The relative contribution of gas-liquid partition and interfacial adsorption to retention was evaluated through the use of columns with different the phase ratio. Four capillary columns with exactly known phase ratios were constructed and employed to measure the solute retention factors at four temperatures between 313.15 and 343.15K. The partition coefficients were calculated from the slopes of the linear regression between solute retention factors and the reciprocal of phase ratio at a given temperature according to the gas-liquid chromatographic theory. Gas-liquid interfacial adsorption was detected for a few solutes and it has been considered for the calculations of partition coefficient. Reliable solute's infinite dilution activity coefficients can be obtained when retention data are determined by a unique partitioning mechanism. The partial molar excess enthalpies at infinite dilution have been estimated from the dependence of experimental values of solute activity coefficients with the column temperature. A thorough discussion of the uncertainties of the experimental measurements and the main advantages of the use of capillary columns to acquire the aforementioned relevant thermodynamic information was performed. Copyright © 2017 Elsevier B.V. All rights reserved.

[Effect of SO2 volume fraction in flue gas on the adsorption behaviors adsorbed by ZL50 activated carbon and kinetic analysis].

PubMed

Gao, Ji-xian; Wang, Tie-feng; Wang, Jin-fu

2010-05-01

The influence of SO2 dynamic adsorption behaviors using ZL50 activated carbon for flue gas desulphurization and denitrification under different SO2 volume fraction was investigated experimentally, and the kinetic analysis was conducted by kinetic models. With the increase of SO2 volume fraction in flue gas, the SO2 removal ratio and the activity ratio of ZL50 activated carbon decreased, respectively, and SO2 adsorption rate and capacity increased correspondingly. The calculated results indicate that Bangham model has the best prediction effect, the chemisorption processes of SO2 was significantly affected by catalytic oxidative reaction. The adsorption rate constant of Lagergren's pseudo first order model increased with the increase of inlet SO, volume fraction, which indicated that catalytic oxidative reaction of SO2 adsorbed by ZL50 activated carbon may be the rate controlling step in earlier adsorption stage. The Lagergren's and Bangham's initial adsorption rate were deduced and defined, respectively. The Ho's and Elovich's initial adsorption rate were also deduced in this paper. The Bangham's initial adsorption rate values were defined in good agreement with those of experiments. The defined Bangham's adsorptive reaction kinetic model can describe the SO2 dynamic adsorption rate well. The studied results indicated that the SO2 partial order of initial reaction rate was one or adjacent to one, while the O2 and water vapor partial order of initial reaction rate were constants ranging from 0.15-0.20 and 0.45-0.50, respectively.

Preparation of a surface-grafted imprinted ceramic membrane for selective separation of molybdate anion from water solutions.

PubMed

Zeng, Jianxian; Dong, Zhihui; Zhang, Zhe; Liu, Yuan

2017-07-05

A surface-grafted imprinted ceramic membrane (IIP-PVI/CM) for recognizing molybdate (Mo(VI)) anion was prepared by surface-initiated graft-polymerization. Firstly, raw alumina ceramic membrane (CM) was deposited with SiO 2 active layer by situ hydrolysis deposition method. Subsequently, γ-methacryloxy propyl trimethoxyl silane (MPS) was used as a coupling agent to introduce double bonds onto the SiO 2 layer (MPS-CM). Then, 1-vinylimidazole (VI) was employed as a functional monomer to graft-polymerization onto the MPS-CM (PVI-CM). During the graft-polymerization, the influence factors of grafting degree of PVI were investigated in detail. Under optimum conditions (monomer concentration 20wt%, temperature 70°C, initiator amount 1.1wt% and reaction time 8h), the grafting degree of 20.39g/100g was obtained. Further, Mo(VI) anion was used as a template to imprint in the PVI-CM by employing 1,6-dibromohexane as a cross-linking agent, and then Mo(VI) was removed, obtaining the IIP-PVI/CM with many imprinted cavities for Mo(VI). Thereafter, static adsorption and dynamic separation properties of IIP-PVI/CM for Mo(VI) were studied. Results indicate that IIP-PVI/CM shows a specific selectivity for Mo(VI) with the adsorption capacity of 0.69mmol/100g, and the selectivity coefficient of IIP-PVI/CM is 7.48 for molybdate to tungstate anions. During the dynamic separation, IIP-PVI/CM has also good selectivity for separation of Mo(VI) and W(VI) anions. Copyright © 2017 Elsevier B.V. All rights reserved.

Single and Competitive Adsorption of 17α-Ethinylestradiol and Bisphenol A with Estrone, β-Estradiol, and Estriol onto Sediment

PubMed Central

Li, Yu; Zhang, Chen; Li, Shanshan; Zhou, Changzhi; Li, Xiaopeng

2014-01-01

The competitive adsorption of bisphenol A (BPA) and17α-ethinylestradiol (EE2) with different endocrine disrupting compounds (EDCs), such as estrone (E1), β-estradiol (E2), and estriol (E3) was investigated in the water-sediment system. The primary and interaction effects of coexisted EDCs on the adsorption of BPA and EE2 were studied in binary and multiple systems. The adsorption selectivity of sediment at different initial concentrations of EDCs was also considered, based on the distribution coefficient (β). In binary systems, coexisted EDCs exhibited a positive effect on the adsorption of BPA, while E3 showed a negative effect on the adsorption of EE2. In ternary systems, the interaction of E1*E3 and E2*BPA showed a synergistic effect on the sorption of BPA and EE2, respectively. In quaternary systems, the interaction of E1*E2*E3 showed a synergistic effect on the adsorption of both BPA and EE2. In the quinary system, coexisted EDCs all showed an antagonistic effect on the adsorption of BPA and EE2, which indicated that the coexisted EDCs competed for adsorption with BPA and EE2. EDCs in the E2-EE2-BPA system presented a superior selectivity of sediment with β values of 43.48–87.86. The order of sediment selectivity (E1 > EE2 > E2 > E3 > BPA) in binary systems was in agreement with EDCs’ adsorption capacity, which suggested that the adsorption was dominated by partition adsorption. PMID:24608971

Electrostatic Interactions Influence Protein Adsorption (but Not Desorption) at the Silica-Aqueous Interface.

PubMed

McUmber, Aaron C; Randolph, Theodore W; Schwartz, Daniel K

2015-07-02

High-throughput single-molecule total internal reflection fluorescence microscopy was used to investigate the effects of pH and ionic strength on bovine serum albumin (BSA) adsorption, desorption, and interfacial diffusion at the aqueous-fused silica interface. At high pH and low ionic strength, negatively charged BSA adsorbed slowly to the negatively charged fused silica surface. At low pH and low ionic strength, where BSA was positively charged, or in solutions at higher ionic strength, adsorption was approximately 1000 times faster. Interestingly, neither surface residence times nor the interfacial diffusion coefficients of BSA were influenced by pH or ionic strength. These findings suggested that adsorption kinetics were dominated by energy barriers associated with electrostatic interactions, but once adsorbed, protein-surface interactions were dominated by short-range nonelectrostatic interactions. These results highlight the ability of single-molecule techniques to isolate elementary processes (e.g., adsorption and desorption) under steady-state conditions, which would be impossible to measure using ensemble-averaging methods.

Comparative study on kinetic adsorption of Cu(II), Cd(II) and Ni(II) ions from aqueous solutions using activated sludge and dried sludge

NASA Astrophysics Data System (ADS)

Ong, Soon-An; Toorisaka, Eiichi; Hirata, Makoto; Hano, Tadashi

2013-03-01

The adsorption of Cu(II), Cd(II) and Ni(II) ions from aqueous solutions by activated sludge and dried sludge was investigated under laboratory conditions to assess its potential in removing metal ions. The adsorption behavior of metal ions onto activated sludge and dried sludge was analyzed with Weber-Morris intra-particle diffusion model, Lagergren first-order model and pseudo second-order model. The rate constant of intra-particle diffusion on activated sludge and dried sludge increased in the sequence of Cu(II) > Ni(II) > Cd(II). According to the regression coefficients, it was observed that the kinetic adsorption data can fit better by the pseudo second-order model compared to the first-order Lagergren model with R 2 > 0.997. The adsorption capacities of metal ions onto activated sludge and dried sludge followed the sequence Ni(II) ≈ Cu(II) > Cd(II) and Cu(II) > Ni(II) > Cd(II).

Precursor state of oxygen molecules on the Si(001) surface during the initial room-temperature adsorption

NASA Astrophysics Data System (ADS)

Hwang, Eunkyung; Chang, Yun Hee; Kim, Yong-Sung; Koo, Ja-Yong; Kim, Hanchul

2012-10-01

The initial adsorption of oxygen molecules on Si(001) is investigated at room temperature. The scanning tunneling microscopy images reveal a unique bright O2-induced feature. The very initial sticking coefficient of O2 below 0.04 Langmuir is measured to be ˜0.16. Upon thermal annealing at 250-600 °C, the bright O2-induced feature is destroyed, and the Si(001) surface is covered with dark depressions that seem to be oxidized structures with -Si-O-Si- bonds. This suggests that the observed bright O2-induced feature is an intermediate precursor state that may be either a silanone species or a molecular adsorption structure.

Correlation Study of PVDF Membrane Morphology with Protein Adsorption: Quantitative Analysis by FTIR/ATR Technique

NASA Astrophysics Data System (ADS)

Ideris, N.; Ahmad, A. L.; Ooi, B. S.; Low, S. C.

2018-05-01

Microporous PVDF membranes were used as protein capture matrices in immunoassays. Because the most common labels in immunoassays were detected based on the colour change, an understanding of how protein concentration varies on different PVDF surfaces was needed. Herein, the correlation between the membrane pore size and protein adsorption was systematically investigated. Five different PVDF membrane morphologies were prepared and FTIR/ATR was employed to accurately quantify the surface protein concentration on membranes with small pore sizes. SigmaPlot® was used to find a suitable curve fit for protein adsorption and membrane pore size, with a high correlation coefficient, R2, of 0.9971.

A molecular dynamics study on the adsorption of a mussel protein on two different films: Polymer film and a SAM

NASA Astrophysics Data System (ADS)

He, Cunxue; Zhang, Heng; Lin, Cunguo; Wang, Li; Yuan, Shiling

2017-05-01

The adhesion of marine life would produce a certain degree of corrosion effect on the hull surface. Shellfish organisms, such as barnacles and mussels, were always used to research the impediment of coating material to protein adsorption. In this work, the adsorbed behaviors of mussel protein on the PDMS and C7F16-SAM surfaces were explored by molecular dynamics (MD) simulations. Simulation results showed that protein was strongly adsorbed onto the hydrophobic surface, as reflected by the large interaction energy; while the adsorption onto the hydrophilic PDMS surface was weak due to two strongly adhered water layers.

Interaction of human adenoviruses and coliphages with kaolinite and bentonite.

PubMed

Bellou, Maria I; Syngouna, Vasiliki I; Tselepi, Maria A; Kokkinos, Petros A; Paparrodopoulos, Spyros C; Vantarakis, Apostolos; Chrysikopoulos, Constantinos V

2015-06-01

Human adenoviruses (hAdVs) are pathogenic viruses responsible for public health problems worldwide. They have also been used as viral indicators in environmental systems. Coliphages (e.g., MS2, ΦX174) have also been studied as indicators of viral pollution in fecally contaminated water. Our objective was to evaluate the distribution of three viral fecal indicators (hAdVs, MS2, and ΦΧ174), between two different phyllosilicate clays (kaolinite and bentonite) and the aqueous phase. A series of static and dynamic experiments were conducted under two different temperatures (4, 25°C) for a time period of seven days. HAdV adsorption was examined in DNase I reaction buffer (pH=7.6, and ionic strength (IS)=1.4mM), whereas coliphage adsorption in phosphate buffered saline solution (pH=7, IS=2mM). Moreover, the effect of IS on hAdV adsorption under static conditions was evaluated. The adsorption of hAdV was assessed by real-time PCR and its infectivity was tested by cultivation methods. The coliphages MS2 and ΦΧ174 were assayed by the double-layer overlay method. The experimental results have shown that coliphage adsorption onto both kaolinite and bentonite was higher for the dynamic than the static experiments; whereas hAdV adsorption was lower under dynamic conditions. The adsorption of hAdV increased with decreasing temperature, contrary to the results obtained for the coliphages. This study examines the combined effect of temperature, agitation, clay type, and IS on hAdV adsorption onto clays. The results provide useful new information on the effective removal of viral fecal indicators (MS2, ΦX174 and hAdV) from dilute aqueous solutions by adsorption onto kaolinite and bentonite. Factors enabling enteric viruses to penetrate soils, groundwater and travel long distances within aquifers are important public health issues. Because the observed adsorption behavior of surrogate coliphages MS2 and ΦΧ174 is substantially different to that of hAdV, neither MS2 nor ΦΧ174 is recommended as a suitable model for adenovirus. Copyright © 2015 Elsevier B.V. All rights reserved.

Response surface modeling of boron adsorption from aqueous solution by vermiculite using different adsorption agents: Box-Behnken experimental design.

PubMed

Demirçivi, Pelin; Saygılı, Gülhayat Nasün

2017-07-01

In this study, a different method was applied for boron removal by using vermiculite as the adsorbent. Vermiculite, which was used in the experiments, was not modified with adsorption agents before boron adsorption using a separate process. Hexadecyltrimethylammonium bromide (HDTMA) and Gallic acid (GA) were used as adsorption agents for vermiculite by maintaining the solid/liquid ratio at 12.5 g/L. HDTMA/GA concentration, contact time, pH, initial boron concentration, inert electrolyte and temperature effects on boron adsorption were analyzed. A three-factor, three-level Box-Behnken design model combined with response surface method (RSM) was employed to examine and optimize process variables for boron adsorption from aqueous solution by vermiculite using HDTMA and GA. Solution pH (2-12), temperature (25-60 °C) and initial boron concentration (50-8,000 mg/L) were chosen as independent variables and coded x 1 , x 2 and x 3 at three levels (-1, 0 and 1). Analysis of variance was used to test the significance of variables and their interactions with 95% confidence limit (α = 0.05). According to the regression coefficients, a second-order empirical equation was evaluated between the adsorption capacity (q i ) and the coded variables tested (x i ). Optimum values of the variables were also evaluated for maximum boron adsorption by vermiculite-HDTMA (HDTMA-Verm) and vermiculite-GA (GA-Verm).

Modeling of the adsorption breakthrough behaviors of Pb2+ in a fixed bed of ETS-10 adsorbent.

PubMed

Lv, Lu; Zhang, Yan; Wang, Kean; Ray, Ajay K; Zhao, X S

2008-09-01

On the basis of experimental breakthrough curves of lead ion adsorption on ETS-10 particles in a fixed-bed column, we simulated the breakthrough curves using the two-phase homogeneous diffusion model (TPHDM). Three important model parameters, namely the external mass-transfer coefficient (k(f)), effective intercrystal diffusivity (D(e)), and axial dispersion coefficient (D(L)), were optimally found to be 8.33x10(-5) m/s, 2.57x10(-10) m(2)/s, and 1.93x10(-10) m(2)/s, respectively. A good agreement was observed between the numerical simulation and the experimental results. Sensitivity analysis revealed that the value of D(e) dictates the model performance while the magnitude of k(f) primarily affects the initial breakthrough point of the breakthrough curves.

Perfluoroalkyl phosphonic acids adsorption behaviour and removal by wastewater organisms.

PubMed

Llorca, Marta; Farré, Marinella; Sànchez-Melsió, Alexandre; Villagrasa, Marta; Knepper, Thomas P; Barceló, Damià

2018-04-26

In this study we have experimentally assessed different physicochemical parameters such as the distribution constant between octanol - water and between water and sludge for three perfluoroakyl substances (PFASs) widely used in waxes and coating materials: perfluorohexane (PFHxPA), perfluorooctane (PFOPA) and perfluorodecane (PFDPA) phosphonic acids. Distribution coefficients were assessed based on the procedures described in the OECD guideline 123 for partition coefficients while the studies of adsorption-desorption in sludge based on the indirect method of the OECD guideline 106. Besides, the removal behaviour of selected compounds has been evaluated using the green algae Desmodesmus subspicatus and microorganisms present in an effluent wastewater. These last experiments were carried out using laboratory scale bioreactors under aerobic conditions according to the OECD guideline 309. The main results of this study showed the resistance to biodegradation of selected compounds by both treatments, <5% was eliminated using D. subspicatus and similar results were obtained by aerobic degradation with wastewater microorganisms. However, it was observed that PFDPA induced changes in algae colour while it was detected to be accumulated in a floccula generated by the microorganisms present in wastewater. According to distribution coefficients the three compounds have values of logD ow below 3, indicating their capability to be present in both phases. Finally, the results of the adsorption/desorption experiments showed that PFOPA and PFDPA reach the equilibrium after 10 days of contact with a sorption percentage higher than 40% and 70%, respectively. Copyright © 2018. Published by Elsevier B.V.

Ab initio molecular dynamics determination of competitive O 2 vs. N 2 adsorption at open metal sites of M 2 (dobdc)

DOE PAGES

Parkes, Marie V.; Greathouse, Jeffery A.; Hart, David B.; ...

2016-04-04

The separation of oxygen from nitrogen using metal–organic frameworks (MOFs) is of great interest for potential pressure-swing adsorption processes for the generation of purified O 2 on industrial scales. This study uses ab initio molecular dynamics (AIMD) simulations to examine for the first time the pure-gas and competitive gas adsorption of O 2 and N 2 in the M 2(dobdc) (M = Cr, Mn, Fe) MOF series with coordinatively unsaturated metal centers. Effects of metal, temperature, and gas composition are explored. Lastly, this unique application of AIMD allows us to study in detail the adsorption/desorption processes and to visualize themore » process of multiple guests competitively binding to coordinatively unsaturated metal sites of a MOF.« less

Molecular dynamics study of the adsorption of anionic surfactant in a nonionic polymer brush.

PubMed

Wang, Hua; Zhang, Heng; Yuan, Shiling; Liu, Chengbu; Xu, Zhen

2014-06-01

The adsorption of the anionic surfactant, sodium dodecylsulfate (SDS) in poly(ethylene oxide) (PEO) brush was studied by molecular dynamics simulations. Our simulations revealed that surfactant can adsorb in polymer brush as micellar aggregates and the polymer would reside at the hydrocarbon-water interface of SDS micelles. This association between surfactant and polymer was mainly driven by the hydrophobic interaction between the polymer and surfactant tails. In the simulation, with the increasing of surfactant concentration, a plateau value representing saturated adsorption was observed. The height of polymer brush was mainly affected by the adsorbed surfactant at low grafting density of polymer; however, it was primarily controlled by the grafting density at high grafting density. Our conclusions at the molecular level were in close agreement with experiment about the adsorption of surfactant in polymer brushes.

Interactions in the aqueous phase and adsorption at the air-water interface of caseinoglycomacropeptide (GMP) and beta-lactoglobulin mixed systems.

PubMed

Martinez, María J; Sánchez, Cecilio Carrera; Patino, Juan M Rodríguez; Pilosof, Ana M R

2009-01-01

The aim of this work was to study the interactions and adsorption of caseinoglycomacropeptide (GMP) and GMP:beta-lactoglobulin (beta-lg) mixed system in the aqueous phase and at the air-water interface. The existence of associative interactions between GMP and beta-lg in the aqueous phase was investigated by dynamic light scattering, differential scanning calorimetry (DSC), fluorometry and native PAGE-electrophoresis. The surface pressure isotherm and the static and dynamic surface pressure were determined by tensiometry and surface dilatational properties. The results showed that GMP presented higher surface activity than beta-lg at a concentration of 4%wt but beta-lg showed higher film forming ability. In the mixed systems beta-lg dominated the static and dynamic surface pressure and the rheological properties of interfacial films suggesting that beta-lg hinders GMP adsorption because, in simple competition, GMP should dominate because of its higher surface activity. The surface predominance of beta-lg can be attributed to binding of GMP to beta-lg in the aqueous phase that prevents GMP adsorption on its own.

Metal-organic frameworks with high capacity and selectivity for harmful gases

PubMed Central

Britt, David; Tranchemontagne, David; Yaghi, Omar M.

2008-01-01

Benchmarks have been established for the performance of six metal-organic frameworks (MOFs) and isoreticular MOFs (IRMOFs, which have the same underlying topology as MOF-5), MOF-5, IRMOF-3, MOF-74, MOF-177, MOF-199, and IRMOF-62, as selective adsorbents for eight harmful gases: sulfur dioxide, ammonia, chlorine, tetrahydrothiophene, benzene, dichloromethane, ethylene oxide, and carbon monoxide. Kinetic breakthrough measurements are used to determine the calculated dynamic adsorption capacity of each “benchmark” MOF for each gas. The capacity of each MOF is compared to that of a sample of Calgon BPL activated carbon. We find that pore functionality plays a dominant role in determining the dynamic adsorption performance of MOFs. MOFs featuring reactive functionality outperform BPL carbon in all but one case and exhibit high dynamic adsorption capacities up to 35% by weight. PMID:18711128

Adsorption of lambda-cyhalothrin and cypermethrin on two typical Chinese soils as affected by copper.

PubMed

Liu, Jun; Lü, Xiaomeng; Xie, Jimin; Chu, Yafei; Sun, Cheng; Wang, Qian

2009-06-01

Pesticides and heavy metals pollution in soil environment has become a serious problem in many countries including China. Repeated applications of bordeaux mixture (a blend of copper sulfate and calcium hydroxide) and pyrethroid (Pys) insecticides have led to elevated copper (Cu) and Pys concentrations in vineyard surface soils. However, few studies focused on the interaction of Pys and heavy metals in the soil environment. Our previous studies had indicated the combined effect of cypermethrin (CPM) and Cu on soil catalase activity. Also, we had suggested that the addition of Cu could catalyze photo-degradation of CPM and lambda-cyhalothrin (lambda-CHT) in aqueous solution and restrain their degradation in soil. To better understand the potential influence of Cu on the fate of Pys in the soil environment, the aim of the present work was to examine the effect of Cu on the adsorption of lambda-CHT and CPM on two typical Chinese soils with different soil characteristics, which was one of the key processes controlling the fate of Pys, and to provide more information about the potential ecological risk of chemicals on the soil ecosystem. Fourier transform infrared and point charges analysis using the MOPAC program of the Gaussian system were also used to reveal the probable adsorption mechanism of lambda-CHT and CPM on soils. Two vineyard soils with different properties were chosen as experimental samples. They were sampled from 0 to 10 cm, dried, and sieved to 2 mm. Each soil was spiked with copper sulfate solution to obtain the following total soil Cu concentrations: 100, 200, 400, 800, and 1,600 mg.kg(-1). The treated soils were incubated for 2 weeks and then dried at 20 degrees C. For each soil sample and at each soil Cu concentration, the adsorption of lambda-CHT and CPM was measured using a batch equilibrium method. The concentration of lambda-CHT was determined by HPLC, and the amount of lambda-CHT and CPM adsorbed by the soil sample at equilibrium was determined by the difference between the initial and equilibrium concentrations in solution corrected by the blank adsorption measurement. Without the addition of Cu, the adsorption of lambda-CHT and CPM on Black soil is greater than that on Red soil, while the adsorption of lambda-CHT on both soils is significantly stronger than that of CPM. As the soil Cu concentration increased from 19 (or 18; background) to 1,600 mg.kg(-1), the adsorption coefficient (K (d)) of lambda-CHT decreased from 12.2 to 5.9 L.kg(-1) for Red soil, and from 26.1 to 16.8 L.kg(-1) for Black soil, whereas the CPM adsorption coefficient in both soils decreased nearly by 100% (K (d) decreased from 9.4 to 0.2 L.kg(-1) for Red soil and from 16.2 to 0.5 L.kg(-1) for Black soil). Pys adsorption is a surface phenomenon which depends on the surface area and the organic matter content. Thus, the Black soil, having higher organic matter and greater surface area than that of the Red soil, show greater adsorption affinity to lambda-CHT and CPM. In our study, the different adsorption affinity of the two Pys was obtained, which was probably attributed to differences with respect to their physical-chemical properties. Further comparison upon the two Pys was conducted. The point charges of halogen atoms in the lambda-CHT and CPM were calculated, the differences of which probably lead to the fact that lambda-CHT has a stronger binding capacity to soils than CPM. Also, FTIR spectra show that competitive adsorption occurs between CPM and Cu for the same adsorption sites, which is responsible for the obtained suppression of CPM adsorption affected by Cu. Lambda-cyhalothrin shows a significantly stronger adsorption than cypermethrin on both soils. This phenomenon may be due to several reasons: (1) lambda-CHT has lower solubility and a higher octanol-water partition coefficient value than CPM; (2) lambda-CHT consists of specific isomers, whereas CPM is mixtures of eight different isomers; (3) the chlorine and fluorine atoms in the lambda-CHT have a negative point charge, whereas the chlorine atoms in the CPM have a positive point charge. As the soil Cu concentrations increased from 19 (or 18) mg.kg(-1) to 1,600 mg.kg(-1), the adsorption coefficient of lambda-CHT and CPM decreased on both soils. This is mainly due to a competition between Cu and Pys for occupying the adsorption sites on soils. The information from this study have important implications for vineyard and orchard soils, which often contain elevated levels of Cu and Pys. These results are also useful in assessing the environmental fate and health effect of lambda-CHT and CPM. It is important for environmental scientists and engineers to get a better understanding of soil-metal-organic contaminant interactions. However, pesticide adsorption involves complex processes, and shortcomings in understanding them still restrict the ability to predict the fate and behavior of pesticide. Therefore, considerable research should be carried out to understand the mechanism of interaction between Pys and heavy metal on soils clearly.

Effect of temperature on the adsorption of sulfanilamide onto aluminum oxide and its molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Ji, Ying-xue; Wang, Feng-he; Duan, Lun-chao; Zhang, Fan; Gong, Xue-dong

2013-11-01

The effect of temperature on the adsorption of sulfanilamide (SA) onto aluminum oxide was researched through batch adsorption experiments, and was then simulated using the molecular dynamics (MD) method. The results show that SA can be adsorbed effectively by the adsorbent of aluminum oxide due to their interactions between SA molecule and the surface of aluminum oxide crystal, and temperature is a key factor which influences the adsorption efficiency obviously. The removal ratio of SA at 298 K is the highest among the selected temperatures (293 K, 298 K, 303 K). MD simulations revealed the interactions between SA molecules and (0 1 2) surface of aluminum oxide crystal at molecular level. The SA molecule has clung to the (0 1 2) face of aluminum oxide crystal, and its structure is deformed during its combining process with the surface. Both binding energies (Eb) and deformation energies (ΔEdeform) in the SA-aluminum oxide system follow the same order as: SA-Al2O3 (298 K) > SA-Al2O3 (293 K) > SA-Al2O3 (303 K). Their deformation energies are far less than their non-bonding energies. Analysis of radial distribution functions (RDFs) indicates that SA can be adsorbed effectively by aluminum oxide crystal mainly through non-bond interactions. The simulation results agree well with the experimental results, which verify the rationality and reliability of the MD simulation. The further MD simulations provide theoretically optimal temperature (301 K) for the adsorption of SA onto aluminum oxide. The molecular dynamics simulation will be useful for better understanding the adsorption mechanism of antibiotics onto metal oxides, which will also be helpful for optimizing experimental conditions to improve the adsorptive removal efficiency of antibiotics.

Confinement, Desolvation, And Electrosorption Effects on the Diffusion of Ions in Nanoporous Carbon Electrodes

PubMed Central

2015-01-01

Supercapacitors are electrochemical devices which store energy by ion adsorption on the surface of a porous carbon. They are characterized by high power delivery. The use of nanoporous carbon to increase their energy density should not hinder their fast charging. However, the mechanisms for ion transport inside electrified nanopores remain largely unknown. Here we show that the diffusion is characterized by a hierarchy of time scales arising from ion confinement, solvation, and electrosorption effects. By combining electrochemistry experiments with molecular dynamics simulations, we determine the in-pore conductivities and diffusion coefficients and their variations with the applied potential. We show that the diffusion of the ions is slower by 1 order of magnitude compared to the bulk electrolyte. The desolvation of the ions occurs on much faster time scales than electrosorption. PMID:26369420

Adsorption properties of biologically active derivatives of quaternary ammonium surfactants and their mixtures at aqueous/air interface II. Dynamics of adsorption, micelles dissociation and cytotoxicity of QDLS.

PubMed

Rojewska, Monika; Prochaska, Krystyna; Olejnik, Anna; Rychlik, Joanna

2014-07-01

The main aim of our study was analysis of adsorption dynamics of mixtures containing quaternary derivatives of lysosomotropic substance (QDLS). Two types of equimolar mixtures were considered: the ones containing two derivatives of lysosomotropic substances (DMALM-12 and DMGM-12) as well as the catanionic mixtures i.e. the systems containing QDLS and DBSNa. Dynamic surface tension measurements of surfactant mixtures were made. The results suggested that the diffusivity of the mixed system could be treated as the average value of rates of diffusion of individual components, micelles and ion pairs, which are present in the mixtures studied. Moreover, an attempt was made to explain the influence of the presence of micelles in the mixtures on their adsorption dynamics. The compounds examined show interesting biological properties which can be useful, especially for drug delivery in medical treatment. In vitro cytotoxic activities of the mixtures studied towards human cancer cells were evaluated. Most of the mixtures showed a high antiproliferative potential, especially the ones containing DMALM-12. Each cancer cell line used demonstrated different sensitivity to the same dose of the mixtures tested. Copyright © 2014 Elsevier B.V. All rights reserved.

Temperature and chemical composition controls on sorption of DOC to iron hydroxides under dynamic flow conditions

NASA Astrophysics Data System (ADS)

Daugherty, E.; Lobo, G.; Pallud, C. E.; Borch, T.

2017-12-01

Mineral-organic associations contribute substantially to the long-term preservation of soil organic matter (SOM) and carbon sequestration. Iron-organic associations are especially important because iron (hydr)oxide minerals and surface coatings are prevalent and effective sorbents of SOM. While mineral-organic associations, and iron-organic associations in particular have been studied extensively, it remains unclear how the abiotic interactions between these soil components will be affected by shifting climate. Will DOM adsorption increase or decrease with rising temperature? Does the adsorption response to temperature depend on the type of DOM? To answer these questions, we investigated the impacts of temperature (7, 25, and 45˚C) and dissolved organic matter (DOM) type on DOM sorption to ferrihydrite-coated sand in a fixed bed column at neutral pH. Breakthrough curves of the standard humic substances at 25˚C indicated that humic acids were in general retained less than fulvic acids. Response to temperature varied from no effect to a marked increase in the quantity adsorbed. Modeling of DOM breakthrough curves using the advection-diffusion equation with a linear adsorption isotherm showed that the equilibrium distribution coefficient increased over time, with retardation factors increasing 4 to 10 times for every simulation. This suggests that the DOM adsorbed to the ferrihydrite-coated sand acts as a sorbent that is 4 to 10 times more powerful than the coated sand alone. Differences in breakthrough due to DOM type and temperature became less pronounced at slower flow rates, and breakthrough occurred at nearly half as many pore volumes at a flow rate of 0.01 mL min-1 vs. 0.05 mL min-1. These results suggest DOM adsorption was diffusion controlled at low flow rates and kinetically controlled at high flow rates, which may explain the increased temperature sensitivity at high flow rates. Analyses to determine adsorptive fractionation are ongoing, but preliminary data suggest that aromatic moieties may be selectively retained during initial contact between DOM and ferrihydrite. Our results suggest that water flow rate is likely to play an important role in determining the relative effects of temperature on DOM sorption to iron minerals.

Adsorption isotherms and kinetics of activated carbons produced from coals of different ranks.

PubMed

Purevsuren, B; Lin, Chin-Jung; Davaajav, Y; Ariunaa, A; Batbileg, S; Avid, B; Jargalmaa, S; Huang, Yu; Liou, Sofia Ya-Hsuan

2015-01-01

Activated carbons (ACs) from six coals, ranging from low-rank lignite brown coal to high-rank stone coal, were utilized as adsorbents to remove basic methylene blue (MB) from an aqueous solution. The surface properties of the obtained ACs were characterized via thermal analysis, N2 isothermal sorption, scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and Boehm titration. As coal rank decreased, an increase in the heterogeneity of the pore structures and abundance of oxygen-containing functional groups increased MB coverage on its surface. The equilibrium data fitted well with the Langmuir model, and adsorption capacity of MB ranged from 51.8 to 344.8 mg g⁻¹. Good correlation coefficients were obtained using the intra-particle diffusion model, indicating that the adsorption of MB onto ACs is diffusion controlled. The values of the effective diffusion coefficient ranged from 0.61 × 10⁻¹⁰ to 7.1 × 10⁻¹⁰ m² s⁻¹, indicating that ACs from lower-rank coals have higher effective diffusivities. Among all the ACs obtained from selected coals, the AC from low-rank lignite brown coal was the most effective in removing MB from an aqueous solution.

Determination of phenol compounds in surface water matrices by bar adsorptive microextraction-high performance liquid chromatography-diode array detection.

PubMed

Neng, Nuno R; Nogueira, José M F

2014-07-03

Bar adsorptive microextraction combined with liquid desorption followed by high performance liquid chromatography with diode array detection (BAµE-LD/HPLC-DAD) is proposed for the determination of trace levels of five phenol compounds (3-nitrophenol, 4-nitrophenol, bisphenol-A, 4-n-octylphenol and 4-n-nonylphenol) in surface water matrices. By using a polystyrene-divinylbenzene copolymer (PS-DVB) sorbent phase, high selectivity and efficiency is achieved even against polydimethylsiloxane through stir bar sorptive extraction. Assays performed by BAµE(PS-DVB)-LD/HPLC-DAD on 25 mL water samples spiked at the 10.0 µg/L levels yielded recoveries over 88.0%±5.7% for all five analytes, under optimized experimental conditions. The analytical performance showed good precision (RSD<15%), detection limits of 0.25 µg/L and linear dynamic ranges (1.0-25.0 μg/L) with determination coefficient higher than 0.9904. By using the standard addition method, the application of the present method to surface water matrices allowed very good performances at the trace level. The proposed methodology proved to be a suitable alternative to monitor phenol compounds in surface water matrices, showing to be easy to implement, reliable, sensitive and requiring a low sample volume.

Multi-Scale Low-Entropy Method for Optimizing the Processing Parameters during Automated Fiber Placement

PubMed Central

Han, Zhenyu; Sun, Shouzheng; Fu, Hongya; Fu, Yunzhong

2017-01-01

Automated fiber placement (AFP) process includes a variety of energy forms and multi-scale effects. This contribution proposes a novel multi-scale low-entropy method aiming at optimizing processing parameters in an AFP process, where multi-scale effect, energy consumption, energy utilization efficiency and mechanical properties of micro-system could be taken into account synthetically. Taking a carbon fiber/epoxy prepreg as an example, mechanical properties of macro–meso–scale are obtained by Finite Element Method (FEM). A multi-scale energy transfer model is then established to input the macroscopic results into the microscopic system as its boundary condition, which can communicate with different scales. Furthermore, microscopic characteristics, mainly micro-scale adsorption energy, diffusion coefficient entropy–enthalpy values, are calculated under different processing parameters based on molecular dynamics method. Low-entropy region is then obtained in terms of the interrelation among entropy–enthalpy values, microscopic mechanical properties (interface adsorbability and matrix fluidity) and processing parameters to guarantee better fluidity, stronger adsorption, lower energy consumption and higher energy quality collaboratively. Finally, nine groups of experiments are carried out to verify the validity of the simulation results. The results show that the low-entropy optimization method can reduce void content effectively, and further improve the mechanical properties of laminates. PMID:28869520

Multi-Scale Low-Entropy Method for Optimizing the Processing Parameters during Automated Fiber Placement.

PubMed

Han, Zhenyu; Sun, Shouzheng; Fu, Hongya; Fu, Yunzhong

2017-09-03

Automated fiber placement (AFP) process includes a variety of energy forms and multi-scale effects. This contribution proposes a novel multi-scale low-entropy method aiming at optimizing processing parameters in an AFP process, where multi-scale effect, energy consumption, energy utilization efficiency and mechanical properties of micro-system could be taken into account synthetically. Taking a carbon fiber/epoxy prepreg as an example, mechanical properties of macro-meso-scale are obtained by Finite Element Method (FEM). A multi-scale energy transfer model is then established to input the macroscopic results into the microscopic system as its boundary condition, which can communicate with different scales. Furthermore, microscopic characteristics, mainly micro-scale adsorption energy, diffusion coefficient entropy-enthalpy values, are calculated under different processing parameters based on molecular dynamics method. Low-entropy region is then obtained in terms of the interrelation among entropy-enthalpy values, microscopic mechanical properties (interface adsorbability and matrix fluidity) and processing parameters to guarantee better fluidity, stronger adsorption, lower energy consumption and higher energy quality collaboratively. Finally, nine groups of experiments are carried out to verify the validity of the simulation results. The results show that the low-entropy optimization method can reduce void content effectively, and further improve the mechanical properties of laminates.

Combining bar adsorptive microextraction with capillary electrophoresis--application for the determination of phenolic acids in food matrices.

PubMed

da Rosa Neng, Nuno; Sequeiros, Rute C P; Florêncio Nogueira, José Manuel

2014-09-01

In this contribution, bar adsorptive microextraction coated with a mixed-mode anion exchange/RP followed by liquid desorption was combined for the first time with a capillary electrophoresis-diode array detection system (BAμE(MAX)-LD/CE-DAD), for the determination of phenolic acids in food matrices, using chlorogenic, ferulic, cumaric, and caffeic acids as model compounds. Assays performed in aqueous media spiked at the 0.8 mg/L level yielded average recoveries up to 40% for all four phenolic acids, under optimized experimental conditions. The analytical performance showed also good precision (RSD < 15%), convenient LODs (18.0-85.0 μg/L) and linear dynamic ranges (0.8-8.0 mg/L) with convenient determination coefficients (r(2) > 0.9900). By using the standard addition method, the application to food matrices such as green tea, red fruit juice, and honey allowed very good performances for the determination of minor amounts of phenolic acids. The proposed methodology proved to be a suitable alternative for the analysis of polar to ionic compounds, showing to be easy to implement, reliable, sensitive, and requiring a low sample volume to determine phenolic acids in food samples. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adsorption and desorption of phthalic acid esters on graphene oxide and reduced graphene oxide as affected by humic acid.

PubMed

Lu, Lun; Wang, Jun; Chen, Baoliang

2018-01-01

The implications of humic acid (HA) regarding surface properties of graphene materials and their interactions with phthalic acid esters (PAEs) are not vivid. We report the role of HA on graphene oxide (GO) and reduced graphene oxide (RGO) for sorption-desorption behavior of PAEs. Besides higher surface area and pore volume, the hydrophobic π-conjugated carbon atoms on RGO ensured prominent adsorption capacity towards PAEs in comparison to hydrophilic GO, highlighting the hydrophobic effect. After adjusting for the hydrophobic effect by calculating the hexadecane-water partition coefficient (K HW ) normalized adsorption coefficient (K d /K HW ), the dimethyl phthalate (DMP) molecule portrayed a higher adsorption affinity towards RGO by π-π electron donor-acceptor (EDA) interaction for active sites on graphene interface via sieving effect. In contrast to RGO, the weak π-π EDA interactions and H-bonding was observed between the carbonyl groups of PAEs and oxygen containing functional groups on GO. There was no obvious change in morphologies of GO and RGO before and desorption as revealed by SEM and TEM images, as desorption hysteresis did not occur in all conditions. The presence of HA also resulted in shielding effect thereby decreasing the adsorption rate and capacity of diethyl phthalate (DEP) on GO and RGO, while it had little effect on DMP, probably due to the adsorbed HA as new active sites. The desorption of DMP and DEP on RGO in presence of HA was quick and enhanced. These results should be important for evaluating the fate and health risk of graphene materials and PAEs in the environment. Copyright © 2017 Elsevier Ltd. All rights reserved.

A hybrid artificial neural network and particle swarm optimization for prediction of removal of hazardous dye brilliant green from aqueous solution using zinc sulfide nanoparticle loaded on activated carbon.

PubMed

Ghaedi, M; Ansari, A; Bahari, F; Ghaedi, A M; Vafaei, A

2015-02-25

In the present study, zinc sulfide nanoparticle loaded on activated carbon (ZnS-NP-AC) simply was synthesized in the presence of ultrasound and characterized using different techniques such as SEM and BET analysis. Then, this material was used for brilliant green (BG) removal. To dependency of BG removal percentage toward various parameters including pH, adsorbent dosage, initial dye concentration and contact time were examined and optimized. The mechanism and rate of adsorption was ascertained by analyzing experimental data at various time to conventional kinetic models such as pseudo-first-order and second order, Elovich and intra-particle diffusion models. Comparison according to general criterion such as relative error in adsorption capacity and correlation coefficient confirm the usability of pseudo-second-order kinetic model for explanation of data. The Langmuir models is efficiently can explained the behavior of adsorption system to give full information about interaction of BG with ZnS-NP-AC. A multiple linear regression (MLR) and a hybrid of artificial neural network and partial swarm optimization (ANN-PSO) model were used for prediction of brilliant green adsorption onto ZnS-NP-AC. Comparison of the results obtained using offered models confirm higher ability of ANN model compare to the MLR model for prediction of BG adsorption onto ZnS-NP-AC. Using the optimal ANN-PSO model the coefficient of determination (R(2)) were 0.9610 and 0.9506; mean squared error (MSE) values were 0.0020 and 0.0022 for the training and testing data set, respectively. Copyright © 2014 Elsevier B.V. All rights reserved.

A hybrid artificial neural network and particle swarm optimization for prediction of removal of hazardous dye brilliant green from aqueous solution using zinc sulfide nanoparticle loaded on activated carbon

NASA Astrophysics Data System (ADS)

Ghaedi, M.; Ansari, A.; Bahari, F.; Ghaedi, A. M.; Vafaei, A.

2015-02-01

In the present study, zinc sulfide nanoparticle loaded on activated carbon (ZnS-NP-AC) simply was synthesized in the presence of ultrasound and characterized using different techniques such as SEM and BET analysis. Then, this material was used for brilliant green (BG) removal. To dependency of BG removal percentage toward various parameters including pH, adsorbent dosage, initial dye concentration and contact time were examined and optimized. The mechanism and rate of adsorption was ascertained by analyzing experimental data at various time to conventional kinetic models such as pseudo-first-order and second order, Elovich and intra-particle diffusion models. Comparison according to general criterion such as relative error in adsorption capacity and correlation coefficient confirm the usability of pseudo-second-order kinetic model for explanation of data. The Langmuir models is efficiently can explained the behavior of adsorption system to give full information about interaction of BG with ZnS-NP-AC. A multiple linear regression (MLR) and a hybrid of artificial neural network and partial swarm optimization (ANN-PSO) model were used for prediction of brilliant green adsorption onto ZnS-NP-AC. Comparison of the results obtained using offered models confirm higher ability of ANN model compare to the MLR model for prediction of BG adsorption onto ZnS-NP-AC. Using the optimal ANN-PSO model the coefficient of determination (R2) were 0.9610 and 0.9506; mean squared error (MSE) values were 0.0020 and 0.0022 for the training and testing data set, respectively.

Adsorption and attenuation behavior of 3-nitro-1,2,4-triazol-5-one (NTO) in eleven soils.

PubMed

Mark, Noah; Arthur, Jennifer; Dontsova, Katerina; Brusseau, Mark; Taylor, Susan

2016-02-01

NTO (3-nitro-1,2,4-triazol-5-one) is one of the new explosive compounds used in insensitive munitions (IM) developed to replace traditional explosives, TNT and RDX. Data on NTO fate and transport is needed to determine its environmental behavior and potential for groundwater contamination. We conducted a series of kinetic and equilibrium batch experiments to characterize the fate of NTO in soils and the effect of soil geochemical properties on NTO-soil interactions. A set of experiments was also conducted using sterilized soils to evaluate the contribution of biodegradation to NTO attenuation. Measured pH values for NTO solutions decreased from 5.98 ± 0.13 to 3.50 ± 0.06 with increase in NTO concentration from 0.78 to 100 mg L(-1). Conversely, the pH of soil suspensions was not significantly affected by NTO in this concentration range. NTO experienced minimal adsorption, with measured adsorption coefficients being less than 1 cm(3) g(-1) for all studied soils. There was a highly significant inverse relationship between the measured NTO adsorption coefficients and soil pH (P = 0.00011), indicating the role of NTO and soil charge in adsorption processes. In kinetic experiments, 1st order transformation rate constant estimates ranged between 0.0004 h(-1) and 0.0142 h(-1) (equivalent to half-lives of 72 and 2 d, respectively), and correlated positively with organic carbon in the soil. Total attenuation of NTO was higher in untreated versus sterilized samples, suggesting that NTO was being biodegraded. The information presented herein can be used to help evaluate NTO potential for natural attenuation in soils. Copyright © 2015 Elsevier Ltd. All rights reserved.

