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.

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.

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.

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.

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.

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

Assessment of natural attenuation of aromatic hydrocarbons in groundwater near a former manufactured-gas plant, South Carolina, USA

USGS Publications Warehouse

Landmeyer, J.E.; Chapelle, F.H.; Petkewich, M.D.; Bradley, P.M.

1998-01-01

Shallow, anaerobic groundwater near a former manufactured-gas plant (MGP) in Charleston, South Carolina, USA, contains mono- and polycyclic aromatic hydrocarbons (MAHs and PAHs, respectively). Between 1994 and 1997, a combination of field, laboratory, and numerical-flow and transport-model investigations were made to assess natural attenuation processes affecting MAH and PAH distributions. This assessment included determination of adsorption coefficients (K(ad)) and first-order biodegradation rate constants (K(bio)) using aquifer material from the MGP site and adjacent properties. Naphthalene adsorption (K(ad) = 1.35 x 10-7 m3/mg) to aquifer sediments was higher than toluene adsorption (K(ad) = 9.34 x 10-10 m3/mg), suggesting preferential toluene transport relative to naphthalene. However, toluene and benzene distributions measured in January 1994 were smaller than the naphthalene distribution. This scenario can be explained, in part, by the differences between biodegradation rates of the compounds. Aerobic first-order rate constants of 14C-toluene, 14C-benzene, and 14C-naphthalene degradation were similar (-0.84, -0.03, and 0.88 day-1, respectively), but anaerobic rate constants were higher for toluene and benzene (-0.002 and -0.00014 day-1, respectively) than for naphthalene (-0.000046 day-1). Both areal and cross-sectional numerical simulations were used to test the hypothesis suggested by these rate differences that MAH compounds will be contained relative to PAHs. Predictive simulations indicated that the distributions of toluene and benzene reach steady-state conditions before groundwater flow lines discharge to an adjacent surface-water body, but do discharge low concentrations of naphthalene. Numerical predictions were 'audited' by measuring concentrations of naphthalene, toluene, and benzene at the site in early 1997. Measured naphthalene and toluene concentrations were substantially reduced and the areal extent of contamination smaller than was both observed in January 1994 and predicted for 1997. Measured 1997 benzene concentrations and distribution were shown to be relatively unchanged from those measured in 1994, and similar to predictions for 1997.The natural attenuation processes affecting mono- and polycyclic aromatic hydrocarbons (MAHs and PAHs, respectively) distributions in groundwater near a former manufactured-gas plant in South Carolina, USA was evaluated. This assessment included determination of adsorption coefficients and first-order biodegradation rate constants. Detailed results obtained in the study are presented.

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.

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.

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).

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.

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.

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.

New sensitive micro-measurements of dynamic surface tension and diffusion coefficients: Validated and tested for the adsorption of 1-Octanol at a microscopic air-water interface and its dissolution into water.

PubMed

Kinoshita, Koji; Parra, Elisa; Needham, David

2017-02-15

Currently available dynamic surface tension (DST) measurement methods, such as Wilhelmy plate, droplet- or bubble-based methods, still have various experimental limitations such as the large size of the interface, convection in the solution, or a certain "dead time" at initial measurement. These limitations create inconsistencies for the kinetic analysis of surfactant adsorption/desorption, especially significant for ionic surfactants. Here, the "micropipette interfacial area-expansion method" was introduced and validated as a new DST measurement having a high enough sensitivity to detect diffusion controlled molecular adsorption at the air-water interfaces. To validate the new technique, the diffusion coefficient of 1-Octanol in water was investigated with existing models: the Ward Tordai model for the long time adsorption regime (1-100s), and the Langmuir and Frumkin adsorption isotherm models for surface excess concentration. We found that the measured diffusion coefficient of 1-Octanol, 7.2±0.8×10 -6 cm 2 /s, showed excellent agreement with the result from an alternative method, "single microdroplet catching method", to measure the diffusion coefficient from diffusion-controlled microdroplet dissolution, 7.3±0.1×10 -6 cm 2 /s. These new techniques for determining adsorption and diffusion coefficients can apply for a range of surface active molecules, especially the less-characterized ionic surfactants, and biological compounds such as lipids, peptides, and proteins. Copyright © 2016 Elsevier Inc. 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

Adsorption of Selected Pharmaceutical Compounds onto Activated Carbon in Dilute Aqueous Solutions Exemplified by Acetaminophen, Diclofenac, and Sulfamethoxazole.