The Adsorption of Cd(II) on Manganese Oxide Investigated by Batch and Modeling Techniques

PubMed Central

Huang, Xiaoming; Chen, Tianhu; Zou, Xuehua; Zhu, Mulan; Chen, Dong

2017-01-01

Manganese (Mn) oxide is a ubiquitous metal oxide in sub-environments. The adsorption of Cd(II) on Mn oxide as function of adsorption time, pH, ionic strength, temperature, and initial Cd(II) concentration was investigated by batch techniques. The adsorption kinetics showed that the adsorption of Cd(II) on Mn oxide can be satisfactorily simulated by pseudo-second-order kinetic model with high correlation coefficients (R2 > 0.999). The adsorption of Cd(II) on Mn oxide significantly decreased with increasing ionic strength at pH < 5.0, whereas Cd(II) adsorption was independent of ionic strength at pH > 6.0, which indicated that outer-sphere and inner-sphere surface complexation dominated the adsorption of Cd(II) on Mn oxide at pH < 5.0 and pH > 6.0, respectively. The maximum adsorption capacity of Mn oxide for Cd(II) calculated from Langmuir model was 104.17 mg/g at pH 6.0 and 298 K. The thermodynamic parameters showed that the adsorption of Cd(II) on Mn oxide was an endothermic and spontaneous process. According to the results of surface complexation modeling, the adsorption of Cd(II) on Mn oxide can be satisfactorily simulated by ion exchange sites (X2Cd) at low pH and inner-sphere surface complexation sites (SOCd+ and (SO)2CdOH− species) at high pH conditions. The finding presented herein plays an important role in understanding the fate and transport of heavy metals at the water–mineral interface. PMID:28956849

Removal Rate of Organic Matter Using Natural Cellulose via Adsorption Isotherm and Kinetic Studies.

PubMed

Din, Mohd Fadhil Md; Ponraj, Mohanadoss; Low, Wen-Pei; Fulazzaky, Mohamad Ali; Iwao, Kenzo; Songip, Ahmad Rahman; Chelliapan, Shreeshivadasan; Ismail, Zulhilmi; Jamal, Mohamad Hidayat

2016-02-01

In this study, the removal of natural organic matter (NOM) using coconut fiber (CF) and palm oil fiber (POF) was investigated. Preliminary analysis was performed using a jar test for the selection of optimal medium before the fabricated column model experiment. The equilibrium studies on isotherms and kinetic models for NOM adsorption were analyzed using linearized correlation coefficient. Results showed that the equilibrium data were fitted to Langmuir isotherm model for both CF and POF. The most suitable adsorption model was the pseudo-first-order kinetic model for POF and pseudo-second-order kinetic model for CF. The adsorption capacities achieved by the CF and POF were 15.67 and 30.8 mg/g respectively. Based on this investigation, it can be concluded that the POF is the most suitable material for the removal of NOM in semi polluted river water.

Evaluation of Adsorption Characteristics of a Fibrous Adsorbent Containing Zwitter-Ionic Functional Group, Targeting Organic Acids.

PubMed

Nakazawa, Akira; Tang, Ning; Inoue, Yoshinori; Kamichatani, Waka; Katoh, Toshifumi; Saito, Mitsuru; Obara, Kenji; Toriba, Akira; Hayakawa, Kazuichi

2017-01-01

Diallylamine-maleic acid copolymer (DAM)-nonwoven fabric (DAM-f), a fibrous adsorbent, contains DAM with zwitter-ionic functional groups and forms a hydration layer on the surface. The aim of this report was to evaluate the adsorption selectivity of DAM-f to semi-volatile organic acid (C1-C5). In the aqueous phase, formic acid dissolved in the hydration layer bound to the imino group of DAM-f due to anion exchange interaction. In the gas phase, the adsorption amounts of organic acids increased with the exposure time. Moreover, the adsorption rate constants correlated with the air/water partition coefficients (log K aw ) for formic acid, propionic acid, butyric acid, valeric acid and isovaleric acid, except for acetic acid. These results indicate that DAM-f is highly selective to hydrophilic compounds which easily move from the air to the hydration layer of DAM-f.

Adsorption and desorption of oxytetracycline and carbamazepine by multiwalled carbon nanotubes.

PubMed

Oleszczuk, Patryk; Pan, Bo; Xing, Baoshan

2009-12-15

We investigated the adsorption-desorption by multiwalled carbon nanotubes (MWCNTs) of two pharmaceuticals, oxytetracycline (OTC) and carbamazepine (CBZ). The pharmaceuticals demonstrated relatively fast sorption kinetics on MWCNTs. All adsorption isotherms were nonlinear and fit the Polanyi-Manes model (PMM). The single point adsorption coefficient (K) values for OTC were more than 1 order of magnitude higher than those for CBZ on corresponding MWCNTs. The adsorbed volume capacity (Q(0)) and K values of PMM showed a significant relationship with surface areas and the meso- and micropore volume of MWCNTs for both chemicals. Depending on the MWCNT outer diameter, 13.8-25.2% and 62.7-90.6% of initially adsorbed OTC and CBZ, respectively, were desorbed after 200 h. The rate of desorption of both OTC and CBZ depended upon pH and the quantity of initially adsorbed pharmaceuticals, as well as aggregation in the case of OTC.

Adsorbent testing and mathematical modeling of a solid amine regenerative CO2 and H2O removal system

NASA Technical Reports Server (NTRS)

Jeng, F. F.; Williamson, R. G.; Quellette, F. A.; Edeen, M. A.; Lin, C. H.

1991-01-01

The paper examines the design and the construction details of the test bed built for testing a solid-amine-based Regenerable CO2 Removal System (RCRS) built at the NASA/Johnson Space Center for the extended Orbiter missions. The results of tests are presented, including those for the adsorption breakthrough and the adsorption and desorption of CO2 and H2O vapor. A model for predicting the performance of regenerative CO2 and H2O vapor adsorption of the solid amine system under various operating conditions was developed in parallel with the testing of the test stand, using the coefficient of mass transfer calculated from test results. The results of simulations are shown to predict the adsorption performance of the Extended Duration Orbiter test bed fairly well. For the application to the RCRS at various operating conditions the model has to be modified.

Preparation of tea catechins using polyamide.

PubMed

Ye, Jian-Hui; Wang, Liu-Xiang; Chen, Hao; Dong, Jun-Jie; Lu, Jian-Liang; Zheng, Xin-Qiang; Wu, Ming-Yan; Liang, Yue-Rong

2011-02-01

An adsorption separation method using Polyamide-6 (PA) as an adsorbent was developed to separate catechins from green tea extract. The adsorption capacity of total catechins for PA was 193.128 mg g⁻¹ with an adsorption selectivity coefficient K(A)(B) of total catechins over caffeine 21.717, which was better than macroporous resin model HPD 600. The Langmuir model and the pseudo-second order mode were primely fitted to describe its equilibrium data and adsorption kinetics, respectively. PA column separation by two-step elution using water and 80% (v/v) aqueous ethanol was established to prepare catechins complex which contained 670.808 mg g⁻¹ total catechins and 1.828 mg g⁻¹ caffeine. It is considered that PA was a promising adsorbent for selective isolation of catechins. Copyright © 2010 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Water-soluble drug partitioning and adsorption in HEMA/MAA hydrogels.

PubMed

Dursch, Thomas J; Taylor, Nicole O; Liu, David E; Wu, Rong Y; Prausnitz, John M; Radke, Clayton J

2014-01-01

Two-photon confocal microscopy and back extraction with UV/Vis-absorption spectrophotometry quantify equilibrium partition coefficients, k, for six prototypical drugs in five soft-contact-lens-material hydrogels over a range of water contents from 40 to 92%. Partition coefficients were obtained for acetazolamide, caffeine, hydrocortisone, Oregon Green 488, sodium fluorescein, and theophylline in 2-hydroxyethyl methacrylate/methacrylic acid (HEMA/MAA, pKa≈5.2) copolymer hydrogels as functions of composition, aqueous pH (2 and 7.4), and salinity. At pH 2, the hydrogels are nonionic, whereas at pH 7.4, hydrogels are anionic due to MAA ionization. Solute adsorption on and nonspecific electrostatic interaction with the polymer matrix are pronounced. To express deviation from ideal partitioning, we define an enhancement or exclusion factor, E ≡ k/φ1, where φ1 is hydrogel water volume fraction. All solutes exhibit E > 1 in 100 wt % HEMA hydrogels owing to strong specific adsorption to HEMA strands. For all solutes, E significantly decreases upon incorporation of anionic MAA into the hydrogel due to lack of adsorption onto charged MAA moieties. For dianionic sodium fluorescein and Oregon Green 488, and partially ionized monoanionic acetazolamide at pH 7.4, however, the decrease in E is more severe than that for similar-sized nonionic solutes. Conversely, at pH 2, E generally increases with addition of the nonionic MAA copolymer due to strong preferential adsorption to the uncharged carboxylic-acid group of MAA. For all cases, we quantitatively predict enhancement factors for the six drugs using only independently obtained parameters. In dilute solution for solute i, Ei is conveniently expressed as a product of individual enhancement factors for size exclusion (Ei(ex)), electrostatic interaction (Ei(el)), and specific adsorption (Ei(ad)):Ei≡Ei(ex)Ei(el)Ei(ad). To obtain the individual enhancement factors, we employ an extended Ogston mesh-size distribution for Ei(ex); Donnan equilibrium for Ei(el); and Henry's law characterizing specific adsorption to the polymer chains for Ei(ad). Predicted enhancement factors are in excellent agreement with experiment. Copyright © 2013 Elsevier Ltd. All rights reserved.

Dynamic laser speckle technique as an alternative tool to determine hygroscopic capacity and specific surface area of microporous zeolites

NASA Astrophysics Data System (ADS)

Mojica-Sepulveda, Ruth Dary; Mendoza-Herrera, Luís Joaquín; Grumel, Eduardo; Soria, Delia Beatriz; Cabello, Carmen Inés; Trivi, Marcelo

2018-07-01

Adsorption phenomena have several technological applications such as desiccants, catalysts, and separation of gases. Their uses depend on the textural properties of the solid adsorbent and the type of the adsorbed liquid or gas. Therefore, it is important to determine these properties. The most common measurement methods are physicochemical based on adsorption of N2 to determine the surface area and the distribution of pores size. However these techniques present certain limitations for microporous materials. In this paper we propose the use of the Dynamic Laser Speckle (DLS) technique to measure the hygroscopic capacity of a microporous natural zeolite and their modified forms. This new approach based on the adsorption of water by solids allows determine their specific surface area (S). To test the DLS results, we compared the obtained S values to those calculated by different conventional isotherms using the N2 adsorption-desorption method.

A supramolecular strategy for self-mobile adsorption sites in affinity membrane.

PubMed

Lin, Ligang; Dong, Meimei; Liu, Chunyu; Wei, Chenjie; Wang, Yuanyuan; Sun, Hui; Ye, Hui

2014-09-01

Disclosed here is the design of a novel supramolecular membrane with self-mobile adsorption sites for biomolecules purification. In the 3D micropore channels of membrane matrix, the ligands are conjugated onto the cyclic compounds in polyrotaxanes for protein adsorption. During membrane filtration, the adsorption sites can rotate and/or slide along the axial chain, which results in the enhanced adsorption capacity. The excellent performance of supra-molecular membrane is related with the dynamic working manner of adsorption sites, which plays a crucial role on avoiding spatial mismatching and short-circuit effect. The supra-molecular strategy described here has general suggestions for the "sites" involved technologies such as catalysis, adsorption, and sensors, which is of broad interest. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface accommodation of molecular contaminants

NASA Technical Reports Server (NTRS)

Chen, Philip T.; Hedgeland, Randy J.; Thomson, Shaun R.

1990-01-01

Theoretical consideration and supporting data are presented regarding the nature of the transport mechanisms which cause the adsorption of gases on spacecraft surfaces. Particular attention is given to the concept of a sticking coefficient which is the ratio of the thermally accommodated mass to the total incident mass. Existing molecular accommodation data are examined in terms of spacecraft applications and recent contamination-control data are introduced. Two distinct yet linked concepts emerge which are the accommodation and sticking coefficients, and surface roughness contributes significantly to both coefficients. A general equation regarding the coefficients is developed, and the data are found to fit the equation basically. It is concluded that a more precise characterization of the coefficients can be obtained through experimentation under simulated spacecraft conditions.

Facile and green preparation of novel adsorption materials by combining sol-gel with ion imprinting technology for selective removal of Cu(II) ions from aqueous solution

NASA Astrophysics Data System (ADS)

Ren, Zhongqi; Zhu, Xinyan; Du, Jian; Kong, Delong; Wang, Nian; Wang, Zhuo; Wang, Qi; Liu, Wei; Li, Qunsheng; Zhou, Zhiyong

2018-03-01

A novel green adsorption polymer was prepared by ion imprinted technology in conjunction with sol-gel process under mild conditions for the selective removal of Cu(II) ions from aqueous solution. Effects of preparation conditions on adsorption performance of prepared polymers were studied. The ion-imprinted polymer was prepared using Cu(II) ion as template, N-[3-(2-aminoethylamino) propyl] trimethoxysilane (AAPTMS) as functional monomer and tetraethyl orthosilicate (TEOS) as cross-linker. Water was used as solvent in the whole preparation process. The imprinted and non-imprinted polymers were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), atomic force microscope (AFM), Brunauer, Emmett and Teller (BET) and zeta potential. Three-dimensional network structure was formed and functional monomer was successfully cross-linked into the network structure of polymers. Effects of adsorption conditions on adsorption performance of prepared polymers were studied too. The pH value is of great influence on adsorption behavior. Adsorption by ion-imprinted polymer was fast (adsorption equilibrium was reached within 60 min). The adsorption capacity of Cu(II) ion-imprinted polymer was always larger than that of non-imprinted polymer. Pseudo-second-order kinetics model and Freundlich isotherm model fitted well with adsorption data. The maximum adsorption capacity of Cu(II) ion-imprinted polymer was 39.82 mg·g-1. However, the preparation conditions used in this work are much milder than those reported in literatures. The Cu(II) ion-imprinted polymer showed high selectivity and relative selectivity coefficients for Pb(II), Ni(II), Cd(II) and Co(II). In addition, the prepared ion-imprinted polymer could be reused several times without significant loss of adsorption capacity.

Method and means for dynamic measurement of rates of adsorption from solutions

DOEpatents

Slomka, Bogdan J.; Buttermore, William H.

1992-05-05

A method and apparatus for dynamic measurement of rates of absorption from solutions. The method has the advantage of avoiding the use of solvent normally used to establish a baseline. The method involves pre-evacuating the adsorbent contained in an adsorbent cell and thereafter rapidly contacting the adsorbent with analytical solution, all without prior exposure of adsorbent to pure solvent. The result is a sharp characteristic adsorption line.

Graphene-coated materials using silica particles as a framework for highly efficient removal of aromatic pollutants in water

PubMed Central

Yang, Kaijie; Chen, Baoliang; Zhu, Lizhong

2015-01-01

The substantial aggregation of pristine graphene nanosheets decreases its powerful adsorption capacity and diminishes its practical applications. To overcome this shortcoming, graphene-coated materials (GCMs) were prepared by loading graphene onto silica nanoparticles (SiO2). With the support of SiO2, the stacked interlamination of graphene was held open to expose the powerful adsorption sites in the interlayers. The adsorption of phenanthrene, a model aromatic pollutant, onto the loaded graphene nanosheets increased up to 100 fold compared with pristine graphene at the same level. The adsorption of GCMs increased with the loading amount of the graphene nanosheets and dramatically decreased with the introduction of oxygen-containing groups in the graphene nanosheets. The highly hydrophobic effect and the strong π-π stacking interactions of the exposed graphene nanosheets contributed to their superior adsorption of GCMs. An unusual GCM peak adsorption coefficient (Kd) was observed with the increase in sorbate concentration. The sorbate concentration at peak Kd shifted to lower values for the reduced graphene oxide and graphene relative to the graphene oxide. Therefore, the replacement of water nanodroplets attached to the graphene nanosheets through weak non-hydrogen bonding with phenanthrene molecules via strong π-π stacking interactions is hypothesized to be an additional adsorption mechanism for GCMs. PMID:26119007

Graphene-coated materials using silica particles as a framework for highly efficient removal of aromatic pollutants in water

NASA Astrophysics Data System (ADS)

Yang, Kaijie; Chen, Baoliang; Zhu, Lizhong

2015-06-01

The substantial aggregation of pristine graphene nanosheets decreases its powerful adsorption capacity and diminishes its practical applications. To overcome this shortcoming, graphene-coated materials (GCMs) were prepared by loading graphene onto silica nanoparticles (SiO2). With the support of SiO2, the stacked interlamination of graphene was held open to expose the powerful adsorption sites in the interlayers. The adsorption of phenanthrene, a model aromatic pollutant, onto the loaded graphene nanosheets increased up to 100 fold compared with pristine graphene at the same level. The adsorption of GCMs increased with the loading amount of the graphene nanosheets and dramatically decreased with the introduction of oxygen-containing groups in the graphene nanosheets. The highly hydrophobic effect and the strong π-π stacking interactions of the exposed graphene nanosheets contributed to their superior adsorption of GCMs. An unusual GCM peak adsorption coefficient (Kd) was observed with the increase in sorbate concentration. The sorbate concentration at peak Kd shifted to lower values for the reduced graphene oxide and graphene relative to the graphene oxide. Therefore, the replacement of water nanodroplets attached to the graphene nanosheets through weak non-hydrogen bonding with phenanthrene molecules via strong π-π stacking interactions is hypothesized to be an additional adsorption mechanism for GCMs.

[Preparation of Pb2+ imprinted acrylic acid-co-styrene and analysis of its adsorption properties by FAAS].

PubMed

Shawket, Abliz; Abdiryim, Supahun; Wang, Ji-De; Ismayil, Nurulla

2011-06-01

With lead ion template, acrylic acid as functional monomer, potassium persulfate as initiator, strytrene as framework monomer, lead ion imprinted polymers (Pb(II)-IIPs) were prepared using free emulsion polymerization method. The structure and morphology of the polymers were analyzed by UV-spectra, FTIR and scanning electron microscopy. The adsorption/ desorption and selectivity for Pb2+ were investigated by flame atomic absorption spectrometry (FAAS) as the detection means. The results show that compared with non-imprinted polymers(NIPs), the Pb(II)-IIPs had higher specific adsorption properties and selective recognition ability for Pb(II). The relative selectivity coefficient of Pb(II)-IIPs for Pb(II) was 6.25, 6.18, 6.25 and 6.38 in the presence of Cd(II), Cu(II), Mn(II) and Zn(II) interferences, respectively. The absorption rate was the best at the pH of adsorbent solution of 6, Adsorption rate reached 96% during the 2.5 h static adsorption time. Using 3.0 mol x L(-1) HCI as the best desorption solvent to desorb the adsorbents, the desorbtion rate reached 98%. Under the best adsorption conditions, the adsorption capacity of Pb(II)-IIPs for Pb(II) was found to be 40. mg x g(-1).

New insights into the pH-dependent interfacial adsorption of dog gastric lipase using the monolayer technique.

PubMed

Bénarouche, Anaïs; Point, Vanessa; Parsiegla, Goetz; Carrière, Frédéric; Cavalier, Jean-François

2013-11-01

The access to kinetic parameters of lipolytic enzyme adsorption onto lipids is essential for a better understanding of interfacial enzymology and lipase-lipid interactions. The interfacial adsorption of dog gastric lipase (DGL) was monitored as a function of pH and surface pressure (Π), independently from the catalytic activity, using non-hydrolysable 1,2-dilauroyl-sn-glycero-3-phosphocholine (DLPC) monomolecular films. The acid-stable DGL, which initiates fat digestion in the stomach, was then selected because its adsorption kinetics onto hydrophobic solid surfaces were already studied. This gastric lipase was therefore used as a model enzyme to validate both experimental and theoretical approaches. Results show that the adsorption process of DGL at the lipid/water interface depends on a pH-dependent adsorption equilibrium coefficient which is optimum at pH 5.0 (K(Ads) = 1.7 ± 0.05 × 10(8)M(-1)). KAds values further allowed an indirect estimation of the molar fraction (ΦE*(%), mol%) as well as the molecular area (AE*) of DGL adsorbed onto DLPC monolayer. Based on these data, a model for DGL adsorption onto DLPC monolayer at pH 5.0 is proposed for a surface pressure range of 15-25 mNm(-1). Copyright © 2013 Elsevier B.V. All rights reserved.

The removal of chloramphenicol from water through adsorption on activated carbon

NASA Astrophysics Data System (ADS)

Lach, Joanna; Ociepa-Kubicka, Agnieszka

2017-10-01

The presented research investigated the removal of chloramphenicol from water solutions on selected activated carbon available in three grades with different porous structure and surface chemical composition. Two models of adsorption kinetics were examined, i.e. the pseudo-first order and the pseudo-second order models. For all examined cases, the results of tests with higher value of coefficient R2 were described by the equation for pseudo-second order kinetics. The adsorption kinetics was also investigated on the activated carbons modified with ozone. The measurements were taken from the solutions with pH values of 2 and 7. Chloramphenicol was the most efficiently adsorbed on the activated carbon F-300 from the solutions with pH=7, and on the activated carbon ROW 08 Supra from the solutions with pH=2. The adsorption of this antibiotic was in the majority of cases higher from the solutions with pH=2 than pH=7. The modification of the activated carbons with ozone enhanced their adsorption capacities for chloramphenicol. The adsorption is influenced by the modification method of activated carbon (i.e. the duration of ozonation of the activated carbon solution and the solution temperature). The results were described with the Freundlich and Langmuir adsorption isotherm equations. Both models well described the obtained results (high R2 values).

Graphene-coated materials using silica particles as a framework for highly efficient removal of aromatic pollutants in water.

PubMed

Yang, Kaijie; Chen, Baoliang; Zhu, Lizhong

2015-06-29

The substantial aggregation of pristine graphene nanosheets decreases its powerful adsorption capacity and diminishes its practical applications. To overcome this shortcoming, graphene-coated materials (GCMs) were prepared by loading graphene onto silica nanoparticles (SiO2). With the support of SiO2, the stacked interlamination of graphene was held open to expose the powerful adsorption sites in the interlayers. The adsorption of phenanthrene, a model aromatic pollutant, onto the loaded graphene nanosheets increased up to 100 fold compared with pristine graphene at the same level. The adsorption of GCMs increased with the loading amount of the graphene nanosheets and dramatically decreased with the introduction of oxygen-containing groups in the graphene nanosheets. The highly hydrophobic effect and the strong π-π stacking interactions of the exposed graphene nanosheets contributed to their superior adsorption of GCMs. An unusual GCM peak adsorption coefficient (Kd) was observed with the increase in sorbate concentration. The sorbate concentration at peak Kd shifted to lower values for the reduced graphene oxide and graphene relative to the graphene oxide. Therefore, the replacement of water nanodroplets attached to the graphene nanosheets through weak non-hydrogen bonding with phenanthrene molecules via strong π-π stacking interactions is hypothesized to be an additional adsorption mechanism for GCMs.

Different CO2 absorbents-modified SBA-15 sorbent for highly selective CO2 capture

NASA Astrophysics Data System (ADS)

Liu, Xiuwu; Zhai, Xinru; Liu, Dongyang; Sun, Yan

2017-05-01

Different CO2 absorbents-modified SBA-15 materials are used as CO2 sorbent to improve the selectivity of CH4/CO2 separation. The SBA-15 sorbents modified by physical CO2 absorbents are very limited to increasing CO2 adsorption and present poor selectivity. However, the SBA-15 sorbents modified by chemical CO2 absorbents increase CO2 adsorption capacity obviously. The separation coefficients of CO2/CH4 increase in this case. The adsorption and regeneration properties of the SBA-15 sorbents modified by TEA, MDEA and DIPA have been compared. The SBA-15 modified by triethanolamine (TEA) presents better CO2/CH4 separation performance than the materials modified by other CO2 absorbents.

Mapping the Limitations of Breakthrough Analysis in Fixed-Bed Adsorption

NASA Technical Reports Server (NTRS)

Knox, James Clinton

2017-01-01

The separation of gases through adsorption plays an important role in the chemical processing industry, where the separation step is often the costliest part of a chemical process and thus worthy of careful study and optimization. This work developed a number of new, archival aspects on the computer simulations used for the refinement and design of these gas adsorption processes: 1. Presented a new approach to fit the undetermined heat and mass transfer coefficients in the axially dispersed plug flow equation and associated balance equations 2. Examined and described the conditions where non-physical simulation results can arise 3. Presented an approach to determine the limits of the axial dispersion and LDF mass transfer terms above which non-physical simulation results occur.

Modelling of moisture adsorption for sugar palm (Arenga pinnata) starch film

NASA Astrophysics Data System (ADS)

Jatmiko, Tri Hadi; Poeloengasih, Crescentiana D.; Prasetyo, Dwi Joko; Hernawan

2017-03-01

Sorption characteristic of food products is important for design, optimization, storage and modelling. Sugar palm starch film with two different plasticizers (sorbitol and glycerol) with varied concentration studied for its adsorption isotherm characteristic. The data of adsorption isotherm fitted with GAB, Oswin, Smith and Peleg models. All models describe the experiment data well, but Peleg model is better than the other models on both sugar palm starch film plasticized with sorbitol and glycerol. Moisture sorption of sugar palm starch increased linearly with plasticizer concentration. A new model by taking account of plasticizer concentration describes the experiment data well with an average of coefficients of determination (R2) 0.9913 and 0.9939 for film plasticized with glycerol and sorbitol respectively.

Measurements of the Activation Energies for Atomic Hydrogen Diffusion on Pure Solid CO

NASA Astrophysics Data System (ADS)

Kimura, Y.; Tsuge, M.; Pirronello, V.; Kouchi, A.; Watanabe, N.

2018-05-01

The diffusion of hydrogen atoms on dust grains is a key process in the formation of interstellar H2 and some hydrogenated molecules such as formaldehyde and methanol. We investigate the adsorption and diffusion of H atoms on pure solid CO as an analog of dust surfaces observed toward some cold interstellar regions. Using a combination of photostimulated desorption and resonance-enhanced multiphoton ionization methods to detect H atoms directly, the relative adsorption probabilities and diffusion coefficients of the H atoms are measured on pure solid CO at 8, 12, and 15 K. There is little difference between the diffusion coefficients of the hydrogen and deuterium atoms, indicating that the diffusion is limited by thermal hopping. The activation energies controlling the H-atom diffusion depend on the surface temperature, and values of 22, 30, and ∼37 meV were obtained for 8, 12, and 15 K, respectively.

Molecular dynamics simulations of the adsorption of bone morphogenetic protein-2 on surfaces with medical relevance.

PubMed

Utesch, Tillmann; Daminelli, Grazia; Mroginski, Maria Andrea

2011-11-01

Bone morphogenetic protein-2 (BMP-2) plays a crucial role in osteoblast differentiation and proliferation. Its effective therapeutic use for ectopic bone and cartilage regeneration depends, among other factors, on the interaction with the carrier at the implant site. In this study, we used classical molecular dynamics (MD) and a hybrid approach of steered molecular dynamics (SMD) combined with MD simulations to investigate the initial stages of the adsorption of BMP-2 when approaching two implant surfaces, hydrophobic graphite and hydrophilic titanium dioxide rutile. Surface adsorption was evaluated for six different orientations of the protein, two end-on and four side-on, in explicit water environment. On graphite, we observed a weak but stable adsorption. Depending on the initial orientation, hydrophobic patches as well as flexible loops of the protein were involved in the interaction with graphite. On the contrary, BMP-2 adsorbed only loosely to hydrophilic titanium dioxide. Despite a favorable interaction energy between protein and the TiO(2) surface, the rapid formation of a two-layer water structure prevented the direct interaction between protein and titanium dioxide. The first water adlayer had a strong repulsive effect on the protein, while the second attracted the protein toward the surface. For both surfaces, hydrophobic graphite and hydrophilic titanium dioxide, denaturation of BMP-2 induced by adsorption was not observed on the nanosecond time scale.

A systematic investigation of SO2 removal dynamics by coal-based activated cokes: The synergic enhancement effect of hierarchical pore configuration and gas components

NASA Astrophysics Data System (ADS)

Sun, Fei; Gao, Jihui; Liu, Xin; Tang, Xiaofan; Wu, Shaohua

2015-12-01

For the aim to break through the long-term roadblock to porous carbon based SO2 removal technology, typical coal-based activated cokes differing in terms of surface area, pore configuration and surface functional properties, were employed to investigate the SO2 removal dynamics. Among the employed activated cokes, the one with a hierarchically porous structure greatly enhanced the SO2 removal dynamics under the simulated flue gas compositions. More detailedly, SO2 separate adsorption property under normal temperature and pressure evidenced that monolayer SO2 molecules anchoring on micropore surface is the main adsorption pattern. The catalytic oxidation of SO2 follows the Eley-Rideal mechanism by which SO2 was firstly oxidized by molecular oxygen into SO3 which could depart partially to release the active sites for further adsorption. For the role of hierarchical pore configuration, it was proposed that micropores serve as gas adsorption and reaction accommodation, meso-/macropores act as byproduct H2SO4 transport and buffing reservoirs, which may in turn gives rise to the recovery of active sites in micropores and guarantees the continuous proceeding of sulfur-containing species transformation in the micropores. The present results suggest that pore configuration or interconnecting pattern, but not mere surface area or pore volume, should be favourably considered for optimizing heterogeneous gas-solid adsorption and reaction.

Adsorption of Cd (II) on Modified Granular Activated Carbons: Isotherm and Column Study.

PubMed

Rodríguez-Estupiñán, Paola; Erto, Alessandro; Giraldo, Liliana; Moreno-Piraján, Juan Carlos

2017-12-20

In this work, equilibrium and dynamic adsorption tests of cadmium Cd (II) on activated carbons derived from different oxidation treatments (with either HNO₃, H₂O₂, or NaOCl, corresponding to GACoxN, GACoxP, and GACoxCl samples) are presented. The oxidation treatments determined an increase in the surface functional groups (mainly the acidic ones) and a decrease in the pH PZC (except for the GACoxCl sample). A slight alteration of the textural parameters was also observed, which was more significant for the GACoxCl sample, in terms of a decrease of both Brunauer-Emmett-Teller ( BET ) surface area and micropore volume. Adsorption isotherms were determined for all the adsorbents and a significant increase in the adsorption performances of the oxidized samples with respect to the parent material was observed. The performances ranking was GACoxCl > GACoxP > GACoxN > GAC, likely due to the chemical surface properties of the adsorbents. Dynamic tests in a fixed bed column were carried out in terms of breakthrough curves at constant Cd inlet concentration and flow rate. GACoxCl and GACoxN showed a significantly higher value of the breakpoint time, likely due to the higher adsorption capacity. Finally, the dynamic tests were analyzed in light of a kinetic model. In the adopted experimental conditions, the results showed that mass transfer is controlled by internal pore diffusion, in which surface diffusion plays a major role.

The interfacial energetics of the oil molecules interactions with shale media using molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Zhang, Z.; Wang, J.

2017-12-01

Characterizing the behavior of oil molecules in nanopore is vital to the understanding of geochemistry of hydrocarbon-bearing fluid in ultra-tight source rocks, such as shale. The heterogeneous nature of hydrocarbon system of nanoscale complicates experimental studies of oil / shale interfacial interaction. Therefore, to gain mechanistic understanding of the interplay of oil molecules in rock nanopore, molecular dynamics simulations have been applied to study the interactions of polar and non-polar oil on both calcite and kerogen surfaces. The effect of surface wetting, oil polarity, and temperature on the Gibbs free energy of adsorption have been investigated. The free energy, entropy, and enthalpy profiles have been calculated using advanced molecular dynamics method: umbrella sampling. In agreement with experiment, 1) surface with adsorbed water layer significantly reduces the oil adsorption energy on kerogen and turns the calcite surface to highly oil-repellent; 2) polar oil has overall stronger adsorption free energy than that of non-polar oil on both non-wetted calcite and kerogen surface; 3) organic interface (e.g. kerogen) exhibits stronger adsorption of oil molecules compared to inorganic one (e.g. calcite). The finding of this study indicates that oil displacement in nanopores can be enhanced by promoting the water adsorption on surface and reducing the polarity of oil on both inorganic and organic interfaces.

Comparison of 4-chloro-2-nitrophenol adsorption on single-walled and multi-walled carbon nanotubes

PubMed Central

2012-01-01

The adsorption characteristics of 4-chloro-2-nitrophenol (4C2NP) onto single-walled and multi-walled carbon nanotubes (SWCNTs and MWCNTs) from aqueous solution were investigated with respect to the changes in the contact time, pH of solution, carbon nanotubes dosage and initial 4C2NP concentration. Experimental results showed that the adsorption efficiency of 4C2NP by carbon nanotubes (both of SWCNTs and MWCNTs) increased with increasing the initial 4C2NP concentration. The maximum adsorption took place in the pH range of 2–6. The linear correlation coefficients of different isotherm models were obtained. Results revealed that the Langmuir isotherm fitted the experimental data better than the others and based on the Langmuir model equation, maximum adsorption capacity of 4C2NP onto SWCNTs and MWCNTs were 1.44 and 4.42 mg/g, respectively. The observed changes in the standard Gibbs free energy, standard enthalpy and standard entropy showed that the adsorption of 4C2NP onto SWCNTs and MWCNTs is spontaneous and exothermic in the temperature range of 298–328 K. PMID:23369489

Adsorption effect on the formation of conductive path in defective TiO2: ab initio calculations

NASA Astrophysics Data System (ADS)

Li, Lei; Li, Wenshi; Qin, Han; Yang, Jianfeng; Mao, Ling-Feng

2017-10-01

Although the metal/TiO2/metal junctions providing resistive switching properties have attracted lots of attention in recent decades, revealing the atomic-nature of conductive path in TiO2 active layer remains a critical challenge. Here the effects of metal adsorption on defective TiO2(1 1 0) surface are theoretically investigated via ab initio calculations. The dependence of the conductive path on the adsorption of Ti/Zr/Cu/Pt/O atoms above a lattice Ti-ion in (1 1 0) plane and at 〈1 1 0〉 direction of the defective TiO2(0 0 1) surface are compared. It is found that Ti adsorptions in both sites give larger contributions to the presence of conductive path with more stability and larger transport coefficients at Fermi level, whereas the O adsorptions at both sites fail to produce conductive path. Moreover, the adsorptions of Zr/Cu/Pt atoms reduce the existence possibility of conductive path, especially absorbed above the lattice Ti-ion at 〈1 1 0〉 direction. Thus, it is helpful to clarify the interaction of the metal electrode and oxide layer in resistive random access memory.

Purification of alpha-glucosidae and invertase from bakers' yeast on modified polymeric supports.

PubMed

Lothe, R R; Purohit, S S; Shaikh, S S; Malshe, V C; Pandit, A B

1999-01-01

In the present work Amberlite XAD-16 and Indion NPA-1, Polystyrene Divinylbenzene macroreticular spherical resins, have been evaluated quantitatively as supports for the adsorption and isolation of the yeast proteins and the enzymes, invertase and alpha-glucosidase. Modification of these supports has been carried out by surface grafting using acrylate polymers to reduce the hydrophobicity and nonspecific adsorption of proteins. Good grafting efficiency, in excess of 90%, has been obtained using ultrasonic irradiation for the surface activation of polystyrene resins. XAD-16 has higher adsorption capacities for the total yeast proteins as well as for both the enzymes, alpha-glucosidase and invertase, than NPA-1 in its respective native and grafted form. Adsorption capacities of XAD-16 and NPA-1 in their respective native and grafted forms for alpha-glucosidase are higher than the capacities for invertase. Nonspecific adsorption of total proteins has been reduced considerably after the grafting of acrylate polymers on hydrophobic supports. At the same time selectivity for the adsorption of both the enzymes has been enhanced on grafted supports. The overall solid-liquid adsorption mass transfer coefficient values (Kla) estimated for adsorption of invertase on XAD are lower than those for alpha-glucosidase. Native and grafted resins could be regenerated and reused for adsorption of alpha-glucosidase for two regeneration cycles studied. Storage stability of invertase and alpha-glucosidase is the same on native and grafted form of XAD-16 and is more than the enzymes in the free form.

Adsorption studies of the herbicide simazine in agricultural soils of the Aconcagua valley, central Chile.

PubMed

Flores, Cecilia; Morgante, Verónica; González, Myriam; Navia, Rodrigo; Seeger, Michael

2009-03-01

Simazine is a s-triazine herbicide that has been applied worldwide for agriculture. This herbicide is the second most commonly detected pesticide in surface and groundwater in the United States, Europe and Australia. In this study, simazine adsorption behaviour was studied in two agricultural soils of the Aconcagua valley, central Chile. The two studied soils were soil A (loam, 8.5% organic matter content) and soil B (clay-loam, 3.5% organic matter content). Three times higher simazine adsorption capacity was observed in soil A (68.03 mg kg(-1)) compared to soil B (22.03 mg kg(-1)). The simazine adsorption distribution coefficients (K(d)) were 9.32 L kg(-1) for soil A and 7.74 L kg(-1) for soil B. The simazine adsorption enthalpy in soil A was -21.0 kJ mol(-1) while in soil B the adsorption enthalpy value was -11.5 kJ mol(-1). These results indicate that simazine adsorption process in these soils is exothermic, governing H bonds the adsorption process of simazine in both the loam and clay-loam soils. These results and the potentiometric profiles of both soils, suggest that simazine adsorption in soil A is mainly governed by simazine-organic matter interactions and in soil B by simazine-clay interactions. The understanding of simazine sorption-desorption processes is essential to determine the pesticide fate and availability in soil for pest control, biodegradation, runoff and leaching.

Molecular simulations of a CO2/CO mixture in MIL-127

NASA Astrophysics Data System (ADS)

Chokbunpiam, Tatiya; Fritzsche, Siegfried; Parasuk, Vudhichai; Caro, Jürgen; Assabumrungrat, Suttichai

2018-03-01

Adsorption and diffusion of an equimolar feed mixture of CO2 and CO in MIL-127 at three different temperatures and pressures up to 12 bar were investigated by molecular simulations. The adsorption was simulated using Gibbs-Ensemble Monte Carlo (GEMC). The structure of the adsorbed phase and the diffusion in the MIL were investigated using Molecular Dynamics (MD) simulations. The adsorption selectivity of MIL-127 for CO2 over CO at 233 K was about 15. When combining adsorption and diffusion selectivities, a membrane selectivity of about 12 is predicted. For higher temperatures, both adsorption and diffusion selectivity are found to be smaller.

First Molecular Dynamics simulation insight into the mechanism of organics adsorption from aqueous solutions on microporous carbons

NASA Astrophysics Data System (ADS)

Terzyk, Artur P.; Gauden, Piotr A.; Zieliński, Wojciech; Furmaniak, Sylwester; Wesołowski, Radosław P.; Klimek, Kamil K.

2011-10-01

The results of 84 MD simulations showing the influence of porosity and carbon surface oxidation on adsorption of three organic compounds from aqueous solutions on carbons are reported. Based on a model of 'soft' activated carbon, three carbon structures with gradually changed microporosity were created. Next, different number of surface oxygen groups was introduced. We observe quantitative agreement between simulation and experiment i.e. the decrease in adsorption from benzene down to paracetamol. Simulation results clearly demonstrate that the balance between porosity and carbon surface chemical composition in organics adsorption on carbons, and the pore blocking determine adsorption properties of carbons.

The Calculation of VOCs Diffusion Coefficient for Building Materials

NASA Astrophysics Data System (ADS)

Zhang, Xin; Deng, Quancai; Chen, Haijiang; Wu, Xiaoyun

2018-05-01

Volatile Organic Compounds (VOCS), as one of the major sources of air contaminations, has an important bearing on one’s general health. The adsorption capacity and velocity of the material for VOCs can be described separately using. In this paper, the detailed process and method of VOCs diffusion and partition coefficients by genetic algorithm is introduced, the algorithm is realized easily by computer program and the result by the method is precise and practical.

Kinetics and thermodynamics studies on the BMP-2 adsorption onto hydroxyapatite surface with different multi-morphological features.

PubMed

Lu, Zhiwei; Huangfu, Changxin; Wang, Yanying; Ge, Hongwei; Yao, Yao; Zou, Ping; Wang, Guangtu; He, Hua; Rao, Hanbing

2015-01-01

The effect of the surface topography on protein adsorption process is of great significance for designing hydroxyapatite (HA) ceramic material surfaces. In this work, three different topographies of HA materials HA-sheet, HA-rod, and HA-whisker were synthesized and testified by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Brunauer-Emmett-Teller (BET) and a field emission scanning electron microscopy (FE-SEM). We have systematically investigated the adsorption kinetics and thermodynamics of bone morphogenetic proteins (BMP-2) on the three different topography surfaces of HA, respectively. The results showed that the maximum adsorption capacities of HA-sheet, HA-rod and HA-whisker were (219.96 ± 10.18), (247.13 ± 12.35), and (354.67 ± 17.73) μg · g(-1), respectively. Kinetic parameters, rate constants, equilibrium adsorption capacities and related correlation coefficients, for each kinetic model were calculated as well as discussed. It demonstrated that the adsorption of BMP-2 onto HA could be described by the pseudo second-order equation. Adsorption of BMP-2 onto HA followed the Langmuir isotherm. It confirmed that compared with other samples HA-whisker had more adsorption sites for its high specific surface area which could provide more opportunities for protein molecules. The adsorption processes were endothermic (ΔH > 0), spontaneous (ΔG < 0) and entropy increasing (ΔS > 0). A possible adsorption mechanism has been proposed. In addition, the BMP-2 could be adsorbed to the surface which existed slight conformational changes by FT-IR. Copyright © 2015 Elsevier B.V. All rights reserved.

Phase transitions in single macromolecules: Loop-stretch transition versus loop adsorption transition in end-grafted polymer chains

NASA Astrophysics Data System (ADS)

Zhang, Shuangshuang; Qi, Shuanhu; Klushin, Leonid I.; Skvortsov, Alexander M.; Yan, Dadong; Schmid, Friederike

2018-01-01

We use Brownian dynamics simulations and analytical theory to compare two prominent types of single molecule transitions. One is the adsorption transition of a loop (a chain with two ends bound to an attractive substrate) driven by an attraction parameter ɛ and the other is the loop-stretch transition in a chain with one end attached to a repulsive substrate, driven by an external end-force F applied to the free end. Specifically, we compare the behavior of the respective order parameters of the transitions, i.e., the mean number of surface contacts in the case of the adsorption transition and the mean position of the chain end in the case of the loop-stretch transition. Close to the transition points, both the static behavior and the dynamic behavior of chains with different length N are very well described by a scaling ansatz with the scaling parameters (ɛ - ɛ*)Nϕ (adsorption transition) and (F - F*)Nν (loop-stretch transition), respectively, where ϕ is the crossover exponent of the adsorption transition and ν is the Flory exponent. We show that both the loop-stretch and the loop adsorption transitions provide an exceptional opportunity to construct explicit analytical expressions for the crossover functions which perfectly describe all simulation results on static properties in the finite-size scaling regime. Explicit crossover functions are based on the ansatz for the analytical form of the order parameter distributions at the respective transition points. In contrast to the close similarity in equilibrium static behavior, the dynamic relaxation at the two transitions shows qualitative differences, especially in the strongly ordered regimes. This is attributed to the fact that the surface contact dynamics in a strongly adsorbed chain is governed by local processes, whereas the end height relaxation of a strongly stretched chain involves the full spectrum of Rouse modes.

Selective removal of 2,4-dichlorophenoxyacetic acid from water by molecularly-imprinted amino-functionalized silica gel sorbent.

PubMed

Han, Deman; Jia, Wenping; Liang, Huading

2010-01-01

A molecularly-imprinted amino-functionalized sorbent for selective removal of 2,4-dichlorophenoxyacetic acid (2,4-D) was prepared by a surface imprinting technique in combination with a sol-gel process. The 2,4-D-imprinted amino-functionalized silica sorbent was characterized by FT-IR, nitrogen adsorption and static adsorption experiments. The selectivity of the sorbent was investigated by a batch competitive binding experiment using an aqueous 2,4-D and 2,4-dichlorophenol (2,4-DCP) mixture or using an aqueous 2,4-D and 2,4-dichlorophenylacetic acid (DPAC) mixture. The largest selectivity coefficient for 2,4-D in the presence of 2,4-DCP was found to be over 18, the largest relative selectivity coefficient between 2,4-D and 2,4-DCP over 9. The static uptake capacity and selectivity coefficient of the 2,4-D-imprinted functionalized sorbent are higher than those of the non-imprinted sorbent. The imprinted functionalized silica gel sorbent offered a fast kinetics for the extraction/stripping of 2,4-D, 73% of binding capacity (200 mg/L 2,4-D onto 20 mg of imprinted sorbent) was obtained within 5 min and the adsorbed 2,4-D can be easily stripped by the mixture solution of ethanol and 6 mol/L HCl (V:V = 1:1). In a test of five extraction/stripping cycles, the adsorption capacity of the sorbent was all above 93% of that of the fresh sorbent. Experimental result showed the potential of molecularly-imprinted amino-functionalized sorbent for selective removal of 2,4-D.

Dynamic adsorption of mixtures of Rhodamine B, Pb (II), Cu (II) and Zn(II) ions on composites chitosan-silica-polyethylene glycol membrane

NASA Astrophysics Data System (ADS)

Mahatmanti, F. W.; Rengga, W. D. P.; Kusumastuti, E.; Nuryono

2018-04-01

The adsorption of a solution mixture of Rhodamine B, Pb (II), Cu (II) and Zn(II) was studied using dynamic methods employing chitosan-silica-polyethylene glycol (Ch/Si/P) composite membrane as an adsorptive membrane. The composite Ch/Si/P membrane was prepared by mixing a chitosan-based membrane with silica isolated from rice husk ash (ASP) and polyethylene glycol (PEG) as a plasticizer. The resultant composite membrane was a stronger and more flexible membrane than the original chitosan-based membrane as indicated by the maximum percentage of elongation (20.5 %) and minimum Young’s Modulus (80.5 MPa). The composite membrane also showed increased mechanical and hydrophilic properties compared to the chitosan membranes. The membrane was used as adsorption membrane for Pb (II), Cu (II), Cd (II) ions and Rhodamine B dyes in a dynamic system where the permeation and selectivity were determined. The permeation of the components was observed to be in the following order: Rhodamine B > Cd (II) > Pb (II) > Cu (II) whereas the selectivity was shown to decrease the order of Cu (II) > Pb (II) > Cd (II) > Rhodamine B.