PubMed

Chang, E-E; Wan, Jan-Chi; Kim, Hyunook; Liang, Chung-Huei; Dai, Yung-Dun; Chiang, Pen-Chi

2015-01-01

The adsorption of three pharmaceuticals, namely, acetaminophen, diclofenac, and sulfamethoxazole onto granular activated carbon (GAC), was investigated. To study competitive adsorption, both dynamic and steady-state adsorption experiments were conducted by careful selection of pharmaceuticals with various affinities and molecular size. The effective diffusion coefficient of the adsorbate was increased with decease in particle size of GAC. The adsorption affinity represented as Langmuir was consistent with the ranking of the octanol-water partition coefficient, K(ow). The adsorption behavior in binary or tertiary systems could be described by competition adsorption. In the binary system adsorption replacement occurred, under which the adsorbate with the smaller K(ow) was replaced by the one with larger K(ow). Results also indicated that portion of the micropores could be occupied only by the small target compound, but not the larger adsorbates. In multiple-component systems the competition adsorption might significantly be affected by the macropores and less by the meso- or micropores.

Adsorption of Selected Pharmaceutical Compounds onto Activated Carbon in Dilute Aqueous Solutions Exemplified by Acetaminophen, Diclofenac, and Sulfamethoxazole

PubMed Central

Chang, E.-E.; Wan, Jan-Chi; Liang, Chung-Huei; Dai, Yung-Dun; Chiang, Pen-Chi

2015-01-01

The adsorption of three pharmaceuticals, namely, acetaminophen, diclofenac, and sulfamethoxazole onto granular activated carbon (GAC), was investigated. To study competitive adsorption, both dynamic and steady-state adsorption experiments were conducted by careful selection of pharmaceuticals with various affinities and molecular size. The effective diffusion coefficient of the adsorbate was increased with decease in particle size of GAC. The adsorption affinity represented as Langmuir was consistent with the ranking of the octanol-water partition coefficient, K ow. The adsorption behavior in binary or tertiary systems could be described by competition adsorption. In the binary system adsorption replacement occurred, under which the adsorbate with the smaller K ow was replaced by the one with larger K ow. Results also indicated that portion of the micropores could be occupied only by the small target compound, but not the larger adsorbates. In multiple-component systems the competition adsorption might significantly be affected by the macropores and less by the meso- or micropores. PMID:26078989

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

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.

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 Behavior of Surfactant on Lignite Surface: A Comparative Experimental and Molecular Dynamics Simulation Study

PubMed Central

He, Meng; Zhang, Wei; Cao, Xiaoqiang; You, Xiaofang; Li, Lin

2018-01-01

Experimental and computational simulation methods are used to investigate the adsorption behavior of the surfactant nonylphenol ethoxylate (NPEO10), which contains 10 ethylene oxide groups, on the lignite surface. The adsorption of NPEO10 on lignite follow a Langmuir-type isotherm. The thermodynamic parameters of the adsorption process show that the whole process is spontaneous. X-ray photoelectron spectroscopic (XPS) analysis indicates that a significant fraction of the oxygen-containing functional groups on the lignitic surface were covered by NPEO10. Molecular dynamics (MD) simulations show that the NPEO10 molecules were found to adsorb at the water-coal interface. Moreover, polar interactions are the main effect in the adsorption process. The density distributions of coal, NPEO10, and water molecules along the Z axis show that the remaining hydrophobic portions of the surfactant extend into the solution, creating a more hydrophobic coal surface that repels water molecules. The negative interaction energy calculated from the density profiles of the head and tail groups along the three spatial directions between the surfactant and the lignitic surface suggest that the adsorption process is spontaneous. The self-diffusion coefficients show that the presence of NPEO10 causes higher water mobility by improving the hydrophobicity of lignite. PMID:29389899

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.

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.

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.

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.

Modeling the influence of variable pH on the transport of zinc in a contaminated aquifer using semiempirical surface complexation models

USGS Publications Warehouse

Kent, D.B.; Abrams, R.H.; Davis, J.A.; Coston, J.A.; LeBlanc, D.R.

2000-01-01

Land disposal of sewage effluent resulted in contamination of a sand and gravel aquifer (Cape Cod, Massachusetts) with zinc (Zn). The distribution of Zn was controlled by pH‐dependent adsorption; the Zn extended 15 m into the 30‐m‐thick sewage plume within approximately 100 m of the source but only 2–4 m into the plume between 100 and 400 m downgradient. A two‐dimensional vertical cross section model coupling groundwater flow with solute transport and equilibrium adsorption is used to simulate the influence of pH on Zn transport. Adsorption is described using semiempirical surface complexation models (SCM) by writing chemical reactions between dissolved Zn and mineral surface sites. SCM parameters were determined in independent laboratory experiments. A 59‐year simulation with a one‐site SCM describes the influence of pH on Zn transport well, with greater mobility at the low pH values near the upper sewage plume boundary than at the higher pH values deeper in the sewage‐contaminated zone. Simulation with a two‐site SCM describes both the sharpness and approximate location of the leading edge of the Zn‐contaminated region. Temporal variations in pH of incoming groundwater can result in large increases in Zn concentration and mobility. The influence of spatial and temporal variability in pH on adsorption and transport of Zn was accomplished much more easily with the semiempirical SCM approach than could be achieved with distribution coefficients or adsorption isotherms.