Preparation of activated carbons from unburnt coal in bottom ash with KOH activation for liquid-phase adsorption.

PubMed

Wu, Feng-Chin; Wu, Pin-Hsueh; Tseng, Ru-Ling; Juang, Ruey-Shin

2010-05-01

In this work, unburnt coal (UC) in bottom ash from coal-fired power plants was soaked in KOH solution and activated for 1 h at 780 degrees C. The yield of activated carbons varied from 47.8 to 54.8% when the KOH/UC weight ratio changed from 2 to 4. Pore properties of these activated carbons including the BET surface area, pore volume, pore size distribution, and pore diameter were characterized based on N(2) adsorption isotherms. It was shown that the isotherms for the adsorption of methylene blue, acid blue 74, and 4-chlorophenol from aqueous solutions on these activated carbons at 30 degrees C were well fitted by the Langmuir equation (correlation coefficient r(2) > 0.9968). The adsorption capacities of methylene blue, acid blue 74, and 4-chlorophenol were obtained to be 2.40-2.88, 0.57-1.29, and 2.34-5.62 mmol/g, respectively. Moreover, the adsorption kinetics could be suitably described by the Elovich equation. Copyright 2010. Published by Elsevier Ltd.

Adsorption and desorption characteristics of methamphetamine, 3,4-methylenedioxymethamphetamine, and pseudoephedrine in soils.

PubMed

Pal, Raktim; Megharaj, Mallavarapu; Kirkbride, K Paul; Naidu, Ravi

2015-06-01

This work presents, for the first time, information on the adsorption-desorption characteristics of illicit drugs and precursors in soils and an estimation of their potential bioavailability. The experiment was conducted using a batch equilibrium technique for the parent drugs methamphetamine and 3,4-methylenedioxymethamphetamine (MDMA) and the precursor pseudoephedrine in three South Australian soils varying in physiochemical properties. The individual compounds exhibited different adsorption mechanisms in the test soils, and the results fitted better with the Freundlich isotherm model (r (2) ≥ 0.99). The maximum adsorption capacity was recorded for pseudoephedrine (2,000 μg g(-1)). However, pseudoephedrine recorded lower organic carbon normalized adsorption coefficient values (<250 mL g(-1)), lower magnitudes of Gibb's free energy change, and higher percent desorption (73-92 %) compared to methamphetamine and MDMA. The results thus showed pseudoephedrine to be the most mobile compound in the soils under study, to have the highest availability for degradation of the three compounds, and to have the highest susceptibility to biotic degradation in test soils.

Modeling adsorption properties of structurally deformed metal–organic frameworks using structure–property map

PubMed Central

Lim, Dae-Woon; Kim, Sungjune; Harale, Aadesh; Yoon, Minyoung; Suh, Myunghyun Paik; Kim, Jihan

2017-01-01

Structural deformation and collapse in metal-organic frameworks (MOFs) can lead to loss of long-range order, making it a challenge to model these amorphous materials using conventional computational methods. In this work, we show that a structure–property map consisting of simulated data for crystalline MOFs can be used to indirectly obtain adsorption properties of structurally deformed MOFs. The structure–property map (with dimensions such as Henry coefficient, heat of adsorption, and pore volume) was constructed using a large data set of over 12000 crystalline MOFs from molecular simulations. By mapping the experimental data points of deformed SNU-200, MOF-5, and Ni-MOF-74 onto this structure–property map, we show that the experimentally deformed MOFs share similar adsorption properties with their nearest neighbor crystalline structures. Once the nearest neighbor crystalline MOFs for a deformed MOF are selected from a structure–property map at a specific condition, then the adsorption properties of these MOFs can be successfully transformed onto the degraded MOFs, leading to a new way to obtain properties of materials whose structural information is lost. PMID:28696307

Method and means for dynamic measurement of rates of adsorption from solutions

DOEpatents

Slomka, B.J.; Buttermore, W.H.

1992-05-05

A method and apparatus are described for the dynamic measurement of rates of absorption from solutions. The method has the advantage of avoiding the use of solvent normally used to establish a baseline. The method involves pre-evacuating the adsorbent contained in an adsorbent cell and thereafter rapidly contacting the adsorbent with analytical solution, all without prior exposure of adsorbent to pure solvent. The result is a sharp characteristic adsorption line. 5 figs.

Synthesis and hydrophobic adsorption properties of microporous/mesoporous hybrid materials.

PubMed

Hu, Qin; Li, Jinjun; Qiao, Shizhang; Hao, Zhengping; Tian, Hua; Ma, Chunyan; He, Chi

2009-05-30

Hybrid materials of silicalite-1 (Sil-1)-coated SBA-15 particles (MSs) have been successfully synthesized by crystallization process under hydrothermal conditions. These MSs materials were characterized by X-ray diffraction, nitrogen adsorption/desorption and TEM techniques, which illustrated that the silicalite-1-coated SBA-15 particles were successfully prepared and had large pore volume and hierarchical pore size distribution. Further experimental studies indicated that longer crystallization time under basic condition caused the mesostructure of SBA-15 materials to collapse destructively and higher calcination temperature tended to disrupt the long-range mesoscopic order while they had little influence on the phase of microcrystalline silicalite-1 zeolite. The resultant MSs materials were investigated by estimating dynamic adsorption capacity under dry and wet conditions to evaluate their adsorptive and hydrophobic properties. The hydrophobicity index (HI) value followed the sequence of silicalite-1>MSs>SBA-15, which revealed that the SBA-15 particles coated with the silicalite-1 seeds enhanced the surface hydrophobicity, and also were consistent with FTIR results. Our studies show that MSs materials combined the advantages of the ordered mesoporous material (high adsorptive capacity, large pore volume) and silicalite-1 zeolite (super-hydrophobic property, high hydrothermal stability), and the presence of micropores directly led to an increase in the dynamic adsorption capacity of benzene under dry and wet conditions.

Copper(II) adsorption on the kaolinite(001) surface: Insights from first-principles calculations and molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Kong, Xiang-Ping; Wang, Juan

2016-12-01

The adsorption behavior of Cu(II) on the basal hydroxylated kaolinite(001) surface in aqueous environment was investigated by first-principles calculations and molecular dynamics simulations. Structures of possible monodentate and bidentate inner-sphere adsorption complexes of Cu(II) were examined, and the charge transfer and bonding mechanism were analyzed. Combining the binding energy of complex, the radial distribution function of Cu(II) with oxygen and the extended X-ray absorption fine structure data, monodentate complex on site of surface oxygen with ;upright; hydrogen and bidentate complex on site of two oxygens (one with ;upright; hydrogen and one with ;lying; hydrogen) of single Al center have been found to be the major adsorption species of Cu(II). Both adsorption species are four-coordinated with a square planar geometry. The distribution of surface hydroxyls with ;lying; hydrogen around Cu(II) plays a key role in the structure and stability of adsorption complex. Upon the Mulliken population analysis and partial density of states, charge transfer occurs with Cu(II) accepting some electrons from both surface oxygens and aqua oxygens, and the bonding Cu 3d-O 2p state filling is primarily responsible for the strong covalent interaction of Cu(II) with surface oxygen.

Effect of ring rotation upon gas adsorption in SIFSIX-3-M (M = Fe, Ni) pillared square grid networks.

PubMed

Elsaidi, Sameh K; Mohamed, Mona H; Simon, Cory M; Braun, Efrem; Pham, Tony; Forrest, Katherine A; Xu, Wenqian; Banerjee, Debasis; Space, Brian; Zaworotko, Michael J; Thallapally, Praveen K

2017-03-01

Dynamic and flexible metal-organic frameworks (MOFs) that respond to external stimuli, such as stress, light, heat, and the presence of guest molecules, hold promise for applications in chemical sensing, drug delivery, gas separations, and catalysis. A greater understanding of the relationship between flexible constituents in MOFs and gas adsorption may enable the rational design of MOFs with dynamic moieties and stimuli-responsive behavior. Here, we detail the effect of subtle structural changes upon the gas sorption behavior of two "SIFSIX" pillared square grid frameworks, namely SIFSIX-3-M (M = Ni, Fe). We observe a pronounced inflection in the Xe adsorption isotherm in the Ni variant. With evidence from X-ray diffraction studies, density functional theory, and molecular simulations, we attribute the inflection to a disordered to ordered transition of the rotational configurations of the pyrazine rings induced by sorbate-sorbent interactions. We also address the effect of cage size, temperature, and sorbate on the guest-induced ring rotation and the adsorption isotherms. The absence of an inflection in the Xe adsorption isotherm in SIFSIX-3-Fe and in the Kr, N 2 , and CO 2 adsorption isotherms in SIFSIX-3-Ni suggest that the inflection is highly sensitive to the match between the size of the cage and the guest molecule.

Molecular dynamics simulation on adsorption of pyrene-polyethylene onto ultrathin single-walled carbon nanotube

NASA Astrophysics Data System (ADS)

Cai, Lu; Lv, Wenzhen; Zhu, Hong; Xu, Qun

2016-07-01

The mechanism of the adsorption of pyrene-polyethylene (Py-PE) onto ultrathin single-walled carbon nanotube (SWNT) was studied by using all-atom molecular dynamics (MD) simulations. We found that solvent polarity and pyrene group are two critical factors in the Py-PE decoration on ultrathin SWNT. Combined MD simulations with free energy calculations, our results indicate that larger solvent polarity can decrease the contribution of conformation entropy, but contributes little to the interaction energy, moreover, larger SWNT diameter can decrease the contribution of conformation entropy but lead to the increasing of the interaction energy. In polar organic solvent (N, N-Dimethylacetamide), the pyrene group plays a key role in the adsorption of Py-PE onto ultrathin SWNT, not only facilitates the spontaneous adsorption of Py-PE onto ultrathin SWNT, but also helps to form compact structure between themselves in the final adsorption states. While in aqueous solution, pyrene group no longer works as an anchor, but still affects a lot to the final adsorption conformation. Our present work provides detailed theoretical clue to understand the noncovalent interaction between aromatic segment appended polymer and ultrathin SWNT, and helps to explore the potential application of ultrathin SWNT in the fields of hybrid material, biomedical and electronic materials.

Molecular simulation of simple fluids and polymers in nanoconfinement

NASA Astrophysics Data System (ADS)

Rasmussen, Christopher John

Prediction of phase behavior and transport properties of simple fluids and polymers confined to nanoscale pores is important to a wide range of chemical and biochemical engineering processes. A practical approach to investigate nanoscale systems is molecular simulation, specifically Monte Carlo (MC) methods. One of the most challenging problems is the need to calculate chemical potentials in simulated phases. Through the seminal work of Widom, practitioners have a powerful method for calculating chemical potentials. Yet, this method fails for dense and inhomogeneous systems, as well as for complex molecules such as polymers. In this dissertation, the gauge cell MC method, which had previously been successfully applied to confined simple fluids, was employed and extended to investigate nanoscale fluids in several key areas. Firstly, the process of cavitation (the formation and growth of bubbles) during desorption of fluids from nanopores was investigated. The dependence of cavitation pressure on pore size was determined with gauge cell MC calculations of the nucleation barriers correlated with experimental data. Additional computational studies elucidated the role of surface defects and pore connectivity in the formation of cavitation bubbles. Secondly, the gauge cell method was extended to polymers. The method was verified against the literature results and found significantly more efficient. It was used to examine adsorption of polymers in nanopores. These results were applied to model the dynamics of translocation, the act of a polymer threading through a small opening, which is implicated in drug packaging and delivery, and DNA sequencing. Translocation dynamics was studied as diffusion along the free energy landscape. Thirdly, we show how computer simulation of polymer adsorption could shed light on the specifics of polymer chromatography, which is a key tool for the analysis and purification of polymers. The quality of separation depends on the physico-chemical mechanisms of polymer/pore interaction. We considered liquid chromatography at critical conditions, and calculated the dependence of the partition coefficient on chain length. Finally, solvent-gradient chromatography was modeled using a statistical model of polymer adsorption. A model for predicting separation of complex polymers (with functional groups or copolymers) was developed for practical use in chromatographic separations.

On the role of electronic friction for dissociative adsorption and scattering of hydrogen molecules at a Ru(0001) surface.

PubMed

Füchsel, Gernot; Schimka, Selina; Saalfrank, Peter

2013-09-12

The role of electronic friction and, more generally, of nonadiabatic effects during dynamical processes at the gas/metal surface interface is still a matter of discussion. In particular, it is not clear if electronic nonadiabaticity has an effect under "mild" conditions, when molecules in low rovibrational states interact with a metal surface. In this paper, we investigate the role of electronic friction on the dissociative sticking and (inelastic) scattering of vibrationally and rotationally cold H2 molecules at a Ru(0001) surface theoretically. For this purpose, classical molecular dynamics with electronic friction (MDEF) calculations are performed and compared to MD simulations without friction. The two H atoms move on a six-dimensional potential energy surface generated from gradient-corrected density functional theory (DFT), that is, all molecular degrees of freedom are accounted for. Electronic friction is included via atomic friction coefficients obtained from an embedded atom, free electron gas (FEG) model, with embedding densities taken from gradient-corrected DFT. We find that within this model, dissociative sticking probabilities as a function of impact kinetic energies and impact angles are hardly affected by nonadiabatic effects. If one accounts for a possibly enhanced electronic friction near the dissociation barrier, on the other hand, reduced sticking probabilities are observed, in particular, at high impact energies. Further, there is always an influence on inelastic scattering, in particular, as far as the translational and internal energy distribution of the reflected molecules is concerned. Additionally, our results shed light on the role played by the velocity distribution of the incident molecular beam for adsorption probabilities, where, in particular, at higher impact energies, large effects are found.

Glyphosate sorption to soils of Argentina. Estimation of affinity coeficient by pedotransfer function

NASA Astrophysics Data System (ADS)

De Geronimo, Eduardo; Aparicio, Virginia; Costa, José Luis

2017-04-01

Argentine agricultural production is fundamentally based on a technological package that combines direct seeding and glyphosate with transgenic crops (soybean, maize and cotton). Therefore, glyphosate is the most employed herbicide in the country, where 180 to 200 million liters are applied every year. Glyphosate is strongly sorbed to soil by binding to clay minerals, layer silicates, metal oxides, non-crystalline materials or organic matter. Sorption of glyphosate is a reversible process that regulates the half-life and mobility of the herbicide and it is therefore related to the risk of contaminating courses of surface and groundwater. However, this behavior may vary depending on the characteristics of the soil on which it is applied. In addition, pH is a determining factor since it modifies the net charge in the molecule and, with it, the force of the electrostatic interaction between the glyphosate and the components of the soil. For a reliable risk assessment of groundwater contamination from pesticides precise predictions of sorption coefficients are needed. The aim of this work is to study the affinity of glyphosate to different soils of Argentina and create a model to estimate the glyphosate Freundlich sorption coefficient (Kf) from easily measurable soil properties. Adsorption of glyphosate was investigated on 12 different agricultural soils of Argentina using batch equilibration technique and fit to Freundlich sorption model. The correlation coefficients and the effects of soil characteristic factors on glyphosate adsorption parameter were analyzed through principal component and multiple lineal regression analysis. Results indicate that pH and clay contents were found to be the most significant soil factors which affect the glyphosate adsorption process. The Freundlich (Kf) pedotransfer function obtained by stepwise regression analysis was Kf = 735.2*Clay - 104.2*pH + 0.7*Polsen - 3.8*Alin. A 97.9% of the variation of glyphosate sorption coefficient could be attributed to the variation of the soil clay contents, pH, Polsen and Alin.

Characterizing particle-scale equilibrium adsorption and kinetics of uranium(VI) desorption from U-contaminated sediments

USGS Publications Warehouse

Stoliker, Deborah L.; Liu, Chongxuan; Kent, Douglas B.; Zachara, John M.

2013-01-01

Rates of U(VI) release from individual dry-sieved size fractions of a field-aggregated, field-contaminated composite sediment from the seasonally saturated lower vadose zone of the Hanford 300-Area were examined in flow-through reactors to maintain quasi-constant chemical conditions. The principal source of variability in equilibrium U(VI) adsorption properties of the various size fractions was the impact of variable chemistry on adsorption. This source of variability was represented using surface complexation models (SCMs) with different stoichiometric coefficients with respect to hydrogen ion and carbonate concentrations for the different size fractions. A reactive transport model incorporating equilibrium expressions for cation exchange and calcite dissolution, along with rate expressions for aerobic respiration and silica dissolution, described the temporal evolution of solute concentrations observed during the flow-through reactor experiments. Kinetic U(VI) desorption was well described using a multirate SCM with an assumed lognormal distribution for the mass-transfer rate coefficients. The estimated mean and standard deviation of the rate coefficients were the same for all <2 mm size fractions but differed for the 2–8 mm size fraction. Micropore volumes, assessed using t-plots to analyze N2 desorption data, were also the same for all dry-sieved <2 mm size fractions, indicating a link between micropore volumes and mass-transfer rate properties. Pore volumes for dry-sieved size fractions exceeded values for the corresponding wet-sieved fractions. We hypothesize that repeated field wetting and drying cycles lead to the formation of aggregates and/or coatings containing (micro)pore networks which provided an additional mass-transfer resistance over that associated with individual particles. The 2–8 mm fraction exhibited a larger average and standard deviation in the distribution of mass-transfer rate coefficients, possibly caused by the abundance of microporous basaltic rock fragments.

Modeling radium distribution in coastal aquifers during sea level changes: The Dead Sea case

USGS Publications Warehouse

Kiro, Yael; Yechieli, Yoseph; Voss, Clifford I.; Starinsky, Abraham; Weinstein, Yishai

2012-01-01

We present a new approach to studying the behavior of radium isotopes in a coastal aquifer. In order to simulate radium isotope distributions in the dynamic flow field of the Dead Sea aquifer, a multi-species density dependent flow model (SUTRA-MS) was used. Field data show that the activity of 226Ra decreases from 140 to 60 dpm/L upon entering the aquifer from the Dead Sea, and then further decreases linearly due to mixing with Ra-poor fresh water. On the other hand, an increase is observed in the activity of the shorter-lived isotopes (up to 52 dpm/L 224Ra and 31 dpm/L 223Ra), which are relatively low in Dead Sea water (up to 2.5 dpm/L 224Ra and 0.5 dpm/L 223Ra). The activities of the short lived radium isotopes also decrease with decreasing salinity, which is due to the effect of salinity on the adsorption of radium. The relationship between 224Ra and salinity suggests that the adsorption partition coefficient (K) is linearly related to salinity. Simulations of the steady-state conditions, show that the distance where equilibrium activity is attained for each radium isotope is affected by the isotope half-life, K and the groundwater velocity, resulting in a longer distance for the long-lived radium isotopes. K affects the radium distribution in transient conditions, especially that of the long-lived radium isotopes. The transient conditions in the Dead Sea system, with a 1 m/yr lake level drop, together with the radium field data, constrains K to be relatively low (226Ra cannot be explained by adsorption, and it is better explained by removal via coprecipitation, probably with barite or celestine.

Dynamics of adsorption in micellar and non micellar solutions of derivatives of lysosomotropic substances.

PubMed

Dopierala, Katarzyna; Prochaska, Krystyna

2010-04-22

Dynamics of adsorption in micellar and non micellar solutions of derivatives of lysosomotropic substances was studied. The following compounds were considered in our research work: alkyl N,N-dimethyl-alaninates methobromides (DMALM-n), alkyl N,N-dimethylglycinates methobromides (DMGM-n), fatty acids N,N-dimethylaminoethylesters methobromides (DMM-n), fatty acids N,N-dimethylaminopropylesters methobromides (DMPM-n), fatty acids 1-dimethylamino-2-propyl methobromides (DMP(2)M-n), and derivatives of aminoesters with double alkyl chains (M(2)M-n). The examined compounds show interesting biological properties which can be useful, especially in medicine. The exact mechanism of interaction of such compounds with biological membrane is not fully known. However, it is supposed that the presence of micelles has an important role in biological systems. In this paper we show the results of dynamic surface tension measurements in solutions containing the investigated compounds at concentrations above and below cmc. Moreover, we analyzed the influence of the chemical structure of molecules on the diameters of the micelles formed in the solutions. It was found that adsorption dynamics for the studied compounds is strongly affected by the chemical structure of the considered derivatives, especially by the presence of the ester bond, linearity of the molecule, as well as its hydrophobicity. The obtained results show that the structure of the bromide M(2)M-n with two short hydrocarbon chains favors a faster and more efficient adsorption of the molecules at the air/water interface, compared with compounds having one long alkyl chain. Moreover, the double chained derivatives of the M(2)M-n type do not form typical spherical micelles but bilayer structures probably exist in these solutions. The micelles present in the solutions influence the dynamics of adsorption drastically. Moreover, the obtained results indicated that the compounds with especially high biological activity form rather small aggregates. Copyright 2010 Elsevier B.V. All rights reserved.

Aggregation control of quantum dots through ion-mediated hydrogen bonding shielding.

PubMed

Liu, Jianbo; Yang, Xiaohai; Wang, Kemin; He, Xiaoxiao; Wang, Qing; Huang, Jin; Liu, Yan

2012-06-26

Nanoparticle stabilization against detrimental aggregation is a critical parameter that needs to be well controlled. Herein, we present a facile and rapid ion-mediated dispersing technique that leads to hydrophilic aggregate-free quantum dots (QDs). Because of the shielding of the hydrogen bonds between cysteamine-capped QDs, the presence of F(-) ions disassembled the aggregates of QDs and afforded their high colloidal stability. The F(-) ions also greatly eliminated the nonspecific adsorption of the QDs on glass slides and cells. Unlike the conventional colloidal stabilized method that requires the use of any organic ligand and/or polymer for the passivation of the nanoparticle surface, the proposed approach adopts the small size and large diffusion coefficient of inorganic ions as dispersant, which offers the disaggregation a fast reaction dynamics and negligible influence on their intrinsic surface functional properties. Therefore, the ion-mediated dispersing strategy showed great potential in chemosensing and biomedical applications.

Efficient Pb(II) removal using sodium alginate-carboxymethyl cellulose gel beads: Preparation, characterization, and adsorption mechanism.

PubMed

Ren, Huixue; Gao, Zhimin; Wu, Daoji; Jiang, Jiahui; Sun, Youmin; Luo, Congwei

2016-02-10

Alginate-carboxymethyl cellulose (CMC) gel beads were prepared in this study using sodium alginate (SA) and sodium CMC through blending and cross-linking. The specific surface area and aperture of the prepared SA-CMC gel beads were tested. The SA-CMC structure was characterized and analyzed via infrared spectroscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. Static adsorption experiment demonstrated that Pb(II) adsorption of SA-CMC exceeded 99% under the optimized conditions. In addition, experiments conducted under the same experimental conditions showed that the lead ion removal efficiency of SA-CMC was significantly higher than that of conventional adsorbents. The Pb(II) adsorption process of SA-CMC followed the Langmuir adsorption isotherm, and the dynamic adsorption model could be described through a pseudo-second-order rate equation. Pb(II) removal mechanisms of SA-CMC, including physical, chemical, and electrostatic adsorptions, were discussed based on microstructure analysis and adsorption kinetics. Chemical adsorption was the main adsorption method among these mechanisms. Copyright © 2015 Elsevier Ltd. All rights reserved.

Study of lysozyme mobility and binding free energy during adsorption on a graphene surface

NASA Astrophysics Data System (ADS)

Nakano, C. Masato; Ma, Heng; Wei, Tao

2015-04-01

Understanding protein adsorption is a key to the development of biosensors and anti-biofouling materials. Hydration essentially controls the adsorption process on hydrophobic surfaces, but its effect is complicated by various factors. Here, we present an ideal model system to isolate hydration effects—lysozyme adsorption on a flat hydrophobic graphene surface. Our all-atom molecular dynamics and molecular-mechanics/Poisson-Boltzmann surface area computation study reveal that lysozyme on graphene displays much larger diffusivity than in bulk water. Protein's hydration free energy within the first hydration shell is dominated by the protein-water electrostatic interactions and acts as an energy barrier for protein adsorption. On the other hand, the surface tension, especially that from the hydrophobic graphene, can effectively weaken the barrier to promote adsorption.

Adsorption of polymethacrylic acid from aqueous solutions on disperse titanium dioxide

NASA Astrophysics Data System (ADS)

Yaremko, Z. M.; Tkachenko, N. G.; Fedushinskaya, L. B.

2011-10-01

The state of macromolecules of polymethacrylic acid adsorbed on the surface of disperse titanium dioxide was assessed using a combination of the differential concentration approach to the determination of adsorption and methods for determining the size of disperse adsorbents by dynamic light scattering and sedimentation analysis in the field of centrifugal forces. Three sections were found on the isotherm of adsorption: in the first, isolated islands of adsorbed macromolecules formed; in the second, layers of macromolecules with a different degree of deformation were observed; in the third, determining the adsorption of macromolecules is complicated by other accompanying processes, and assessing the state of macromolecules in the adsorption layer becomes difficult.

Surface chemistry characterization of hydrodesulfurization and methanol synthesis model nanocatalysts

NASA Astrophysics Data System (ADS)

Komarneni, Mallikharjuna Rao

Surface science investigations of model catalysts have contributed significantly to heterogeneous catalysis over the past several decades. The unique properties of nanomaterials are being exploited in catalysis for the development of highly active and selective catalysts. Surface science investigations of model catalysts such as inorganic fullerene-like (IF) nanoparticles (NP), inorganic nanotubes (INT), and the oxide-supported nanoclusters are included in this dissertation. Thermal desorption spectroscopy and molecular beam scattering were respectively utilized to study the adsorption kinetics and dynamics of gas phase molecules on catalyst surfaces. In addition, ambient pressure kinetics experiments were performed to characterize the catalytic activity of hydrodesulfurization (HDS) nanocatalysts. The nanocatalysts were characterized with a variety of techniques, including Auger electron spectroscopy, x-ray photoelectron spectroscopy, electron microscopy, and x-ray diffraction. The adsorption kinetics studies of thiophene on novel HDS catalysts provided the first evidence for the presence of different adsorption sites on INT-WS2. Additionally, the adsorption sites on IF-MoS2 NP and silica-supported Mo clusters (Mo/silica) were characterized. Furthermore, the C-S bond activation energy of thiophene on Mo/silica was determined. These studies finally led to the fabrication of Ni/Co coated INT-WS2, which showed good catalytic activity towards HDS of thiophene. The studies of methanol synthesis catalysts include the adsorption kinetics and dynamics studies of CO and CO2 on Cu/silica and silica-supported EBL-fabricated Cu/CuOx nanoclusters. The adsorption dynamics of CO on Cu/silica are modeled within the frame work of the capture zone model (CZM), and the active sites of the silica-supported Au/Cu catalysts are successfully mapped. Studies on EBL model catalysts identify the rims of the CuOx nanoclusters as catalytically active sites. This observation has implications for new methanol catalyst design.

Mechanisms of chain adsorption on porous substrates and critical conditions of polymer chromatography.

PubMed

Cimino, Richard T; Rasmussen, Christopher J; Brun, Yefim; Neimark, Alexander V

2016-11-01

Polymer adsorption is a ubiquitous phenomenon with numerous technological and healthcare applications. The mechanisms of polymer adsorption on surfaces and in pores are complex owing to a competition between various entropic and enthalpic factors. Due to adsorption of monomers to the surface, the chain gains in enthalpy yet loses in entropy because of confining effects. This competition leads to the existence of critical conditions of adsorption when enthalpy gain and entropy loss are in balance. The critical conditions are controlled by the confining geometry and effective adsorption energy, which depends on the solvent composition and temperature. This phenomenon has important implications in polymer chromatography, since the retention at the critical point of adsorption (CPA) is chain length independent. However, the mechanisms of polymer adsorption in pores are poorly understood and there is an ongoing discussion in the theoretical literature about the very existence of CPA for polymer adsorption on porous substrates. In this work, we examine the mechanisms of chain adsorption on a model porous substrate using Monte Carlo (MC) simulations. We distinguish three adsorption mechanisms depending on the chain location: on external surface, completely confined in pores, and also partially confined in pores in so-called "flower" conformations. The free energies of different conformations of adsorbed chains are calculated by the incremental gauge cell MC method that allows one to determine the partition coefficient as a function of the adsorption potential, pore size, and chain length. We confirm the existence of the CPA for chain length independent separation on porous substrates, which is explained by the dominant contributions of the chain adsorption at the external surface, in particular in flower conformations. Moreover, we show that the critical conditions for porous and nonporous substrates are identical and depend only on the surface chemistry. The theoretical results are confirmed by comparison with experimental data on chromatographic separation of a series of linear polystyrenes. Copyright © 2016 Elsevier Inc. All rights reserved.

Possibility of using adsorption refrigeration unit in district heating network

NASA Astrophysics Data System (ADS)

Grzebielec, Andrzej; Rusowicz, Artur; Jaworski, Maciej; Laskowski, Rafał

2015-09-01

Adsorption refrigeration systems are able to work with heat sources of temperature starting with 50 °C. The aim of the article is to determine whether in terms of technical and economic issues adsorption refrigeration equipment can work as elements that produce cold using hot water from the district heating network. For this purpose, examined was the work of the adsorption air conditioning equipment cooperating with drycooler, and the opportunities offered by the district heating network in Warsaw during the summer. It turns out that the efficiency of the adsorption device from the economic perspective is not sufficient for production of cold even during the transitional period. The main problem is not the low temperature of the water supply, but the large difference between the coefficients of performance, COPs, of adsorption device and a traditional compressor air conditioning unit. When outside air temperature is 25 °C, the COP of the compressor type reaches a value of 4.49, whereas that of the adsorption device in the same conditions is 0.14. The ratio of the COPs is 32. At the same time ratio between the price of 1 kWh of electric power and 1 kWh of heat is only 2.85. Adsorption refrigeration equipment to be able to compete with compressor devices, should feature COPads efficiency to be greater than 1.52. At such a low driving temperature and even changing the drycooler into the evaporative cooler it is not currently possible to achieve.

Application of a biosorbent to soil: a potential method for controlling water pollution by pesticides.

PubMed

Álvarez-Martín, Alba; Rodríguez-Cruz, M Sonia; Andrades, M Soledad; Sánchez-Martín, María J

2016-05-01

Different strategies are now being optimized to prevent water from agricultural areas being contaminated by pesticides. The aim of this work was to optimize the adsorption of non-polar (tebuconazole, triadimenol) and polar (cymoxanil, pirimicarb) pesticides by soils after applying the biosorbent spent mushroom substrate (SMS) at different rates. The adsorption isotherms of pesticides by three soils and SMS-amended soils were obtained and the adsorption constants were calculated. The distribution coefficients (K d) increased 1.40-23.1 times (tebuconazole), 1.08-23.7 times (triadimenol), 1.31-42.1 times (cymoxanil), and 0.55-23.8 times (pirimicarb) for soils amended with biosorbent at rates between 2 and 75 %. Increasing the SMS rates led to a constant increase in adsorption efficiency for non-polar pesticides but not for polar pesticides, due to the increase in the organic carbon (OC) content of soils as indicated by K OC values. The OC content of SMS-amended soils accounted for more than 90 % of the adsorption variability of non-polar pesticides, but it accounted for only 56.3 % for polar pesticides. The estimated adsorption of SMS-amended soils determined from the individual adsorption of soils and SMS was more consistent with real experimental values for non-polar pesticides than for polar pesticides. The results revealed the use of SMS as a tool to optimize pesticide adsorption by soils in dealing with specific contamination problems involving these compounds.

A study on the adsorption of heavy metals by using raw wheat bran bioadsorbent in aqueous solution phase.

PubMed

Ogata, Fumihiko; Kangawa, Moe; Iwata, Yuka; Ueda, Ayaka; Tanaka, Yuko; Kawasaki, Naohito

2014-01-01

Raw wheat bran (R-WB) was used as a biomass adsorbent. The properties of R-WB were investigated. Moreover, the adsorption of cadmium and lead ions onto R-WB was evaluated. Adsorption equilibrium of cadmium and lead ions onto R-WB was achieved within 10 h, indicating that the adsorption followed a pseudo-second-order model rather than a pseudo-first-order kinetic model. The adsorption amount increased with increasing temperature. Correlation coefficient of the Langmuir equation is 0.999 for cadmium and 0.996 for lead ions, and that of the Freundlich equation is 0.994 for cadmium and 0.993 for lead ions. The negative ΔG value implied that the adsorption of cadmium and lead ions onto R-WB is a spontaneous process. The positive ΔS value indicated an increase in randomness at the solid-liquid interface. The optimal conditions for the adsorption column experiment were investigated (space velocity (SV) 2.2 1/h, linear velocity (LV) 0.1 m/h for cadmium; SV 6.51 1/h, LV 0.23 m/h for lead ions). Further, repeated adsorption-desorption of the cadmium and lead ions could be effected by using 0.01 mol/L HCl or 0.01 mol/L HNO3 solution. Consequently, polluted water could be successfully purified by using a column filled with this bioadsorbent.

Application of surface complexation models to anion adsorption by natural materials.

PubMed

Goldberg, Sabine

2014-10-01

Various chemical models of ion adsorption are presented and discussed. Chemical models, such as surface complexation models, provide a molecular description of anion adsorption reactions using an equilibrium approach. Two such models, the constant capacitance model and the triple layer model, are described in the present study. Characteristics common to all the surface complexation models are equilibrium constant expressions, mass and charge balances, and surface activity coefficient electrostatic potential terms. Methods for determining parameter values for surface site density, capacitances, and surface complexation constants also are discussed. Spectroscopic experimental methods of establishing ion adsorption mechanisms include vibrational spectroscopy, nuclear magnetic resonance spectroscopy, electron spin resonance spectroscopy, X-ray absorption spectroscopy, and X-ray reflectivity. Experimental determinations of point of zero charge shifts and ionic strength dependence of adsorption results and molecular modeling calculations also can be used to deduce adsorption mechanisms. Applications of the surface complexation models to heterogeneous natural materials, such as soils, using the component additivity and the generalized composite approaches are described. Emphasis is on the generalized composite approach for predicting anion adsorption by soils. Continuing research is needed to develop consistent and realistic protocols for describing ion adsorption reactions on soil minerals and soils. The availability of standardized model parameter databases for use in chemical speciation-transport models is critical. Published 2014 Wiley Periodicals Inc. on behalf of SETAC. This article is a US Government work and as such, is in the public domain in the in the United States of America.

Dynamic surface tension and adsorption mechanism of surfactin biosurfactant at the air-water interface.

PubMed

Onaizi, Sagheer A

2018-03-01

The dynamic adsorption of the anionic biosurfactant, surfactin, at the air-water interface has been investigated in this work and compared to those of two synthetic surfactants: the anionic sodium dodecylbenzenesulfonate (SDBS) and the nonionic octaethylene glycol monotetradecyl ether (C 14 E 8 ). The results revealed that surfactin adsorption at the air-water interface is purely controlled by diffusion mechanism at the initial stage of the adsorption process (i.e., [Formula: see text]), but shifts towards a mixed diffusion-barrier mechanism when surface tension approaches equilibrium (i.e., [Formula: see text]) due to the development of an energy barrier for adsorption. Such energy barrier has been found to be a function of the surfactin bulk concentration (increases with increasing surfactin concentration) and it is estimated to be in the range of 1.8-9.5 kJ/mol. Interestingly, such a trend (pure diffusion-controlled mechanism at [Formula: see text] and mixed diffusion-barrier mechanism at [Formula: see text]) has been also observed for the nonionic C 14 E 8 surfactant. Unlike the pure diffusion-controlled mechanism of the initial surfactin adsorption, which was the case in the presence and the absence of the sodium ion (Na + ), SDBS showed a mixed diffusion-barrier controlled at both short and long time, with an energy barrier of 3.0-9.0 and 3.8-18.0 kJ/mol, respectively. Such finding highlights the nonionic-like adsorption mechanism of surfactin despite its negative charge.

Adsorption of tetracycline on soil and sediment: effects of pH and the presence of Cu(II).

PubMed

Zhang, Zheyun; Sun, Ke; Gao, Bo; Zhang, Guixiang; Liu, Xitao; Zhao, Ye

2011-06-15

Tetracycline (TC) is frequently detected in the environment, however, knowledge on the environmental fate and transport of TC is still limited. Batch adsorption experiments of TC by soil and sediment samples were conducted. The distribution of charge and electrostatic potential of individual atoms of various TC species in the aqueous solution were determined using MOPAC version 0.034 W program in ChemBio3D Ultra software. Most of the adsorption isotherms on the soil, river and marine sediments were well fitted with the Freundlich and Polanyi-Manes (PMM) models. The single point organic carbon (OC)-normalized adsorption distribution coefficients (K(OC)) and PMM saturated adsorption capacity (Q(OC)(0)) values of TC were associated with the mesopore volume and clay content to a greater extent, indicating the mesopore volume of the soil and sediments and their clay content possibly influenced the fate and transport of TC in the natural environment. The adsorption of TC on soil and sediments strongly depended on the pH and presence of Cu(II). The presence of Cu(II) facilitated TC adsorption on soil and sediments at low pH (pH<5), possibly due to the metallic complexation and surface-bridging mechanism by Cu(II) adsorption on soil and sediments. The cation exchange interaction, metallic complexation and Coulombic interaction of mechanisms for adsorption of TC to soils and sediments were further supported by quantum chemical calculation of various TC species in different pH. Copyright © 2011 Elsevier B.V. All rights reserved.

Insight into the heterogeneous adsorption of humic acid fluorescent components on multi-walled carbon nanotubes by excitation-emission matrix and parallel factor analysis.

PubMed

Yang, Chenghu; Liu, Yangzhi; Cen, Qiulin; Zhu, Yaxian; Zhang, Yong

2018-02-01

The heterogeneous adsorption behavior of commercial humic acid (HA) on pristine and functionalized multi-walled carbon nanotubes (MWCNTs) was investigated by fluorescence excitation-emission matrix and parallel factor (EEM- PARAFAC) analysis. The kinetics, isotherms, thermodynamics and mechanisms of adsorption of HA fluorescent components onto MWCNTs were the focus of the present study. Three humic-like fluorescent components were distinguished, including one carboxylic-like fluorophore C1 (λ ex /λ em = (250, 310) nm/428nm), and two phenolic-like fluorophores, C2 (λ ex /λ em = (300, 460) nm/552nm) and C3 (λ ex /λ em = (270, 375) nm/520nm). The Lagergren pseudo-second-order model can be used to describe the adsorption kinetics of the HA fluorescent components. In addition, both the Freundlich and Langmuir models can be suitably employed to describe the adsorption of the HA fluorescent components onto MWCNTs with significantly high correlation coefficients (R 2 > 0.94, P< 0.05). The dissimilarity in the adsorption affinity (K d ) and nonlinear adsorption degree from the HA fluorescent components to MWCNTs was clearly observed. The adsorption mechanism suggested that the π-π electron donor-acceptor (EDA) interaction played an important role in the interaction between HA fluorescent components and the three MWCNTs. Furthermore, the values of the thermodynamic parameters, including the Gibbs free energy change (ΔG°), enthalpy change (ΔH°) and entropy change (ΔS°), showed that the adsorption of the HA fluorescent components on MWCNTs was spontaneous and exothermic. Copyright © 2017 Elsevier Inc. All rights reserved.

Effect of pH and Electrolytes on Adsorption of 2,4-D onto Kaolinite

NASA Astrophysics Data System (ADS)

Sharma, A.; Kawamoto, K.; Komatsu, T.; Moldrup, P.

2006-12-01

The fate and transport of pesticides in soil can be greatly influenced by adsorption onto clay minerals such as kaolinite. The ionic pesticide 2,4-D (2,4-dichlorophenoxyacetic acid) is one of the most commonly used herbicides. The purpose of this study is to investigate the effect of electrolytes and pH on the adsorption of 2,4- D onto kaolinite. The adsorption coefficient (Kd) of 2,4-D on two types of kaolinite was measured in batch experiments using water and 4 different electrolytes (0.005M CaSO4, 0.005M CaCl2, 0.01M KCl, and 0.01M NaCl). The experiments were carried out with 0.5 g kaolinite at a solid:liquid ratio of 1:20 and at different pH (1.9-6.3). The pH of the solution was controlled by addition of 0.2N of HCl. X-ray diffraction analysis of both kaolinite with and without adsorbed 2,4-D was also done to understand the location of 2,4-D adsorption. The effects of pH and electrolytes on Kd were compared and possible adsorption mechanisms were revealed for 2,4-D adsorption onto the two different types of kaolinite. The results implied that 2,4-D adsorption was higher for an electrolyte solution with monovalent cation than with divalent cation for one type of kaolinite, while no such trend was observed for the other kaolinite. The adsorption of 2,4-D increased significantly with decreasing pH for both types of kaolinite.

Adsorption of benzo(a)pyrene on to asbestos and manmade mineral fibres in an aqueous solution and in a biological model solution.

PubMed Central

Gerde, P; Scholander, P

1988-01-01

The adsorption of benzo(a)pyrene (BaP) on to three types of asbestos (chrysotile antophyllite, and amosite) and three types of manmade mineral fibres (MMMF) (rock wool, slag wool, and glass wool) in a physiological water solution was studied. Adsorption was determined from the decrease in the liquid concentration of BaP on the addition of the solid material. Results show that all the fibres weakly adsorb BaP, approximately within the same order of magnitude. The combined adsorption of BaP and phosphatidylcholine (PC) on to chrysotile and amosite asbestos and on to rock wool in aqueous solution was also studied. PC, one of the major constituents in lung surfactant, forms a separate lipid phase in water consisting of micellar liposomes or lipid bilayers. A decrease in the liquid concentration of PC was found when any of the three materials was added, indicating adsorption of the lipid phase on to the fibres. A coincident decrease in the liquid concentration of BaP was also found indicating that BaP is readily solubilised in PC and will accompany the adsorption of this compound on to the fibres. Owing to the high lipid aqueous partition coefficient of BaP, it is concluded that the direct adsorption of BaP on to the fibres will be negligible when PC is present in the system even at low concentrations. Phospholipid adsorption by the fibres and not their direct adsorption of aromatic hydrocarbons should therefore be the crucial parameter for this indirect interaction between fibres and aromatic hydrocarbons. PMID:3196662

Synthesis of molecularly imprinted polymers using acrylamide-β-cyclodextrin as a cofunctional monomer for the specific capture of tea saponins from the defatted cake extract of Camellia oleifera.

PubMed

Guo, Huiqin; Xiong, Jingjing; Ma, Wentian; Wu, Minghuo; Yan, Liushui; Li, Kexin; Liu, Yu

2016-11-01

Molecularly imprinted polymers were synthesized using mixed tea saponins as a template and acrylamide-β-cyclodextrin as a cofunctional monomer for the specific binding and purification of tea saponins from the defatted cake extract of Camellia oleifera. The adsorption properties of the prepared polymers were systematically evaluated including adsorption kinetics, adsorption isotherms, and selective recognition characteristics. It showed that the adsorption kinetics followed the pseudo first-order kinetic model (R 2 = 0.995) with an equilibrium time of 3 h, adsorption isotherm data fitted well with the Langmuir-Freundlich model (R 2 = 0.984) with an adsorption capacity of 14.23 mg/g. The relative selectivity coefficient (k´) in the presence of the analogues glycyrrhizic acid and glycyrrhetinic acid were 1.16 and 17.21, respectively. The performance of the molecularly imprinted polymers as solid-phase extraction materials was investigated and the results indicated that using acrylamide-β-cyclodextrin as a cofunctional monomer improved both the adsorption capacity and active sites stability of the imprinted polymers. The solid-phase extraction using the polymers as packing materials was subsequently applied for the separation of tea saponins in raw C. oleifera press extract, and targets were obtained with a purity reaching 89%. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adsorption characteristics of selected hydrophilic and hydrophobic micropollutants in water using activated carbon.

PubMed

Nam, Seung-Woo; Choi, Dae-Jin; Kim, Seung-Kyu; Her, Namguk; Zoh, Kyung-Duk

2014-04-15

In this study, we investigated adsorption characteristics of nine selected micropollutants (six pharmaceuticals, two pesticides, and one endocrine disruptor) in water using an activated carbon. The effects of carbon dosage, contact time, pH, DOM (dissolved organic matter), and temperature on the adsorption removal of micropollutants were examined. Increasing carbon dosage and contact time enhanced the removal of micropollutants. Sorption coefficients of hydrophilic compounds (caffeine, acetaminophen, sulfamethoxazole, and sulfamethazine) fit a linear isotherm and hydrophobic compounds (naproxen, diclofenac, 2, 4-D, triclocarban, and atrazine) fit a Freundlich isotherm. The removal of hydrophobic pollutants and caffeine were independent of pH changes, but acetaminophen, sulfamethazine, and sulfamethoxazole were adsorbed by mainly electrostatic interaction with activated carbon and so were affected by pH. The decrease in adsorption removal in surface water samples was observed and this decrease was more significant for hydrophobic than hydrophilic compounds. The decline in the adsorption capacity in surface water samples is caused by the competitive inhibition of DOM with micropollutants onto activated carbon. Low temperature (5°C) also decreased the adsorption removal of micropollutants, and affected hydrophobic compounds more than hydrophilic compounds. The results obtained in this study can be applied to optimize the adsorption capacities of micropollutants using activated carbon in water treatment process. Copyright © 2014 Elsevier B.V. All rights reserved.

A comparative examination of the adsorption mechanism of an anionic textile dye (RBY 3GL) onto the powdered activated carbon (PAC) using various the isotherm models and kinetics equations with linear and non-linear methods

NASA Astrophysics Data System (ADS)

Açıkyıldız, Metin; Gürses, Ahmet; Güneş, Kübra; Yalvaç, Duygu

2015-11-01

The present study was designed to compare the linear and non-linear methods used to check the compliance of the experimental data corresponding to the isotherm models (Langmuir, Freundlich, and Redlich-Peterson) and kinetics equations (pseudo-first order and pseudo-second order). In this context, adsorption experiments were carried out to remove an anionic dye, Remazol Brillant Yellow 3GL (RBY), from its aqueous solutions using a commercial activated carbon as a sorbent. The effects of contact time, initial RBY concentration, and temperature onto adsorbed amount were investigated. The amount of dye adsorbed increased with increased adsorption time and the adsorption equilibrium was attained after 240 min. The amount of dye adsorbed enhanced with increased temperature, suggesting that the adsorption process is endothermic. The experimental data was analyzed using the Langmuir, Freundlich, and Redlich-Peterson isotherm equations in order to predict adsorption isotherm. It was determined that the isotherm data were fitted to the Langmuir and Redlich-Peterson isotherms. The adsorption process was also found to follow a pseudo second-order kinetic model. According to the kinetic and isotherm data, it was found that the determination coefficients obtained from linear method were higher than those obtained from non-linear method.

Assessment of kinetic models on Fe adsorption in groundwater using high-quality limestone

NASA Astrophysics Data System (ADS)

Akbar, N. A.; Kamil, N. A. F. Mohd; Zin, N. S. Md; Adlan, M. N.; Aziz, H. A.

2018-04-01

During the groundwater pumping process, dissolved Fe2+ is oxidized into Fe3+ and produce rust-coloured iron mineral. Adsorption kinetic models are used to evaluate the performance of limestone adsorbent and describe the mechanism of adsorption and the diffusion processes of Fe adsorption in groundwater. This work presents the best kinetic model of Fe adsorption, which was chosen based on a higher value of coefficient correlation, R2. A batch adsorption experiment was conducted for various contact times ranging from 0 to 135 minutes. From the results of the batch study, three kinetic models were analyzed for Fe removal onto limestone sorbent, including the pseudo-first order (PFO), pseudo-second order (PSO) and intra-particle diffusion (IPD) models. Results show that the adsorption kinetic models follow the sequence: PSO > PFO > IPD, where the values of R2 are 0.997 > 0.919 > 0.918. A high value of R2 (0.997) reveals better fitted experimental data. Furthermore, the value of qe cal in the PSO kinetic model is very near to qe exp rather than that in other models. This finding therefore suggests that the PSO kinetic model has the good fitted with the experimental data which involved chemisorption process of divalent Fe removal in groundwater solution. Thus, limestone adsorbent media found to be an alternative and effective treatment of Fe removal from groundwater.

On the vibrational behavior of single- and double-walled carbon nanotubes under the physical adsorption of biomolecules in the aqueous environment: a molecular dynamics study.

PubMed

Ajori, S; Ansari, R; Darvizeh, M

2016-03-01

The adsorption of biomolecules on the walls of carbon nanotubes (CNTs) in an aqueous environment is of great importance in the field of nanobiotechnology. In this study, molecular dynamics (MD) simulations were performed to understand the mechanical vibrational behavior of single- and double-walled carbon nanotubes (SWCNTs and DWCNTs) under the physical adsorption of four important biomolecules (L-alanine, guanine, thymine, and uracil) in vacuum and an aqueous environment. It was observed that the natural frequencies of these CNTs in vacuum reduce under the physical adsorption of biomolecules. In the aqueous environment, the natural frequency of each pure CNT decreased as compared to its natural frequency in vacuum. It was also found that the frequency shift for functionalized CNTs as compared to pure CNTs in the aqueous environment was dependent on the radius and the number of walls of the CNT, and could be positive or negative.

Rosé Wine Fining Using Polyvinylpolypyrrolidone: Colorimetry, Targeted Polyphenomics, and Molecular Dynamics Simulations.

PubMed

Gil, Mélodie; Avila-Salas, Fabian; Santos, Leonardo S; Iturmendi, Nerea; Moine, Virginie; Cheynier, Véronique; Saucier, Cédric

2017-12-06

Polyvinylpolypyrrolidone (PVPP) is a fining agent polymer used in winemaking to adjust rosé wine color and to prevent organoleptic degradations by reducing polyphenol content. The impact of this polymer on color parameters and polyphenols of rosé wines was investigated, and the binding specificity of polyphenols toward PVPP was determined. Color measured by colorimetry decreased after treatment, thus confirming the adsorption of anthocyanins and other pigments. Phenolic composition was determined before and after fining by targeted polyphenomics (Ultra Performance Liquid Chromatography (UPLC)-Electrospray Ionization(ESI)-Mass Spectrometry (MS/MS)). MS analysis showed adsorption differences among polyphenol families. Flavonols (42%) and flavanols (64%) were the most affected. Anthocyanins were not strongly adsorbed on average (12%), but a specific adsorption of coumaroylated anthocyanins was observed (37%). Intermolecular interactions were also studied using molecular dynamics simulations. Relative adsorptions of flavanols were correlated with the calculated interaction energies. The specific affinity of coumaroylated anthocyanins toward PVPP was also well explained by the molecular modeling.

Impact of biochar produced from post-harvest residue on the adsorption behavior of diesel oil on loess soil.

PubMed

Jiang, Yu Feng; Sun, Hang; Yves, Uwamungu J; Li, Hong; Hu, Xue Fei

2016-02-01

The primary objective of this study was to investigate the effect of biochar, produced from wheat residue at different temperatures, on the adsorption of diesel oil by loess soil. Kinetic and equilibrium data were processed to understand the adsorption mechanism of diesel by biochar-affected loess soil; dynamic and thermodynamic adsorption experiments were conducted to characterize this adsorption. The surface features and chemical structure of biochar, modified at varying pyrolytic temperatures, were investigated using surface scanning electron microscopy and Fourier transform infrared analysis. The kinetic data showed that the adsorption of diesel oil onto loess soil could be described by a pseudo-second-order kinetic model, with the rate-controlling step being intraparticle diffusion. However, in the presence of biochar, boundary layer control and intraparticle diffusion were both involved in the adsorption. Besides, the adsorption equilibrium data were well described by the Freundlich isothermal model. The saturated adsorption capacity weakened as temperature increased, suggesting a spontaneous exothermic process. Thermodynamic parameter analysis showed that adsorption was mainly a physical process and was enhanced by chemical adsorption. The adsorption capacity of loess soil for diesel oil was weakened with increasing pH. The biochar produced by pyrolytic wheat residue increased the adsorption behavior of petroleum pollutants in loess soil.

Adsorption-desorption reactions of selenium (VI) in tropical cultivated and uncultivated soils under Cerrado biome.

PubMed

Lessa, J H L; Araujo, A M; Silva, G N T; Guilherme, L R G; Lopes, G

2016-12-01

Soil management may affect selenium (Se) adsorption capacity. This study investigated adsorption and desorption of Se (VI) in selected Brazilian soils from the Cerrado biome, an area of ever increasing importance for agriculture expansion in Brazil. Soil samples were collected from cultivated and uncultivated soils, comprising clayed and sandy soils. Following chemical and mineralogical characterization, soil samples were subjected to Se adsorption and desorption tests. Adsorption was evaluated after a 72-h reaction with increasing concentrations of Se (0-2000 μg L -1 ) added as Na 2 SeO 4 in a NaCl electrolyte solution (pH 5.5; ionic strength 15 mmol L -1 ). Desorption, as well as distribution coefficients (K d ) for selenate were also assessed. Soil management affected Se adsorption capacity, i.e., Se adsorbed amounts were higher for uncultivated soils, when compared to cultivated ones. Such results were also supported by data of K d and maximum adsorption capacity of Se. This fact was attributed mainly to the presence of greater amounts of competing anions, especially phosphate, in cultivated soils, due to fertilizer application. Phosphate may compete with selenate for adsorption sites, decreasing Se retention. For the same group of soils (cultivated and uncultivated), Se adsorption was greater in the clayed soils compared to sandy ones. Our results support the idea that adding Se (VI) to the soil is a good strategy to increase Se levels in food crops (agronomic biofortification), especially when crops are grown in soils that have been cultivated over the time due to their low Se adsorption capacity (high Se availability). Copyright © 2016 Elsevier Ltd. All rights reserved.

Removal of nitroimidazole antibiotics from aqueous solution by adsorption/bioadsorption on activated carbon.

PubMed

Rivera-Utrilla, J; Prados-Joya, G; Sánchez-Polo, M; Ferro-García, M A; Bautista-Toledo, I

2009-10-15

The objective of the present study was to analyse the behaviour of activated carbon with different chemical and textural properties in nitroimidazole adsorption, also assessing the combined use of microorganisms and activated carbon in the removal of these compounds from waters and the influence of the chemical nature of the solution (pH and ionic strength) on the adsorption process. Results indicate that the adsorption of nitroimidazoles is largely determined by activated carbon chemical properties. Application of the Langmuir equation to the adsorption isotherms showed an elevated adsorption capacity (X(m)=1.04-2.04 mmol/g) for all contaminants studied. Solution pH and electrolyte concentration did not have a major effect on the adsorption of these compounds on activated carbon, confirming that the principal interactions involved in the adsorption of these compounds are non-electrostatic. Nitroimidazoles are not degraded by microorganisms used in the biological stage of a wastewater treatment plant. However, the presence of microorganisms during nitroimidazole adsorption increased their adsorption on the activated carbon, although it weakened interactions between the adsorbate and carbon surface. In dynamic regime, the adsorptive capacity of activated carbon was markedly higher in surface water and groundwater than in urban wastewaters.

Protein adsorption in microengraving immunoassays.

PubMed

Song, Qing

2015-10-16

Microengraving is a novel immunoassay for characterizing multiple protein secretions from single cells. During the immunoassay, characteristic diffusion and kinetic time scales  and  determine the time for molecular diffusion of proteins secreted from the activated single lymphocytes and subsequent binding onto the glass slide surface respectively. Our results demonstrate that molecular diffusion plays important roles in the early stage of protein adsorption dynamics which shifts to a kinetic controlled mechanism in the later stage. Similar dynamic pathways are observed for protein adsorption with significantly fast rates and rapid shifts in transport mechanisms when  is increased a hundred times from 0.313 to 31.3. Theoretical adsorption isotherms follow the trend of experimentally obtained data. Adsorption isotherms indicate that amount of proteins secreted from individual cells and subsequently captured on a clean glass slide surface increases monotonically with time. Our study directly validates that protein secretion rates can be quantified by the microengraving immunoassay. This will enable us to apply microengraving immunoassays to quantify secretion rates from 10⁴-10⁵ single cells in parallel, screen antigen-specific cells with the highest secretion rate for clonal expansion and quantitatively reveal cellular heterogeneity within a small cell sample.

Protein Adsorption in Microengraving Immunoassays

PubMed Central

Song, Qing

2015-01-01

Microengraving is a novel immunoassay forcharacterizing multiple protein secretions from single cells. During the immunoassay, characteristic diffusion and kinetic time scales τD and τK determine the time for molecular diffusion of proteins secreted from the activated single lymphocytes and subsequent binding onto the glass slide surface respectively. Our results demonstrate that molecular diffusion plays important roles in the early stage of protein adsorption dynamics which shifts to a kinetic controlled mechanism in the later stage. Similar dynamic pathways are observed for protein adsorption with significantly fast rates and rapid shifts in transport mechanisms when C0* is increased a hundred times from 0.313 to 31.3. Theoretical adsorption isotherms follow the trend of experimentally obtained data. Adsorption isotherms indicate that amount of proteins secreted from individual cells and subsequently captured on a clean glass slide surface increases monotonically with time. Our study directly validates that protein secretion rates can be quantified by the microengraving immunoassay. This will enable us to apply microengraving immunoassays to quantify secretion rates from 104–105 single cells in parallel, screen antigen-specific cells with the highest secretion rate for clonal expansion and quantitatively reveal cellular heterogeneity within a small cell sample. PMID:26501282

Multivalent-Ion-Activated Protein Adsorption Reflecting Bulk Reentrant Behavior.

PubMed

Fries, Madeleine R; Stopper, Daniel; Braun, Michal K; Hinderhofer, Alexander; Zhang, Fajun; Jacobs, Robert M J; Skoda, Maximilian W A; Hansen-Goos, Hendrik; Roth, Roland; Schreiber, Frank

2017-12-01

Protein adsorption at the solid-liquid interface is an important phenomenon that often can be observed as a first step in biological processes. Despite its inherent importance, still relatively little is known about the underlying microscopic mechanisms. Here, using multivalent ions, we demonstrate the control of the interactions and the corresponding adsorption of net-negatively charged proteins (bovine serum albumin) at a solid-liquid interface. This is demonstrated by ellipsometry and corroborated by neutron reflectivity and quartz-crystal microbalance experiments. We show that the reentrant condensation observed within the rich bulk phase behavior of the system featuring a nonmonotonic dependence of the second virial coefficient on salt concentration c_{s} is reflected in an intriguing way in the protein adsorption d(c_{s}) at the interface. Our findings are successfully described and understood by a model of ion-activated patchy interactions within the framework of the classical density functional theory. In addition to the general challenge of connecting bulk and interface behavior, our work has implications for, inter alia, nucleation at interfaces.

Multivalent-Ion-Activated Protein Adsorption Reflecting Bulk Reentrant Behavior

NASA Astrophysics Data System (ADS)

Fries, Madeleine R.; Stopper, Daniel; Braun, Michal K.; Hinderhofer, Alexander; Zhang, Fajun; Jacobs, Robert M. J.; Skoda, Maximilian W. A.; Hansen-Goos, Hendrik; Roth, Roland; Schreiber, Frank

2017-12-01

Protein adsorption at the solid-liquid interface is an important phenomenon that often can be observed as a first step in biological processes. Despite its inherent importance, still relatively little is known about the underlying microscopic mechanisms. Here, using multivalent ions, we demonstrate the control of the interactions and the corresponding adsorption of net-negatively charged proteins (bovine serum albumin) at a solid-liquid interface. This is demonstrated by ellipsometry and corroborated by neutron reflectivity and quartz-crystal microbalance experiments. We show that the reentrant condensation observed within the rich bulk phase behavior of the system featuring a nonmonotonic dependence of the second virial coefficient on salt concentration cs is reflected in an intriguing way in the protein adsorption d (cs) at the interface. Our findings are successfully described and understood by a model of ion-activated patchy interactions within the framework of the classical density functional theory. In addition to the general challenge of connecting bulk and interface behavior, our work has implications for, inter alia, nucleation at interfaces.

Nonlinear isotherm and kinetics of adsorption of copper from aqueous solutions on bentonite

NASA Astrophysics Data System (ADS)

Sadeghalvad, Bahareh; Khosravi, Sara; Azadmehr, Amir Reza

2016-11-01

Bentonite is one of the most significant of clay minerals that has been studied extensively due to its potential applications in removal of various environmental pollutants. This ability is related to its high ionic exchange capacity and high specific surface area. Copper is one of the important elements of non-ferrous metals found in industrial waste waters. In the present work, the removal of copper from aqueous solutions with Iranian bentonite (from Birjand area, southeastern Iran) used without any chemical pretreatment, was studied. The experimental results were fitted by adsorption isotherms equations with two or three parameters, which include Langmuir, Freundlich, Dubinin-Radushkevich (D-R), Redlich-Peterson, Khan, and Toth models. The best correlation coefficient ( r 2) is 0.9879 observed for Langmuir model, maximum adsorption capacity of bentonite was 55.71 mg/g. The first-order and pseudo-second-order kinetic equations were used to describe the kinetics of adsorption. The experimental data were well fitted by the pseudo-second-order kinetics.

Removal of pesticides from aqueous solution: Quantitative relationship between activated carbon characteristics and adsorption properties.

PubMed

Cougnaud, A; Faur, C; Le Cloirec, P

2005-08-01

The adsorption of pesticides (atrazin, atrazin-desethyl and triflusulfuron-methyl) from aqueous solution is performed by activated carbon fibers (ACF) and granular activated carbons (GAC) in static and dynamic reactors, in order to study the co-influence of adsorbent and adsorbate characteristics on the adsorption mechanisms. First, mono-component adsorption equilibrium is carried out in a batch reactor for a wide range of concentrations (from 5 microg 1(-1) to 21.4 mg 1(-1)). Classic models, like Freundlich and Langmuir equations, are applied: the maximum adsorption capacities are high, ranging between 63 and 509 mg g(-1). The comparison of single-solute isotherms tends to confirm the decisive role of the adsorbent properties in the adsorption capacity of pesticides by the activated carbons: the performance of ACF is significantly higher than that of GAC due to a narrower pore size distribution of fibers in the area of micropores. Furthermore, their small diameter (10 microm compared with 1 mm for grains) enables faster adsorption kinetics because of the larger surface area exposed to the fluid. The influence of adsorbate size is also demonstrated. A multiple linear regression enables the co-influence of adsorbent and adsorbate properties to be quantified, a relationship being assessed between Langmuir maximum adsorption capacity and pesticide molecular weight and adsorbent diameter (R2 = 0.90). Secondly, the adsorption of the three pesticides is studied in a dynamic reactor: in this case, the influence of operating conditions (inlet concentration C0, flow velocity U0) is also taken into account. As the initial concentration or flow velocity decreases, the column performance significantly improves. Both operating factors are included in a multiple linear regression (R2 = 0.91) used to predict saturation adsorption capacity, with molecular weight and particle diameter being again designed as influent explicative variables.

Protein adsorption on electrospun zinc doped hydroxyapatite containing nylon 6 membrane: kinetics and isotherm.

PubMed

Esfahani, Hamid; Prabhakaran, Molamma P; Salahi, Esmaeil; Tayebifard, Ali; Keyanpour-Rad, Mansour; Rahimipour, Mohamad Reza; Ramakrishna, Seeram

2015-04-01

Surface modification of electrospun polymeric membrane surfaces is a critical step towards the separation process including protein adsorption. In this study, the electrospun Nylon fibers was incorporated with positively charged zinc doped hydroxyapatite (HAp) nanoparticles to study the adsorption of negatively charged proteins, namely bovine serum albumin (BSA). Effects of zinc amount within the atomic structure of HAp (nZH; n=0, 4, 8 At.%) was evaluated on produced scaffolds and consequently protein adsorption. The results showed that the ability of Nylon membrane to adsorb BSA increased with incorporation of nZH nanoparticles within the nylon structure. This phenomenon is appeared to be relate to different electrostatic charge and not to physical characteristic of scaffolds. The incorporated membrane (N-4ZH) by nanoparticles with highest zeta (ξ) potential adsorbed the maximum amount of protein. The adsorption of BSA was best fitted with pseudo-second order kinetic model. The experimental isotherm data were further analyzed by using Langmuir and Freundlich equations. By comparing the correlation coefficients obtained for each linear transformation of isotherm analysis, it was found that the Langmuir equation was the best fit equilibrium model that described the adsorption of BSA on these membranes. Copyright © 2014 Elsevier Inc. All rights reserved.

Preparation, characterization and dye adsorption of Au nanoparticles/ZnAl layered double oxides nanocomposites

NASA Astrophysics Data System (ADS)

Zhang, Yu Xin; Hao, Xiao Dong; Kuang, Min; Zhao, Han; Wen, Zhong Quan

2013-10-01

In this work, Au/ZnAl-layer double oxides (LDO) nanocomposties were prepared through a facile calcination process of AuCl4- intercalated ZnAl-layered double hydroxides (LDHs) nanocomposites. The morphology and crystal structure of these nanocomposites were characterized by Scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder X-ray diffraction (XRD), and N2 sorption analysis. By tailoring the process parameter, such as calcination temperature, heating time and the component composition, the adsorption properties of methyl orange (MO) on the Au/ZnAl-LDO nanocomposites were investigated in this work. In a typical adsorption process, it was found that 0.985 mg of MO (0.01 g L-1, 100 mL, 1 mg of MO in total) can be removed in 60 min by utilizing only 2.5 mg of Au/ZnAl-LDO (Au content, 1%) as adsorbents. Our adsorption data obtained from the Langmuir model also gave good values of the determination coefficient, and the saturated adsorption capacity of Au/ZnAl-LDO nanocomposites for MO was found to be 627.51 mg/g under ambient condition (e.g., room temperature, 1 atm). In principle, these hybrid nanostructures with higher adsorption abilities could be very promising adsorbents for wastewater treatment.

Distribution law of temperature changes during methane adsorption and desorption in coal using infrared thermography technology

NASA Astrophysics Data System (ADS)

Zhao, Dong; Chen, Hao; An, Jiangfei; Zhou, Dong; Feng, Zengchao

2018-05-01

Gas adsorption and desorption is a thermodynamic process that takes place within coal as temperature changes and that is related to methane (CH4) storage. As infrared thermographic technology has been applied in this context to measure surface temperature changes, the aim of this research was to further elucidate the distribution law underlying this process as well as the thermal effects induced by heat adsorption and desorption in coal. Specimens of two different coal ranks were used in this study, and the surface temperature changes seen in the latter were detected. A contour line map was then drawn on the basis of initial results enabling a distribution law of temperature changes for samples. The results show that different regions of coal sample surfaces exhibit different heating rates during the adsorption process, but they all depends on gas storage capacity to a certain extent. It proposes a correlation coefficient that expresses the relationship between temperature change and gas adsorption capacity that could also be used to evaluate the feasibility of coalbed CH4 extraction in the field. And finally, this study is deduced a method to reveal the actual adsorption capacity of coal or CH4 reservoirs in in situ coal seams.

Adsorption behavior of sulfamethazine in an activated sludge process treating swine wastewater.

PubMed

Ben, Weiwei; Qiang, Zhimin; Yin, Xiaowei; Qu, Jiuhui; Pan, Xun

2014-08-01

Swine wastewater is an important pollution source of antibiotics entering the aquatic environment. In this work, the adsorption behavior of sulfamethazine (SMN), a commonly-used sulfonamide antibiotic, on activated sludge from a sequencing batch reactor treating swine wastewater was investigated. The results show that the adsorption of SMN on activated sludge was an initially rapid process and reached equilibrium after 6hr. The removal efficiency of SMN from the water phase increased with an increasing concentration of mixed liquor suspended solids, while the adsorbed concentration of SMN decreased. Solution pH influenced both the speciation of SMN and the surface properties of activated sludge, thus significantly impacting the adsorption process. A linear partition model could give a good fit for the equilibrium concentrations of SMN at the test temperatures (i.e., 10, 20 and 30°C). The partition coefficient (Kd) was determined to be 100.5L/kg at 20°C, indicating a quite high adsorption capacity for SMN. Thermodynamic analysis revealed that SMN adsorption on activated sludge was an exothermic process. This study could help to clarify the fate and behavior of sulfonamide antibiotics in the activated sludge process and assess consequent environmental risks arising from sludge disposal as well. Copyright © 2014. Published by Elsevier B.V.

Determinations of gas-liquid partition coefficients using capillary chromatographic columns. Alkanols in squalane.

PubMed

Tascon, Marcos; Romero, Lílian M; Acquaviva, Agustín; Keunchkarian, Sonia; Castells, Cecilia

2013-06-14

This study focused on an investigation into the experimental quantities inherent in the determination of partition coefficients from gas-liquid chromatographic measurements through the use of capillary columns. We prepared several squalane - (2,6,10,15,19,23-hexamethyltetracosane) - containing columns with very precisely known phase ratios and determined solute retention and hold-up times at 30, 40, 50 and 60°C. We calculated infinite dilution partition coefficients from the slopes of the linear regression of retention factors as a function of the reciprocal of the phase ratio by means of fundamental chromatographic equations. In order to minimize gas-solid and liquid-solid interface contributions to retention, the surface of the capillary inner wall was pretreated to guarantee a uniform coat of stationary phase. The validity of the proposed approach was first tested by estimating the partition coefficients of n-alkanes between n-pentane and n-nonane, for which compounds data from the literature were available. Then partition coefficients of sixteen aliphatic alcohols in squalane were determined at those four temperatures. We deliberately chose these highly challenging systems: alcohols in the reference paraffinic stationary phase. These solutes exhibited adsorption in the gas-liquid interface that contributed to retention. The corresponding adsorption constant values were estimated. We fully discuss here the uncertainties associated with each experimental measurement and how these fundamental determinations can be performed precisely by circumventing the main drawbacks. The proposed strategy is reliable and much simpler than the classical chromatographic method employing packed columns. Copyright © 2013 Elsevier B.V. All rights reserved.

Controlled drug release from hydrogels for contact lenses: Drug partitioning and diffusion.

PubMed

Pimenta, A F R; Ascenso, J; Fernandes, J C S; Colaço, R; Serro, A P; Saramago, B

2016-12-30

Optimization of drug delivery from drug loaded contact lenses assumes understanding the drug transport mechanisms through hydrogels which relies on the knowledge of drug partition and diffusion coefficients. We chose, as model systems, two materials used in contact lens, a poly-hydroxyethylmethacrylate (pHEMA) based hydrogel and a silicone based hydrogel, and three drugs with different sizes and charges: chlorhexidine, levofloxacin and diclofenac. Equilibrium partition coefficients were determined at different ionic strength and pH, using water (pH 5.6) and PBS (pH 7.4). The measured partition coefficients were related with the polymer volume fraction in the hydrogel, through the introduction of an enhancement factor following the approach developed by the group of C. J. Radke (Kotsmar et al., 2012; Liu et al., 2013). This factor may be decomposed in the product of three other factors E HS , E el and E ad which account for, respectively, hard-sphere size exclusion, electrostatic interactions, and specific solute adsorption. While E HS and E el are close to 1, E ad >1 in all cases suggesting strong specific interactions between the drugs and the hydrogels. Adsorption was maximal for chlorhexidine on the silicone based hydrogel, in water, due to strong hydrogen bonding. The effective diffusion coefficients, D e , were determined from the drug release profiles. Estimations of diffusion coefficients of the non-adsorbed solutes D=D e ×E ad allowed comparison with theories for solute diffusion in the absence of specific interaction with the polymeric membrane. Copyright © 2016 Elsevier B.V. All rights reserved.

Nuclear quantum effects on adsorption of H 2 and isotopologues on metal ions

DOE PAGES

Savchenko, Ievgeniia; Gu, Bing; Heine, Thomas; ...

2017-01-03

The nuclear quantum effects on the zero-point energy (ZPE), influencing adsorption of Hmore » $$_2$$ and isotopologues on metal ions, are examined in this study using normal mode analysis of ab initio electronic structure results for complexes with 17 metal cations. To estimate for the anharmonicity, a nuclear wavepacket dynamics on the ground state electronic potential energy surfaces (PES) have been employed for complexes of Li$^+$ and Cu$$^{+2}$$ with H$$_2$$, D$$_2$$, HD. The dynamics analysis shows that incorporation of the PES anharmonicity changes the ZPE by up to 9%. Finally, the lightest metallic nuclei, Li and Be, are found to be the most 'quantum'. The largest selectivity in adsorption is predicted for Cu, Ni and Co ions.« less

Molecular dynamics simulations of β2-microglobulin interaction with hydrophobic surfaces.

PubMed

Dongmo Foumthuim, Cedrix J; Corazza, Alessandra; Esposito, Gennaro; Fogolari, Federico

2017-11-21

Hydrophobic surfaces are known to adsorb and unfold proteins, a process that has been studied only for a few proteins. Here we address the interaction of β2-microglobulin, a paradigmatic protein for the study of amyloidogenesis, with hydrophobic surfaces. A system with 27 copies of the protein surrounded by a model cubic hydrophobic box is studied by implicit solvent molecular dynamics simulations. Most proteins adsorb on the walls of the box without major distortions in local geometry, whereas free molecules maintain proper structures and fluctuations as observed in explicit solvent molecular dynamics simulations. The major conclusions from the simulations are as follows: (i) the adopted implicit solvent model is adequate to describe protein dynamics and thermodynamics; (ii) adsorption occurs readily and is irreversible on the simulated timescale; (iii) the regions most involved in molecular encounters and stable interactions with the walls are the same as those that are important in protein-protein and protein-nanoparticle interactions; (iv) unfolding following adsorption occurs at regions found to be flexible by both experiments and simulations; (v) thermodynamic analysis suggests a very large contribution from van der Waals interactions, whereas unfavorable electrostatic interactions are not found to contribute much to adsorption energy. Surfaces with different degrees of hydrophobicity may occur in vivo. Our simulations show that adsorption is a fast and irreversible process which is accompanied by partial unfolding. The results and the thermodynamic analysis presented here are consistent with and rationalize previous experimental work.

[Effects of soil trituration size on adsorption of oxytetracycline on soils].

PubMed

Qi, Rui-Huan; Li, Zhao-Jun; Long, Jian; Fan, Fei-Fei; Liang, Yong-Chao

2011-02-01

In order to understand the effects of soil trituration size on adsorption of oxytetracycline (OTC) on soils, two contrasting soils including moisture soil and purplish soil were selected to investigate adsorption of OTC on these soils, at the scales of no more than 0.20 mm, 0.84 mm, 0.25 mm and 0.15 mm, using the method of batch equilibrium experiments respectively. The results presented as the following: (1) Adsorption amount of OTC on moisture soil and purplish soil increased with the sampling time, and reached to equilibration at 24 h. First-order kinetic model, second-order kinetic model, parabolic-diffusion kinetic model, Elovich kinetic model, and two-constant kinetic model could be used to fit the changes in adsorption on soils with sampling time. Adsorption of OTC on two soils consisted of two processes such as quick adsorption and slow adsorption. Quick adsorption process happened during the period of 0-0.5 h. The adsorption rates of OTC on soils were higher at the small trituration size than those at the large trituration size, and at the same trituration size, the k(f) of purplish soil was about two times higher than those of moisture soil. (2) Adsorption isotherms of OTC on two soils with different trituration sizes were deviated from the linear model. The data were fitted well to Freundlich and Langmuir models, with the correlation coefficients between 0.956 and 0.999. The values of k(f) and q(m) for purplish soil were higher than those for moisture soil. At the same soil, adsorption amount of OTC increased with the decreases of soil trituration size. The results suggested that it is important to select the appropriate trituration size, based on the physical and chemical properties such as soil particle composition and so on, when the fate of antibiotics on soils was investigated.

Adsorption of lead onto smectite from aqueous solution.

PubMed

Mhamdi, M; Galai, H; Mnasri, N; Elaloui, E; Trabelsi-Ayadi, M

2013-03-01

The purpose of this research is to study the effect of a new method of adsorption using membrane filtration to determine the maximum amount of lead adsorbed by clay and investigate the behavior of the clay after adsorption of the said metal. Treatment of wastewater contaminated with heavy metals depends on the characteristics of the effluent, the amount of final discharge, the cost of treatment, and the compatibility of the treatment process. The process of adsorption of heavy metals by clays may be a simple, selective, and economically viable alternative to the conventional physical-chemical treatment. This is justified by the importance of the surface developed by this material, the presence of negative charges on the said surface, the possibility of ion exchange taking place, and its wide availability in nature. The removal of lead from wastewater was studied by using the adsorption technique and using clay as the adsorbent. A method was optimized for adsorption through a membrane approaching natural adsorption. This new method is simple, selective, and the lead adsorption time is about 3 days. The various properties of clay were determined. It was observed that the cation exchange capacity of the clay was 56 meq/100 g of hydrated clay for the raw sample and 82 meq/100 g for the purified sample. The total surface area determined by the methylene blue method was equal to 556 and 783 m(2)/g for the raw and purified samples, respectively. The adsorption kinetics depends on several parameters. The Pb(II) clay, obeys the Langmuir, Freundlich, and the Elovich adsorption isotherms with high regression coefficients. The use of this adsorbent notably decreases the cost of treatment. It was concluded that clay shows a strong adsorption capacity on Pb(II), the maximum interaction occurring with purified clay treated at high concentration of lead. It is proposed that this adsorption through a membrane be extended for the treatment of effluents containing other metals.

Dynamic surface tension measurements of ionic surfactants using maximum bubble pressure tensiometry

NASA Astrophysics Data System (ADS)

Ortiz, Camilla U.; Moreno, Norman; Sharma, Vivek

Dynamic surface tension refers to the time dependent variation in surface tension, and is intimately linked with the rate of mass transfer of a surfactant from liquid sub-phase to the interface. The diffusion- or adsorption-limited kinetics of mass transfer to interfaces is said to impact the so-called foamability and the Gibbs-Marangoni elasticity of surfaces. Dynamic surface tension measurements carried out with conventional methods like pendant drop analysis, Wilhelmy plate, etc. are limited in their temporal resolution (>50 ms). In this study, we describe design and application of maximum bubble pressure tensiometry for the measurement of dynamic surface tension effects at extremely short (1-50 ms) timescales. Using experiments and theory, we discuss the overall adsorption kinetics of charged surfactants, paying special attention to the influence of added salt on dynamic surface tension.

Study of lysozyme mobility and binding free energy during adsorption on a graphene surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nakano, C. Masato; Ma, Heng; Wei, Tao, E-mail: twei@lamar.edu

Understanding protein adsorption is a key to the development of biosensors and anti-biofouling materials. Hydration essentially controls the adsorption process on hydrophobic surfaces, but its effect is complicated by various factors. Here, we present an ideal model system to isolate hydration effects—lysozyme adsorption on a flat hydrophobic graphene surface. Our all-atom molecular dynamics and molecular-mechanics/Poisson-Boltzmann surface area computation study reveal that lysozyme on graphene displays much larger diffusivity than in bulk water. Protein's hydration free energy within the first hydration shell is dominated by the protein-water electrostatic interactions and acts as an energy barrier for protein adsorption. On the othermore » hand, the surface tension, especially that from the hydrophobic graphene, can effectively weaken the barrier to promote adsorption.« less

Adsorption of ions onto nanosolids dispersed in liquid crystals: Towards understanding the ion trapping effect in nanocolloids

NASA Astrophysics Data System (ADS)

Garbovskiy, Yuriy

2016-05-01

The ion capturing effect in liquid crystal nanocolloids was quantified by means of the ion trapping coefficient. The dependence of the ion trapping coefficient on the concentration of nano-dopants and their ionic purity was calculated for a variety of nanosolids dispersed in liquid crystals: carbon nanotubes, graphene nano-flakes, diamond nanoparticles, anatase nanoparticles, and ferroelectric nanoparticles. The proposed method perfectly fits existing experimental data and can be useful in the design of highly efficient ion capturing nanomaterials.

Diffusion coefficients of Fokker-Planck equation for rotating dust grains in a fusion plasma

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bakhtiyari-Ramezani, M., E-mail: mahdiyeh.bakhtiyari@gmail.com; Alinejad, N., E-mail: nalinezhad@aeoi.org.ir; Mahmoodi, J., E-mail: mahmoodi@qom.ac.ir

2015-11-15

In the fusion devices, ions, H atoms, and H{sub 2} molecules collide with dust grains and exert stochastic torques which lead to small variations in angular momentum of the grain. By considering adsorption of the colliding particles, thermal desorption of H atoms and normal H{sub 2} molecules, and desorption of the recombined H{sub 2} molecules from the surface of an oblate spheroidal grain, we obtain diffusion coefficients of the Fokker-Planck equation for the distribution function of fluctuating angular momentum. Torque coefficients corresponding to the recombination mechanism show that the nonspherical dust grains may rotate with a suprathermal angular velocity.

Diffusion coefficients of Fokker-Planck equation for rotating dust grains in a fusion plasma

NASA Astrophysics Data System (ADS)

Bakhtiyari-Ramezani, M.; Mahmoodi, J.; Alinejad, N.

2015-11-01

In the fusion devices, ions, H atoms, and H2 molecules collide with dust grains and exert stochastic torques which lead to small variations in angular momentum of the grain. By considering adsorption of the colliding particles, thermal desorption of H atoms and normal H2 molecules, and desorption of the recombined H2 molecules from the surface of an oblate spheroidal grain, we obtain diffusion coefficients of the Fokker-Planck equation for the distribution function of fluctuating angular momentum. Torque coefficients corresponding to the recombination mechanism show that the nonspherical dust grains may rotate with a suprathermal angular velocity.

Comparison of linear and non-linear models for the adsorption of fluoride onto geo-material: limonite.

PubMed

Sahin, Rubina; Tapadia, Kavita

2015-01-01

The three widely used isotherms Langmuir, Freundlich and Temkin were examined in an experiment using fluoride (F⁻) ion adsorption on a geo-material (limonite) at four different temperatures by linear and non-linear models. Comparison of linear and non-linear regression models were given in selecting the optimum isotherm for the experimental results. The coefficient of determination, r², was used to select the best theoretical isotherm. The four Langmuir linear equations (1, 2, 3, and 4) are discussed. Langmuir isotherm parameters obtained from the four Langmuir linear equations using the linear model differed but they were the same when using the nonlinear model. Langmuir-2 isotherm is one of the linear forms, and it had the highest coefficient of determination (r² = 0.99) compared to the other Langmuir linear equations (1, 3 and 4) in linear form, whereas, for non-linear, Langmuir-4 fitted best among all the isotherms because it had the highest coefficient of determination (r² = 0.99). The results showed that the non-linear model may be a better way to obtain the parameters. In the present work, the thermodynamic parameters show that the absorption of fluoride onto limonite is both spontaneous (ΔG < 0) and endothermic (ΔH > 0). Scanning electron microscope and X-ray diffraction images also confirm the adsorption of F⁻ ion onto limonite. The isotherm and kinetic study reveals that limonite can be used as an adsorbent for fluoride removal. In future we can develop new technology for fluoride removal in large scale by using limonite which is cost-effective, eco-friendly and is easily available in the study area.

Abiotic, biotic and photolytic degradation affinity of 14 antibiotics and one metabolite - batch experiments and a model framework.

PubMed

Kaeseberg, Thomas; Zhang, Jin; Schubert, Sara; Oertel, Reinhard; Krebs, Peter

2018-05-26

In this study, degradation affinities of 14 antibiotics and one metabolite were determined in batch experiments. A modelling framework was applied to decrypt potential ranges of abiotic, biotic and photolytic degradation coefficients. In detail, we performed batch experiments with three different sewages in the dark at 7 °C and 22 °C. Additionally, we conducted further batch experiments with artificial irradiation and different dilutions of the sewage at 30 °C - de novo three different sewages were used. The batch experiments were initially spiked with a stock solution with 14 antibiotics and one metabolite to increase background concentrations by 1 μg L -1 for each compound. The final antibiotic concentrations were sub-inhibitory with regard to sewage bacteria. The here presented modelling framework based on the Activated Sludge Model No. 3 in combination with adsorption and desorption processes. The model was calibrated with monitored standard sewage compounds before antibiotic degradation rates were quantified. The model decrypted ranges of abiotic, biotic and photolytic degradation coefficients. In detail, six antibiotics were not abiotic degradable at 7 °C, five antibiotics not at 22 °C and only 2 antibiotics at 30 °C. Finally, nine antibiotics were not significantly biodegradable at 7 °C and 22 °C. The model determined the link between adsorption characteristics and biodegradation rates. In detail, the rate was significantly affected by the bio-solid partition coefficient and the duration until adsorption was balanced. All antibiotics and the metabolite were photolytic degradable. In general, photolytic degradation was the most efficient elimination pathway of presented antibiotics except for the given metabolite and penicillin antibiotics. Copyright © 2018 Elsevier Ltd. All rights reserved.

Facile Preparation of Magnetic Graphene Oxide and Attapulgite Composite Adsorbent for the Adsorption of Ni (II)

NASA Astrophysics Data System (ADS)

Bigui, Wei; Xiaofei, Zhu; Xiabing, Cheng

2017-12-01

Graphene oxide (GO) is an excellent absorbent for heavy ion from wastewater, but it is hard to separate from water. To improve the adsorption capacity and separation performance of GO to nickel-containing wastewater, a composite magnetic GO-ATP adsorbent (MGA) was prepared by magnetizing GO and attapulgite (ATP) using ferroferric oxide and then carrying out hydrothermal reaction. The adsorption capacity and mechanism of MGA were investigated based on Ni2+ as targeted pollutant. Experimental results showed that the pH value significantly affects the removal rate of Ni2+, which is mainly due to that OH- in wastewater reacts with Ni2+, resulting in sediment that leads to the increase of removal rate. MGA can achieve max adsorption capacity of Ni2+ to 190.8 mg/g at pH = 5, and the adsorption process was mainly determined by chemical adsorption, which was in line with pseudo-secondary dynamics model. The adsorption was basically homogeneous monolayer adsorption with heat release, which was more agree with Langmuir adsorption isotherm equation. the adsorption process of Ni2+ by MGA. The adsorption process was a spontaneous process and an exothermic reaction. It can be confirmed that the prepared MGA adsorbent can realize slurry separation using magnetic separation principle and has high adsorption capacity to Ni2+.

Sorption isotherms, kinetic and optimization process of amino acid proline based polymer nanocomposite for the removal of selected textile dyes from industrial wastewater.

PubMed

Raghunath, Sharista; Anand, K; Gengan, R M; Nayunigari, Mithil Kumar; Maity, Arjun

2016-12-01

In this article, adsorption and kinetic studies were carried out on three textile dyes, namely Reactive Blue 222 (RB 222), Reactive Red 195 (RR 195) and Reactive Yellow 145 (RY 145). The dyes studied in a mixture were adsorbed under various conditions onto PRO-BEN, a bentonite modified with a new cationic proline polymer (l-proline-epichlorohydrin polymer). The proline polymer was characterized by 1 H NMR, Fourier transform infrared spectroscopy (FT-IR), dynamic light scattering (DLS) and TEM. The PRO-BEN composite was characterized by FT-IR, dynamic light scattering (DLS) (zeta potential), TEM imaging, SEM/EDX and X-ray photoelectron spectroscopy (characterize the binding energy). During adsorption studies, factors involving pH, temperature, the initial concentrations of the dyes and the quantity of PRO-BEN used during adsorption were established. The results revealed that the adsorption mechanism was categorized by the Langmuir type 1 isotherm. The adsorption data followed the pseudo-second order kinetic model. The intraparticle diffusion model indicated that adsorption did not only depend on the intraparticle diffusion of the dyes. The thermodynamic parameters verified that the adsorption process was spontaneous and exothermic. The Gibbs free energy values indicated that physisorption had occurred. Successful adsorption of dyes from an industrial effluent was achieved. Desorption studies concluded that PRO-BEN desorbed the dyes better than alumina. This can thereby be viewed as a recyclable remediation material. The PRO-BEN composite could be a cost efficient alternative towards the removal of organic dyes in wastewater treatment. Copyright © 2016 Elsevier B.V. All rights reserved.

Dynamics analysis of SIR epidemic model with correlation coefficients and clustering coefficient in networks.

PubMed

Zhang, Juping; Yang, Chan; Jin, Zhen; Li, Jia

2018-07-14

In this paper, the correlation coefficients between nodes in states are used as dynamic variables, and we construct SIR epidemic dynamic models with correlation coefficients by using the pair approximation method in static networks and dynamic networks, respectively. Considering the clustering coefficient of the network, we analytically investigate the existence and the local asymptotic stability of each equilibrium of these models and derive threshold values for the prevalence of diseases. Additionally, we obtain two equivalent epidemic thresholds in dynamic networks, which are compared with the results of the mean field equations. Copyright © 2018 Elsevier Ltd. All rights reserved.

Mass transfer equation for proteins in very high-pressure liquid chromatography.

PubMed

Gritti, Fabrice; Guiochon, Georges

2009-04-01

The mass transfer kinetics of human insulin was investigated on a 50 mm x 2.1 mm column packed with 1.7 microm BEH-C(18) particles, eluted with a water/acetonitrile/trifluoroacetic acid (TFA) (68/32/0.1, v/v/v) solution. The different contributions to the mass transfer kinetics, e.g., those of longitudinal diffusion, eddy dispersion, the film mass transfer resistance, cross-particle diffusivity, adsorption-desorption kinetics, and transcolumn differential sorption, were incorporated into a general mass transfer equation designed to account for the mass transfer kinetics of proteins under high pressure. More specifically, this equation includes the effects of pore size exclusion, pressure, and temperature on the band broadening of a protein. The flow rate was first increased from 0.001 to 0.250 mL/min, the pressure drop increasing from 2 to 298 bar, and the column being placed in stagnant air at 296.5 K, in order to determine the effective diffusivity of insulin through the porous particles, the mass transfer rate constants, and the adsorption equilibrium constant in the low-pressure range. Then, the column inlet pressure was increased by using capillary flow restrictors downstream the column, at the constant flow rate of 0.03 mL/min. The column temperature was kept uniform by immersing the column in a circulating water bath thermostatted at 298.7 and 323.15 K, successively. The results showed that the surface diffusion coefficient of insulin decreases faster than its bulk diffusion coefficient with increasing average column pressure. This is consistent with the adsorption energy of insulin onto the BEH-C(18) surface increasing strongly with increasing pressure. In contrast, given the precision of the height equivalent to a theoretical plate (HETP) measurement (+/-12%), the adsorption kinetics of insulin appears to be rather independent of the pressure. On average, the adsorption rate constant of insulin is doubled from about 40 to 80 s(-1) when the temperature increases from 298.7 to 323.15 K.