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

Assessment of atmospheric distribution of polycyclic aromatic hydrocarbons using a molecular structure model

NASA Astrophysics Data System (ADS)

Turk Sekulić, Maja; Okuka, Marija; Šenk, Nevena; Radonić, Jelena; Vojinović Miloradov, Mirjana; Vidicki, Branko

2013-07-01

In this paper, a comparison of experimentally obtained and SPARC software v4.6 modelled values of gas/particle partitioning coefficients was conducted to determine whether the evaluation of atmospheric distribution of PAH molecules can be performed using a molecular structure model. Partitioning coefficients were calculated for sixteen EPA PAHs, in thirty-nine samples of ambient air collected at nineteen urban, industrial, highly contaminated and background sites in the Republic of Serbia and Bosnia and Herzegovina. For obtaining samples of ambient air, the conventional high volume (Hi-Vol) methodology was applied, whereby gaseous and particulate phase data collection was conducted simultaneously by glass fibre filters (GFFs) and polyurethane foam filters (PUFs). The best prediction was for PAHs with 5 or more rings (benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, indeno(1,2,3-cd)perylene and benzo(ghi)perylene). For evaluating the applicability of SPARC software predictions of gas/particle partitioning coefficients for the existing conditions, the results were compared with those obtained by applying other frequently used and highly ranked theoretical models of phase distributions, namely Junge-Pankow adsorption model, KOA absorption model, Dachs-Eisenreich dual model and PP-LFER model.

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.

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.

Carrier Mediated Distribution System (CAMDIS): a new approach for the measurement of octanol/water distribution coefficients.

PubMed

Wagner, Bjoern; Fischer, Holger; Kansy, Manfred; Seelig, Anna; Assmus, Frauke

2015-02-20

Here we present a miniaturized assay, referred to as Carrier-Mediated Distribution System (CAMDIS) for fast and reliable measurement of octanol/water distribution coefficients, log D(oct). By introducing a filter support for octanol, phase separation from water is facilitated and the tendency of emulsion formation (emulsification) at the interface is reduced. A guideline for the best practice of CAMDIS is given, describing a strategy to manage drug adsorption at the filter-supported octanol/buffer interface. We validated the assay on a set of 52 structurally diverse drugs with known shake flask log D(oct) values. Excellent agreement with literature data (r(2) = 0.996, standard error of estimate, SEE = 0.111), high reproducibility (standard deviation, SD < 0.1 log D(oct) units), minimal sample consumption (10 μL of 100 μM DMSO stock solution) and a broad analytical range (log D(oct) range = -0.5 to 4.2) make CAMDIS a valuable tool for the high-throughput assessment of log D(oc)t. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

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 isotherms of some alkyl aromatic hydrocarbons and surface energies on partially dealuminated Y faujasite zeolite by inverse gas chromatography.

PubMed

Kondor, Anett; Dallos, András

2014-10-03

Adsorption isotherm data of some alkyl aromatic hydrocarbons (benzene, toluene, ethylbenzene, o-xylene, m-xylene and p-xylene) measured in the temperature range of 423-523K on a partially dealuminated faujasite type DAY F20 zeolite by inverse gas chromatography are presented in this work. The temperature dependent form of Tóth's equation has been fitted to the multiple temperature adsorption isotherms of benzene, toluene, ethylbenzene, o-xylene, m-xylene and p-xylene with standard deviations of 4.6, 5.0, 5.9, 4.3, 5.1 and 6.3mmolkg(-1) and coefficients of determinations (r(2)) of 0.977, 0.971, 0.974, 0.975, 0.991 and 0.991, respectively. The gas-solid equilibria and modeling were interpreted on the basis of the interfacial properties of the zeolite, by dispersive, specific and total surface energy heterogeneity profiles and distributions of the adsorbent measured by surface energy analysis. Copyright © 2014 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.

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.

Removal of radium from acidic solutions containing same by adsorption on coal fly ash

DOEpatents

Scheitlin, Frank M.

1984-01-01

The invention is a process for the removal of radium from acidic aqueous solutions. In one aspect, the invention is a process for removing radium from an inorganic-acid solution. The process comprises contacting the solution with coal fly ash to effect adsorption of the radium on the ash. The radium-containing ash then is separated from the solution. The process is simple, comparatively inexpensive, and efficient. High radium-distribution coefficients are obtained even at room temperature. Coal fly ash is an inexpensive, acid-resistant, high-surface-area material which is available in large quantities throughout the United States. The invention is applicable, for example, to the recovery of .sup.226 Ra from nitric acid solutions which have been used to leach radium from uranium-mill tailings.

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.

Kinetics of heavy metal adsorption and desorption in soil: Developing a unified model based on chemical speciation

NASA Astrophysics Data System (ADS)

Peng, Lanfang; Liu, Paiyu; Feng, Xionghan; Wang, Zimeng; Cheng, Tao; Liang, Yuzhen; Lin, Zhang; Shi, Zhenqing

2018-03-01

Predicting the kinetics of heavy metal adsorption and desorption in soil requires consideration of multiple heterogeneous soil binding sites and variations of reaction chemistry conditions. Although chemical speciation models have been developed for predicting the equilibrium of metal adsorption on soil organic matter (SOM) and important mineral phases (e.g. Fe and Al (hydr)oxides), there is still a lack of modeling tools for predicting the kinetics of metal adsorption and desorption reactions in soil. In this study, we developed a unified model for the kinetics of heavy metal adsorption and desorption in soil based on the equilibrium models WHAM 7 and CD-MUSIC, which specifically consider metal kinetic reactions with multiple binding sites of SOM and soil minerals simultaneously. For each specific binding site, metal adsorption and desorption rate coefficients were constrained by the local equilibrium partition coefficients predicted by WHAM 7 or CD-MUSIC, and, for each metal, the desorption rate coefficients of various binding sites were constrained by their metal binding constants with those sites. The model had only one fitting parameter for each soil binding phase, and all other parameters were derived from WHAM 7 and CD-MUSIC. A stirred-flow method was used to study the kinetics of Cd, Cu, Ni, Pb, and Zn adsorption and desorption in multiple soils under various pH and metal concentrations, and the model successfully reproduced most of the kinetic data. We quantitatively elucidated the significance of different soil components and important soil binding sites during the adsorption and desorption kinetic processes. Our model has provided a theoretical framework to predict metal adsorption and desorption kinetics, which can be further used to predict the dynamic behavior of heavy metals in soil under various natural conditions by coupling other important soil processes.

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...

Adsorption of aliphatic polyhydroxy carboxylic acids on gibbsite: pH dependency and importance of adsorbate structure.

PubMed

Schneckenburger, Tatjana; Riefstahl, Jens; Fischer, Klaus

2018-01-01

Aliphatic (poly)hydroxy carboxylic acids [(P)HCA] occur in natural, e.g. soils, and in technical (waste disposal sites, nuclear waste repositories) compartments . Their distribution, mobility and chemical reactivity, e.g. complex formation with metal ions and radionuclides, depend, among others, on their adsorption onto mineral surfaces. Aluminium hydroxides, e.g. gibbsite [α-Al(OH) 3 ], are common constituents of related solid materials and mimic the molecular surface properties of clay minerals. Thus, the study was pursued to characterize the adsorption of glycolic, threonic, tartaric, gluconic, and glucaric acids onto gibbsite over a wide pH and (P)HCA concentration range. To consider specific conditions occurring in radioactive wastes, adsorption applying an artificial cement pore water (pH 13.3) as solution phase was investigated additionally. The sorption of gluconic acid at pH 4, 7, 9, and 12 was best described by the "two-site" Langmuir isotherm, combining "high affinity" sorption sites (adsorption affinity constants [Formula: see text] > 1 L mmol -1 , adsorption capacities < 6.5 mmol kg -1 ) with "low affinity" sites ([Formula: see text] < 0.1 L mmol -1 , adsorption capacities ≥ 19 mmol kg -1 ). The total adsorption capacities at pH 9 and 12 were roughly tenfold of that at pH 4 and 7. The S-shaped pH sorption edge of gluconic acid was modelled applying a constant capacitance model, considering electrostatic interactions, hydrogen bonding, surface complex formation, and formation of solved polynuclear complexes between Al 3+ ions and gluconic acid. A Pearson and Spearman rank correlation between (P)HCA molecular properties and adsorption parameters revealed the high importance of the size and the charge of the adsorbates. The adsorption behaviour of (P)HCAs is best described by a combination of adsorption properties of carboxylic acids at acidic pH and of polyols at alkaline pH. Depending on the molecular properties of the adsorbates and on pH, electrostatic interactions, hydrogen bonding, and ternary surface complexation contribute in varying degrees to the adsorption process. Linear distribution coefficients K d between 8.7 and 60.5 L kg -1 (1 mmol L -1 initial PHCA concentration) indicate a considerable mineral surface affinity at very high pH, thus lowering the PHCA fraction available for the complexation of metal ions including radionuclides in solution and their subsequent mobilization.

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.

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 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.

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.

Modeling the Performance of Water-Zeolite 13X Adsorption Heat Pump

NASA Astrophysics Data System (ADS)

Kowalska, Kinga; Ambrożek, Bogdan

2017-12-01

The dynamic performance of cylindrical double-tube adsorption heat pump is numerically analysed using a non-equilibrium model, which takes into account both heat and mass transfer processes. The model includes conservation equations for: heat transfer in heating/cooling fluids, heat transfer in the metal tube, and heat and mass transfer in the adsorbent. The mathematical model is numerically solved using the method of lines. Numerical simulations are performed for the system water-zeolite 13X, chosen as the working pair. The effect of the evaporator and condenser temperatures on the adsorption and desorption kinetics is examined. The results of the numerical investigation show that both of these parameters have a significant effect on the adsorption heat pump performance. Based on computer simulation results, the values of the coefficients of performance for heating and cooling are calculated. The results show that adsorption heat pumps have relatively low efficiency compared to other heat pumps. The value of the coefficient of performance for heating is higher than for cooling

Evaluation of sewage sludge and slow pyrolyzed sewage sludge-derived biochar for adsorption of phenanthrene and pyrene.