Factors influencing antibiotics adsorption onto engineered adsorbents.

PubMed

Xia, Mingfang; Li, Aimin; Zhu, Zhaolian; Zhou, Qin; Yang, Weiben

2013-07-01

The study evaluated the adsorption of two antibiotics by four engineered adsorbents (hypercrosslinked resin MN-202, macroporous resin XAD-4, activated carbon F-400, and multi-walled carbon nanotubes (MWCNT)) from aqueous solutions. The dynamic results demonstrated the dominant influence of pore size in adsorption. The adsorption amounts of antibiotics on XAD-4 were attributed to the hydrophobic effect, whereas steric hindrance or micropore-filling played a main role in the adsorption of antibiotics by F-400 because of its high microporosity. Aside from F-400, similar patterns of pH-dependent adsorption were observed, implying the importance of antibiotic molecular forms to the adsorption process for adsorbents. Increasing the ionic concentration with CaC12 produced particular adsorption characteristics on MWCNT at pH 2.0 and F-400 at pH 8.0, which were attributed to the highly available contact surfaces and molecular sieving, respectively. Its hybrid characteristics incorporating a considerable portion of mesopores and micropores made hypercross linked MN-202 a superior antibiotic adsorbent with high adsorption capacity. Furthermore, the adsorption capacity of MWCNT on the basis of surface area was more advantageous than that of the other adsorbents because MWCNT has a much more compact molecular arrangement.

Study toward high-performance thermally driven air-conditioning systems

NASA Astrophysics Data System (ADS)

Miyazaki, Takahiko; Miyawaki, Jin; Ohba, Tomonori; Yoon, Seong-Ho; Saha, Bidyut Baran; Koyama, Shigeru

2017-01-01

The Adsorption heat pump is a technology for cooling and heating by using hot water as a driving heat source. It will largely contribute to energy savings when it is driven by solar thermal energy or waste heat. The system is available in the market worldwide, and there are many examples of application to heat recovery in factories and to solar cooling systems. In the present system, silica gel and zeolite are popular adsorbents in combination with water refrigerant. Our study focused on activated carbon-ethanol pair for adsorption cooling system because of the potential to compete with conventional systems in terms of coefficient of performance. In addition, activated-ethanol pair can generally produce larger cooling effect by an adsorption-desorption cycle compared with that of the conventional pairs in terms of cooling effect per unit adsorbent mass. After the potential of a commercially available activated carbon with highest level specific surface area was evaluated, we developed a new activated carbon that has the optimum pore characteristics for the purpose of solar or waste heat driven cooling systems. In this paper, comparison of refrigerants for adsorption heat pump application is presented, and a newly developed activated carbon for ethanol adsorption heat pump is introduced.

New insight into adsorption characteristics and mechanisms of the biosorbent from waste activated sludge for heavy metals.

PubMed

Zhou, Yun; Zhang, Zhiqiang; Zhang, Jiao; Xia, Siqing

2016-07-01

The adsorption characteristics and mechanisms of the biosorbent from waste activated sludge were investigated by adsorbing Pb(2+) and Zn(2+) in aqueous single-metal solutions. A pH value of the metal solutions at 6.0 was beneficial to the high adsorption quantity of the biosorbent. The optimal mass ratio of the biosorbent to metal ions was found to be 2. A higher adsorption quantity of the biosorbent was achieved by keeping the reaction temperature below 55°C. Response surface methodology was applied to optimize the biosorption processes, and the developed mathematical equations showed high determination coefficients (above 0.99 for both metal ions) and insignificant lack of fit (p=0.0838 and 0.0782 for Pb(2+) and Zn(2+), respectively). Atomic force microscopy analyses suggested that the metal elements were adsorbed onto the biosorbent surface via electrostatic interaction. X-ray photoelectron spectroscopy analyses indicated the presence of complexation (between -NH2, -CN and metal ions) and ion-exchange (between -COOH and metal ions). The adsorption mechanisms could be the combined action of electrostatic interaction, complexation and ion-exchange between functional groups and metal ions. Copyright © 2016. Published by Elsevier B.V.

Comparison of adsorption coefficient (K[sub oc]) for soils and HPLC retention factors of aromatic hydrocarbons using a chemically immobilized humic acid column in RP-HPLC

DOE Office of Scientific and Technical Information (OSTI.GOV)

Szabo, G.; Bulman, R.A.

The determination of soil adsorption coefficients (K[sub oc]) via HPLC capacity factors (k[prime]) has been studied, including the effect of column type and mobile phase composition on the correlation between log K[sub oc] and log k[prime]. K[sub oc] values obtained by procedures other than HPLC correlate well with HPLC capacity factors determined on a chemically immobilized humic acid stationary phase, and it is suggested that this phase is a better model for the sorption onto soil or sediment than the octadecyl-, phenyl- and ethylsilica phases. By using log k[prime][sub w] a theoretical capacity factor has been obtained by extrapolation ofmore » the retention data in a binary solvent system to pure aqueous eluent. There is a better correlation between log K[sub oc] and log k[prime][sub w] than the correlation between log K[sub oc] and log k[prime].« less

The Langmuir isotherm: a commonly applied but misleading approach for the analysis of protein adsorption behavior.

PubMed

Latour, Robert A

2015-03-01

The Langmuir adsorption isotherm provides one of the simplest and most direct methods to quantify an adsorption process. Because isotherm data from protein adsorption studies often appear to be fit well by the Langmuir isotherm model, estimates of protein binding affinity have often been made from its use despite that fact that none of the conditions required for a Langmuir adsorption process may be satisfied for this type of application. The physical events that cause protein adsorption isotherms to often provide a Langmuir-shaped isotherm can be explained as being due to changes in adsorption-induced spreading, reorientation, clustering, and aggregation of the protein on a surface as a function of solution concentration in contrast to being due to a dynamic equilibrium adsorption process, which is required for Langmuir adsorption. Unless the requirements of the Langmuir adsorption process can be confirmed, fitting of the Langmuir model to protein adsorption isotherm data to obtain thermodynamic properties, such as the equilibrium constant for adsorption and adsorption free energy, may provide erroneous values that have little to do with the actual protein adsorption process, and should be avoided. In this article, a detailed analysis of the Langmuir isotherm model is presented along with a quantitative analysis of the level of error that can arise in derived parameters when the Langmuir isotherm is inappropriately applied to characterize a protein adsorption process. © 2014 Wiley Periodicals, Inc.

Study of the adsorbed layer on a solid electrode surface by specular reflection measurement

NASA Astrophysics Data System (ADS)

Kusu, Fumiyo; Takamura, Kiyoko

1985-07-01

Specular reflection measurements were carried out to study the adsorbed layers of certain heterocyclic compounds such as adenine, barbital, 2'-deoxyadenosine, phenobarbital, pyridine and thymine. When pyridine was present in 0.1M NaClO 4, a marked decrease in the reflectivity of a gold electrode was observed. In the potential range near the point of zero charge on the reflectivity-potential curve, the decrease was due to the adsorption of pyridine. Assuming the reflectivity change to be proportional to the surface coverage, the potential and concentration dependence of pyridine adsorption was determined and analysed on the basis of a Langmuir-type adsorption isotherm. The refractive indices and extinction coefficients for the adsorbed layers of the compounds investigated were evaluated using the observed reflectivity change, according to relations proposed by McIntyre and Aspnes.

Alzheimer Abeta(1-42) monomer adsorbed on the self-assembled monolayers.

PubMed

Wang, Qiuming; Zhao, Jun; Yu, Xiang; Zhao, Chao; Li, Lingyan; Zheng, Jie

2010-08-03

Amyloid-beta (Abeta) peptide aggregation on the cell membranes is a key pathological event responsible for neuron cell death in Alzheimer's disease (AD). We present a collection of molecular docking and molecular dynamics simulations to study the conformational dynamics and adsorption behavior of Abeta monomer on the self-assembled monolayer (SAM), in comparison to Abeta structure in bulk solution. Two distinct Abeta conformations (i.e., alpha-helix and beta-hairpin) are selected as initial structures to mimic different adsorption states, whereas four SAM surfaces with different end groups in hydrophobicity and charge distribution are used to examine the effect of surface chemistry on Abeta structure and adsorption. Simulation results show that alpha-helical monomer displays higher structural stability than beta-hairpin monomer on all SAMs, suggesting that the preferential conformation of Abeta monomer could be alpha-helical or random structure when bound to surfaces. Structural stability and adsorption behavior of Abeta monomer on the SAMs originates from competitive interactions between Abeta and SAM and between SAM and interfacial water, which involve the conformation of Abeta, the surface chemistry of SAM, and the structure and dynamics of interfacial waters. The relative net binding affinity of Abeta with the SAMs is in the favorable order of COOH-SAM > NH(2)-SAM > CH(3)-SAM > OH-SAM, highlighting the importance of electrostatic and hydrophobic interactions for driving Abeta adsorption at the SAMs, but both interactions contribute differently to each Abeta-SAM complex. This work provides parallel insights into the understanding of Abeta structure and aggregation on cell membrane.

Cesium adsorption and distribution onto crushed granite under different physicochemical conditions.

PubMed

Tsai, Shih-Chin; Wang, Tsing-Hai; Li, Ming-Hsu; Wei, Yuan-Yaw; Teng, Shi-Ping

2009-01-30

The adsorption of cesium onto crushed granite was investigated under different physicochemical conditions including contact time, Cs loading, ionic strength and temperature. In addition, the distribution of adsorbed Cs was examined by X-ray diffraction (XRD) and EDS mapping techniques. The results showed that Cs adsorption to crushed granite behaved as a first-order reaction with nice regression coefficients (R(2) > or = 0.971). Both Freundlich and Langmuir models were applicable to describe the adsorption. The maximum sorption capacity determined by Langmuir model was 80 micromol g(-1) at 25 degrees C and 10 micromol g(-1) at 55 degrees C. The reduced sorption capacity at high temperature was related to the partial enhancement of desorption from granite surface. In general, Cs adsorption was exothermic (DeltaH<0, with median of -12 kJ mol(-1)) and spontaneous (DeltaG<0, with median of -6.1 at 25 degrees C and -5.0 kJ mol(-1) at 55 degrees C). The presence of competing cations such as sodium and potassium ions in synthetic groundwater significantly reduces the Cs adsorption onto granite. The scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM/EDS) mapping method provided substantial evidences that micaceous minerals (biotite in this case) dominate Cs adsorption. These adsorbed Cs ions were notably distributed onto the frayed edges of biotite minerals. More importantly, the locations of these adsorbed Cs were coincided with the potassium depletion area, implying the displacement of K by Cs adsorption. Further XRD patterns displayed a decreased intensity of signal of biotite as the Cs loading increased, revealing that the interlayer space of biotite was affected by Cs adsorption.

Fixed-bed adsorption study of methylene blue onto pyrolytic tire char

NASA Astrophysics Data System (ADS)

Makrigianni, Vassiliki; Giannakas, Aris; Papadaki, Maria; Albanis, Triantafyllos; Konstantinou, Ioannis

2016-04-01

In this work, the adsorption efficiency of acid treated pyrolytic tire char to cationic methylene blue (MB) dye adsorption from aqueous solutions was investigated by fixed-bed adsorption column experiments. The effects of the initial dye concentration (10 - 40 mg L-1) and feed flow rate (50 - 150 mL min -1) with a fixed bed height (15 cm) were studied in order to determine the breakthrough characteristics of the adsorption system. The Adams-Bohart, Yoon-Nelson and Thomas model were applied to the adsorption of MB onto char at different operational conditions to predict the breakthrough curves and to determine the characteristic parameters of the column. The results showed that the maximum adsorbed quantities decreased with increasing flow rate and increased with increasing initial MB concentration. Breakthrough time and exhaustion time increased with decreasing inlet dye concentration and flow rate. In contrast with Adams-Bohart model, Yoon-Nelson model followed by Thomas model were found more suitable to describe the fixed-bed adsorption of methylene blue by char. The correlation coefficient values R2 for both models at different operating conditions are higher than 0.9 and the low average relative error values provided very good fittings of experimental data at different operating conditions. Higher adsorption capacity of 3.85 mg g -1 was obtained at 15 cm of adsorbent bed height, flow rate of 100 mL min -1and initial MB concentration of 40 mg L-1. Although that activated carbons exhibited higher adsorption capacities in the literature, acid-treated pyrolytic tire char was found to be considerably efficient adsorbent for the removal of MB dye column taking into account the advantages of the simpler production process compared to activated carbons, as well as, the availability of waste tire feedstock and concurrent waste tire management.

Effects of carbon nanotubes on phosphorus adsorption behaviors on aquatic sediments.

PubMed

Qian, Jin; Li, Kun; Wang, Peifang; Wang, Chao; Shen, Mengmeng; Liu, Jingjing; Tian, Xin; Lu, Bianhe

2017-08-01

Aquatic sediments are believed to be an important sink for carbon nanotubes (CNTs). With novel properties, CNTs can potentially disturb the fate and mobility of the co-existing contaminants in the sediments. Only toxic pollutants have been investigated previously, and to the best of our knowledge, no data has been published on how CNTs influence phosphorus (P) adsorption on aquatic sediments. In this study, multi-walled carbon nanotubes (MWCNTs) were selected as model CNTs. Experimental results indicated that compared to pseudo-first order and intraparticle diffusion models, the pseudo-second-order model is better for describing the adsorption kinetics of sediments and MWCNT-contaminated sediments. Adsorption isotherm studies suggested that the Langmuir model fits the isotherm data well. With the increase in the MWCNT-to-sediment ratio from 0.0% to 5.0%, the theoretical maximum monolayer adsorption capacity (Q max ) for P increased from 0.664 to 0.996mg/g. However, the Langmuir isotherm coefficient (K L ) significantly decreased from 4.231L/mg to 2.874L/mg, indicating the decrease in the adsorption free energy of P adsorbed on the sediments after MWCNT contamination. It was suggested that P was released more easily to the overlying water after the re-suspension of sediments. Moreover, the adsorption of sediments and sediment-MWCNT mixture was endothermic and physical in nature. Results obtained herein suggested that the change in the specific surface area and zeta potential of sediments is related to MWCNT contamination, and the large adsorption capacity of MWCNTs is probably the main factor responsible for the variation in the adsorption of P on aquatic sediments. Copyright © 2017 Elsevier Inc. All rights reserved.

Adsorption of polar organic molecules on sediments: Case-study on Callovian-Oxfordian claystone.

PubMed

Rasamimanana, S; Lefèvre, G; Dagnelie, R V H

2017-08-01

The release and transport of anthropogenic organic matter through the geosphere is often an environmental criterion of safety. Sedimentary rocks are widely studied in this context as geological barriers for waste management. It is the case of Callovian-Oxfordian claystone (COx), for which several studies report adsorption of anthropogenic organic molecules. In this study, we evaluated and reviewed adsorption data of polar organic molecules on COx claystone. Experiments were performed on raw claystone, decarbonated and clay fractions. Adsorption isotherms were measured with adsorbates of various polarities: adipate, benzoate, ortho-phthalate, succinate, gluconate, oxalate, EDTA, citrate. A significant adsorption was observed for multidentate polycarboxylic acids as evidenced with phthalate, succinate, oxalate, gluconate, EDTA and citrate (R d  = 1.53, 3.52, 8.4, 8.8, 12.4, 54.7 L kg -1 respectively). Multiple linear regression were performed as a statistical analysis to determine the predictors from these adsorption data. A linear correlation between adsorption data (R d ) and dipole moment (μ) of adsorbates was evidenced (R 2  = 0.91). Molecules with a high dipole moment, μ(D) > 2.5, displayed a significant adsorption, R d ≫1 L kg -1 . A qualitative correlation can be easily estimated using the water/octanol partition coefficient, P ow , of adsorbates (R 2  = 0.77). In this case, two opposite trends were distinguished for polar and apolar molecules. The use of organic carbon content in sediments is relevant for predicting adsorption of apolar compounds, log (P ow )>+1. The oxides/clays contents may be relevant regarding polar molecules, log ( apparent P ow )<-1. The proposed scheme offers a general methodology for investigation of geo-barriers towards heterogeneous organic plumes. Copyright © 2017 Elsevier Ltd. All rights reserved.

The effect of carbon surface chemical composition on the adsorption of acetanilide.

PubMed

Terzyk, Artur P

2004-04-01

The study of acetanilide adsorption-desorption performed at three temperatures (300, 310, and 320 K) and at two pH levels (7.0 and 1.5) on the series of D43/1 carbons (initial and modified with HNO3, fuming H2SO4, and gaseous NH3) is reported. Sorption data are additionally supplemented with the results of thermal analysis and calorimetric and kinetic measurements. It is shown that, generally, acetanilide adsorption at the neutral pH level is reversible (only on the more acidic carbons and at the lowest temperature does hysteresis occur due to the formation of hydrogen bonds with surface OH groups), and it decreases for the chemically modified carbons. In contrast, at the acidic pH level acetanilide adsorption is irreversible. A mechanism of irreversibility is proposed and it is shown that hysteresis is caused by the chemical reaction between the nucleophile (carbon) and the protonized acetanilide molecules. For all studied carbons, at the acidic pH level, adsorption increases and this is caused by the weakly basic character of acetanilide molecule. Adsorption results are described applying adsorbability and Dubinin-Astakhov, quasi-Freundlich and solution analogue of the Toth adsorption isotherm equations. Using the kinetic data, the effective diffusion coefficients and the energy of diffusion are calculated. It is shown that the diffusion is mainly a surface process, and the contribution of the pore diffusion increases with the rise in temperature. By applying different correlations between the parameters obtained from the theoretical description of experimental data and those characterizing the chemical composition of the studied carbons, the role of the latter in the adsorption and kinetics of acetanilide adsorption is determined.

Amino-functionalized mesoporous MCM-41 silica as an efficient adsorbent for water treatment: batch and fixed-bed column adsorption of the nitrate anion

NASA Astrophysics Data System (ADS)

Ebrahimi-Gatkash, Mehdi; Younesi, Habibollah; Shahbazi, Afsaneh; Heidari, Ava

2017-07-01

In the present study, amino-functionalized Mobil Composite Material No. 41 (MCM-41) was used as an adsorbent to remove nitrate anions from aqueous solutions. Mono-, di- and tri-amino functioned silicas (N-MCM-41, NN-MCM-41 and NNN-MCM-41) were prepared by post-synthesis grafting method. The samples were characterized by means of X-ray powder diffraction, FTIR spectroscopy, thermogravimetric analysis, scanning electron microscopy and nitrogen adsorption-desorption. The effects of pH, initial concentration of anions, and adsorbent loading were examined in batch adsorption system. Results of adsorption experiments showed that the adsorption capacity increased with increasing adsorbent loading and initial anion concentration. It was found that the Langmuir mathematical model indicated better fit to the experimental data than the Freundlich. According to the constants of the Langmuir equation, the maximum adsorption capacity for nitrate anion by N-MCM-41, NN-MCM-41 and NNN-MCM-41 was found to be 31.68, 38.58 and 36.81 mg/g, respectively. The adsorption kinetics were investigated with pseudo-first-order and pseudo-second-order model. Adsorption followed the pseudo-second-order rate kinetics. The coefficients of determination for pseudo-second-order kinetic model are >0.99. For continuous adsorption experiments, NNN-MCM-41 adsorbent was used for the removal of nitrate anion from solutions. Breakthrough curves were investigated at different bed heights, flow rates and initial nitrate anion concentrations. The Thomas and Yan models were utilized to calculate the kinetic parameters and to predict the breakthrough curves of different bed height. Results from this study illustrated the potential utility of these adsorbents for nitrate removal from water solution.

Adsorption of crystal violet onto functionalised multi-walled carbon nanotubes: Equilibrium and kinetic studies.

PubMed

Sabna, V; Thampi, Santosh G; Chandrakaran, S

2016-12-01

Synthetic dyes present in effluent from textile, paper and paint industries contain crystal violet (CV), a known carcinogenic agent. This study investigates the modification of multiwalled carbon nanotubes by acid reflux method and equilibrium and kinetic behaviour of adsorption of CV onto functionalized multi-walled carbon nanotubes (fMWNTs) in batch system. High stability of the fMWNTs suspension in water indicates the hydrophilicity of fMWNTs induced due to the formation of functional groups that make hydrogen bonds with water molecules. fMWNTs were characterized by Fourier Transform Infra Red (FTIR) spectroscopy and the functional groups present on the fMWNTs were confirmed. Characteristic variation was observed in the FTIR spectra of fMWNTs after adsorption of crystal violet onto it. Adsorption characteristics were evaluated as a function of system variables such as contact time, dosage of fMWNTs and initial concentration and pH of the crystal violet solution. Adsorption capacity of fMWNTs and percentage removal of the dye increased with increase in contact time, adsorbent dosage and pH but declined with increase in initial concentration of the dye. fMWNTs showed higher adsorption capacity compared to that of pristine MWNTs. Data showed good fit with the Langmuir and Freundlich isotherm models and the pseudo-second order kinetic model; the maximum adsorption capacity was 90.52mg/g. Kinetic parameters such as rate constants, equilibrium adsorption capacities and regression coefficients were estimated. Results indicate that fMWNTs are an effective adsorbent for the removal of crystal violet from aqueous solution. Copyright © 2015 Elsevier Inc. All rights reserved.

Selective removal of erythromycin by magnetic imprinted polymers synthesized from chitosan-stabilized Pickering emulsion.

PubMed

Ou, Hongxiang; Chen, Qunhui; Pan, Jianming; Zhang, Yunlei; Huang, Yong; Qi, Xueyong

2015-05-30

Magnetic imprinted polymers (MIPs) were synthesized by Pickering emulsion polymerization and used to adsorb erythromycin (ERY) from aqueous solution. The oil-in-water Pickering emulsion was stabilized by chitosan nanoparticles with hydrophobic Fe3O4 nanoparticles as magnetic carrier. The imprinting system was fabricated by radical polymerization with functional and crosslinked monomer in the oil phase. Batches of static and dynamic adsorption experiments were conducted to analyze the adsorption performance on ERY. Isotherm data of MIPs well fitted the Freundlich model (from 15 °C to 35 °C), which indicated heterogeneous adsorption for ERY. The ERY adsorption capacity of MIPs was about 52.32 μmol/g at 15 °C. The adsorption kinetics was well described by the pseudo-first-order model, which suggested that physical interactions were primarily responsible for ERY adsorption. The Thomas model used in the fixed-bed adsorption design provided a better fit to the experimental data. Meanwhile, ERY exhibited higher affinity during adsorption on the MIPs compared with the adsorption capacity of azithromycin and chloramphenicol. The MIPs also exhibited excellent regeneration capacity with only about 5.04% adsorption efficiency loss in at least three repeated adsorption-desorption cycles. Copyright © 2015 Elsevier B.V. All rights reserved.

Facile preparation of polyethylenimine-tannins coated SiO2 hybrid materials for Cu2+ removal

NASA Astrophysics Data System (ADS)

Huang, Qiang; Liu, Meiying; Zhao, Jiao; Chen, Junyu; Zeng, Guangjian; Huang, Hongye; Tian, Jianwen; Wen, Yuanqing; Zhang, Xiaoyong; Wei, Yen

2018-01-01

Polyethylenimine-tannins coated SiO2 (SiO2@PEI-TA) hybrid materials have been prepared via a single-step multifunctional coating with polyethylenimine (PEI) and tannins (TA), and characterized by transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS). The as-prepared SiO2@PEI-TA composites were examined as adsorbents to remove the Cu2+ from aqueous solution. The effects of contact time, initial Cu2+ concentration, solution pH and temperature, on Cu2+ adsorption have been investigated. The results show that the adsorption of Cu2+ onto SiO2@PEI-TA is dependent on the contact time, Cu2+ concentration, pH and temperature. The SiO2@PEI-TA composites show a 2.4-fold increase in adsorption capacity, implying that the introduction of PEI-TA coating is in favor of the Cu2+ adsorption. Based on the analysis of kinetic data, the kinetics of Cu2+ adsorption is more accurately described by the pseudo-second-order model. The equilibrium data are analyzed by Langmuir and Freundlich isotherms. Results of isotherms show that the better agreement is Freundlich isotherm model with correlation coefficient of 0.9914, which suggests that the adsorption of Cu2+ onto SiO2@PEI-TA is mainly a heterogeneous adsorption process. Thermodynamic analyses show that the adsorption interaction is actually a spontaneous and endothermic chemical process, which might involve the chemical chelation between Cu2+ and functional groups (amine and carboxyl groups) on the surface of SiO2@PEI-TA. In addition, the Cu2+ ions could desorb from SiO2@PEI-TA by using acid solution and the adsorption efficiency remains at high level after five adsorption-desorption recycles. These results provide potential applications of these novel adsorbents for the removal of heavy metal Cu2+ from aqueous solution and also provide strong evidence to support the adsorption mechanism proposed in the study.

Effects of pH and phosphate on glyphosate adsorption to Argentina soils.

NASA Astrophysics Data System (ADS)

De Geronimo, Eduardo; Aparicio, Virginia; Costa, José Luis

2017-04-01

Glyphosate is a non-selective, post-emergence herbicide that is widely used in Argentina. Due to the similar molecular structures, glyphosate and phosphate compete for the same adsorption sites in soil. Soil pH has a strong influence in glyphosate and phosphate adsorption since it modifies the net charge of the molecules and, consequently, the force of the electrostatic interaction between these molecules and soil components. Glyphosate adsorption generally decreases as the soil pH was increased, although there were exceptions. In this work, we study the effects of pH and the presence of phosphate on the adsorption of glyphosate on six different types of Argentina soils. Batch equilibrium technique was employed to study the adsorption of glyphosate onto soils at different pH values (from 3 to 9) and phosphate content (0.5 and 1 mM). Stepwise multiple linear regression analysis was applied to obtain a relationship between the sorption parameters and soil properties. The results indicated that Freundlich equations used to simulate glyphosate adsorption isotherms gave high correlation coefficients with Kf values range from 24.9 to 397.4. Clay contents and soil pH were found to be the most significant soil factors affecting the glyphosate adsorption process. The presence of phosphate significantly decreased the adsorption of glyphosate to soils. The Kf values obtained for all six soils decreased a 40% at 0.5 mM of phosphate and a 55% at 1 mM of phosphate. On the other hand, the affinity parameters of glyphosate to soils varied with changes in pH. A general trend of decrease in glyphosate adsorption with increase in pH was observed for all six studied soils. In turn, there appears to be a maximum glyphosate adsorption at pH close to 6 for most soils when the net charge of the molecule at this pH was approximately -1.7.

The enrichment of chlorogenic acid from Eucommia ulmoides leaves extract by mesoporous carbons.

PubMed

Qin, Guotong; Ma, Jing; Wei, Wei; Li, Jaja; Yue, Fangqing

2018-06-15

Herein, we report an efficient separation and enrichment method for chlorogenic acid from crude extracts of Eucommia ulmoides leaves using carbon adsorbents. The effects of the pore structure of the carbon adsorbents on the adsorption capacity were studied. Of the four adsorbents investigated, mesoporous carbon (MC3) showed the highest adsorption capacity (294 mg/g of carbon) for chlorogenic acid due to its high mesopore volume. The static adsorption of CGA on carbon can be accurately described using the Freundlich equation. The kinetics of adsorption follow a pseudo-second-order process. External mass transfer was the controlling step of the adsorption process. Dynamic adsorption on MC3 demonstrated that chlorogenic acid began to break through after 28 bed volumes of extract was loaded. This mesoporous carbon-treatment procedure is safe, economic and has the potential to be scaled up for commercial application. Copyright © 2018 Elsevier B.V. All rights reserved.

Adsorption characteristics of methylene blue onto agricultural wastes lotus leaf in bath and column modes.

PubMed

Han, Xiuli; Wang, Wei; Ma, Xiaojian

2011-01-01

The adsorption potential of lotus leaf to remove methylene blue (MB) from aqueous solution was investigated in batch and fixed-bed column experiments. Langmuir, Freundlich, Temkin and Koble-Corrigan isotherm models were employed to discuss the adsorption behavior. The results of analysis indicated that the equilibrium data were perfectly represented by Temkin isotherm and the Langmuir saturation adsorption capacity of lotus leaf was found to be 239.6 mg g(-1) at 303 K. In fixed-bed column experiments, the effects of flow rate, influent concentration and bed height on the breakthrough characteristics of adsorption were discussed. The Thomas and the bed-depth/service time (BDST) models were applied to the column experimental data to determine the characteristic parameters of the column adsorption. The two models were found to be suitable to describe the dynamic behavior of MB adsorbed onto the lotus leaf powder column.

Effects of aging process on adsorption-desorption and bioavailability of fomesafen in an agricultural soil amended with rice hull biochar.

PubMed

Khorram, Mahdi Safaei; Lin, Dunli; Zhang, Qian; Zheng, Yuan; Fang, Hua; Yu, Yunlong

2017-06-01

Biochar has been introduced as an acceptable soil amendment due to its environmental benefits such as sequestering soil contaminants. However, the aging process in biochar amended soil probably decreases the adsorption capacity of biochar through changing its physico-chemical properties. Adsorption, leaching and bioavailability of fomesafen to corn in a Chinese soil amended by rice hull biochar after 0, 30, 90 and 180days were investigated. Results showed that the addition of 0.5%-2% fresh biochar significantly increases the adsorption of fomesafen 4-26 times compare to unamended soil due to higher SSA of biochar. Biochar amendment also decreases fomesafen concentration in soil pore water by 5%-23% resulting lower risk of the herbicide for cultivated plants. However, the aging process decreased the adsorption capacity of biochar since the adsorption coefficient values which was 1.9-12.4 in 0.5%-2% fresh biochar amended soil, declined to 1.36-4.16, 1.13-2.78 and 0.95-2.31 in 1, 3 and 6-month aged treatments, respectively. Consequently, higher desorption, leaching and bioavailable fraction of fomesafen belonged to 6-month aged treatment. Nevertheless, rice hull biochar was effective for sequestering fomesafen as the adsorption capacity of biochar amended soil after 6months of aging was still 2.5-5 times higher compared to that of unamended soil. Copyright © 2016. Published by Elsevier B.V.

Lattice Boltzmann simulation of the gas-solid adsorption process in reconstructed random porous media.

PubMed

Zhou, L; Qu, Z G; Ding, T; Miao, J Y

2016-04-01

The gas-solid adsorption process in reconstructed random porous media is numerically studied with the lattice Boltzmann (LB) method at the pore scale with consideration of interparticle, interfacial, and intraparticle mass transfer performances. Adsorbent structures are reconstructed in two dimensions by employing the quartet structure generation set approach. To implement boundary conditions accurately, all the porous interfacial nodes are recognized and classified into 14 types using a proposed universal program called the boundary recognition and classification program. The multiple-relaxation-time LB model and single-relaxation-time LB model are adopted to simulate flow and mass transport, respectively. The interparticle, interfacial, and intraparticle mass transfer capacities are evaluated with the permeability factor and interparticle transfer coefficient, Langmuir adsorption kinetics, and the solid diffusion model, respectively. Adsorption processes are performed in two groups of adsorbent media with different porosities and particle sizes. External and internal mass transfer resistances govern the adsorption system. A large porosity leads to an early time for adsorption equilibrium because of the controlling factor of external resistance. External and internal resistances are dominant at small and large particle sizes, respectively. Particle size, under which the total resistance is minimum, ranges from 3 to 7 μm with the preset parameters. Pore-scale simulation clearly explains the effect of both external and internal mass transfer resistances. The present paper provides both theoretical and practical guidance for the design and optimization of adsorption systems.

Lattice Boltzmann simulation of the gas-solid adsorption process in reconstructed random porous media

NASA Astrophysics Data System (ADS)

Zhou, L.; Qu, Z. G.; Ding, T.; Miao, J. Y.

2016-04-01

The gas-solid adsorption process in reconstructed random porous media is numerically studied with the lattice Boltzmann (LB) method at the pore scale with consideration of interparticle, interfacial, and intraparticle mass transfer performances. Adsorbent structures are reconstructed in two dimensions by employing the quartet structure generation set approach. To implement boundary conditions accurately, all the porous interfacial nodes are recognized and classified into 14 types using a proposed universal program called the boundary recognition and classification program. The multiple-relaxation-time LB model and single-relaxation-time LB model are adopted to simulate flow and mass transport, respectively. The interparticle, interfacial, and intraparticle mass transfer capacities are evaluated with the permeability factor and interparticle transfer coefficient, Langmuir adsorption kinetics, and the solid diffusion model, respectively. Adsorption processes are performed in two groups of adsorbent media with different porosities and particle sizes. External and internal mass transfer resistances govern the adsorption system. A large porosity leads to an early time for adsorption equilibrium because of the controlling factor of external resistance. External and internal resistances are dominant at small and large particle sizes, respectively. Particle size, under which the total resistance is minimum, ranges from 3 to 7 μm with the preset parameters. Pore-scale simulation clearly explains the effect of both external and internal mass transfer resistances. The present paper provides both theoretical and practical guidance for the design and optimization of adsorption systems.

Adsorption of Cu(II) Ions in Aqueous Solutions by HCl Activated Carbon of Oil Palm

NASA Astrophysics Data System (ADS)

Muslim, A.; Syamsuddin, Y.; Salamun, A.; Abubakar; Ramadhan, D.; Peiono, D.

2017-06-01

Activated carbon was prepared from oil palm empty fruit bunch (OPEFB) by pyrolysis at 873.15 K in a furnace and chemical activation using 0.01 M HCl. Fourier Transform Infrared Spectroscopy, Scanning Electron Microscopy and BET (Brunauer, Emmett and Teller) surface area analyses were taken into account to investigate the chemical functional group, to characterise the surface morphology and to determine total surface area the OPEFB AC, respectively. Experiments in batch mode were conducted to investigate Cu(II) adsorption capacity by the OPEFB AC whereas the system consisted of 1 g the OPEFB AC in 100 mL Cu(II) aqueous solution with initial concentration in the range of 10-70 mg/L, magnetic stirring at 75 rpm, room temperature of 300.15 K (± 2 K), at 1 atm and neutral pH over contact time in the range of 0-150 min. As the result, Cu(II) adsorption capacity increased exponentially over contact time and initial concentration. The Cu(II) adsorption kinetics followed the pseudo second order kinetics with the correlation coefficients (R 2), kinetics rate constant and equilibrium adsorption capacity being 0.98, 4.81 mg/g and 0.15/min, respectively for initial Cu(II) concentration being 58.71 mg/L. In addition, Cu(II) adsorption isotherm followed the Langmuir equation with the R2 value, the mono-layer and over-all adsorption capacity being 0.99, 5.92 mg/g and 0.17 L/mg, respectively.

Dynamic modelling of an adsorption storage tank using a hybrid approach combining computational fluid dynamics and process simulation

USGS Publications Warehouse

Mota, J.P.B.; Esteves, I.A.A.C.; Rostam-Abadi, M.

2004-01-01

A computational fluid dynamics (CFD) software package has been coupled with the dynamic process simulator of an adsorption storage tank for methane fuelled vehicles. The two solvers run as independent processes and handle non-overlapping portions of the computational domain. The codes exchange data on the boundary interface of the two domains to ensure continuity of the solution and of its gradient. A software interface was developed to dynamically suspend and activate each process as necessary, and be responsible for data exchange and process synchronization. This hybrid computational tool has been successfully employed to accurately simulate the discharge of a new tank design and evaluate its performance. The case study presented here shows that CFD and process simulation are highly complementary computational tools, and that there are clear benefits to be gained from a close integration of the two. ?? 2004 Elsevier Ltd. All rights reserved.

Dye adsorption mechanisms in TiO2 films, and their effects on the photodynamic and photovoltaic properties in dye-sensitized solar cells.

PubMed

Hwang, Kyung-Jun; Shim, Wang-Geun; Kim, Youngjin; Kim, Gunwoo; Choi, Chulmin; Kang, Sang Ook; Cho, Dae Won

2015-09-14

The adsorption mechanism for the N719 dye on a TiO2 electrode was examined by the kinetic and diffusion models (pseudo-first order, pseudo-second order, and intra-particle diffusion models). Among these methods, the observed adsorption kinetics are well-described using the pseudo-second order model. Moreover, the film diffusion process was the main controlling step of adsorption, which was analysed using a diffusion-based model. The photodynamic properties in dye-sensitized solar cells (DSSCs) were investigated using time-resolved transient absorption techniques. The photodynamics of the oxidized N719 species were shown to be dependent on the adsorption time, and also the adsorbed concentration of N719. The photovoltaic parameters (Jsc, Voc, FF and η) of this DSSC were determined in terms of the dye adsorption amounts. The solar cell performance correlates significantly with charge recombination and dye regeneration dynamics, which are also affected by the dye adsorption amounts. Therefore, the photovoltaic performance of this DSSC can be interpreted in terms of the adsorption kinetics and the photodynamics of oxidized N719.

Pentaethylenehexamine-Loaded Hierarchically Porous Silica for CO2 Adsorption

PubMed Central

Ji, Changchun; Huang, Xin; Li, Lei; Xiao, Fukui; Zhao, Ning; Wei, Wei

2016-01-01

Recently, amine-functionalized materials as a prospective chemical sorbent for post combustion CO2 capture have gained great interest. However, the amine grafting for the traditional MCM-41, SBA-15, pore-expanded MCM-41 or SBA-15 supports can cause the pore volume and specific surface area of sorbents to decrease, significantly affecting the CO2 adsorption-desorption dynamics. To overcome this issue, hierarchical porous silica with interparticle macropores and long-range ordering mesopores was prepared and impregnated with pentaethylenehexamine. The pore structure and amino functional group content of the modified silicas were analyzed by scanning electron microscope, transmission electron microscope, N2 adsorption, X-ray powder diffraction, and Fourier transform infrared spectra. Moreover, the effects of the pore structure as well as the amount of PEHA loading of the samples on the CO2 adsorption capacity were investigated in a fixed-bed adsorption system. The CO2 adsorption capacity reached 4.5 mmol CO2/(g of adsorbent) for HPS−PEHA-70 at 75 °C. Further, the adsorption capacity for HPS-PEHA-70 was steady after a total of 15 adsorption-desorption cycles. PMID:28773956

Molecular Dynamics Simulations and XAFS (MD-XAFS)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schenter, Gregory K.; Fulton, John L.

2017-01-20

MD-XAFS (Molecular Dynamics X-ray Adsorption Fine Structure) makes the connection between simulation techniques that generate an ensemble of molecular configurations and the direct signal observed from X-ray measurement.

Quantitative models for predicting adsorption of oxytetracycline, ciprofloxacin and sulfamerazine to swine manures with contrasting properties.

PubMed

Cheng, Dengmiao; Feng, Yao; Liu, Yuanwang; Li, Jinpeng; Xue, Jianming; Li, Zhaojun

2018-09-01

Understanding antibiotic adsorption in livestock manures is crucial to assess the fate and risk of antibiotics in the environment. In this study, three quantitative models developed with swine manure-water distribution coefficients (LgK d ) for oxytetracycline (OTC), ciprofloxacin (CIP) and sulfamerazine (SM1) in swine manures. Physicochemical parameters (n=12) of the swine manure were used as independent variables using partial least-squares (PLSs) analysis. The cumulative cross-validated regression coefficients (Q 2 cum ) values, standard deviations (SDs) and external validation coefficient (Q 2 ext ) ranged from 0.761 to 0.868, 0.027 to 0.064, and 0.743 to 0.827 for the three models; as such, internal and external predictability of the models were strong. The pH, soluble organic carbon (SOC) and nitrogen (SON), and Ca were important explanatory variables for the OTC-Model, pH, SOC, and SON for the CIP-model, and pH, total organic nitrogen (TON), and SOC for the SM1-model. The high VIPs (variable importance in the projections) of pH (1.178-1.396), SOC (0.968-1.034), and SON (0.822 and 0.865) established these physicochemical parameters as likely being dominant (associatively) in affecting transport of antibiotics in swine manures. Copyright © 2018 Elsevier B.V. All rights reserved.

Mass dependence of calcium isotope fractionations in crown-ether resin chromatography.

PubMed

Fujii, Yasuhiko; Nomura, Masao; Kaneshiki, Tositaka; Sakuma, Yoichi; Suzuki, Tatsuya; Umehara, Saori; Kishimoto, Tadahumi

2010-06-01

Benzo 18-crown-6-ether resin was synthesised by the phenol condensation polymerisation process in porous silica beads, of which particle diameter was ca 60micro Calcium adsorption chromatography was performed with the synthesised resin packed in a glass column. The effluent was sampled in fractions, and the isotopic abundance ratios of (42)Ca, (43)Ca, (44)Ca, and (48)Ca against (40)Ca were measured by a thermo-ionisation mass spectrometer. The enrichment of heavier calcium isotopes was observed at the front boundary of calcium adsorption chromatogram. The mass dependence of mutual separation of calcium isotopes was analysed by using the three-isotope-plots method. The slopes of three-isotope-plots indicate the relative values of mutual separation coefficients for concerned isotopic pairs. The results have shown the normal mass dependence; isotope fractionation is proportional to the reduced mass difference, (M - M')/MM', where M and M' are masses of heavy and light isotope, respectively. The mass dependence clarifies that the isotope fractionations are originated from molecular vibration. The observed separation coefficient epsilon is 3.1x10(-3) for the pair of (40)Ca and (48)Ca. Productivity of enriched (48)Ca by crown-ether-resin was discussed as the function of the separation coefficient and the height equivalent to the theoretical plate.

Statistical mechanical models for dissociative adsorption of O2 on metal(100) surfaces with blocking, steering, and funneling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Evans, James W.; Liu, Da-Jiang

We develop statistical mechanical models amenable to analytic treatment for the dissociative adsorption of O2 at hollow sites on fcc(100) metal surfaces. The models incorporate exclusion of nearest-neighbor pairs of adsorbed O. However, corresponding simple site-blocking models, where adsorption requires a large ensemble of available sites, exhibit an anomalously fast initial decrease in sticking. Thus, in addition to blocking, our models also incorporate more facile adsorption via orientational steering and funneling dynamics (features supported by ab initio Molecular Dynamics studies). Behavior for equilibrated adlayers is distinct from those with finite adspecies mobility. We focus on the low-temperature limited-mobility regime wheremore » analysis of the associated master equations readily produces exact results for both short- and long-time behavior. Kinetic Monte Carlo simulation is also utilized to provide a more complete picture of behavior. These models capture both the initial decrease and the saturation of the experimentally observed sticking versus coverage, as well as features of non-equilibrium adlayer ordering as assessed by surface-sensitive diffraction.« less

Statistical mechanical models for dissociative adsorption of O{sub 2} on metal(100) surfaces with blocking, steering, and funneling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Evans, James W.; Department of Physics and Astronomy, Iowa State University, Ames, Iowa 50011; Liu, Da-Jiang

We develop statistical mechanical models amenable to analytic treatment for the dissociative adsorption of O{sub 2} at hollow sites on fcc(100) metal surfaces. The models incorporate exclusion of nearest-neighbor pairs of adsorbed O. However, corresponding simple site-blocking models, where adsorption requires a large ensemble of available sites, exhibit an anomalously fast initial decrease in sticking. Thus, in addition to blocking, our models also incorporate more facile adsorption via orientational steering and funneling dynamics (features supported by ab initio Molecular Dynamics studies). Behavior for equilibrated adlayers is distinct from those with finite adspecies mobility. We focus on the low-temperature limited-mobility regimemore » where analysis of the associated master equations readily produces exact results for both short- and long-time behavior. Kinetic Monte Carlo simulation is also utilized to provide a more complete picture of behavior. These models capture both the initial decrease and the saturation of the experimentally observed sticking versus coverage, as well as features of non-equilibrium adlayer ordering as assessed by surface-sensitive diffraction.« less

Numerical and analytical assessment of radon diffusion in various media and potential of charcoal as radon detector

NASA Astrophysics Data System (ADS)

Rybalkin, Andrey

Numerical assessments of radon diffusion together with analytical estimates for short-time and long-time exposure were the first objective of this thesis with the goal to demonstrate how radon propagates in various media. Theoretical predictions were compared to numerical simulations, and obtained values of total radon activities inside each material match quite well with the analytical estimates. These estimates, for activated and nonactivated charcoal, were then used to evaluate the possibility of designing a charcoal system to be used as a radon detector. Another objective was to use nonactivated charcoal samples and measure the level of radon accumulation, and use these data to estimate radon diffusion and adsorption coefficients. The analytical approach was developed to estimate these values. Radon adsorption coefficient in nonactivated charcoal was found to be from 0.2 to 0.4 m3/kg. Radon diffusion coefficient for nonactivated charcoal is in the range of 1.2×10-11 to 5.1×10-10 m2/s in comparison to activated charcoal with adsorption coefficient of 4 m3/kg and diffusion coefficient of 1.43×10-9 m2/s. The third objective was to use GEANT4 numerical code to simulate decay of 238U series and 222Rn in an arbitrary soil sample. Based on that model, the goal was to provide a guideline for merging GEANT4 radioactive decay modeling with the diffusion of radon in a soil sample. It is known that radon can be used as an earthquake predictor by measuring its concentration in groundwater, or if possible, along the faults. Numerical simulations of radon migration by diffusion only were made to estimate how fast and how far radon can move along the fault strands. Among the known cases of successful correlations between radon concentration anomalies and earthquake are the 1966 Tashkent and 1976 Songpan-Pingwu earthquakes. Thus, an idea of radon monitoring along the Wasatch Fault, using system of activated/nonactivated charcoals together with solid state radon detectors is suggested in the thesis. Also, the use of neutron activation analysis for soil samples, collected along and away from Wasatch Fault, and looking for the trace elements can result in correlation with earthquakes, occurred in the past. This approach can be used for earthquake prediction in future.

Measuring dynamic oil film coefficients of sliding bearing

NASA Technical Reports Server (NTRS)

Feng, G.; Tang, X.

1985-01-01

A method is presented for determining the dynamic coefficients of bearing oil film. By varying the support stiffness and damping, eight dynamic coefficients of the bearing were determined. Simple and easy to apply, the method can be used in solving practical machine problems.

From aggregative adsorption to surface depletion: Aqueous systems of C nE m amphiphiles at hydrophilic surfaces

DOE PAGES

Rother, Gernot; Müter, Dirk; Bock, Henry; ...

2017-03-27

Adsorption of a short-chain nonionic amphiphile (C 6E 3) at the surface of mesoporous silica glass (CPG-10) was studied by a combination of adsorption measurements and mesoscale simulations. Adsorption measurements covering a wide composition range of the C 6E 3 + water system show that no adsorption occurs up to the critical micelle concentration (cmc), at which a sharp increase of adsorption is observed that is attributed to ad-micelle formation at the pore walls. Intriguingly, as the concentration is increased further, the surface excess of the amphiphile begins to decrease and eventually becomes negative, which corresponds to preferential adsorption ofmore » water rather than amphiphile at high amphiphile concentrations. The existence of such a surface-azeotropic point has not previously been reported in the surfactant adsorption field. Dissipative particle dynamics (DPD) simulations were performed to reveal the structural origin of this transition from aggregative adsorption to surface depletion. Finally, the simulations indicate that this transition can be attributed to the repulsive interaction between head groups, causing amphiphilic depletion in the region around the corona of the surface micelles.« less

Investigation of Dynamic Oxygen Adsorption in Molten Solder Jetting Technology

NASA Technical Reports Server (NTRS)

Megaridis, Constantine M.; Bellizia, Giulio; McNallan, Michael; Wallace, David B.

2003-01-01

Surface tension forces play a critical role in fluid dynamic phenomena that are important in materials processing. The surface tension of liquid metals has been shown to be very susceptible to small amounts of adsorbed oxygen. Consequently, the kinetics of oxygen adsorption can influence the capillary breakup of liquid-metal jets targeted for use in electronics assembly applications, where low-melting-point metals (such as tin-containing solders) are utilized as an attachment material for mounting of electronic components to substrates. By interpreting values of surface tension measured at various surface ages, adsorption and diffusion rates of oxygen on the surface of the melt can be estimated. This research program investigates the adsorption kinetics of oxygen on the surface of an atomizing molten-metal jet. A novel oscillating capillary jet method has been developed for the measurement of dynamic surface tension of liquids, and in particular, metal melts which are susceptible to rapid surface degradation caused by oxygen adsorption. The experimental technique captures the evolution of jet swells and necks continuously along the jet propagation axis and is used in conjunction with an existing linear, axisymmetric, constant-property model to determine the variation of the instability growth rate, and, in turn, surface tension of the liquid as a function of surface age measured from the exit orifice. The conditions investigated so far focus on a time window of 2-4ms from the jet orifice. The surface properties of the eutectic 63%Sn-37%Pb solder alloy have been investigated in terms of their variation due to O2 adsorption from a N2 atmosphere containing controlled amounts of oxygen (from 8 ppm to 1000 ppm). The method performed well for situations where the oxygen adsorption was low in that time window. The value of surface tension for the 63Sn-37Pb solder in pure nitrogen was found to be 0.49 N/m, in good agreement with previously published work. A characteristic time of O(1ms) or less was determined for the molten-metal surface to be saturated by oxygen at 1000 ppm concentration in N2.

Investigation of formaldehyde interaction with carbon nanotubes and quartz sand

NASA Astrophysics Data System (ADS)

Georgopoulou, Maria P.; Chrysikopoulos, Constantinos V.

2017-04-01

Assessment of the potential impact of synthetic carbon nanotubes on the fate and transport of common chemical contaminants (pesticides, pharmaceuticals, etc.) in groundwater systems is considered to be an increasingly important aspect of environmental research. This study investigates the interaction of formaldehyde with multi-walled carbon nanotubes (MWCNTs) and quartz sand under static and dynamic conditions. Due to polarity, formaldehyde, is expected to develop strong adsorptive interactions with carbon nanotubes. Several batch adsorption experiments were conducted in test tubes, under controlled conditions. Various initial formaldehyde solution concentration (2, 5, 8 ppm), contact times, and temperatures (8, 18, 25 °C) were considered. Supernatant liquid samples were collected at regular intervals, and centrifuged. Subsequently, the formaldehyde concentration in the supernatant was quantified indirectly, by derivatization with Nash reagent and subsequent measurement of the resulting complex using spectrophotometry in the visible spectral range. Experimental results suggested that formaldehyde has a low affinity for quartz sand, but an enhanced potential for adsorption onto carbon nanotubes. Formaldehyde adsorption onto both absorbents (quartz sand and MWCNTs) was more pronounced under dynamic than static conditions, probably, because agitation improves the mixing of the absorbent within the solution. Also, it was shown that the adsorption data were adequately described by the pseudo-second order kinetic model, suggesting that the primary adsorption mechanism was chemisorption, where two or more (sequential or parallel) processes (e.g. surface chemisorption, intraparticle diffusion) were taking place. Therefore, MWCNTs could be promising adsorbent materials for groundwater remediation.

Adsorption equilibrium and dynamics of gasoline vapors onto polymeric adsorbents.

PubMed

Jia, Lijuan; Yu, Weihua; Long, Chao; Li, Aimin

2014-03-01

The emission of gasoline vapors is becoming a significant environmental problem especially for the population-dense area and also results in a significant economic loss. In this study, adsorption equilibrium and dynamics of gasoline vapors onto macroporous and hypercrosslinked polymeric resins at 308 K were investigated and compared with commercial activated carbon (NucharWV-A 1100). The results showed that the equilibrium and breakthrough adsorption capacities of virgin macroporous and hypercrosslinked polymeric resins were lower than virgin-activated carbon. Compared with origin adsorbents, however, the breakthrough adsorption capacities of the regenerated activated carbon for gasoline vapors decreased by 58.5 % and 61.3 % when the initial concentration of gasoline vapors were 700 and 1,400 mg/L, while those of macroporous and hypercrosslinked resins decreased by 17.4 % and 17.5 %, and 46.5 % and 45.5 %, respectively. Due to the specific bimodal property in the region of micropore (0.5-2.0 nm) and meso-macropore (30-70 nm), the regenerated hypercrosslinked polymeric resin exhibited the comparable breakthrough adsorption capacities with the regenerated activated carbon at the initial concentration of 700 mg/L, and even higher when the initial concentration of gasoline vapors was 1,400 mg/L. In addition, 90 % of relative humidity had ignorable effect on the adsorption of gasoline vapors on hypercrosslinked polymeric resin. Taken together, it is expected that hypercrosslinked polymeric adsorbent would be a promising adsorbent for the removal of gasoline vapors from gas streams.

The effects of intra-particle concentration gradient on consecutive adsorption-desorption of oryzanol from rice bran oil in packed-column

NASA Astrophysics Data System (ADS)

Susanti, Ari Diana; Sediawan, Wahyudi Budi; Wirawan, Sang Kompiang; Budhijanto

2017-05-01

Utilization of valuable trace components in agriculture by product such as rice bran oil is interesting to be explored. Among the valuables, oryzanol, a healthy nutrition for cardiovascular prevention, is the most promising one. Literature studies suggest that adsorption-desorption is a prospective method for oryzanol isolation. Design of commercial scale adsorption-desorption system for oryzanol needs a quantitative description of the phenomena involved. In this study, quantitative modeling of the consecutive adsorption-desorption in packed column has been proposed and verified through experimental data. The offered model takes into account the intra-particle concentration gradient in the adsorbent particle. In this model, the rate of mass transfer from the bulk of the liquid to the surface of the adsorbent particle or vice versa is expressed by film theory. The mass transfer of oryzanol from the liquid in the pore of the particle to the adjacent pore surface is assumed to be instantaneous, so solid-liquid equilibrium on the surface of the pores is always attained. For simplicity, the adsorption equilibrium model applied was coefficient distribution approach. The values of the parameters implicated in the model were obtained by curve fitting to the experimental data. It verified that the model proposed works well to quantitatively describe the consecutive adsorption-desorption of oryzanol from rice bran oil in packed column.

Adsorption isotherm studies of Cu (II) and Co (II) in high concentration aqueous solutions on photocatalytically modified diatomaceous ceramic adsorbents

NASA Astrophysics Data System (ADS)

Ajenifuja, E.; Ajao, J. A.; Ajayi, E. O. B.

2017-11-01

Photocatalytically modified ceramic adsorbents were synthesized for the removal of high concentration Cu (II) and Co (II) ions from their aqueous solutions. The raw material, diatomaceous aluminosilicate mineral was modified using silver and anatase titanium oxide nanoparticles. Batch adsorption experiment was carried out on the targeted metal ions and the results were analyzed by the Langmuir and Freundlich equation at different concentrations (100-1000 mg/l) and the characteristic parameters for each adsorption isotherm were determined. As-received raw materials do not exhibit any sorption capacity for high concentration Cu2+ and Co2+ adsorbates. However, the adsorption isotherms for modified diatomaceous ceramic adsorbents could be fitted well by the Langmuir model for both Cu2+ and Co2+ with correlation coefficient ( R) of up to 0.99953. The highest and lowest monolayer coverage ( q max) were 121.803 and 31.289 mg/g for Cu2+ and Co2+, respectively. The separation factor ( R L) in the experiment was less than one (<1), indicating that the adsorption of metal ions on the Ag-TiO2-modified ceramic adsorbent is favorable. The highest adsorption capacity ( K f) and intensity ( n) constants obtained from Freundlich model are 38.832 (Cu2+ on ZEO-T) and 5.801 (Co2+ on STOX-Z).

Kinetic and Conformational Insights of Protein Adsorption onto Montmorillonite Revealed Using in Situ ATR-FTIR/2D-COS.

PubMed

Schmidt, Michael P; Martínez, Carmen Enid

2016-08-09

Protein adsorption onto clay minerals is a process with wide-ranging impacts on the environmental cycling of nutrients and contaminants. This process is influenced by kinetic and conformational factors that are often challenging to probe in situ. This study represents an in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopic investigation of the adsorption of a model protein (bovine serum albumin (BSA)) onto a clay mineral (montmorillonite) at four concentrations (1.50, 3.75, 7.50, and 15.0 μM) under environmentally relevant conditions. At all concentrations probed, FTIR spectra show that BSA readily adsorbs onto montmorillonite. Adsorption kinetics follow an Elovich model, suggesting that primary limitations on adsorption rates are surface-related heterogeneous energetic restrictions associated with protein rearrangement and lateral protein-protein interaction. BSA adsorption onto montmorillonite fits the Langmuir model, yielding K = 5.97 × 10(5) M(-1). Deconvolution and curve fitting of the amide I band at the end of the adsorption process (∼120 min) shows a large extent of BSA unfolding upon adsorption at 1.50 μM, with extended chains and turns increasing at the expense of α-helices. At higher concentrations/surface coverages, BSA unfolding is less pronounced and a more compact structure is assumed. Two-dimensional correlation spectroscopic (2D-COS) analysis reveals three different pathways corresponding to adsorbed conformations. At 1.50 μM, adsorption increases extended chains, followed by a loss in α-helices and a subsequent increase in turns. At 3.75 μM, extended chains decrease and then aggregated strands increase and side chains decrease, followed by a decrease in turns. With 7.50 and 15.0 μM BSA, the loss of side-chain vibrations is followed by an increase in aggregated strands and a subsequent decrease in turns and extended chains. Overall, the BSA concentration and resultant surface coverage have a profound impact on the dynamics of BSA adsorption onto montmorillonite. These results enhance our understanding of the molecular-level protein dynamics and stabilization of organic matter at mineral surfaces.

Optimization of polyphenol removal from kiwifruit juice using a macroporous resin.

PubMed

Gao, Zhenpeng; Yu, Zhifang; Yue, Tianli; Quek, Siew Young

2017-06-01

The separation of polyphenols from kiwifruit juice is essential for enhancing sensory properties and prevent the browning reaction in juice during processing and storage. The present study investigated the dynamic adsorption and desorption of polyphenols in kiwifruit juice using AB-8 resin. The model obtained could be successfully applied to predict the experimental results of dynamic adsorption capacity (DAC) and dynamic desorption quantity (DDQ). The results showed that dynamic adsorption of polyphenols could be optimised in a juice concentration of 19 °Brix, with a feed flow-rate of 1.3 mL min -1 and a feed volume of 7 bed volume (BV). The optimum conditions for dynamic desorption of polyphenols from the AB-8 resin were an ethanol concentration of 43% (v/v), an elute flow-rate of 2.2 mL min -1 and an elute volume of 3 BV. The optimized DAC value was 3.16 g of polyphenols kg -1 resin, whereas that for DDQ was 917.5 g kg -1 , with both values being consistent with the predicted values generated by the regression models. The major polyphenols in the dynamic desorption solution consisted of seven compositions. The present study could be scaled-up using a continuous column system for industrial application, thus contributing to the improved flavor and color of kiwifruit juice. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Trichoderma sp. spores and Kluyveromyces marxianus cells magnetic separation: Immobilization on chitosan-coated magnetic nanoparticles.

PubMed

Palacios-Ponce, Sócrates; Ramos-González, Rodolfo; Ruiz, Héctor A; Aguilar, Miguel A; Martínez-Hernández, José L; Segura-Ceniceros, Elda P; Aguilar, Cristóbal N; Michelena, Georgina; Ilyina, Anna

2017-07-03

In the present study, the interactions between chitosan-coated magnetic nanoparticles (C-MNP) and Trichoderma sp. spores as well as Kluyveromyces marxianus cells were studied. By Plackett-Burman design, it was demonstrated that factors which directly influenced on yeast cell immobilization and magnetic separation were inoculum and C-MNP quantity, stirring speed, interaction time, and volume of medium, while in the case of fungal spores, the temperature also was disclosed as an influencing factor. Langmuir and Freundlich models were applied for the mathematical analysis of adsorption isotherms at 30°C. For Trichoderma sp. spore adsorption isotherm, the highest correlation coefficient was observed for lineal function of Langmuir model with a maximum adsorption capacity at 5.00E + 09 spores (C-MNP g -1 ). Adsorption isotherm of K. marxianus cells was better adjusted to Freundlich model with a constant (K f ) estimated as 2.05E + 08 cells (C-MNP g -1 ). Both systems may have a novel application in fermentation processes assisted with magnetic separation of biomass.

Optimizing adsorption of fluoride from water by modified banana peel dust using response surface modelling approach

NASA Astrophysics Data System (ADS)

Bhaumik, Ria; Mondal, Naba Kumar

2016-06-01

The present work highlighted the effective application of banana peel dust (BPD) for removal of fluoride (F-) from aqueous solution. The effects of operating parameters such as pH, initial concentration, adsorbent dose, contact time, agitation speed and temperature were analysed using response surface methodology. The significance of independent variables and their interactions were tested by the analysis of variance and t test statistics. Experimental results revealed that BPD has higher F- adsorption capacity (17.43, 26.31 and 39.5 mg/g). Fluoride adsorption kinetics followed pseudo-second-order model with high correlation of coefficient value (0.998). On the other hand, thermodynamic data suggest that adsorption is favoured at lower temperature, exothermic in nature and enthalpy driven. The adsorbents were characterised through scanning electron microscope, Fourier transform infrared spectroscopy and point of zero charges (pHZPC) ranges from pH 6.2-8.2. Finally, error analysis clearly demonstrates that all three adsorbents are well fitted with Langmuir isotherm compared to the other isotherm models. The reusable properties of the material support further development for commercial application purpose.

Effective synthesis of magnetic porous molecularly imprinted polymers for efficient and selective extraction of cinnamic acid from apple juices.

PubMed

Shi, Shuyun; Fan, Dengxin; Xiang, Haiyan; Li, Huan

2017-12-15

An effective strategy was proposed to prepare novel magnetic porous molecularly imprinted polymers (MPMIPs) for highly selective extraction of cinnamic acid (CMA) from complex matrices. Characterization and various parameters affecting adsorption and desorption behaviors were investigated. Results revealed adsorption behavior between CMA and MPMIPs followed Freundlich equation adsorption isotherm with a maximum adsorption capacity at 4.35mg/g and pseudo-second-order reaction kinetics with equilibrium time at 60min. Subsequently, MPMIPs were successfully used to selectively extract CMA from apple juice with a relatively satisfactory recovery (92.7-101.4%). Coupling with high-performance liquid chromatography and ultraviolet detection (HPLC-UV), the limit of detection (LOD) for CMA was 0.006µg/mL, and the linear range (0.02-10μg/mL) was wide with correlation coefficient at 0.9995. Finally, the contents of CMA in two kinds of apple juices were determined as 0.132 and 0.120μg/mL. Results indicated the superiority of MPMIPs in the selective extraction field. Copyright © 2017 Elsevier Ltd. All rights reserved.

Preparation of steam activated carbon from rubberwood sawdust (Hevea brasiliensis) and its adsorption kinetics.

PubMed

Prakash Kumar, B G; Shivakamy, K; Miranda, Lima Rose; Velan, M

2006-08-25

Activated carbon was produced from a biowaste product, rubberwood sawdust (RWSD) using steam in a high temperature fluidized bed reactor. Experiments were carried out to investigate the influence of various process parameters such as activation time, activation temperature, particle size and fluidising velocity on the quality of the activated carbon. The activated carbon was characterized based on its iodine number, methylene blue number, Brauner Emmet Teller (BET) surface area and surface area obtained using the ethylene glycol mono ethyl ether (EGME) retention method. The best quality activated carbon was obtained at an activation time and temperature of 1h and 750 degrees C for an average particle size of 0.46 mm. The adsorption kinetics shows that pseudo-second-order rate fitted the adsorption kinetics better than pseudo-first-order rate equation. The adsorption capacity of carbon produced from RWSD was found to be 1250 mg g(-1) for the Bismark Brown dye. The rate constant and diffusion coefficient for intraparticle transport were determined for steam activated carbon. The characteristic of the prepared activated carbon was found comparable to the commercial activated carbon.

Enrichment and separation of chlorogenic acid from the extract of Eupatorium adenophorum Spreng by macroporous resin.

PubMed

Liu, Boyan; Dong, Beitao; Yuan, Xiaofan; Kuang, Qirong; Zhao, Qingsheng; Yang, Mei; Liu, Jie; Zhao, Bing

2016-01-01

A simple and efficient chromatographic method for separation of chlorogenic acid from Eupatorium adenophorum Spreng extract was developed. The adsorption properties of nine macroporous resins were evaluated. NKA-II resin showed much better adsorption/desorption properties. The adsorption of chlorogenic acid on NKA-II resin at 25°C was well fitted to Langmuir isotherm model and pseudo-second-order kinetic model. The dynamic adsorption and desorption experiments were carried out on columns packed with NKA-II resin to optimize the separation process. The content of chlorogenic acid in the product increased to 22.17%, with a recovery yield of 82.41%. Copyright © 2015 Elsevier B.V. All rights reserved.

Design and Analysis of a Two-Stage Adsorption Air Chiller

NASA Astrophysics Data System (ADS)

Benrajesh, P.; Rajan, A. John

2017-05-01

The objective of this article is to design and build a bio-friendly air-conditioner, by using adsorption method in the presence of 15% of calcium carbide in water. Aluminum sheet metals are used to form three identical tunnels, to pass the air for processing. Exhaust heat generated from the dairy sterilizing unit process is reutilized, for cooling the environment through this equipment. This equipment is designed, and the analysis is carried out to quantify the COP, SCP, and cooling power. Heat exchangers are designed; its Performance Parameters are quantified and correlated with the conventional designs. It is observed that the new adsorption chiller can produce the coefficient of performance of chiller as 1.068; the Specific cooling power of 10.66 (W/Kg); and the Cooling power of 4.2 KW. This equipment needs 0 to 15 minutes to reach the desired cool breeze (24°c) from the existing room temperature (29°c).

Excellent fluoride decontamination and antibacterial efficacy of Fe-Ca-Zr hybrid metal oxide nanomaterial.

PubMed

Dhillon, Ankita; Nair, Manjula; Bhargava, Suresh K; Kumar, Dinesh

2015-11-01

The aim of the present study is to develop an efficient nanomaterial for the removal of fluoride and disinfection of harmful bacteria in order to make water potable according to Environmental Protection Agency (EPA) guidelines. Hydrous hybrid Fe-Ca-Zr oxide nanoadsorbent presented a marked fluoride adsorption capacity of 250 mg/g at pH 7.0 (±0.1) much greater than other commercially accessible adsorbents for both synthetic and real water samples. The adsorption isotherms, Freundlich and Dubinin-Radushkevich (D-R) fitted reasonably well fine having high coefficient of regression values. The adsorption of fluoride was established well using pseudo-second-order kinetics. The fluoride loaded adsorbent was efficiently regenerated by using an alkali solution. Interestingly, the developed nanomaterial not only showed excellent fluoride removal capacity but also demonstrated good antibacterial activity against Escherichia coli with IC50 (25 μg/mL). Copyright © 2015 Elsevier Inc. All rights reserved.

Study of the adsorption of mercury (II) on lignocellulosic materials under static and dynamic conditions.

PubMed

Arias Arias, Fabian E; Beneduci, Amerigo; Chidichimo, Francesco; Furia, Emilia; Straface, Salvatore

2017-08-01

WHO has declared mercury as one of the most dangerous pollutants for human health. Unfortunately, several cases of rivers and aquifers contaminated by mercury inevitably poses the problem on how to remediate them. Considerable efforts are being addressed to develop cost-effective methodologies, among which the use of low-cost adsorbing materials. In this paper, the adsorption performances of an alternative lignocellulosic material derived from the Spanish broom plant, are presented. This plant is widely diffused in the world and its usage for Hg(II) removal from water in real working conditions requires only minimal pretreatment steps. A thoroughly investigation on the kinetics and thermodynamics of Hg(II) adsorption on Spanish broom is presented, by using Hg(II) polluted aqueous solutions specifically prepared in order to simulate typical groundwater conditions. Several batch experiments, under static conditions, were carried out in order to evaluate the effect of pH, contact time, adsorbent dosage, initial concentration, temperature. A maximum adsorption capacity of 20 mg L -1 can be obtained at pH 5, following a pseudo second order kinetics. Moreover, adsorption experiments in dynamic conditions were carried out using Spanish broom filters. Interestingly, a systematic, unconventional double S-shape breakthrough curve was observed under different experimental conditions, revealing the occurrence of two adsorption processes with different time scales. This behavior has been fitted by a bimodal Thomas model which, unlike the single Thomas fitting, gives satisfactory results with the introduction of a new parameter related to the fraction of surface active sites involved in the adsorption processes. Copyright © 2017 Elsevier Ltd. All rights reserved.

The molecular mechanism of the inhibition effects of PVCaps on the growth of sI hydrate: an unstable adsorption mechanism.

PubMed

Xu, Jiafang; Li, Liwen; Liu, Jinxiang; Wang, Xiaopu; Yan, Youguo; Zhang, Jun

2018-03-28

The inhibition properties of kinetic hydrate inhibitor (KHI) molecules on the dynamic growth of a hydrate/water interface are investigated by using molecular dynamics simulations. The shape of the hydrate interface is transformed from laminar to funnel by PVCaps. Results indicate that the inhibition effects not only depend on the adsorption capacity which was believed to determine inhibition, but also on the fact that PVCaps must have some non-binding-hydrate sites that don't tend to combine with hydrate. By observing the time evolution of the distance between each component of PVCaps and hydrate, the heterocyclic ring of PVCaps mainly contributes to adsorption and can preferentially adjust itself to come into contact with a hydrate semi-large-cage. The distance between the amide of PVCaps and hydrate is about 4 Å and exceeds the range of a general hydrogen bond (3.5 Å), which proves that the non-binding-hydrate sites of PVCaps exist. On the other hand, the amide of PVCaps is at the intersection of the solid-liquid interface but has no adsorption affinity for hydrate, so this adsorption pattern indicates that the PVCaps at the hydrate interface are not stable. Due to this unstable adsorption, a repeated hydrate destruction phenomenon was revealed by the identification algorithm of hydrate and the calculation of the local number density of methane. The statistical evolution of water rings further proved the existence of non-binding-hydrate sites in PVCaps and the inhibition mechanism to destroy the hydrate cages by PVCaps. This unstable adsorption mechanism may shed light on the development of novel efficient KHIs.

Removal of anionic dye Congo red from aqueous solution by raw pine and acid-treated pine cone powder as adsorbent: equilibrium, thermodynamic, kinetics, mechanism and process design.

PubMed

Dawood, Sara; Sen, Tushar Kanti

2012-04-15

Pine cone a natural, low-cost agricultural by-product in Australia has been studied for its potential application as an adsorbent in its raw and hydrochloric acid modified form. Surface study of pine cone and treated pine cone was investigated using Fourier transform infrared (FTIR) and scanning electron microscopy (SEM). The modification process leads to increases in the specific surface area and decreases mean particle sizes of acid-treated pine cone when compared to raw pine cone biomass. Batch adsorption experiments were performed to remove anionic dye Congo red from aqueous solution. It was found that the extent of Congo red adsorption by both raw pine cone biomass and acid-treated biomass increased with initial dye concentration, contact time, temperature but decreased with increasing solution pH and amount of adsorbent of the system. Overall, kinetic studies showed that the dye adsorption process followed pseudo-second-order kinetics based on pseudo-first-order and intra-particle diffusion models. The different kinetic parameters including rate constant, half-adsorption time, and diffusion coefficient were determined at different physico-chemical conditions. Equilibrium data were best represented by Freundlich isotherm model among Langmuir and Freundlich adsorption isotherm models. It was observed that the adsorption was pH dependent and the maximum adsorption of 32.65 mg/g occurred at pH of 3.55 for an initial dye concentration of 20 ppm by raw pine cone, whereas for acid-treated pine cone the maximum adsorption of 40.19 mg/g for the same experimental conditions. Freundlich constant 'n' also indicated favourable adsorption. Thermodynamic parameters such as ∆G(0), ∆H(0), and ∆S(0) were calculated. A single-stage batch absorber design for the Congo red adsorption onto pine cone biomass also presented based on the Freundlich isotherm model equation. Copyright © 2012 Elsevier Ltd. All rights reserved.

Correlations and adsorption mechanisms of aromatic compounds on biochars produced from various biomass at 700 °C.

PubMed

Yang, Kun; Jiang, Yuan; Yang, Jingjing; Lin, Daohui

2018-02-01

Knowledge of adsorption behavior of organic contaminants on high heat temperature treated biochars is essential for application of biochars as adsorbents in wastewater treatment and soil remediation. In this study, isotherms of 25 aromatic compounds adsorption on biochars pyrolyzed at 700 °C from biomass including wood chips, rice straw, bamboo chips, cellulose, lignin and chitin were investigated to establish correlations between adsorption behavior and physicochemical properties of biochars. Isotherms were well fitted by Polanyi theory-based Dubinin-Ashtakhov (DA) model with three parameters, i.e., adsorption capacity (Q 0 ) and adsorption affinity (E and b). Besides the negative correlation of Q 0 with molecular maximum cross-sectional areas (σ) of organic compounds, positive correlations of Q 0 with total pore volume (V total ) and average diameter of micropore (D) of biochars were observed, indicating that adsorption by biochars is captured by the pore-filling mechanism with molecular sieving effect in biochar pores. Linear solvation energy relationships (LSERs) of adsorption affinity (E) with solvatochromic parameters of organic compounds (i. e., α m and π ∗ ) were established, suggesting that hydrophobic effect, π-π interaction and hydrogen-bonding interaction are the main forces responsible for adsorption. The regression coefficient (π 1 ) and intercept (C) of obtained LSERs are correlated with biochar H/C and R micro , respectively, implying that biochars with higher aromaticity and more micropores have stronger π-π bonding potential and hydrophobic effect potential with aromatic molecule, respectively. However, hydrogen-bonding potential of biochars for organic molecules is not changed significantly with properties of biochars. A negative correlation of b with biochar H/C is also obtained. These correlations could be used to predict the adsorption behavior of organic compounds on high heat temperature treated biochars from various biomass for the application of biochars as sorbents and for the estimating of environmental risks of organic compounds in the present of biochars. Copyright © 2017 Elsevier Ltd. All rights reserved.

Molecular dynamics simulations of low-ordered alzheimer β-amyloid oligomers from dimer to hexamer on self-assembled monolayers.

PubMed

Zhao, Jun; Wang, Qiuming; Liang, Guizhao; Zheng, Jie

2011-12-20

Accumulation of small soluble oligomers of amyloid-β (Aβ) in the human brain is thought to play an important pathological role in Alzheimer's disease. The interaction of these Aβ oligomers with cell membrane and other artificial surfaces is important for the understanding of Aβ aggregation and toxicity mechanisms. Here, we present a series of exploratory molecular dynamics (MD) simulations to study the early adsorption and conformational change of Aβ oligomers from dimer to hexamer on three different self-assembled monolayers (SAMs) terminated with CH(3), OH, and COOH groups. Within the time scale of MD simulations, the conformation, orientation, and adsorption of Aβ oligomers on the SAMs is determined by complex interplay among the size of Aβ oligomers, the surface chemistry of the SAMs, and the structure and dynamics of interfacial waters. Energetic analysis of Aβ adsorption on the SAMs reveals that Aβ adsorption on the SAMs is a net outcome of different competitions between dominant hydrophobic Aβ-CH(3)-SAM interactions and weak CH(3)-SAM-water interactions, between dominant electrostatic Aβ-COOH-SAM interactions and strong COOH-SAM-water interactions, and between comparable hydrophobic and electrostatic Aβ-OH-SAM interactions and strong OH-SAM-water interactions. Atomic force microscopy images also confirm that all of three SAMs can induce the adsorption and polymerization of Aβ oligomers. Structural analysis of Aβ oligomers on the SAMs shows a dramatic increase in structural stability and β-sheet content from dimer to trimer, suggesting that Aβ trimer could act as seeds for Aβ polymerization on the SAMs. This work provides atomic-level understanding of Aβ peptides at interface. © 2011 American Chemical Society

Poliovirus adsorption by 34 minerals and soils.

PubMed

Moore, R S; Taylor, D H; Sturman, L S; Reddy, M M; Fuhs, G W

1981-12-01

The adsorption of radiolabeled infectious poliovirus type 2 by 34 well-defined soils and mineral substrates was analyzed in a synthetic freshwater medium containing 1 mM CaCl(2) and 1.25 mM NaHCO(3) at pH 7. In a model system, adsorption of poliovirus by Ottawa sand was rapid and reached equilibrium within 1 h at 4 degrees C. Near saturation, the adsorption could be described by the Langmuir equation; the apparent surface saturation was 2.5 x 10(6) plaque-forming units of poliovirus per mg of Ottawa sand. At low surface coverage, adsorption was described by the Freundlich equation. The soils and minerals used ranged from acidic to basic and from high in organic content to organic free. The available negative surface charge on each substrate was measured by the adsorption of a cationic polyelectrolyte, polydiallyldimethylammonium chloride. Most of the substrates adsorbed more than 95% of the virus. In general, soils, in comparison with minerals, were weak adsorbents. Among the soils, muck and Genesee silt loam were the poorest adsorbents; among the minerals, montmorillonite, glauconite, and bituminous shale were the least effective. The most effective adsorbents were magnetite sand and hematite, which are predominantly oxides of iron. Correlation coefficients for substrate properties and virus adsorption revealed that the elemental composition of the adsorbents had little effect on poliovirus uptake. Substrate surface area and pH, by themselves, were not significantly correlated with poliovirus uptake. A strong negative correlation was found between poliovirus adsorption and both the contents of organic matter and the available negative surface charge on the substrates as determined by their capacities for adsorbing the cationic polyelectrolyte, polydiallyldimethylammonium chloride.

Quantities, sources and adsorption of polybrominated diphenyl ethers in components of surficial sediments collected in Songhua River (Jilin City), China.

PubMed

Wang, Ting; Li, Shanshan; Zhang, Chen; Li, Yu

2015-01-01

Quantities of polybrominated diphenyl ethers (PBDEs, BDE-28, 47, 99, 100, 153, 154, 183 and 209) in surficial sediments (SSs) of the Songhua River, China were extracted and detected by Soxhlet extractor and gas chromatography/mass spectrometry (GC/MS). Sources of the PBDEs were investigated by factor analysis. Contributions of Fe oxides, Mn oxides and organic matters (OMs), and their interactions of SSs to the adsorption of PBDEs were described based on multiple linear regressions. The analysis results from GC/MS indicated that the concentrations of PBDEs ranged from 2.90 to 9871 ng g(-)(1) (dry weight) with a mean value of 397 ng g(-)(1). The congener profiles of the SSs were dominated by BDE-209 (⩾71.8%). Relatively high contents of PBDEs were observed in SSs from the upstream section. Deca-BDE commercial formulations constituted the largest contribution (33.6%) to PBDEs in the SSs, followed by Penta-BDE commercial formulations (21.7%) and Octa-BDE commercial formulations (13.2%). Each of the components in the SSs contributes positively to PBDEs' adsorption. Synergism of Fe oxides and OMs was observed in the PBDEs' adsorption. The interactions of Mn oxides and other components inhibited the PBDEs' adsorption onto SSs, and the antagonism in the BDE-209 adsorption was stronger than other Σ7PBDEs (BDE-28, 47, 99, 100, 153, 154 and 183). However, the synergism observed in the Σ7PBDEs adsorption was stronger than BDE-209. The BDE-209 in SSs mainly came from Deca-BDE commercial formulations. The adsorption of PBDEs onto SSs was affected by the octanol-water coefficient (Kow) of the PBDEs' congeners and the components of the SSs. Copyright © 2014 Elsevier Ltd. All rights reserved.

Influence of humic acids on the adsorption of Basic Yellow 28 dye onto an iron organo-inorgano pillared clay and two hydrous ferric oxides.

PubMed

Zermane, Faiza; Cheknane, Benamar; Basly, Jean Philippe; Bouras, Omar; Baudu, Michel

2013-04-01

Effect of humic acids (HAs), macromolecules from natural organic matter, on the adsorption of Basic Yellow 28 is the aim of the present work. Three adsorbents were investigated in this study: an iron organo-inorgano pillared clay and two synthetic Hydrous Iron Oxide (Goethite and HFO). The surface charge was positive in the pH range of this study for the pillared clay; in contrast, it changes from positive to negative when the pH value increased (pH>9) for the two (oxy)hydroxides. Pseudo-first order kinetic rate constants and adsorption capacities increase from humic acid to BY 28. Adsorption isotherms of BY 28 and HA in single component were analysed using the Freundlich equation. Adsorption capacities increased sharply when the pH value of the dye solution was raised from 3 to 9. Increasing the pH medium from 3 to 9 reduces the HA adsorption capacities onto Fe-SMPM and iron oxyhydroxides, respectively. Fitting between measured and predicted sorption capacities of BY 28 and HA in a binary component system indicates that the Sheindorf-Rebuhn-Sheintuch (SRS) model, an extended Freundlich model, is able to describe the simultaneous adsorption of BY 28 and HA. Humic acids favourably affect the adsorption of BY 28, and a cooperative mechanism could be suggested. The synergetic effect existing between BY 28 and HA is shown by the interaction coefficients η12, which are generally high and increase with pH. Some phenomena have been advanced to explain this mechanism. Copyright © 2012 Elsevier Inc. All rights reserved.

Charging and Transport Dynamics of a Flow-Through Electrode Capacitive Deionization System.

PubMed

Qu, Yatian; Campbell, Patrick G; Hemmatifar, Ali; Knipe, Jennifer M; Loeb, Colin K; Reidy, John J; Hubert, Mckenzie A; Stadermann, Michael; Santiago, Juan G

2018-01-11

We present a study of the interplay among electric charging rate, capacitance, salt removal, and mass transport in "flow-through electrode" capacitive deionization (CDI) systems. We develop two models describing coupled transport and electro-adsorption/desorption which capture salt removal dynamics. The first model is a simplified, unsteady zero-dimensional volume-averaged model which identifies dimensionless parameters and figures of merits associated with cell performance. The second model is a higher fidelity area-averaged model which captures both spatial and temporal responses of charging. We further conducted an experimental study of these dynamics and considered two salt transport regimes: (1) advection-limited regime and (2) dispersion-limited regime. We use these data to validate models. The study shows that, in the advection-limited regime, differential charge efficiency determines the salt adsorption at the early stage of the deionization process. Subsequently, charging transitions to a quasi-steady state where salt removal rate is proportional to applied current scaled by the inlet flow rate. In the dispersion-dominated regime, differential charge efficiency, cell volume, and diffusion rates govern adsorption dynamics and flow rate has little effect. In both regimes, the interplay among mass transport rate, differential charge efficiency, cell capacitance, and (electric) charging current governs salt removal in flow-through electrode CDI.

Dynamic Cooperation of Hydrogen Binding and π Stacking in ssDNA Adsorption on Graphene Oxide.

PubMed

Xu, Zhen; Lei, Xiaoling; Tu, Yusong; Tan, Zhi-Jie; Song, Bo; Fang, Haiping

2017-09-21

Functional nanoscale structures consisting of a DNA molecule coupled to graphene or graphene oxide (GO) have great potential for applications in biosensors, biomedicine, nanotechnology, and materials science. Extensive studies using the most sophisticated experimental techniques and theoretical methods have still not clarified the dynamic process of single-stranded DNA (ssDNA) adsorbed on GO surfaces. Based on a molecular dynamics simulation, this work shows that an ssDNA segment could be stably adsorbed on a GO surface through hydrogen bonding and π-π stacking interactions, with preferential binding to the oxidized rather than to the unoxidized region of the GO surface. The adsorption process shows a dynamic cooperation adsorption behavior; the ssDNA segment first captures the oxidized groups of the GO surface by hydrogen bonding interaction, and then the configuration relaxes to maximize the π-π stacking interactions between the aromatic rings of the nucleobases and those of the GO surface. We attributed this behavior to the faster forming hydrogen bonding interaction compared to π-π stacking; the π-π stacking interaction needs more relaxation time to regulate the configuration of the ssDNA segment to fit the aromatic rings on the GO surface. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sorption and biodegradation characteristics of the selected pharmaceuticals and personal care products onto tropical soil.

PubMed

Foolad, Mahsa; Hu, Jiangyong; Tran, Ngoc Han; Ong, Say Leong

2016-01-01

In the present study, the sorption and biodegradation characteristics of five pharmaceutical and personal care products (PPCPs), including acetaminophen (ACT), carbamazepine (CBZ), crotamiton (CTMT), diethyltoluamide (DEET) and salicylic acid (SA), were studied in laboratory-batch experiments. Sorption kinetics experimental data showed that sorption systems under this study were more appropriately described by the pseudo second-order kinetics with a correlation coefficient (R2)>0.98. Sorption equilibrium data of almost all target compounds onto soil could be better described by the Freundlich sorption isotherm model. The adsorption results showed higher soil affinity for SA, following by ACT. Results also indicated a slight effect of pH on PPCP adsorption with lower pH causing lower adsorption of compounds onto the soil except for SA at pH 12. Moreover, adsorption of PPCPs onto the soil was influenced by natural organic matter (NOM) since the higher amount of NOM caused lower adsorption to the soil. Biodegradation studies of selected PPCPs by indigenous microbial community present in soil appeared that the removal rates of ACT, SA and DEET increased with time while no effect had been observed for the rest. This study suggests that the CBZ and CTMT can be considered as suitable chemical sewage indicators based on their low sorption affinity and high resistance to biodegradation.

Application of Box-Behnken design for modeling of lead adsorption onto unmodified and NaCl-modified zeolite NaA obtained from biosilica.

PubMed

Terzioğlu, Pinar; Yücel, Sevil; Öztürk, Mehmet

2017-01-01

The main objective of the present study was to optimize lead adsorption onto zeolite NaA. For this purpose, to synthesize zeolite NaA under hydrothermal conditions, local wheat husk was precleaned with chemical treatment using hydrochloric acid solution. The unmodified (ZU) and NaCl-modified (ZN) zeolites were characterized by Brunauer-Emmett-Teller, scanning electron microscopy coupled with energy dispersive spectroscopy and X-ray diffraction. The optimization of adsorption process was examined using Box-Behnken Experimental Design in response surface methodology by Design Expert Version 7.0.0 (Stat-Ease, USA). The effects of initial lead (II) concentration, temperature, and time were selected as independent variables. Lack of fit test indicates that the quadratic regression model was significant with the high coefficients of determination values for both adsorbents. Optimum process conditions for lead (II) adsorption onto ZU and ZN were found to be 64.40°C and 64.80°C, respectively, and 90.80 min, and 350 mg L -1 initial lead(II) concentration for both adsorbents. Under these conditions, maximum adsorption capacities of ZU and ZN for lead (II) were 293.38 mg g -1 and 321.85 mg g -1 , respectively.

Removal of nickel from aqueous solution using supported zeolite-Y hollow fiber membranes.

PubMed

Muhamad, Norfazilah; Abdullah, Norfazliana; Rahman, Mukhlis A; Abas, Khairul Hamimah; Aziz, Azian Abd; Othman, Mohd Hafiz Dzarfan; Jaafar, Juhana; Ismail, Ahmad Fauzi

2018-05-02

This work describes the development of supported zeolite-Y membranes, prepared using the hydrothermal method, for the removal of nickel from an aqueous solution. Alumina hollow fibers prepared using the phase inversion and sintering technique were used as an inert support. The supported zeolite-Y membranes were characterized using the field emission scanning electron microscope (FESEM), X-ray diffraction (XRD), and the water permeation and rejection test. The performance of the supported zeolite-Y membranes for heavy metal removal using batch adsorption and filtration test was studied using the atomic absorption spectroscopy (AAS). The adsorption study shows that the removal of nickel was pH-dependent but affected by the presence of α-alumina. The seeded zeolite-Y membrane gave the highest adsorption capacity which was 126.2 mg g -1 . This enabled the membrane to remove 63% of nickel ions from the aqueous solution within 180 min of contact time. The adsorption mechanism of nickel onto the zeolite-Y membrane was best fitted to the Freundlich isotherm. The kinetic study concluded that the adsorption was best fitted to pseudo-second-order model with higher correlation coefficient (R 2  = 0.9996). The filtration study proved that the zeolite-Y membrane enabled to reduce the concentration of heavy metal at parts per billion level.

Sequestration of toxic Pb(II) ions by chemically treated rubber (Hevea brasiliensis) leaf powder.

PubMed

Kamal, Megat Hanafiah Megat Ahmad; Azira, Wan Mat Khalir Wan Khaima; Kasmawati, Mohamed; Haslizaidi, Zakaria; Saime, Wan Ngah Wan

2010-01-01

Rubber leaf powder (an agricultural waste) was treated with potassium permanganate followed by sodium carbonate and its performance in the removal of Pb(II) ions from aqueous solution was evaluated. The interactions between Pb(II) ions and functional groups on the adsorbent surface were confirmed by Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM) coupled with X-ray energy dispersive spectroscopy (EDX). The effects of several important parameters which can affect adsorption capacity such as pH, adsorbent dosage, initial lead concentration and contact time were studied. The optimum pH range for lead adsorption was 4-5. Even at very low adsorbent dosage of 0.02 g, almost 100% of Pb(II) ions (23 mg/L) could be removed. The adsorption capacity was also dependent on lead concentration and contact time, and relatively a short period of time (60-90 min) was required to reach equilibrium. The equilibrium data were analyzed with Langmuir, Freundlich and Dubinin-Radushkevich isotherms. Based on Langmuir model, the maximum adsorption capacity of lead was 95.3 mg/g. Three kinetic models including pseudo first-order, pseudo second-order and Boyd were used to analyze the lead adsorption process, and the results showed that the pseudo second-order fitted well with correlation coefficients greater than 0.99.

Critical analysis of adsorption data statistically

NASA Astrophysics Data System (ADS)

Kaushal, Achla; Singh, S. K.

2017-10-01

Experimental data can be presented, computed, and critically analysed in a different way using statistics. A variety of statistical tests are used to make decisions about the significance and validity of the experimental data. In the present study, adsorption was carried out to remove zinc ions from contaminated aqueous solution using mango leaf powder. The experimental data was analysed statistically by hypothesis testing applying t test, paired t test and Chi-square test to (a) test the optimum value of the process pH, (b) verify the success of experiment and (c) study the effect of adsorbent dose in zinc ion removal from aqueous solutions. Comparison of calculated and tabulated values of t and χ 2 showed the results in favour of the data collected from the experiment and this has been shown on probability charts. K value for Langmuir isotherm was 0.8582 and m value for Freundlich adsorption isotherm obtained was 0.725, both are <1, indicating favourable isotherms. Karl Pearson's correlation coefficient values for Langmuir and Freundlich adsorption isotherms were obtained as 0.99 and 0.95 respectively, which show higher degree of correlation between the variables. This validates the data obtained for adsorption of zinc ions from the contaminated aqueous solution with the help of mango leaf powder.