PubMed

Zielińska, Anna; Oleszczuk, Patryk

2015-09-01

The present study investigated the sorption of phenanthrene (PHE) and pyrene (PYR) by sewage sludges and sewage sludge-derived biochars. The organic carbon normalized distribution coefficient (log K(OC) for C(w) = 0.01 S(w)) for the sewage sludges ranged from 5.62 L kg(-1) to 5.64 L kg(-1) for PHE and from 5.72 L kg(-1) to 5.75 L kg(-1) for PYR. The conversion of sewage sludges into biochar significantly increased their sorption capacity. The value of log K(OC) for the biochars ranged from 5.54 L kg(-1) to 6.23 L kg(-1) for PHE and from 5.95 L kg(-1) to 6.52 L kg(-1) for PYR depending on temperature of pyrolysis. The dominant process was monolayer adsorption in the micropores and/or multilayer surface adsorption (in the mesopores), which was indicated by the significant correlations between log K(OC) and surface properties of biochars. PYR was sorbed better on the tested materials than PHE. Copyright © 2015 Elsevier Ltd. All rights reserved.

Quantifying the equilibrium partitioning of substituted polycyclic aromatic hydrocarbons in aerosols and clouds using COSMOtherm.

PubMed

Awonaike, Boluwatife; Wang, Chen; Goss, Kai-Uwe; Wania, Frank

2017-03-22

Functional groups attached to polycyclic aromatic hydrocarbons (PAHs) can significantly modify the environmental fate of the parent compound. Equilibrium partition coefficients, which are essential for describing the environmental phase distribution of a compound, are largely unavailable for substituted PAHs (SPAHs). Here, COSMOtherm, a software based on quantum-chemical calculations is used to estimate the atmospherically relevant partition coefficients between the gas phase, the aqueous bulk phase, the water surface and the water insoluble organic matter phase, as well as the salting-out coefficients, for naphthalene, anthracene, phenanthrene, benz(a)anthracene, benzo(a)pyrene and dibenz(a,h)anthracene and 62 of their substituted counterparts. They serve as input parameters for the calculation of equilibrium phase distribution of these compounds in aerosols and clouds. Our results, which were compared with available experimental data, show that the effect of salts, the adsorption to the water surface and the dissolution in a bulk aqueous phase can be safely neglected when estimating the gas-particle partitioning of SPAHs in aerosols. However, for small PAHs with more than one polar functional group the aqueous phase can be the dominant reservoir in a cloud.

Fate and mobility of pharmaceuticals in solid matrices.

PubMed

Drillia, Panagiota; Stamatelatou, Katerina; Lyberatos, Gerasimos

2005-08-01

The sorption and mobility of six pharmaceuticals were investigated in two soil types with different organic carbon and clay content, and in bacterial biomass (aerobic and anaerobic). The pharmaceuticals examined were carbamazepine, propranolol, diclofenac sodium, clofibric acid, sulfamethoxazole and ofloxacin. The sorption experiments were performed according to the OECD test Guideline 106. The distribution coefficients determined by this batch equilibrium method varied with the pharmaceutical tested and the solid matrix type. Ofloxacin was particularly strongly adsorbed (except of the case of using anaerobic biomass for the solid matrix) while clofibric acid was found to be weakly adsorbed. The fate of pharmaceuticals in soil was also assessed using lysimeters. Important parameters that were studied were: the pharmaceutical loading rate and the hydraulic loading rate for adsorption and the rate and duration of a "rain" event for desorption. Major differences in the mobility of the six pharmaceuticals were observed and correlated with the adsorption/desorption properties of the compounds.

Selective Adsorption and Selective Transport Diffusion of CO2-CH4 Binary Mixture in Coal Ultramicropores.