Kinetics and Mechanisms of Phosphorus Adsorption in Soils from Diverse Ecological Zones in the Source Area of a Drinking-Water Reservoir

PubMed Central

Zhang, Liang; Loáiciga, Hugo A.; Xu, Meng; Du, Chao; Du, Yun

2015-01-01

On-site soils are increasingly used in the treatment and restoration of ecosystems to harmonize with the local landscape and minimize costs. Eight natural soils from diverse ecological zones in the source area of a drinking-water reservoir in central China are used as adsorbents for the uptake of phosphorus from aqueous solutions. The X-ray fluorescence (XRF) spectrometric and BET (Brunauer-Emmett-Teller) tests and the Scanning Electron Microscopy (SEM) and Fourier Transform Infrared (FTIR) spectral analyses are carried out to investigate the soils’ chemical properties and their potential changes with adsorbed phosphorous from aqueous solutions. The intra-particle diffusion, pseudo-first-order, and pseudo-second-order kinetic models describe the adsorption kinetic processes. Our results indicate that the adsorption processes of phosphorus in soils occurred in three stages and that the rate-controlling steps are not solely dependent on intra-particle diffusion. A quantitative comparison of two kinetics models based on their linear and non-linear representations, and using the chi-square (χ2) test and the coefficient of determination (r2), indicates that the adsorptive properties of the soils are best described by the non-linear pseudo-second-order kinetic model. The adsorption characteristics of aqueous phosphorous are determined along with the essential kinetic parameters. PMID:26569278

Adsorption of Pb2+ ions on novel ternary nanocomposite of tin, iron and titania

NASA Astrophysics Data System (ADS)

Rehman, Mahfooz ur; Rehman, Wajid; Waseem, Muhammad; Haq, Sirajul; Hussain Shah, Khizar; Kang, Peng

2018-02-01

In this study, ternary nanocomposite (TNC) was synthesized by microemulsion method by taking Sn, Ti and Fe in (1:1:1) molar ratio. The BET surface area and pore size were measured by nitrogen adsorption method. The morphological features of TNC like particle size, elemental percentage and crystallite size were studied by scanning electron microscopy (SEM), energy dispersive x-rays (EDX) and x-rays diffraction (XRD) respectively, whereas the surface functional groups were detected by Fourier Transform Infrared (FTIR) spectroscopy. The crystallite size was found to be 11 nm, calculated from FWHM of diffraction peak with relative intensity 100%. For the thermal stability of TNC, thermogravimetric analysis (TGA) was performed. Batch adsorption tests were used for the removal of Pb2+ ions from aqueous solutions. The maximum adsorption capacity in this study was found to be 79.56 mg g-1 at 40 °C which is promising than the values reported in the literature. Based on the regression coefficient (r 2), the adsorption data was found well fitted to the Langmuir as compared to Freundlich model. The exchange of a single proton with every Pb2+ ion was calculated. Thermodynamic parameters were indicative for the sorption process to be endothermic and spontaneous.

Adsorptive removal of Cu(II) from aqueous solution and industrial effluent using natural/agricultural wastes.

PubMed

Singha, Biswajit; Das, Sudip Kumar

2013-07-01

The potentiality of low cost natural/agricultural waste biomasses for the removal of Cu(II) ion from aqueous solution has been investigated in batch experiments. The effect of various physico-chemical parameters such as initial pH, initial Cu(II) concentration, adsorbent dosage, contact time and temperature has been studied. The optimum pH for adsorption was found to be 6 for all adsorbents used. Kinetics data were best described by the pseudo-2nd-order model. The experimental data were fitted well with Freundlich and Halsey isotherm models. The diffusion coefficient and sorption energy indicated that the adsorption process was chemical in nature. Thermodynamic parameters such as ΔG°, ΔH° and ΔS° were calculated, and it was observed that the adsorption process was spontaneous and endothermic. The mean sorption energy was calculated using Dubinin-Radushkevich isotherm model and it confirmed that the sorption process was chemical in nature. Different active functional groups were identified by FTIR studies which were responsible for Cu(II) ion adsorption process. Application study using electroplating industrial waste water and regeneration experiment of the adsorbent were also investigated. Design procedure for the batch process was also reported. Copyright © 2013 Elsevier B.V. All rights reserved.

Multiparameter Analysis of Gas Transport Phenomena in Shale Gas Reservoirs: Apparent Permeability Characterization.

PubMed

Shen, Yinghao; Pang, Yu; Shen, Ziqi; Tian, Yuanyuan; Ge, Hongkui

2018-02-08

The large amount of nanoscale pores in shale results in the inability to apply Darcy's law. Moreover, the gas adsorption of shale increases the complexity of pore size characterization and thus decreases the accuracy of flow regime estimation. In this study, an apparent permeability model, which describes the adsorptive gas flow behavior in shale by considering the effects of gas adsorption, stress dependence, and non-Darcy flow, is proposed. The pore size distribution, methane adsorption capacity, pore compressibility, and matrix permeability of the Barnett and Eagle Ford shales are measured in the laboratory to determine the critical parameters of gas transport phenomena. The slip coefficients, tortuosity, and surface diffusivity are predicted via the regression analysis of the permeability data. The results indicate that the apparent permeability model, which considers second-order gas slippage, Knudsen diffusion, and surface diffusion, could describe the gas flow behavior in the transition flow regime for nanoporous shale. Second-order gas slippage and surface diffusion play key roles in the gas flow in nanopores for Knudsen numbers ranging from 0.18 to 0.5. Therefore, the gas adsorption and non-Darcy flow effects, which involve gas slippage, Knudsen diffusion, and surface diffusion, are indispensable parameters of the permeability model for shale.

H2S adsorption by municipal solid waste incineration (MSWI) fly ash with heavy metals immobilization.

PubMed

Wu, Huanan; Zhu, Yu; Bian, Songwei; Ko, Jae Hac; Li, Sam Fong Yau; Xu, Qiyong

2018-03-01

As a byproduct of municipal solid waste incineration (MSWI) plant, fly ash is becoming a challenge for waste management in recent years. In this study, MSWI fly ash (FA) was evaluated for the potential capacity of odorous gas H 2 S removal. Results showed that fly ash demonstrated longer breakthrough time and higher H 2 S capacities than coal fly ash and sandy soil, due to its high content of alkali oxides of metals including heavy metals. H 2 S adsorption capacities of FA1 and FA2 were 15.89 and 12.59 mg H 2 S/g, respectively for 750 ppm H 2 S. The adsorption of H 2 S on fly ash led to formation of elemental sulfur and metal sulfide. More importantly, the formation of metal sulfide significantly reduced the leachability of heavy metals, such as Cr, Cu, Cd and Pb as shown by TCLP tests. The adsorption isotherms fit well with Langmuir model with the correlation coefficient over 0.99. The adsorption of H 2 S on fly ash features simultaneous H 2 S removal and stabilization and heavy metals found in most MSWI fly ash, making fly ash the potential low cost recycled sorbent material. Copyright © 2017 Elsevier Ltd. All rights reserved.

Kinetic and isotherm modeling of Cd (II) adsorption by L-cysteine functionalized multi-walled carbon nanotubes as adsorbent.

PubMed

Taghavi, Mahmoud; Zazouli, Mohammad Ali; Yousefi, Zabihollah; Akbari-adergani, Behrouz

2015-11-01

In this study, multi-walled carbon nanotubes were functionalized by L-cysteine to show the kinetic and isotherm modeling of Cd (II) ions onto L-cysteine functionalized multi-walled carbon nanotubes. The adsorption behavior of Cd (II) ion was studied by varying parameters including dose of L-MWCNTs, contact time, and cadmium concentration. Equilibrium adsorption isotherms and kinetics were also investigated based on Cd (II) adsorption tests. The results showed that an increase in contact time and adsorbent dosage resulted in increase of the adsorption rate. The optimum condition of the Cd (II) removal process was found at pH=7.0, 15 mg/L L-MWCNTs dosage, 6 mg/L cadmium concentration, and contact time of 60 min. The removal percent was equal to 89.56 at optimum condition. Langmuir and Freundlich models were employed to analyze the experimental data. The data showed well fitting with the Langmuir model (R2=0.994) with q max of 43.47 mg/g. Analyzing the kinetic data by the pseudo-first-order and pseudo-second-order equations revealed that the adsorption of cadmium using L-MWSNTs following the pseudo-second-order kinetic model with correlation coefficients (R2) equals to 0.998, 0.992, and 0.998 for 3, 6, and 9 mg/L Cd (II) concentrations, respectively. The experimental data fitted very well with the pseudo-second-order. Overall, treatment of polluted solution to Cd (II) by adsorption process using L-MWCNT can be considered as an effective technology.

Adsorption of lignite-derived humic acids on coal-based mesoporous activated carbons.

PubMed

Lorenc-Grabowska, Ewa; Gryglewicz, Grazyna

2005-04-15

The adsorption by a coal-based mesoporous activated carbon of humic acids (HAs) isolated from two Polish lignites was studied. For comparison, a commercial Aldrich humic acid was also included into this study. The differences in chemical structure and functional groups of HAs were determined by elemental analysis and infrared spectroscopy DRIFT. Two activated carbons used differed in terms of mesopore volume, mesopore size distribution, and chemical properties of the surface. The kinetics of adsorption of HAs have been discussed using three kinetic models, i.e., the first-order Lagergren model, the pseudo-second-order model, and the intraparticle diffusion model. It was found that the adsorption of HAs from alkaline solution on mesoporous activated carbon proceeds according to the pseudo-second-order model. The correlation coefficients were close to 1. The intraparticle diffusion of HA molecules within the carbon particle was identified to be the rate-limiting step. Comparing the two activated carbons, the carbon with a higher volume of pores with widths of 10-50 nm showed a greater removal efficiency of HA. An increase in the Freundlich adsorption capacity with decreasing carbon content of HA was observed. Among the HAs studied, S-HA shows characteristics indicating the highest contribution of small-size fraction. The S-HA was removed by both activated carbons to the highest extent. The effect of pH solution on the adsorption of HA was examined over the range pH 5.4-12.2. It was found that the extent of adsorption decreased with decreasing pH of the solution.

Modeling the effect of adsorption on the degradation rate of propiconazole in profiles of Polish Luvisols.

PubMed

Paszko, Tadeusz; Jankowska, Monika

2018-06-18

Laboratory adsorption and degradation studies were carried out to determine the effect of time-dependent adsorption on propiconazole degradation rates in samples from three Polish Luvisols. Strong propiconazole adsorption (organic carbon normalized adsorption coefficients K oc in the range of 1217-7777 mL/g) was observed in batch experiments, with a typical biphasic mechanism with a fast initial step followed by the time-dependent step, which finished within 48 h in the majority of soils. The time-dependent step observed in incubation experiments was longer (duration from 5 to 23 d), and its contribution to total adsorption was from 20% to 34%. The half-lives obtained at 25 °C and 40% maximum water holding capacity of soil, were in the range of 34.7-112.9 d in the Ap horizon and in the range of 42.3-448.8 d for subsoils. The very strong correlations, between degradation rates in pore water and soil organic carbon and soil microbial activity, indicated that microbial degradation of propiconazole was most likely the only significant process responsible for the decay of this compound under aerobic conditions for the whole of the examined soil profiles. Modeling of the processes showed that only models coupling adsorption and degradation were able to correctly describe the experimental data. The analysis of the bioavailability factor values showed that degradation was not limited by the rate of propiconazole desorption from soil, but sorption affected the degradation rate by decreasing its availability for microorganisms. Copyright © 2018. Published by Elsevier Inc.

Adsorption of methyl green dye onto multi-walled carbon nanotubes decorated with Ni nanoferrite

NASA Astrophysics Data System (ADS)

Bahgat, Mohamed; Farghali, Ahmed Ali; El Rouby, Waleed; Khedr, Mohamed; Mohassab-Ahmed, Mohassab Y.

2013-06-01

This research was carried out to evaluate the capability of multi-walled carbon nanotubes (CNTs) and NiFe2O4-decorated multi-walled carbon nanotubes (NiFe2O4-CNTs) toward waste water treatment relevant to organic dyes. CNTs were prepared via chemical vapor deposition method. NiFe2O4-CNTs were prepared by in-situ chemical precipitation of metal hydroxides followed by hydrothermal processing. The samples were characterized using XRD and TEM. The adsorption efficiency of CNTs and NiFe2O4-CNTs of methyl green dye at various temperatures was examined. The adsorbed amount increased with the CNTs and NiFe2O4-CNTs dosage. The linear correlation coefficients and standard deviations of Langmuir and Freundlich isotherms were determined. It was found that Langmuir isotherm fitted the experimental results well in both adsorption cases n of methyl green onto CNTs and NiFe2O4-CNTs. Kinetics analyses were conducted using pseudo first-order, second-order and the intraparticle diffusion models. The results showed that the adsorption kinetics was controlled by a pseudo second-order model for adsorption of methyl green onto CNTs and best controlled by pseudo first-order in case of NiFe2O4-CNTs. Changes in the free energy of adsorption (Δ G°), enthalpy (Δ H°), entropy (Δ S°), and the activation energy ( E a) were determined. The Δ H°, Δ G° and E a values indicated that the adsorption of methyl green onto MWCNTs and NiFe2O4-MWCNTs was physisorption.

A batch adsorption study on bentonite clay Pertinence to transport modeling?

NASA Astrophysics Data System (ADS)

BOURG, I.; BOURG, A. C.; SPOSITO, G.

2001-12-01

Bentonite clay is often used as a component of engineered barriers for the isolation of high-level toxic wastes. This swelling clay is used for its physical (impermeability, self-healing) but also for its chemical properties, mostly a high cation exchange capacity (CEC). The adsorbed cations being temporarily immobilized, this should slow down the release of cations from the waste to the surrounding environment. In order to assess the performance of the engineered barrier, the partitioning of solutes between the liquid and solid phases needs to be quantified for use in transport models. The usual method for characterizing the adsorption is through batch adsorption experiments on dispersed suspensions of the solid, yielding an adsorption isotherm (adsorbed concentration vs. dissolved concentration). This isotherm however should be a function of various environmental variables (e.g., pH, ionic strength, concentrations of various ligands and competing adsorbents), so that extrapolation of lab data to performance assessment in the field is problematic. We present results from a study of the adsorption of cesium, strontium, cadmium and lead on dispersed suspensions of the standard BX-80 bentonite. Through a wide range of experimental parameters (pH, ionic strength, reaction time, reactor open or closed to the atmosphere, study of a range of cations of differing properties), we seek a mechanistic interpretation of the results instead of an empirical determination of adsorption parameters. Depending on the mechanisms that control the adsorption in different experimental ranges, we discuss the degree to which the partitioning coefficient (Kd) obtained in the lab can be extrapolated to a transport model through compacted bentonite in a natural environment.

Adsorption-desorption of oxytetracycline on marine sediments: Kinetics and influencing factors.

PubMed

Li, Jia; Zhang, Hua

2016-12-01

To reveal the kinetics and mechanisms of antibiotic adsorption/desorption processes, batch and stirred flow chamber (SFC) experiments were carried out with oxytetracycline (OTC) on two marine sediments. The OTC adsorption capacities of the marine sediments were relatively weak and related to their organic carbon (OC) and contents of fine particles. Sorption isotherms of OTC on marine sediment can be well described by both the Langmuir and Freundlich models. Langmuir adsorption maxima (q max ) and Freundlich distribution coefficients (K f ) increased with the decrease of salinity and pH, which indicated the importance of variable charged sites on sediment surfaces. A second order kinetic model successfully described adsorption and desorption kinetics of OTC and well reproduced the concentration change during stop-flow. The adsorption kinetic rates (k a ) for OTC under different experimental conditions ranged from 2.00 × 10 -4 to 1.97 × 10 -3  L (mg min) -1 . Results of SFC experiments indicated that diffusive mass transfer was the dominant mechanism of the time-dependent adsorption of OTC and its release from marine sediment was mildly hysteretic. The high desorption percentage (43-75% for LZB and 58-75% for BHB) implied that binding strength of OTC on two marine sediments was weak. In conclusion, marine sediment characteristics and environmental factors such as salinity, pH, and flow rate are critical factors determine extent of OTC sorption on marine sediment and need to be incorporated in modeling fate and transport of OTC in marine environment. Copyright © 2016 Elsevier Ltd. All rights reserved.

Adsorption of Anionic, Cationic and Nonionic Surfactants on Carbonate Rock in Presence of ZrO 2 Nanoparticles

NASA Astrophysics Data System (ADS)

Esmaeilzadeh, Pouriya; Bahramian, Alireza; Fakhroueian, Zahra

The adsorption of surfactants at the solid-water interface is important for the control of wetting, lubrication, detergency and in mineral flotation.We have studied the adsorptions of different types of surfactants, cationic (Dodecyl trimethylammonium bromide, DTAB), anionic (sodium dodecyl sulfate, SDS) and non-anionic (lauryl alcohol-7 mole ethoxylate, LA7) on carbonate rock in presence of zirconium oxide spherical nanoparticles (17-19 nm). ZrO2 nanoparticles with tetrahedral structure have significant effect on adsorption of surfactants on the carbonate rock. We have used the measured conductivities to determine the rate of adsorption of surfactants at rock-water interfaces. The conductivity of DTAB in aqueous solutions containing calcite powder decreases more than the other surfactants in contact with ZrO2 nanoparticles. We have also investigated the adsorption of surfactants at the air-water interface. The presence of nanoparticles, as demonstrated by our experiments, enhances the surface activity and surface adsorption of the surfactants through electrostatic forces or formation of nanostructures. Dynamic light structuring data shows similar aggregation number of nanoparticles in presence of nanoparticles.

The studies on gas adsorption properties of MIL-53 series MOFs materials

NASA Astrophysics Data System (ADS)

Jiao, Yuqiu; Li, Zhenyu; Ma, Yue; Zhou, Guanggang; Wang, Shuangxi; Lu, Guiwu

2017-08-01

Molecular dynamics (MD), grand canonical Monte Carlo (GCMC) and ideal adsorbed solution theory (IAST) were used to study the structures and gas adsorption properties of MIL-53(M)[M=Cr, Fe, Sc, Al] metal organic framework (MOF) materials. The results show that the volumes of those MOF materials increase significantly at high temperature. By analyzing the adsorption isotherms, we found that the temperature had a paramount effect on the gas adsorption behaviors of these MOF materials. For MIL-53(Cr), the orders of the quantities of adsorbed gases were CH4>N2>CO2>H2S, CH4>H2S>CO2>N2 and CH4>CO2>H2S>N2 at 100K, 293K and 623K, respectively. We also calculated the adsorption of several combinations of two gases by MIL-53(Cr) at 293K, the results indicate that the material had selective adsorption of CH4 over CO2, H2S and N2. Our calculations provide microscopic insights into the gas adsorption performances of these MOFs and may further guide the practice of gas separation.

Molecular simulation of hydrophobin adsorption at an oil-water interface.

PubMed

Cheung, David L

2012-06-12

Hydrophobins are small, amphiphilic proteins expressed by strains of filamentous fungi. They fulfill a number of biological functions, often related to adsorption at hydrophobic interfaces, and have been investigated for a number of applications in materials science and biotechnology. In order to understand the biological function and applications of these proteins, a microscopic picture of the adsorption of these proteins at interfaces is needed. Using molecular dynamics simulations with a chemically detailed coarse-grained potential, the behavior of typical hydrophobins at the water-octane interface is studied. Calculation of the interfacial adsorption strengths indicates that the adsorption is essentially irreversible, with adsorption strengths of the order of 100 k(B)T (comparable to values determined for synthetic nanoparticles but significantly larger than small molecule surfactants and biomolecules). The protein structure at the interface is unchanged at the interface, which is consistent with the biological function of these proteins. Comparison of native proteins with pseudoproteins that consist of uniform particles shows that the surface structure of these proteins has a large effect on the interfacial adsorption strengths, as does the flexibility of the protein.

Surface modification of pitch-based spherical activated carbon by CVD of NH 3 to improve its adsorption to uric acid

NASA Astrophysics Data System (ADS)

Liu, Chaojun; Liang, Xiaoyi; Liu, Xiaojun; Wang, Qin; Zhan, Liang; Zhang, Rui; Qiao, Wenming; Ling, Licheng

2008-08-01

Surface chemistry of pitch-based spherical activated carbon (PSAC) was modified by chemical vapor deposition of NH 3 (NH 3-CVD) to improve the adsorption properties of uric acid. The texture and surface chemistry of PSAC were studied by N 2 adsorption, pH PZC (point of zero charge), acid-base titration and X-ray photoelectron spectroscopy (XPS). NH 3-CVD has a limited effect on carbon textural characteristics but it significantly changed the surface chemical properties, resulting in positive effects on uric acid adsorption. After modification by NH 3-CVD, large numbers of nitrogen-containing groups (especially valley-N and center-N) are introduced on the surface of PSAC, which is responsible for the increase of pH PZC, surface basicity and uric acid adsorption capacity. Pseudo-second-order kinetic model can be used to describe the dynamic adsorption of uric acid on PSAC, and the thermodynamic parameters show that the adsorption of uric acid on PSAC is spontaneous, endothermic and irreversible process in nature.

Real-time single-molecule observations of proteins at the solid-liquid interface

NASA Astrophysics Data System (ADS)

Langdon, Blake Brianna

Non-specific protein adsorption to solid surfaces is pervasive and observed across a broad spectrum of applications including biomaterials, separations, pharmaceuticals, and biosensing. Despite great interest in and considerable literature dedicated to the phenomena, a mechanistic understanding of this complex phenomena is lacking and remains controversial, partially due to the limits of ensemble-averaging techniques used to study it. Single-molecule tracking (SMT) methods allow us to study distinct protein dynamics (e.g. adsorption, desorption, diffusion, and intermolecular associations) on a molecule-by-molecule basis revealing the protein population and spatial heterogeneity inherent in protein interfacial behavior. By employing single-molecule total internal reflection fluorescence microscopy (SM-TIRFM), we have developed SMT methods to directly observe protein interfacial dynamics at the solid-liquid interface to build a better mechanistic understanding of protein adsorption. First, we examined the effects of surface chemistry (e.g. hydrophobicity, hydrogen-bonding capacity), temperature, and electrostatics on isolated protein desorption and interfacial diffusion for fibrinogen (Fg) and bovine serum albumin (BSA). Next, we directly and indirectly probed the effects of protein-protein interactions on interfacial desorption, diffusion, aggregation, and surface spatial heterogeneity on model and polymeric thin films. These studies provided many useful insights into interfacial protein dynamics including the following observations. First, protein adsorption was reversible, with the majority of proteins desorbing from all surface chemistries within seconds. Isolated protein-surface interactions were relatively weak on both hydrophobic and hydrophilic surfaces (apparent desorption activation energies of only a few kBT). However, proteins could dynamically and reversibly associate at the interface, and these interfacial associations led to proteins remaining on the surface for longer time intervals. Surface chemistry and surface spatial heterogeneity (i.e. surface sites with different binding strengths) were shown to influence adsorption, desorption, and interfacial protein-protein associations. For example, faster protein diffusion on hydrophobic surfaces increased protein-protein associations and, at higher protein surface coverage, led to proteins remaining on hydrophobic surfaces longer than on hydrophilic surfaces. Ultimately these studies suggested that surface properties (chemistry, heterogeneity) influence not only protein-surface interactions but also interfacial mobility and protein-protein associations, implying that surfaces that better control protein adsorption can be designed by accounting for these processes.

Development of a bar adsorptive micro-extraction-large-volume injection-gas chromatography-mass spectrometric method for pharmaceuticals and personal care products in environmental water matrices.

PubMed

Neng, N R; Nogueira, J M F

2012-01-01

The combination of bar adsorptive micro-extraction using activated carbon (AC) and polystyrene-divinylbenzene copolymer (PS-DVB) sorbent phases, followed by liquid desorption and large-volume injection gas chromatography coupled to mass spectrometry, under selected ion monitoring mode acquisition, was developed for the first time to monitor pharmaceutical and personal care products (PPCPs) in environmental water matrices. Assays performed on 25 mL water samples spiked (100 ng L(-1)) with caffeine, gemfibrozil, triclosan, propranolol, carbamazepine and diazepam, selected as model compounds, yielded recoveries ranging from 74% to 99% under optimised experimental conditions (equilibrium time, 16 h (1,000 rpm); matrix characteristics: pH 5, 5% NaCl for AC phase; LD: methanol/acetonitrile (1:1), 45 min). The analytical performance showed good precision (RSD < 18%), convenient detection limits (5-20 ng L(-1)) and excellent linear dynamic range (20-800 ng L(-1)) with remarkable determination coefficients (r(2) > 0.99), where the PS-DVB sorbent phase showed a much better efficiency. By using the standard addition methodology, the application of the present analytical approach on tap, ground, sea, estuary and wastewater samples allowed very good performance at the trace level. The proposed method proved to be a suitable sorption-based micro-extraction alternative for the analysis of priority pollutants with medium-polar to polar characteristics, showing to be easy to implement, reliable, sensitive and requiring a low sample volume to monitor PPCPs in water matrices.

Enhancement for trace analysis of sulfonamide antibiotics in water matrices using bar adsorptive microextraction (BAμE).

PubMed

Ide, A H; Ahmad, S M; Neng, N R; Nogueira, J M F

2016-09-10

In this study, the enhancement for trace analysis of sulfonamide antibiotics (sulfathiazole, sulfamethoxazole and sulfadimethoxine) and trimethoprim in water matrices is proposed using bar adsorptive microextraction combined with micro-liquid desorption followed by high-performance liquid chromatography with diode array detection (BAμE-μLD/HPLC-DAD). By comparing different polymers and activated carbons as sorbent coatings for BAμE, the polystyrene-divinylbenzene polymer (PS-DVB) showed the best selectivity for the compounds under study. Assays performed through BAμE(PS-DVB)-μLD on 25mL of ultrapure water samples spiked at the 8.0μgL(-1) level showed recoveries ranging from 63.8±1.5% to 84.2±1.9%, under optimized experimental conditions. The validated method provided satisfactory limits of detection (0.08-0.16μgL(-1)) and good linear dynamic ranges (0.16-8.00μgL(-1)) with determination coefficients higher than 0.9958. The proposed analytical methodology was applied to real matrices, such as tap, estuarine and wastewater samples using the standard addition method. It showed to be easy to implement, with good reproducibility, sensitivity and requiring small amount of sample. Furthermore, negligible consumption of organic solvents was used in compliance with the green analytical chemistry principles. When compared to other well-established microextraction approaches, BAμE demonstrated better performance concerning recovery yields and sensitivity. Copyright © 2016 Elsevier B.V. All rights reserved.

Molecular dynamics simulations of adsorption and diffusion of gases in silicon-carbide nanotubes.

PubMed

Malek, Kourosh; Sahimi, Muhammad

2010-01-07

Silicon carbide nanotubes (SiCNTs) are new materials with excellent properties, such as high thermal stability and mechanical strength, which are much improved over those of their carboneous counterparts, namely, carbon nanotubes (CNTs). Gas separation processes at high temperatures and pressures may be improved by developing mixed-matrix membranes that contain SiCNTs. Such nanotubes are also of interest in other important processes, such as hydrogen production and its storage, as well as separation by supercritical adsorption. The structural parameters of the nanotubes, i.e., their diameter, curvature, and chirality, as well as the interaction strength between the gases and the nanotubes' walls, play a fundamental role in efficient use of the SiCNTs in such processes. We employ molecular dynamics simulations in order to examine the adsorption and diffusion of N(2), H(2), CO(2), CH(4), and n-C(4)H(10) in the SiCNTs, as a function of the pressure and the type of the nanotubes, namely, the zigzag, armchair, and chiral tubes. The simulations indicate the strong effect of the nanotubes' chirality and curvature on the pressure dependence of the adsorption isotherms and the self-diffusivities. Detailed comparison is made between the results and those for the CNTs. In particular, we find that the adsorption capacity of the SiCNTs for hydrogen is higher than the CNTs' under the conditions that we have studied.

Molecular dynamics simulations of adsorption and diffusion of gases in silicon-carbide nanotubes

NASA Astrophysics Data System (ADS)

Malek, Kourosh; Sahimi, Muhammad

2010-01-01

Silicon carbide nanotubes (SiCNTs) are new materials with excellent properties, such as high thermal stability and mechanical strength, which are much improved over those of their carboneous counterparts, namely, carbon nanotubes (CNTs). Gas separation processes at high temperatures and pressures may be improved by developing mixed-matrix membranes that contain SiCNTs. Such nanotubes are also of interest in other important processes, such as hydrogen production and its storage, as well as separation by supercritical adsorption. The structural parameters of the nanotubes, i.e., their diameter, curvature, and chirality, as well as the interaction strength between the gases and the nanotubes' walls, play a fundamental role in efficient use of the SiCNTs in such processes. We employ molecular dynamics simulations in order to examine the adsorption and diffusion of N2, H2, CO2, CH4, and n-C4H10 in the SiCNTs, as a function of the pressure and the type of the nanotubes, namely, the zigzag, armchair, and chiral tubes. The simulations indicate the strong effect of the nanotubes' chirality and curvature on the pressure dependence of the adsorption isotherms and the self-diffusivities. Detailed comparison is made between the results and those for the CNTs. In particular, we find that the adsorption capacity of the SiCNTs for hydrogen is higher than the CNTs' under the conditions that we have studied.

Chemo-mechanical coupling in kerogen gas adsorption/desorption.

PubMed

Ho, Tuan Anh; Wang, Yifeng; Criscenti, Louise J

2018-05-09

Kerogen plays a central role in hydrocarbon generation in an oil/gas reservoir. In a subsurface environment, kerogen is constantly subjected to stress confinement or relaxation. The interplay between mechanical deformation and gas adsorption of the materials could be an important process for shale gas production but unfortunately is poorly understood. Using a hybrid Monte Carlo/molecular dynamics simulation, we show here that a strong chemo-mechanical coupling may exist between gas adsorption and mechanical strain of a kerogen matrix. The results indicate that the kerogen volume can expand by up to 5.4% and 11% upon CH4 and CO2 adsorption at 192 atm, respectively. The kerogen volume increases with gas pressure and eventually approaches a plateau as the kerogen becomes saturated. The volume expansion appears to quadratically increase with the amount of gas adsorbed, indicating a critical role of the surface layer of gas adsorbed in the bulk strain of the material. Furthermore, gas uptake is greatly enhanced by kerogen swelling. Swelling also increases the surface area, porosity, and pore size of kerogen. Our results illustrate the dynamic nature of kerogen, thus questioning the validity of the current assumption of a rigid kerogen molecular structure in the estimation of gas-in-place for a shale gas reservoir or gas storage capacity for subsurface carbon sequestration. The coupling between gas adsorption and kerogen matrix deformation should be taken into consideration.

Switchable Chiral Selection of Aspartic Acids by Dynamic States of Brushite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiang, Wenge; Pan, Haihua; Zhang, Zhisen

Here, we show the chiral recognition and separation of aspartic acid (Asp) enantiomers by achiral brushite due to the asymmetries of their dynamical steps in its nonequilibrium states. Growing brushite has a higher adsorption affinity to d-Asp, while l-Asp is predominant on the dissolving brushite surface. Microstructural characterization reveals that chiral selection is mainly attributed to brushite [101] steps, which exhibit two different configurations during crystal growth and dissolution, respectively, with each preferring a distinct enantiomer due to this asymmetry. Because these transition step configurations have different stabilities, they subsequently result in asymmetric adsorption. Furthermore, by varying free energy barriersmore » through solution thermodynamic driving force (i.e., supersaturation), the dominant nonequilibrium intermediate states can be switched and chiral selection regulated. This finding highlights that the dynamic steps can be vital for chiral selection, which may provide a potential pathway for chirality generation through the dynamic nature.« less

Switchable Chiral Selection of Aspartic Acids by Dynamic States of Brushite

DOE PAGES

Jiang, Wenge; Pan, Haihua; Zhang, Zhisen; ...

2017-06-15

Here, we show the chiral recognition and separation of aspartic acid (Asp) enantiomers by achiral brushite due to the asymmetries of their dynamical steps in its nonequilibrium states. Growing brushite has a higher adsorption affinity to d-Asp, while l-Asp is predominant on the dissolving brushite surface. Microstructural characterization reveals that chiral selection is mainly attributed to brushite [101] steps, which exhibit two different configurations during crystal growth and dissolution, respectively, with each preferring a distinct enantiomer due to this asymmetry. Because these transition step configurations have different stabilities, they subsequently result in asymmetric adsorption. Furthermore, by varying free energy barriersmore » through solution thermodynamic driving force (i.e., supersaturation), the dominant nonequilibrium intermediate states can be switched and chiral selection regulated. This finding highlights that the dynamic steps can be vital for chiral selection, which may provide a potential pathway for chirality generation through the dynamic nature.« less

Tracer counterpermeation analysis of diffusivity in finite-length nanopores with and without single-file dynamics

DOE PAGES

Ackerman, David M.; Evans, James W.

2017-01-19

Here, we perform a tracer counterpermeation (TCP) analysis for a stochastic model of diffusive transport through a narrow linear pore where passing of species within the pore is inhibited or even excluded (single-file diffusion). TCP involves differently labeled but otherwise identical particles from two decoupled infinite reservoirs adsorbing into opposite ends of the pore, and desorbing from either end. In addition to transient behavior, we assess steady-state concentration profiles, spatial correlations, particle number fluctuations, and diffusion fluxes through the pore. From the profiles and fluxes, we determine a generalized tracer diffusion coefficient D tr(x), at various positions x within themore » pore. D tr(x) has a plateau value in the pore center scaling inversely with the pore length, but it is enhanced near the pore openings. The latter feature reflects the effect of fluctuations in adsorption and desorption, and it is also associated with a nontrivial scaling of the concentration profiles near the pore openings.« less

Tracer counterpermeation analysis of diffusivity in finite-length nanopores with and without single-file dynamics

NASA Astrophysics Data System (ADS)

Ackerman, David M.; Evans, James W.

2017-01-01

We perform a tracer counterpermeation (TCP) analysis for a stochastic model of diffusive transport through a narrow linear pore where passing of species within the pore is inhibited or even excluded (single-file diffusion). TCP involves differently labeled but otherwise identical particles from two decoupled infinite reservoirs adsorbing into opposite ends of the pore, and desorbing from either end. In addition to transient behavior, we assess steady-state concentration profiles, spatial correlations, particle number fluctuations, and diffusion fluxes through the pore. From the profiles and fluxes, we determine a generalized tracer diffusion coefficient Dtr(x ) , at various positions x within the pore. Dtr(x ) has a plateau value in the pore center scaling inversely with the pore length, but it is enhanced near the pore openings. The latter feature reflects the effect of fluctuations in adsorption and desorption, and it is also associated with a nontrivial scaling of the concentration profiles near the pore openings.

Fibronectin module FN(III)9 adsorption at contrasting solid model surfaces studied by atomistic molecular dynamics.

PubMed

Kubiak-Ossowska, Karina; Mulheran, Paul A; Nowak, Wieslaw

2014-08-21

The mechanism of human fibronectin adhesion synergy region (known as integrin binding region) in repeat 9 (FN(III)9) domain adsorption at pH 7 onto various and contrasting model surfaces has been studied using atomistic molecular dynamics simulations. We use an ionic model to mimic mica surface charge density but without a long-range electric field above the surface, a silica model with a long-range electric field similar to that found experimentally, and an Au {111} model with no partial charges or electric field. A detailed description of the adsorption processes and the contrasts between the various model surfaces is provided. In the case of our model silica surface with a long-range electrostatic field, the adsorption is rapid and primarily driven by electrostatics. Because it is negatively charged (-1e), FN(III)9 readily adsorbs to a positively charged surface. However, due to its partial charge distribution, FN(III)9 can also adsorb to the negatively charged mica model because of the absence of a long-range repulsive electric field. The protein dipole moment dictates its contrasting orientation at these surfaces, and the anchoring residues have opposite charges to the surface. Adsorption on the model Au {111} surface is possible, but less specific, and various protein regions might be involved in the interactions with the surface. Despite strongly influencing the protein mobility, adsorption at these model surfaces does not require wholesale FN(III)9 conformational changes, which suggests that the biological activity of the adsorbed protein might be preserved.

Unraveling the Dynamics of Aminopolymer/Silica Composites

DOE PAGES

Carrillo, Jan-Michael Y.; Sakwa-Novak, Miles A.; Holewinski, Adam; ...

2016-02-25

Branched poly(ethylenimine) (PEI) encapsulated within mesoporous silica (SBA-15), has proven to be an eective sorbent for developing carbon capture technologies. However, the structure-property correlations which govern their adsorptive properties is not well understood. By combining coarse-grained molecular dynamics simulations and neutron scattering experiments we are able to construct, and validate, a detailed model of the dynamics and morphology of the conned polymer within the mesoporous support. By varying the simulation properties we are able to probe, for the rst time, the direct relationship between the structure of the polymer and the non-monotonic dynamics of the polymer as a function ofmore » monomer concentration within an adsorbing cylindrical pore. Overall the simulation results are in good agreement with quasi-elastic neutron scattering (QENS) studies, suggesting an approach that can be a useful guide for understanding how to tune porous polymer composites for enhancing desired dynamical and structural behavior targeting enhanced carbon dioxide adsorption.« less

Modifying Effects of Plasticizer, Chain Connectivity, and Chain Adsorption on the Physical Aging and Interfacial Gradient in Dynamics in Thin Polystyrene Films

NASA Astrophysics Data System (ADS)

Thees, Michael; Roth, Connie

How the glass transition and physical aging in thin films change with confinement is nontrival, with studies in the literature showing that these effects can be modified by various factors including chain adsorption to substrate interfaces and addition of diluents. Some studies indicate that addition of plasticizer appears to eliminate confinement effects such as Tg gradients and possibly impacts chain adsorption to substrates. In contrast, how plasticizer affects physical aging in glassy polymers has been largely unexplored experimentally, despite various theoretical and simulation efforts. Previously we have shown that for neat polystyrene (PS) films, with molecular weights MW < 3000 kg/mol, physical aging rates in thin films decrease with decreasing film thickness consistent with expectations from local Tg gradients. However, we have recently found that for very high molecular weights, MW > 7000 kg/mol, the physical aging rate in thin films was more bulk like, suggesting a diminished gradient in dynamics related to chain connectivity and possibly chain adsorption to the substrate interface. Here, we explore how the addition of dioctyl phthalate (DOP) plasticizer to PS can alter the physical aging rate of thin films and possibly modify the adsorbed layer.

Dynamics, Stability, and Adsorption States of Water on Oxidized RuO 2 (110)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nguyen, Manh-Thuong; Mu, Rentao; Cantu, David C.

Identifying and understanding how excess oxygen atoms affect the adsorption of water on metal oxides is crucial for their use in water splitting. Here, by means of high-resolution scanning tunneling microscopy and density-functional calculations, we show that excess oxygen atoms on the stoichiometric RuO2(110) significantly change the clustering, conformation, and deprotonation equilibrium of adsorbed water. We considered two reactive scenarios during which the stoichiometric surface was exposed to: (i) first to oxygen followed by water, and (ii) first to water followed by oxygen. In both cases the [OH-OH] complex on Ru rows is the dominant species, showing a significant differencemore » from water-only adsorption on the stoichiometric surface in which the [OH-H2O] species is found to be prevalent. Surface reactivity at almost full O coverage is also addressed; there we show that site selectivity of the surface for H adsorption and dissociation of H2O is hindered, notwithstanding the increase of the dynamical motion of both species. We found that the work function of RuO2 can serve as a descriptor for the reactivity of this surface to water and its constituents.« less

Molecular dynamics simulations of cesium adsorption on illite nanoparticles.

PubMed

Lammers, Laura N; Bourg, Ian C; Okumura, Masahiko; Kolluri, Kedarnath; Sposito, Garrison; Machida, Masahiko

2017-03-15

The charged surfaces of micaceous minerals, especially illite, regulate the mobility of the major radioisotopes of Cs ( 134 Cs, 135 Cs, 137 Cs) in the geosphere. Despite the long history of Cs adsorption studies, the nature of the illite surface sites remains incompletely understood. To address this problem, we present atomistic simulations of Cs competition with Na for three candidate illite adsorption sites - edge, basal plane, and interlayer. Our simulation results are broadly consistent with affinities and selectivities that have been inferred from surface complexation models. Cation exchange on the basal planes is thermodynamically ideal, but exchange on edge surfaces and within interlayers shows complex, thermodynamically non-ideal behavior. The basal planes are weakly Cs-selective, while edges and interlayers have much higher affinity for Cs. The dynamics of NaCs exchange are rapid for both cations on the basal planes, but considerably slower for Cs localized on edge surfaces. In addition to new insights into Cs adsorption and exchange with Na on illite, we report the development of a methodology capable of simulating fully-flexible clay mineral nanoparticles with stable edge surfaces using a well-tested interatomic potential model. Copyright © 2016 Elsevier Inc. All rights reserved.

Contaminant transport in soil with depth-dependent reaction coefficients and time-dependent boundary conditions.

PubMed

Gao, Guangyao; Fu, Bojie; Zhan, Hongbin; Ma, Ying

2013-05-01

Predicting the fate and movement of contaminant in soils and groundwater is essential to assess and reduce the risk of soil contamination and groundwater pollution. Reaction processes of contaminant often decreased monotonously with depth. Time-dependent input sources usually occurred at the inlet of natural or human-made system such as radioactive waste disposal site. This study presented a one-dimensional convection-dispersion equation (CDE) for contaminant transport in soils with depth-dependent reaction coefficients and time-dependent inlet boundary conditions, and derived its analytical solution. The adsorption coefficient and degradation rate were represented as sigmoidal functions of soil depth. Solute breakthrough curves (BTCs) and concentration profiles obtained from CDE with depth-dependent and constant reaction coefficients were compared, and a constant effective reaction coefficient, which was calculated by arithmetically averaging the depth-dependent reaction coefficient, was proposed to reflect the lumped depth-dependent reaction effect. With the effective adsorption coefficient and degradation rate, CDE could produce similar BTCs and concentration profiles as those from CDE with depth-dependent reactions in soils with moderate chemical heterogeneity. In contrast, the predicted concentrations of CDE with fitted reaction coefficients at a certain depth departed significantly from those of CDE with depth-dependent reactions. Parametric analysis was performed to illustrate the effects of sinusoidally and exponentially decaying input functions on solute BTCs. The BTCs and concentration profiles obtained from the solutions for finite and semi-infinite domain were compared to investigate the effects of effluent boundary condition. The finite solution produced higher concentrations at the increasing limb of the BTCs and possessed a higher peak concentration than the semi-infinite solution which had a slightly long tail. Furthermore, the finite solution gave a higher concentration in the immediate vicinity of the exit boundary than the semi-infinite solution. The applicability of the proposed model was tested with a field herbicide and tracer leaching experiment in an agricultural area of northeastern Greece. The simulation results indicated that the proposed CDE with depth-dependent reaction coefficients was able to capture the evolution of metolachlor concentration at the upper soil depths. However, the simulation results at deep depths were not satisfactory as the proposed model did not account for preferential flow observed in the field. Copyright © 2013 Elsevier Ltd. All rights reserved.

Adsorption of selected pharmaceuticals and an endocrine disrupting compound by granular activated carbon. 1. Adsorption capacity and kinetics.

PubMed

Yu, Zirui; Peldszus, Sigrid; Huck, Peter M

2009-03-01

The adsorption of two representative PhACs (naproxen and carbamazepine) and one EDC (nonylphenol) were evaluated on two granular activated carbons (GAC). The primary objective was to investigate preloading effects by natural organic matter (NOM) on adsorption capacity and kinetics under conditions and concentrations (i.e., ng/L) relevantfor drinking water treatment Isotherms demonstrated that all compounds were significantly negatively impacted by NOM fouling. Adsorption capacity reduction was most severe for the acidic naproxen, followed by the neutral carbamazepine and then the more hydrophobic nonylphenol. The GAC with the wider pore size distribution had considerably greater NOM loading, resulting in lower adsorption capacity. Different patterns forthe change in Freundlich K(F) and 1/n with time revealed different competitive mechanisms for the different compounds. Mass transport coefficients determined by short fixed-bed (SFB) tests with virgin and preloaded GAC demonstrated thatfilm diffusion primarily controls mass transfer on virgin and preloaded carbon. Naproxen suffered the greatest deteriorative effect on kinetic parameters due to preloading, followed by carbamazepine, and then nonylphenol. A type of surface NOM/biofilm, which appeared to add an additional masstransfer resistance layer and thus reduce film diffusion, was observed. In addition, electrostatic interactions between NOM/biofilm and the investigated compounds are proposed to contribute to the reduction of film diffusion. A companion paper building on this work describes treatability studies in pilot-scale GAC adsorbers and the effectiveness of a selected fixed-bed model.

Sorption kinetics and isotherm modelling of imidacloprid on bentonite and organobentonites.