PubMed

Zhao, Yongliang; Feng, Yanhui; Zhang, Xinxin

2016-09-06

The adsorption and diffusion of the CO2-CH4 mixture in coal and the underlying mechanisms significantly affect the design and operation of any CO2-enhanced coal-bed methane recovery (CO2-ECBM) project. In this study, bituminous coal was fabricated based on the Wiser molecular model and its ultramicroporous parameters were evaluated; molecular simulations were established through Grand Canonical Monte Carlo (GCMC) and Molecular Dynamic (MD) methods to study the effects of temperature, pressure, and species bulk mole fraction on the adsorption isotherms, adsorption selectivity, three distinct diffusion coefficients, and diffusivity selectivity of the binary mixture in the coal ultramicropores. It turns out that the absolute adsorption amount of each species in the mixture decreases as temperature increases, but increases as its own bulk mole fraction increases. The self-, corrected, and transport diffusion coefficients of pure CO2 and pure CH4 all increase as temperature or/and their own bulk mole fractions increase. Compared to CH4, the adsorption and diffusion of CO2 are preferential in the coal ultramicropores. Adsorption selectivity and diffusivity selectivity were simultaneously employed to reveal that the optimal injection depth for CO2-ECBM is 800-1000 m at 308-323 K temperature and 8.0-10.0 MPa.

Mechanism and kinetics of uranium adsorption onto soil around coal-fired power plant

NASA Astrophysics Data System (ADS)

Yasim, Nurzulaifa Shaheera Erne Mohd; Ariffin, Nik Azlin Nik; Mohammed, Noradila; Ayob, Syafina

2017-11-01

Coal is the largest source of energy in Malaysia providing approximately 80 % of all entire power needs. The combustion of coal concentrates a high content of heavy metals and radioactive elements in the ashes and sludge. Hazardous emissions from coal combustion were deposited into the soil and most likely transported into the groundwater system. The presence of radioactive materials in the ground water system can cause a wide range of environmental impacts and adverse health effects like cancer, impairment of neurological function and cardiovascular disease. However, the soil has a natural capability in adsorption of radioactive materials. Thus, this study was evaluated the adsorption capacity of Uranium onto the soil samples collected nearby the coal-fired power plants. In the batch experiment, parameters that were set constant include pH, the amount of soil and contact time. Various initial concentrations of radionuclides elements in the range of 2 mg/L - 10 mg/L were used. The equilibrium adsorption data was analyzed by the Freundlich isotherm and Langmuir isotherms. Then, the influences of solution pH, contact time and temperature on the adsorption process were investigated. The kinetics of radioactive materials was discussed by pseudo-first-order and pseudo-second-order rate equation. Thus, the data from this study could provide information about the potentiality of soil in sorption of radioactive materials that can be leached into groundwater. Besides that, this study could also be used as baseline data for future reference in the development of adsorption modeling in the calculation of distribution coefficient.

Butyltin sorption onto freshwater sediments: from batch experiments to the field values

NASA Astrophysics Data System (ADS)

Bancon-Montingy, C.; Aubert, G.; Chahinian, N.; Meyer, J.; Brunel, V.; Tournoud, M. G.

2009-04-01

Butyltins, and most particularly TBT were widely used by the industry in the 1970s and 1980s, namely as anti-fouling paints on ships. Although banned since 2003 in Europe, surveys still point out the presence of these compounds both in coastal and terrestrial environments. The resilience of organotin (OT) compounds can be explained by their high adsorption capacity. OTs can bond easily to particulate matter and "migrate" from the water column unto the sediments where their half-life can extend to a few decades. Consequently sediments can become important organotin stores and release OT compounds during dredging operations, storms, tides or floods. Studies on OT behavior in freshwater environments, mainly sediments, are scarce in the literature compared with marine sediments. However, it is known that sorption behaviour of organotin compounds on sediments is governed by the constituents of sediments, and the composition of interstitial water in the sediments and overlying water, i.e. grain size distribution, clay minerals, organic matter, iron, aluminium (hydr)oxides and carbonate in the sediments; salinity, ionic composition, and pH of interstitial water in the sediments and overlying water. The main objective of this work is to assess butyltin adsorption into the sediments of an intermittent river located in southern France: The Vène. Sediments were collected during high and low flow conditions and batch experiments were set up using "natural" and "crushed" sediments to assess the adsorption kinetics. Classical batch experiments and GC-ICP-MS analysis were carried out to measure the distribution coefficient (Kd). The influence of organic substances on sorption processes for organotin species was studied and the role of grain size distribution assessed by comparing natural and crushed sediments. The results indicated that organotin compounds are sorbed easily and quickly on freshwater sediments. The adsorption isotherm for butyltins follows the Freundlich equation which is used to describe the adsorption behaviour of non-polar organic matters. This is due to their organic substituent groups. The presence of organic matter modifies the sorption process: less OT is adsorbed onto the sediments. This leads to increased OT concentrations in solution and consequently a higher probability for assimilation by freshwater organisms. The comparison of our results to those reported in the literature for marine environments could not be carried out because of the wide differences in salinity and grain size distribution between the two environments.