PubMed

Jain, Shailesh K; Shakil, Najam A; Dutta, Anirban; Kumar, Jitendra; Saini, Mukesh K

2017-05-04

Bentonite was modified by quaternary ammonium cations viz. cetytrimethylammonium (CTA), cetylpyridinium (CP), rioctylmethylammonium (TOM) and pcholine (PTC) at 100% cation exchange capacity of bentonite and was characterized by X-ray diffraction, CHNS elemental analyser and Fourier transform infrared spectroscopy. The sorption of imidacloprid on organobentonites/bentonite was studied by batch method. Normal bentonite could adsorb imidacloprid only upto 19.31-22.18% while all organobentonites except PTC bentonite (PTCB), enhanced its adsorption by three to four times. Highest adsorption was observed in case of TOM bentonite (TOMB) (76.94-83.16%). Adsorption kinetic data were fitted to pseudo-first-order, pseudo-second-order and intraparticle diffusion models. For normal bentonite data were best fitted to pseudo-first-order kinetic, while for organobentonites fitted to pseudo-second-order kinetics. Sorption data were analysed using Freundlich, Langmuir, Temkin and Dubinin-Radushkevich isotherm models. Data were well fitted to Freundlich adsorption isotherm. Product of Freundlich adsorption constant and heterogeneity parameter (K f .1/n) was in following order: TOMB (301.87) > CTA bentonite (CTAB) (152.12) > CP bentonite (CPB) (92.58) > bentonite (27.25). Desorption study confirmed hysteresis and concentration dependence. The present study showed that the organobentonite could be a good sorbent for removal of imidacloprid from natural water sample also. Percentage adsorption and Distribution coefficient (mL g -1 ) value of different adsorbent was in following order: TOMB (74.85% and 297.54) > CTAB (55.78% and 126.15) > CPB (45.81% and 84.55) > bentonite (10.65% and 11.92).

Effect of Temperature to Adsorption Capacity and Coefficient Distribution on Rare Earth Elements Adsorption (Y, Gd, Dy) Using SIR

NASA Astrophysics Data System (ADS)

Aziz, N.; Mindaryani, A.; Supranto; Taftazani, A.; Biyantoro, D.

2018-04-01

The use of REE like element of Yttrium (Y) as a superconducting material requires a purity of more than 90%, so it needs to increase the purity of Y from the settling process. The purpose of this research is to study the separation process of REE that is Y, Gd, Dy elements from REE hydroxide (REE(OH)3) using SIR method are consisting of Amberlite XAD-16 resin impregnated with Di-(2-ethylhexyl) phosphate ( D2EHPA) and Tributyl Phosphate (TBP) and determine the isotherm model on REE adsorption and determine the kinetic model of pseudo adsorption reaction. This research was started by activating XAD-16 resin and is mixed with TBP-D2EHPA solvents so it will form SIR, then it is conducted on variation of SIR composition, temperature variation of adsorption process, determination of equilibrium equation and kinetic sorption occurring in SIR adsorption based on experimental data of liquid concentration as function of time. Based on the calculation result, the most effective SIR composition for REE separation is 0.75 g, the equilibrium equation for Y, Gd and Dy follows the Henry equilibrium model and the pseudo kinetic model of the reaction order Y, Gd, and Dy is followed by the pseudo reaction of order 2 The result of separation of LTJ with SIR is said to be effective from another method because purity is obtained that is 96.73% and qualify as a super conductor material.

Insight into the adsorption mechanisms of trace organic carbon on biological treatment process.

PubMed

Zolfaghari, Mehdi; Drogui, Patrick; Brar, Satinder Kaur; Buelna, Gerardo; Dubé, Rino

2017-09-01

The presence of recalcitrant dissolved organic matter (DOM) could have a significant effect on the adsorption mechanism and capacity of the sludge for many trace organic carbons (TrOCs). In this study, adsorption of three TrOCs on the sludge and HA was investigated. The results revealed that neutral hydrophilic compounds had an insignificant interaction with both sludge and HA. Positively charged compounds, such as fluoranthene, had more affinity toward HA than sludge with solid/liquid partitioning of 57 and 3.2 L/g, respectively. The adsorption intensity (K f ) of di-2-ethyl hexyl phthalate was 0.5 and 1.13 for the HA and the sludge, respectively. By introducing the sludge to the solution of HA and TrOCs that already reached equilibrium, the sludge adsorption capacity in the presence of HA was investigated. The finding showed that at the lower concentration, adsorption of HA on the sludge was considered as the main removal pathway for the adsorbed emerging contaminants, as 70 mg of HA was adsorbed by a gram of sludge. For the higher concentration, desorption of TrOCs from DOM into the sludge comprised 15-30% of total removal efficiency. CBZ: carbamazepine; DEHP: di-2-ethyl hexyl phthalate; DOM: dissolved organic matter; FLAN: fluoranthene; f oc : fraction of organic carbon; HA: humic acid; Log Kow: octanol-water partition coefficient; PAH: polycyclic aromatic hydrocarbon TS: total solid; TrOCs: trace organic carbons VS: volatile solid.

Adsorption behavior of lead on aquatic sediments contaminated with cerium dioxide nanoparticles.

PubMed

Wang, Chao; Fan, Xiulei; Wang, Peifang; Hou, Jun; Ao, Yanhui; Miao, Lingzhan

2016-12-01

Aquatic sediments serve as an important sink for engineered nanomaterials (ENMs), such as metal oxide nanoparticles (MeO NPs) and carbon nanotubes (CNTs). Owing to their remarkable properties, ENMs demonstrate significant potential to disturb the adsorption behavior of other contaminants in aquatic sediments, thereby altering the bioavailability and toxicity of these contaminants. Thus far, most studies have investigated the effect of CNTs on the adsorption of other contaminants on sediments. Cerium dioxide nanoparticles (CeO 2 NPs), as one of the important MeO NPs, are also inevitably discharged into aquatic sediments because of their widespread use. In this study, we investigated the adsorption behavior of Pb 2+ on sediments spiked with CeO 2 NPs at a weight ratio of 5.0%. The results showed that the adsorption rates at three stages occurring during adsorption clearly increase for sediments contaminated with CeO 2 NPs. Moreover, the results obtained from the adsorption isotherms indicated that the Langmuir isotherm model best fits the isotherm data for both sediments and those contaminated with CeO 2 NPs. After spiking the sediments with CeO 2 NPs, the theoretical maximum monolayer adsorption capacity (Q max ) for Pb 2+ increased from 4.433 to 4.995 mg/g and the Langmuir isotherm coefficient (K L ) decreased from 8.813 to 7.730 L/g. The effects of CeO 2 NPs on the surface charge and pore surface properties of sediments were also studied as these properties affect the adsorption of several chemicals in sediments. The results showed that pH zpc , S BET , S ext , and average pore size of sediments clearly decrease for sediments contaminated with CeO 2 NPs. Hence, the strong adsorption capacity of CeO 2 NPs and the changes of sediment surface charge and pore surface properties caused by CeO 2 NPs are important factors affecting the adsorption behavior of Pb 2+ . The potential risk of Pb 2+ in aquatic environment may increase with CeO 2 NPs buried in sediments. Copyright © 2016 Elsevier Ltd. All rights reserved.

Ionic Adsorption and Desorption of CNT Nanoropes

PubMed Central

Shang, Jun-Jun; Yang, Qing-Sheng; Yan, Xiao-Hui; He, Xiao-Qiao; Liew, Kim-Meow

2016-01-01

A nanorope is comprised of several carbon nanotubes (CNTs) with different chiralities. A molecular dynamic model is built to investigate the ionic adsorption and desorption of the CNT nanoropes. The charge distribution on the nanorope is obtained by using a modified gradient method based on classical electrostatic theory. The electrostatic interactions among charged carbon atoms are calculated by using the Coulomb law. It was found here that the charged nanorope can adsorb heavy metal ions, and the adsorption and desorption can be realized by controlling the strength of applied electric field. The distance between the ions and the nanorope as well as the amount of ions have an effect on the adsorption capacity of the nanorope. The desorption process takes less time than that of adsorption. The study indicates that the CNT nanorope can be used as a core element of devices for sewage treatment. PMID:28335306

Adsorption performance of coconut shell activated carbon for the removal of chlorate from chlor-alkali brine stream.

PubMed

Lakshmanan, Shyam; Murugesan, Thanapalan

2016-12-01

Activated carbon from coconut shell was used to investigate the adsorption of chlorate from a chlor-alkali plant's brine stream. The effect of pH, flowrate, chlorate and chloride concentration on the breakthrough curves were studied in small-scale column trials. The results obtained show enhanced adsorption at low flowrates, higher chlorate concentrations, and at a pH of 10. These studies show that introducing an activated carbon adsorption column just before the saturator would remove sufficient quantities of chlorate to allow more of the chlor-alkali plant's brine stream to be reused. From column dynamic studies, the Thomas model showed close approximation when the chlorate in the effluent was higher than breakthrough concentrations and there was close correlation at high influent concentration. The q o (maximum adsorption capacity) values were close to those obtained experimentally, indicating close representation of the breakthrough curve by the Thomas model.

Ionic Adsorption and Desorption of CNT Nanoropes.

PubMed

Shang, Jun-Jun; Yang, Qing-Sheng; Yan, Xiao-Hui; He, Xiao-Qiao; Liew, Kim-Meow

2016-09-28

A nanorope is comprised of several carbon nanotubes (CNTs) with different chiralities. A molecular dynamic model is built to investigate the ionic adsorption and desorption of the CNT nanoropes. The charge distribution on the nanorope is obtained by using a modified gradient method based on classical electrostatic theory. The electrostatic interactions among charged carbon atoms are calculated by using the Coulomb law. It was found here that the charged nanorope can adsorb heavy metal ions, and the adsorption and desorption can be realized by controlling the strength of applied electric field. The distance between the ions and the nanorope as well as the amount of ions have an effect on the adsorption capacity of the nanorope. The desorption process takes less time than that of adsorption. The study indicates that the CNT nanorope can be used as a core element of devices for sewage treatment.

Preparation and characterization of novel carbon dioxide adsorbents based on polyethylenimine-modified Halloysite nanotubes.

PubMed

Cai, Haohao; Bao, Feng; Gao, Jie; Chen, Tao; Wang, Si; Ma, Rui

2015-01-01

New nano-sized carbon dioxide (CO2) adsorbents based on Halloysite nanotubes impregnated with polyethylenimine (PEI) were designed and synthesized, which were excellent adsorbents for the capture of CO2 at room temperature and had relatively high CO2 adsorption capacity. The prepared adsorbents were characterized by various techniques such as Fourier transform infrared spectrometry, gel permeation chromatography, dynamic light scattering, thermogravimetry, thermogravimetry-Fourier transform-infrared spectrometry, scanning electron microscopy and transmission electron microscopy. The adsorption characteristics and capacity were studied at room temperature, the highest CO2 adsorption capacity of 156.6 mg/g-PEI was obtained and the optimal adsorption capacity can reach a maximum value of 54.8 mg/g-adsorbent. The experiment indicated that this kind of adsorbent has a high stability at 80°C and PEI-impregnated adsorbents showed good reversibility and stability during cyclic adsorption-regeneration tests.

Metal adsorption onto bacterial surfaces: development of a predictive approach

NASA Astrophysics Data System (ADS)

Fein, Jeremy B.; Martin, Aaron M.; Wightman, Peter G.

2001-12-01

Aqueous metal cation adsorption onto bacterial surfaces can be successfully modeled by means of a surface complexation approach. However, relatively few stability constants for metal-bacterial surface complexes have been measured. In order to determine the bacterial adsorption behavior of cations that have not been studied in the laboratory, predictive techniques are required that enable estimation of the stability constants of bacterial surface complexes. In this study, we use a linear free-energy approach to compare previously measured stability constants for Bacillus subtilis metal-carboxyl surface complexes with aqueous metal-organic acid anion stability constants. The organic acids that we consider are acetic, oxalic, citric, and tiron. We add to this limited data set by conducting metal adsorption experiments onto Bacillus subtilis, determining bacterial surface stability constants for Co, Nd, Ni, Sr, and Zn. The adsorption behavior of each of the metals studied here was described well by considering metal-carboxyl bacterial surface complexation only, except for the Zn adsorption behavior, which required carboxyl and phosphoryl complexation to obtain a suitable fit to the data. The best correlation between bacterial carboxyl surface complexes and aqueous organic acid anion stability constants was obtained by means of metal-acetate aqueous complexes, with a linear correlation coefficient of 0.97. This correlation applies only to unhydrolyzed aqueous cations and only to carboxyl binding of those cations, and it does not predict the binding behavior under conditions where metal binding to other bacterial surface site types occurs. However, the relationship derived in this study permits estimation of the carboxyl site adsorption behavior of a wide range of aqueous metal cations for which there is an absence of experimental data. This technique, coupled with the observation of similar adsorption behaviors across bacterial species (Yee and Fein, 2001), enables estimation of the effects of bacterial adsorption on metal mobilities for a large number of environmental and geologic applications.

Molecular dynamics simulation of siderite-hematite-quartz flotation with sodium oleate

NASA Astrophysics Data System (ADS)

Li, Lixia; Hao, Haiqing; Yuan, Zhitao; Liu, Jiongtian

2017-10-01

Models of sodium oleate adsorption on siderite, hematite and quartz were investigated by molecular dynamic simulation, respectively. Surface energy was calculated to confirm the cleavage plan of hematite and quartz. Both natural cleavage plane of siderite and calculated plane were used to investigate the flotation of the three minerals. Based on the molecular simulation in solution with water as medium, adsorption quantity and interaction capability of oleate ions on the three minerals indicated that siderite could be collected efficiently by sodium oleate at neutral pH. Results of flotation experiments were further demonstrated by analysis of relative concentration of carbon atoms and oxygen atoms.

Effects of temperature, pH, and ionic strength on the adsorption of nanoparticles at liquid-liquid interfaces

NASA Astrophysics Data System (ADS)

Ferdous, Sultana; Ioannidis, Marios A.; Henneke, Dale E.

2012-05-01

The effects of temperature, pH and sodium chloride (NaCl) concentration on the equilibrium and dynamic interfacial tension (IFT) of 4.4-nm gold nanoparticles capped with n-dodecanethiol at hydrocarbon-water interfaces was studied. The pendant drop technique was used to study the adsorption properties of these nanoparticles at the hexane-water and nonane-water interfaces. The physical size of the gold nanoparticles was determined by TEM image analysis. The interfacial properties of mixtures of these nanoparticles, having different sizes and capping agents, were then studied. The addition of NaCl was found to cause a decrease of the equilibrium and dynamic IFT greater than that which accompanies the adsorption of nanoparticles at the interface in the absence of NaCl. Although IFT values for acidic and neutral conditions were found to be similar, a noticeable decrease in the IFT was found for more basic conditions. Increasing the temperature of the system was found to cause an increase in both dynamic and equilibrium IFT values. These findings have implications for the self-assembly of functionalized gold nanoparticles at liquid-liquid interfaces.

Single-Molecule Probing of Adsorption and Diffusion on Silica Surfaces

NASA Astrophysics Data System (ADS)

Wirth, Mary J.; Legg, Michael A.

2007-05-01

Single-molecule spectroscopy has emerged as a valuable tool in probing kinetics and dynamic equilibria in adsorption because advances in instrumentation and technology have enabled researchers to obtain high signal-to-noise ratios for common dyes at room temperature. Single-molecule spectroscopy was applied to the study of an important problem in chromatography: peak broadening and asymmetry in the chromatograms of pharmaceuticals, peptides, and proteins. Using DiI, a cationic dye that exhibits the same problematic chromatographic behavior, investigators showed that the adsorption sites that cause chromatographic problems are located at defects on the silica crystal surface.

The dynamic adsorption characteristics of phenol by granular activated carbon.

PubMed

Namane, A; Hellal, A

2006-09-01

The objective of the present work is to determine the operating conditions of an activated carbon filter, based on the characteristics of breakthrough curves. For this we apply the technical developed by Mickaels for the ionic exchange and applied by Luchkis for the adsorption, and which is the mass transfer zone. To reach our goal, an evaluation of the operating conditions (height of the bed, flow and concentration of effluent) on the characteristics of the mass transfer zone was made and an explanation of the mechanism of adsorption was given. Thereafter a modeling of the experimental results was done.

A preliminary study of the electro-oxidation of L-ascorbic acid on polycrystalline silver in alkaline solution

NASA Astrophysics Data System (ADS)

Majari Kasmaee, L.; Gobal, F.

Electrochemical oxidation of L-ascorbic acid on polycrystalline silver in alkaline aqueous solutions is studied by cyclic voltammetry (CV), chronoamperometry (CA) and impedance spectroscopy (IS). The anodic electro-oxidation starts at -500 mV versus SCE and shows continued anodic oxidation in the cathodic half cycle in the CV regime signifying slowly oxidizing adsorbates. Diffusion coefficient of ascorbate ion measured under both voltammetric regimes is around 1.4 × 10 -5 cm 2 s -1. Impedance spectroscopy measures the capacitances associated with double layer and adsorption around 50 μF cm -2 and 4 mF cm -2 as well as the adsorption and decomposition resistances (rates).

Methane mobility in carbon nanotubes

NASA Astrophysics Data System (ADS)

Bienfait, M.; Asmussen, B.; Johnson, M.; Zeppenfeld, P.

2000-07-01

Quasi-elastic neutron scattering has been used to characterize the diffusivity of CH 4 molecules condensed in single-wall carbon nanotubes. It is shown that the two sites of adsorption, previously observed by adsorption volumetry and calorimetry measurements, correspond to a solid-like phase for the more strongly bound site at T<120 K and to a liquid-like component for the more weakly bound site at 70< T<120 K. The diffusion coefficients of the mobile molecules range between 3×10 -7 to 15×10 -7 cm 2 s -1. The fraction of this viscous liquid diminishes as the temperature is decreased; the adsorbate is fully solidified at 50 K and below.

X-ray photoelectron spectroscopy and friction studies of nickel-zinc and manganese-zinc ferrites in contact with metals

NASA Technical Reports Server (NTRS)

Miyoshi, K.; Buckley, D. H.

1983-01-01

X-ray photoelectron spectroscopy analysis and sliding friction experiments were conducted with hot-pressed, polycrystalline Ni-Zn and Mn-Zn ferrites in sliding contact with various transition metals at room temperature in a vacuum of 30 nPa. The results indicate that the coefficients of friction for Ni-Zn and Mn-Zn ferrites in contact with metals are related to the relative chemical activity in these metals: the more active the metal, the higher is the coefficient of friction. The coefficients of friction for the ferrites correlate with the free energy of formation of the lowest metal oxide. The interfacial bond can be regarded as a chemical bond between the metal atoms and the oxygen anions in the ferrite surfaces. The adsorption of oxygen on clean metal and ferrite surfaces increases the coefficients of friction for the Ni-Zn and Mn-Zn ferrite-metal interfaces.

ReaxFF Grand Canonical Monte Carlo simulation of adsorption and dissociation of oxygen on platinum (111)

NASA Astrophysics Data System (ADS)

Valentini, Paolo; Schwartzentruber, Thomas E.; Cozmuta, Ioana

2011-12-01

Atomic-level Grand Canonical Monte Carlo (GCMC) simulations equipped with a reactive force field (ReaxFF) are used to study atomic oxygen adsorption on a Pt(111) surface. The off-lattice GCMC calculations presented here rely solely on the interatomic potential and do not necessitate the pre-computation of surface adlayer structures and their interpolation. As such, they provide a predictive description of adsorbate phases. In this study, validation is obtained with experimental evidence (steric heats of adsorption and isotherms) as well as DFT-based state diagrams available in the literature. The ReaxFF computed steric heats of adsorption agree well with experimental data, and this study clearly shows that indirect dissociative adsorption of O2 on Pt(111) is an activated process at non-zero coverages, with an activation energy that monotonically increases with coverage. At a coverage of 0.25 ML, a highly ordered p(2 × 2) adlayer is found, in agreement with several low-energy electron diffraction observations. Isotherms obtained from the GCMC simulations compare qualitatively and quantitatively well with previous DFT-based state diagrams, but are in disagreement with the experimental data sets available. ReaxFF GCMC simulations at very high coverages show that O atoms prefer to bind in fcc hollow sites, at least up to 0.8 ML considered in the present work. At moderate coverages, little to no disorder appears in the Pt lattice. At high coverages, some Pt atoms markedly protrude out of the surface plane. This observation is in qualitative agreement with recent STM images of an oxygen covered Pt surface. The use of the GCMC technique based on a transferable potential is particularly valuable to produce more realistic systems (adsorbent and adsorbate) to be used in subsequent dynamical simulations (Molecular Dynamics) to address recombination reactions (via either Eley-Rideal or Langmuir-Hinshelwood mechanisms) on variously covered surfaces. By using GCMC and Molecular Dynamics simulations, the ReaxFF force field can be a valuable tool for understanding heterogeneous catalysis on a solid surface. Finally, the use of a reactive potential is a necessary requirement to investigate problems where dissociative adsorption occurs, as typical of many important catalytic processes.

Adsorptive removal of pharmaceuticals from water by commercial and waste-based carbons.

PubMed

Calisto, Vânia; Ferreira, Catarina I A; Oliveira, João A B P; Otero, Marta; Esteves, Valdemar I

2015-04-01

This work describes the single adsorption of seven pharmaceuticals (carbamazepine, oxazepam, sulfamethoxazole, piroxicam, cetirizine, venlafaxine and paroxetine) from water onto a commercially available activated carbon and a non-activated carbon produced by pyrolysis of primary paper mill sludge. Kinetics and equilibrium adsorption studies were performed using a batch experimental approach. For all pharmaceuticals, both carbons presented fast kinetics (equilibrium times varying from less than 5 min to 120 min), mainly described by a pseudo-second order model. Equilibrium data were appropriately described by the Langmuir and Freundlich isotherm models, the last one giving slightly higher correlation coefficients. The fitted parameters obtained for both models were quite different for the seven pharmaceuticals under study. In order to evaluate the influence of water solubility, log Kow, pKa, polar surface area and number of hydrogen bond acceptors of pharmaceuticals on the adsorption parameters, multiple linear regression analysis was performed. The variability is mainly due to log Kow followed by water solubility, in the case of the waste-based carbon, and due to water solubility in the case of the commercial activated carbon. Copyright © 2015 Elsevier Ltd. All rights reserved.

Interaction of organic contaminants with natural clay type geosorbents: potential use as geologic barrier in urban landfill.

PubMed

Sánchez-Jiménez, N; Sevilla, M T; Cuevas, J; Rodríguez, M; Procopio, J R

2012-03-01

The aim of this work is to characterize the capability of several clay materials as preservative of organic pollution for use as landfill barrier. Interaction of representative organic pollutants with different polarity and water solubility (atrazine, benzamide, methomyl, paraquat and toluene) with several clay materials coming from several locations of Spain were studied. Batch suspension method was used to study the pesticide adsorption onto the clay sorbents in solution conditions that simulate the composition of a young leachate in its aerobic acetogenic stage (pH=5 and I=0.15) The obtained data of the analytes sorption were modelized by several sorption isotherm models, and the best fitted data were got with a generalized Langmuir adsorption isotherm. The higher maxima adsorptions were observed for paraquat (50-62 mmol kg(-1)) and toluene (19-34 mmol kg(-1)) whereas more hydrophobic compounds present lower adsorption (0.7-2.5 mmol kg(-1)). Paraquat is the compound that presents the higher bonding coefficients. Therefore these clays could be used as components of the multibarriers in controlled urban landfill. Copyright © 2011 Elsevier Ltd. All rights reserved.

Adsorptive removal of Auramine-O: kinetic and equilibrium study.

PubMed

Mall, Indra Deo; Srivastava, Vimal Chandra; Agarwal, Nitin Kumar

2007-05-08

Present study deals with the adsorption of Auramine-O (AO) dye by bagasse fly ash (BFA) and activated carbon-commercial grade (ACC) and laboratory grade (ACL). BFA is a solid waste obtained from the particulate collection equipment attached to the flue gas line of the bagasse fired boilers of cane sugar mills. Batch studies were performed to evaluate the influences of various experimental parameters like initial pH (pH(0)), contact time, adsorbent dose and initial concentration (C(0)) for the removal of AO. Optimum conditions for AO removal were found to be pH(0) approximately 7.0 and equilibrium time approximately 30 min for BFA and approximately 120 min for activated carbons. Optimum BFA, ACC and ACL dosages were found to be 1, 20 and 2g/l, respectively. Adsorption of AO followed pseudo-second order kinetics with the initial sorption rate for adsorption on BFA being the highest followed by those on ACL and ACC. The sorption process was found to be controlled by both film and pore diffusion with film diffusion at the earlier stages followed by pore diffusion at the later stages. Equilibrium isotherms for the adsorption of AO on BFA, ACC and ACL were analyzed by Freundlich, Langmuir, Dubinin-Radushkevich, and Temkin isotherm equations using linear correlation coefficient. Langmuir isotherm gave the best correlation of adsorption for all the adsorbents studied. Thermodynamic study showed that adsorption of AO on ACC (with a more negative Gibbs free energy value) is more favoured. BFA which was used without any pretreatment showed high surface area, pore volume and pore size exhibiting its potential to be used as an adsorbent for the removal of AO.

Kinetic study on removal of heavy metal ions from aqueous solution by using soil.

PubMed

Lim, Soh-Fong; Lee, Agnes Yung Weng

2015-07-01

In the present study, the feasibility of soil used as a low-cost adsorbent for the removal of Cu(2+), Zn(2+), and Pb(2+) ions from aqueous solution was investigated. The kinetics for adsorption of the heavy metal ions from aqueous solution by soil was examined under batch mode. The influence of the contact time and initial concentration for the adsorption process at pH of 4.5, under a constant room temperature of 25 ± 1 °C were studied. The adsorption capacity of the three heavy metal ions from aqueous solution was decreased in order of Pb(2+) > Cu(2+) > Zn(2+). The soil was characterized by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopic-energy dispersive X-ray (SEM-EDX), and Brunauer, Emmett, and Teller (BET) surface area analyzer. From the FTIR analysis, the experimental data was corresponded to the peak changes of the spectra obtained before and after adsorption process. Studies on SEM-EDX showed distinct adsorption of the heavy metal ions and the mineral composition in the study areas were determined to be silica (SiO2), alumina (Al2O3), and iron(III) oxide (FeO3). A distinct decrease of the specific surface area and total pore volumes of the soil after adsorption was found from the BET analysis. The experimental results obtained were analyzed using four adsorption kinetic models, namely pseudo-first-order, pseudo-second-order, Elovich, and intraparticle diffusion. Evaluating the linear correlation coefficients, the kinetic studies showed that pseudo-second-order equation described the data appropriable than others. It was concluded that soil can be used as an effective adsorbent for removing Cu(2+), Zn(2+), and Pb(2+) ions from aqueous solution.

α-keratin/Alginate Biosorbent for Removal of Methylene Blue on Aqueous Solution in a Batch System

NASA Astrophysics Data System (ADS)

Fadillah, G.; Putri, E. N. K.; Febrianastuti, S.; Munawaroh, H.; Purnawan, C.; Wahyuningsih, S.

2018-03-01

Methylene Blue (MB) is a cationic dyes which is commonly used in textile industries for coloring agent. The precence of MB in water caused some negative effect on the environment and human health. Many common technologies such as membrane filtration, electrophoresis and adsorption have been widely empolyed for removal of MB in water, but the adsorption technique still has advantages than the others. In this study, removal of MB used a biosorbent α-keratin/alginate (KA). The biosorbent KA was prepared by using the encapsulation technique in CaCl2 2 % (w/v) solution. The biosorbent was characterized by Fourier Transform Infrared (FTIR) and Scanning Electron Microscope (SEM). The effect of composition of α-keratin and alginate, the pH of solution and contact time on the adsorption were investigated. The optimum adsorption of MB in aqueous solution was found at the composition of α-keratin and alginate of 1:2 (w/w), the pH at 5.0 and contact time at 4 hours. The adsorption of MB on KA biosorbent was comparatively higher than α-keratin and alginate only. Adsorption of MB dyes in aqueous solution followed the Langmuir adsorption isotherm, and the dynamic adsorption model could be described through a pseudo-second order kinetics.

Reactive adsorption of SO2 on activated carbons with deposited iron nanoparticles.

PubMed

Arcibar-Orozco, Javier A; Rangel-Mendez, J Rene; Bandosz, Teresa J

2013-02-15

The effect of iron particle size anchored on the surface of commercial activated carbon on the removal of SO(2) from a gas phase was studied. Nanosize iron particles were deposited using forced hydrolysis of FeCl(3) with or without H(3)PO(4) as a capping agent. Dynamic adsorption experiments were carried out on either dry or pre-humidified materials and the adsorption capacities were calculated. The surface of the initial and exhausted materials was extensively characterized by microscopic, porosity, thermogravimetric and surface chemistry. The results indicate that the SO(2) adsorption capacity increased two and half times after the prehumidification process owing to the formation of H(2)SO(4) in the porous system. Iron species enhance the SO(2) adsorption capacity only when very small nanoparticles are deposited on the pore walls as a thin layer. Large iron nanoparticles block the ultramicropores decreasing the accessibility of the active sites and consuming oxygen that rest adsorption centers for SO(2) molecules. Iron nanoparticles of about 3-4 nm provide highly dispersed adsorption sites for SO(2) molecules and thus increase the adsorption capacity of about 80%. Fe(2)(SO(4))(3) was detected on the surface of exhausted samples. Copyright © 2012 Elsevier B.V. All rights reserved.

Modeling pH-Responsive Adsorption of Polyelectrolytes at Oil-Water Interfaces

NASA Astrophysics Data System (ADS)

Qin, Shiyi; Yong, Xin

We use dissipative particle dynamics (DPD) to discover the interfacial adsorption of pH-responsive polyelectrolytes in oil-water binary systems under different pH values. The electrostatic interactions between charged beads and the dielectric discontinuity across the interface are modeled by exploiting a modified Particle-Particle-Particle-Mesh (PPPM) method, which uses an iterative method to solve the Poisson equation on a uniform grid. We first model the adsorption behavior of a single linear polyelectrolyte from the aqueous phase. The Henderson-Hasselbalch equation describes the relation between pH and the degree of ionization of the modeled polyelectrolytes. Through changing the degree of ionization, we explore the influence of pH on the adsorption behavior and show that the electrostatic interactions significantly modulate the adsorption. Time evolutions of the position and conformation of the polyelectrolytes and the variation in the oil-water surface tension will be measured to characterize the adsorption behavior. Furthermore, we model the pH-dependent adsorption behavior of polyelectrolytes with more complicated structures, namely, branched polyelectrolytes with hydrophobic backbones and hydrophilic side chains. We also find that the addition of salts in the medium and the lengths of the backbone and ionized side chain affect the adsorption. This research supported by the American Chemical Society Petroleum Research Fund (Award 56884-DNI9).

Effect of water on methane adsorption on the kaolinite (0 0 1) surface based on molecular simulations

NASA Astrophysics Data System (ADS)

Zhang, Bin; Kang, Jianting; Kang, Tianhe

2018-05-01

CH4 adsorption isotherms of kaolinite with moisture contents ranging from 0 to 5 wt% water, the effects of water on maximum adsorption capacity, kaolinite swelling, and radial distribution function were modelled by the implementing combined Monte Carlo (MC) and molecular dynamics (MD) simulations at 293.15 K (20 °C) and a pressure range of 1-20 MPa. The simulation results showed that the absolute adsorption of CH4 on both dry and moist kaolinite followed a Langmuir isotherm within the simulated pressure range, and both the adsorption capacity and the rate of CH4 adsorption decreased with the water content increases. The adsorption isosteric heats of CH4 on kaolinite decreased linearly with increasing water content, indicating that at higher water contents, the interaction energy between the CH4 and kaolinite was weaker. The interaction between kaolinite and water dominates and was the main contributing factor to kaolinite clay swelling. Water molecules were preferentially adsorbed onto oxygen and hydrogen atoms in kaolinite, while methane showed a tendency to be adsorbed only onto oxygen. The simulation results of our study provide the quantitative analysis of effect of water on CH4 adsorption capacity, adsorption rate, and interaction energy from a microscopic perspective. We hope that our study will contribute to the development of strategies for the further exploration of coal bed methane and shale gas.

Effective removal of hydrogen sulfide using 4A molecular sieve zeolite synthesized from attapulgite.

PubMed

Liu, Xinpeng; Wang, Rui

2017-03-15

In this work, 4A molecular sieve zeolite was synthesized from attapulgite (ATP) in different conditions and was applied initially for H 2 S removal. The sorbent was characterized by scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectra and N 2 adsorption/desorption. The effects of the synthesis condition and adsorption temperature were studied by dynamic adsorption experiment. The optimal adsorption temperature is 50°C. The H 2 S adsorption results have showed that the optimal synthesis conditions are as follows: the ratio of silicon to aluminum and ratio of sodium to silicon are both 1.5, the ratio of water to sodium is 30, crystallization temperature and crystallization time is 90°C, 4h, respectively. The breakthrough and saturation sulfur sorption capacities of zeolite synthesized under optimum conditions are up to nearly 10 and 15mg/g-sorbent, respectively, and the H 2 S removal rate is nearly 100%. The adsorption kinetics nonlinear fitting results show that the adsorption system follows Bingham model. These results indicate that 4A molecular sieve zeolite synthesized from attapulgite can be used for H 2 S removal promisingly. Copyright © 2016 Elsevier B.V. All rights reserved.

Fate and transport with material response characterization of green sorption media for copper removal via adsorption process.

PubMed

Chang, Ni-Bin; Houmann, Cameron; Lin, Kuen-Song; Wanielista, Martin

2016-02-01

Green adsorption media with the inclusion of renewable and recycled materials can be applied as a stormwater best management practice for copper removal. A green adsorption media mixture composed of recycled tire chunk, expanded clay aggregate, and coconut coir was physicochemically evaluated for its potential use in an upflow media filter. A suite of tests were conducted on the media mixture and the individual media components including studies of particle size distribution, isotherms, column adsorption and reaction kinetics. Isotherm test results revealed that the coconut coir had the highest affinity for copper (q(max) = 71.1 mg g(-1)), and that adsorption was maximized at a pH of 7.0. The coconut coir also performed the best under dynamic conditions, having an equilibrium uptake of 1.63 mg g(-1). FE-SEM imaging found a strong correlation between the porosity of the micro pore structure and the adsorptive capacity. The use of the green adsorption media mixture in isolation or the coconut coir with an expanded clay filtration chamber could be an effective and reliable stormwater best management practice for copper removal. Copyright © 2015 Elsevier Ltd. All rights reserved.

Surface Curvature Relation to Protein Adsorption for Carbon-based Nanomaterials

NASA Astrophysics Data System (ADS)

Gu, Zonglin; Yang, Zaixing; Chong, Yu; Ge, Cuicui; Weber, Jeffrey K.; Bell, David R.; Zhou, Ruhong

2015-06-01

The adsorption of proteins onto carbon-based nanomaterials (CBNs) is dictated by hydrophobic and π-π interactions between aliphatic and aromatic residues and the conjugated CBN surface. Accordingly, protein adsorption is highly sensitive to topological constraints imposed by CBN surface structure; in particular, adsorption capacity is thought to increase as the incident surface curvature decreases. In this work, we couple Molecular Dynamics (MD) simulations with fluorescence spectroscopy experiments to characterize this curvature dependence in detail for the model protein bovine serum albumin (BSA). By studying BSA adsorption onto carbon nanotubes of increasing radius (featuring descending local curvatures) and a flat graphene sheet, we confirm that adsorption capacity is indeed enhanced on flatter surfaces. Naïve fluorescence experiments featuring multi-walled carbon nanotubes (MWCNTs), however, conform to an opposing trend. To reconcile these observations, we conduct additional MD simulations with MWCNTs that match those prepared in experiments; such simulations indicate that increased mass to surface area ratios in multi-walled systems explain the observed discrepancies. In reduction, our work substantiates the inverse relationship between protein adsorption capacity and surface curvature and further demonstrates the need for subtle consideration in experimental and simulation design.

Extracting surface diffusion coefficients from batch adsorption measurement data: application of the classic Langmuir kinetics model.

PubMed

Chu, Khim Hoong

2017-11-09

Surface diffusion coefficients may be estimated by fitting solutions of a diffusion model to batch kinetic data. For non-linear systems, a numerical solution of the diffusion model's governing equations is generally required. We report here the application of the classic Langmuir kinetics model to extract surface diffusion coefficients from batch kinetic data. The use of the Langmuir kinetics model in lieu of the conventional surface diffusion model allows derivation of an analytical expression. The parameter estimation procedure requires determining the Langmuir rate coefficient from which the pertinent surface diffusion coefficient is calculated. Surface diffusion coefficients within the 10 -9 to 10 -6  cm 2 /s range obtained by fitting the Langmuir kinetics model to experimental kinetic data taken from the literature are found to be consistent with the corresponding values obtained from the traditional surface diffusion model. The virtue of this simplified parameter estimation method is that it reduces the computational complexity as the analytical expression involves only an algebraic equation in closed form which is easily evaluated by spreadsheet computation.

Simulation of adsorbed hydrogen on tungsten surface

NASA Astrophysics Data System (ADS)

Degtyarenko, N. N.; Pisarev, A. A.

2017-12-01

Calculations of the energy of the H-W system were performed using DFT method based on plane waves. Adsorption energies, equilibrium states, vibration spectra, saddle points, activation energies of jumps, and diffusion paths have been analyzed for H atom on W(100) and W(110). Diffusion coefficient for H on W(110) agrees very well with experimental data.

Milk whey proteins and xanthan gum interactions in solution and at the air-water interface: a rheokinetic study.

PubMed

Perez, Adrián A; Sánchez, Cecilio Carrera; Patino, Juan M Rodríguez; Rubiolo, Amelia C; Santiago, Liliana G

2010-11-01

In this contribution, we present experimental information about the effect of xanthan gum (XG) on the adsorption behaviour of two milk whey protein samples (MWP), beta-lactoglobulin (beta-LG) and whey protein concentrate (WPC), at the air-water interface. The MWP concentration studied corresponded to the protein bulk concentration which is able to saturate the air-water interface (1.0 wt%). Temperature, pH and ionic strength of aqueous systems were kept constant at 20 degrees C, pH 7 and 0.05 M, respectively, while the XG bulk concentration varied in the range 0.00-0.25 wt%. Biopolymer interactions in solution were analyzed by extrinsic fluorescence spectroscopy using 1-anilino-8-naphtalene sulphonic acid (ANS) as a protein fluorescence probe. Interfacial biopolymer interactions were evaluated by dynamic tensiometry and surface dilatational rheology. Adsorption behaviour was discussed from a rheokinetic point of view in terms of molecular diffusion, penetration and conformational rearrangement of adsorbed protein residues at the air-water interface. Differences in the interaction magnitude, both in solution and at the interface vicinity, and in the adsorption rheokinetic parameters were observed in MWP/XG mixed systems depending on the protein type (beta-LG or WPC) and biopolymer relative concentration. beta-LG adsorption in XG presence could be promoted by mechanisms based on biopolymer segregative interactions and thermodynamic incompatibility in the interface vicinity, resulting in better surface and viscoelastic properties. The same mechanism could be responsible of WPC interfacial adsorption in the presence of XG. The interfacial functionality of WPC was improved by the synergistic interactions with XG, although WPC chemical complexity might complicate the elucidation of molecular events that govern adsorption dynamics of WPC/XG mixed systems at the air-water interface. Copyright (c) 2010 Elsevier B.V. All rights reserved.

Advanced functional materials in solid phase extraction for ICP-MS determination of trace elements and their species - A review.

PubMed

He, Man; Huang, Lijin; Zhao, Bingshan; Chen, Beibei; Hu, Bin

2017-06-22

For the determination of trace elements and their species in various real samples by inductively coupled plasma mass spectrometry (ICP-MS), solid phase extraction (SPE) is a commonly used sample pretreatment technique to remove complex matrix, pre-concentrate target analytes and make the samples suitable for subsequent sample introduction and measurements. The sensitivity, selectivity/anti-interference ability, sample throughput and application potential of the methodology of SPE-ICP-MS are greatly dependent on SPE adsorbents. This article presents a general overview of the use of advanced functional materials (AFMs) in SPE for ICP-MS determination of trace elements and their species in the past decade. Herein the AFMs refer to the materials featuring with high adsorption capacity, good selectivity, fast adsorption/desorption dynamics and satisfying special requirements in real sample analysis, including nanometer-sized materials, porous materials, ion imprinting polymers, restricted access materials and magnetic materials. Carbon/silica/metal/metal oxide nanometer-sized adsorbents with high surface area and plenty of adsorption sites exhibit high adsorption capacity, and porous adsorbents would provide more adsorption sites and faster adsorption dynamics. The selectivity of the materials for target elements/species can be improved by using physical/chemical modification, ion imprinting and restricted accessed technique. Magnetic adsorbents in conventional batch operation offer unique magnetic response and high surface area-volume ratio which provide a very easy phase separation, greater extraction capacity and efficiency over conventional adsorbents, and chip-based magnetic SPE provides a versatile platform for special requirement (e.g. cell analysis). The performance of these adsorbents for the determination of trace elements and their species in different matrices by ICP-MS is discussed in detail, along with perspectives and possible challenges in the future development. Copyright © 2017 Elsevier B.V. All rights reserved.

Fibronectin and bovine serum albumin adsorption and conformational dynamics on inherently conducting polymers: a QCM-D study.

PubMed

Molino, Paul J; Higgins, Michael J; Innis, Peter C; Kapsa, Robert M I; Wallace, Gordon G

2012-06-05

Quartz crystal microbalance with dissipation monitoring (QCM-D) was employed to characterize the adsorption of the model proteins, bovine serum albumin (BSA) and fibronectin (FN), to polypyrrole doped with dextran sulfate (PPy-DS) as a function of DS loading and surface roughness. BSA adsorption was greater on surfaces of increased roughness and was above what could be explained by the increase in surface area alone. Furthermore, the additional mass adsorbed on the rough films was concomitant with an increase in the rigidity of the protein layer. Analysis of the dynamic viscoelastic properties of the protein adlayer reveal BSA adsorption on the rough films occurs in two phases: (1) arrival and initial adsorption of protein to the polymer surface and (2) postadsorption molecular rearrangement to a more dehydrated and compact conformation that facilitates further recruitment of protein to the polymer interface, likely forming a multilayer. In contrast, FN adsorption was independent of surface roughness. However, films prepared from solutions containing the highest concentration of DS (20 mg/mL) demonstrated both an increase in adsorbed mass and adlayer viscoelasticity. This is attributed to the higher DS loading in the conducting polymer film resulting in presentation of a more hydrated molecular structure indicative of a more unfolded and bioactive conformation. Modulating the redox state of the PPy-DS polymers was shown to modify both the adsorbed mass and viscoelastic nature of FN adlayers. An oxidizing potential increased both the total adsorbed mass and the adlayer viscoelasticity. Our findings demonstrate that modification of polymer physicochemical and redox condition alters the nature of protein-polymer interaction, a process that may be exploited to tailor the bioactivity of protein through which interactions with cells and tissues may be controlled.

The distribution and adsorption behavior of aliphatic amines in marine and lacustrine sediments

NASA Astrophysics Data System (ADS)

Wang, Xu-chen; Lee, Cindy

1990-10-01

The methylated amines—monomethyl-, dimethyl-, and trimethyl amine (MMA, DMA, TMA)—are commonly found in aquatic environments, apparently as a result of decomposition processes. Adsorption of these amines to clay minerals and organic matter significantly influences their distribution in sediments. Laboratory measurements using 14C-radiolabelled amines and application of a linear partitioning model resulted in calculated adsorption coefficients of 2.4-4.7 (MMA), 3.3 (DMA), and 3.3-4.1 (TMA). Further studies showed that adsorption of amines is influenced by salinity of the porewaters, and clay mineral and organic matter content of the sediment solid phase. Concentrations of monomethyl- and dimethyl amine were measured in the porewaters and the solid phase of sediment samples collected from Flax Pond and Lake Ronkonkoma (NY), Long Island Sound, and the coastal Peru upwelling area. These two amines were present in all sediments investigated. A clear seasonal increase in the solid-phase concentration of MMA and DMA in Flax Pond sediments was likely related to the annual senescence of salt marsh grasses, either directly as a source of these compounds or indirectly by providing additional exchange capacity to the sediments. The distribution of amines in the solid and dissolved phases observed in all sediments investigated suggests that the distribution of these compounds results from a balance among production, decomposition, and adsorption processes.

Effects of metal ions and pH on ofloxacin sorption to cassava residue-derived biochar.

PubMed

Huang, Peng; Ge, Chengjun; Feng, Dan; Yu, Huamei; Luo, Jiwei; Li, Jiatong; Strong, P J; Sarmah, Ajit K; Bolan, Nanthi S; Wang, Hailong

2018-03-01

In this study, the impacts of various cations, cation strength and pH on ofloxacin (OFL) adsorption to cassava residue-derived biochars were determined. The associated adsorption mechanisms are discussed. The biochars were prepared at pyrolysis temperatures ranging from 350°C to 750°C, and labeled as CW350, CW450, CW550, CW650 and CW750. The Freundlich model provided the best fit to describe the adsorption capacity of OFL and the Freundlich coefficient (logK f ) increased with increasing pyrolysis temperature. The inclusion of Zn 2+ or Al 3+ increased OFL sorption capacities of five biochars, while Cu 2+ reduced sorption to CW450 and CW550. No significant impacts on OFL sorption were observed in the presence of K + and Ca 2+ . The concentration of Ca 2+ affected the adsorption capacity of CW550, but had no significant impact on other biochars. The pH of OFL solution, ranging from 3 to 9, had no significant changes on OFL adsorption by all the tested biochars. Results of FTIR spectra and zeta potential indicated that electrostatic interactions, cationic exchange, metal bridging and micropore filling could be the main sorption mechanism between OFL and biochars. These studies indicated that cassava residue can be converted into biochars that are effective adsorbents for removing OFL from aqueous solution. Copyright © 2017 Elsevier B.V. All rights reserved.