Adsorption energy distribution of carbon tetrachloride on carbon nanofiber arrays prepared by template synthesis

NASA Astrophysics Data System (ADS)

Wu, Chi-Hsin; Shr, Jin-Fang; Wu, Chu-Fu; Hsieh, Chien-Te

2008-02-01

The influence of pore size distribution on adsorption energy distributions (AEDs) of aligned carbon nanofiber (CNF) arrays in vapor phase was conducted in the present study. A template-assisted synthesis was employed to fabricate aligned CNF arrays with different pore size distributions (PSDs). Adsorption isotherms of CCl 4 onto the CNF arrays were investigated within an entire pressure of 0.05-0.18 atm at 30 °C. The adsorptive surface coverage was found to decrease with the average pore size, indicating the presence of heterogeneity for gas adsorption. An AED model was postulated to describe the heterogeneous surface consisting of numerous surface pitchwises that obey a localized Langmuir model. It was found that all CNF arrays exhibit a similar Gaussian-type AED, in where the peak adsorption energy shifts to a higher energy with decreasing the pore size of CNFs. This finding can be ascribed to a fact that micropores are major providers of adsorption sites, whereas in mesopores only weaker adsorption is observed, thus resulting in the shift of energy distribution. An excellent prediction to the adsorption isotherms of CCl 4 by the AED model indicates that the PSD of CNFs acts a crucial factor in affecting the adsorptive coverage.

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.

Dependence of particle concentration effect on pH and redox for arsenic removal by FeS-coated sand under anoxic conditions.

PubMed

Han, Young-Soo; Demond, Avery H; Gallegos, Tanya J; Hayes, Kim F

2015-09-01

FeS has been recognized as a good scavenger for arsenic under anoxic conditions. To create a suitable adsorbent for flow-through reactors such as permeable reactive barriers, it has been suggested that this material may be coated onto sand. However, previous work on FeS-coated sand has focused on batch reactors, while flow-through reactors usually have higher solid-solution ratios. To ascertain whether differences in the solid-solution ratio (SSR) are important in this system, batch sorption experiments were conducted as a function of pH using As(III) and FeS-coated sands at various solid-solution ratios. The results showed little variation in the distribution coefficient with SSR at pH 7 and 9. However, at pH 5, the results showed lower values of the distribution coefficient at lower SSRs, the reverse of typically reported SSR effects. Measured pe values showed a dependence on SSR, which, when coupled with chemical modeling of the Fe-As-S-H2O system, suggested a change in the removal mechanism with SSR, from adsorption to a reduced Fe(II) oxyhydroxide phase (represented by Fe2(OH)5) to precipitation as As2S3 or AsS. On the other hand, at pH 7 and 9, arsenite adsorption is the most probable removal mechanism regardless of the pe. Thus, this study identified variations in pH and redox conditions, and the removal mechanisms that these parameters govern, as the reason for the apparent SSR effect. Copyright © 2014 Elsevier Ltd. All rights reserved.

SEPARATION OF PROTACTINIUM FROM THORIUM IN NITRIC ACID SOLUTIONS BY SOLVENT EXTRACTION WITH TRIBUTYL PHOSPHATE OR BY ADSORPTION ON PULVERIZED UNFIRED VYCOR GLASS OR SILICA GEL

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

Moore, J.G.; Rainey, R.H.

1963-04-01

Two methods were investigated for the separation and recovery of Pa from short-decayed Th fuel in HNO/sub 3/ solutions. The Pa/sub 233/, Th, and U may be coextracted from highly acidic feed solutions with 30% tributyl phosphate, or the Pa may be preferentially adsorbed on pulverized unfired Vycor glass or silica gel. Major effort has been on the adsorption method. Adsorption experiments with tracer concentrations of Pa/sup 233/ in HNO/sub 3/ solutions showed distribution coefficient maxima for Pa of about 1000, 325, and 175 from 6 to 10 M HNO/sub 3/ for laboratory-prepared silica gel, unfired Vycor, and commercial silicamore » gel, respectively. Unfired Vycor, a commercial, leached borosilicate glass containing 96% SiO/sub 2/ and about 3% B/sub 2/O/sub 3/, was used for most of the studies. Fired Vycor glass adsorbed little or no Pa. The adsorption coefficient of Pa by unfired Vycor glass from HNO/sub 3/ solutions increased as the contact time increased or as the particle size of the glass decreased and was dependent on the concentration of salt or HNO/sub 3/ in the solution. The adsorbed Pa may be eluted with oxalic or tartaric acids. Although optimum conditions for column operations were not determined, decontamination factors of Pa from Th, U, Ru, Zr- Nb and total rare earths of 6x 10/sup 3/, 1.6 x 101,4 x 10/sup 3/, 3, and 5.8 x 10/sup 5/, respectively, were obtained in tracer experiments. Batch countercurrent scouting experiments with tracer Pa showed that about 90% of the Pa was extracted with the Th and U from 5 M HNO/sub 3/-1 M Al(NO/sub 3/)/sub 3/ solutions, with a decontamination factor of 70 from Ru and about 10/sup 5/ from rare earths. (P.C.H.)« less

High-resolution insight into the competitive adsorption of heavy metals on natural sediment by site energy distribution.

PubMed

Huang, Limin; Jin, Qiang; Tandon, Puja; Li, Aimin; Shan, Aidang; Du, Jiajie

2018-04-01

Investigating competitive adsorption on river/lake sediments is valuable for understanding the fate and transport of heavy metals. Most studies have studied the adsorption isotherms of competitive heavy metals, which mainly comparing the adsorption information on the same concentration. However, intrinsically, the concentration of each heavy metal on competitive adsorption sites is different, while the adsorption energy is identical. Thus, this paper introduced the site energy distribution theory to increase insight into the competitive adsorption of heavy metals (Cu, Cd and Zn). The site energy distributions of each metal with and without other coexisting heavy metals were obtained. It illustrated that site energy distributions provide much more information than adsorption isotherms through screening of the full energy range. The results showed the superior heavy metal in each site energy area and the influence of competitive metals on the site energy distribution of target heavy metal. Site energy distributions can further help in determining the competitive sites and ratios of coexisting metals. In particular, in the high-energy area, which has great environmental significance, the ratios of heavy metals in the competitive adsorption sites obtained for various competitive systems were as follows: slightly more than 3:1 (Cu-Cd), slightly less than 3:1 (Cu-Zn), slightly more than 1:1 (Cd-Zn), and nearly 7:2:2 (Cu-Cd-Zn). The results from this study are helpful to deeply understand competitive adsorption of heavy metals (Cu, Cd, Zn) on sediment. Therefore, this study was effective in presenting a general pattern for future reference in competitive adsorption studies on sediments. Copyright © 2018 Elsevier Ltd. 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.

Functionalisation of mesoporous silica gel with 2-[(phosphonomethyl)-amino]acetic acid functional groups. Characterisation and application

NASA Astrophysics Data System (ADS)

Caldarola, Dario; Mitev, Dimitar P.; Marlin, Lucile; Nesterenko, Ekaterina P.; Paull, Brett; Onida, Barbara; Bruzzoniti, Maria Concetta; Carlo, Rosa Maria De; Sarzanini, Corrado; Nesterenko, Pavel N.

2014-01-01

A new complexing adsorbent was prepared by chemical modification of mesoporous silica Kieselgel 60 (dp = 37-63 μm, average pore size 6 nm, specific surface area 425 m2 g-1) with 3-glycidoxypropyltrimethoxysilane and 2-[(phosphonomethyl)amino]acetic acid (PMA), commonly known as glyphosate. The prepared adsorbent was fully characterised using elemental analysis, thermal gravimetric analysis (TGA), acid-base potentiometric titration, Fourier Transform Infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption isotherms at 77 K (BET), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS). The concentration of bonded PMA groups calculated from the nitrogen content was 0.38 mmol per gram. The adsorption of transition metal ions on PMA functionalised silica (HEPMAS) was studied from aqueous solutions having different pH and the following selectivity was established, Zn(II) < Co(II) < Cd(II) < Mn(II) < Ni(II) < Cu(II). The calculated values of distribution coefficients D for the adsorption of ecotoxic metal ions on HEPMAS are 5.0 × 104, 4.9 × 105 and 2.6 × 104 for Zn(II), Pb(II) and Cd(II), respectively.

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.

The removal of uranium (VI) from aqueous solutions onto activated carbon developed from grinded used tire.

PubMed

Belgacem, Ahmed; Rebiai, Rachid; Hadoun, Hocine; Khemaissia, Sihem; Belmedani, Mohamed

2014-01-01

In this study, activated carbon was prepared from waste tire by KOH chemical activation. The pore properties including the BET surface area, pore volume, pore size distribution, and average pore diameter were characterized. BET surface area of the activated carbon was determined as 558 m(2)/g. The adsorption of uranium ions from the aqueous solution using this activated carbon has been investigated. Various physico-chemical parameters such as pH, initial metal ion concentration, and adsorbent dosage level and equilibrium contact time were studied by a batch method. The optimum pH for adsorption was found to be 3. The removal efficiency has also been determined for the adsorption system as a function of initial concentration. The experimental results were fitted to Langmuir, Freundlich, and Dubinin-Radushkevich (D-R) isotherm models. A comparison of best-fitting was performed using the coefficient of correlation and the Langmuir isotherm was found to well represent the measured sorption data. According to the evaluation using the Langmuir equation, the saturated monolayer sorption capacity of uranium ions onto waste tire activated carbon was 158.73 mg/g. The thermodynamic equilibrium constant and the Gibbs free energy were determined and results indicated the spontaneous nature of the adsorption process. Kinetics data were best described by pseudo-second-order model.

Understanding the sorption mechanisms of aflatoxin B1 to kaolinite, illite, and smectite clays via a comparative computational study.

PubMed

Kang, Fuxing; Ge, Yangyang; Hu, Xiaojie; Goikavi, Caspar; Waigi, Michael Gatheru; Gao, Yanzheng; Ling, Wanting

2016-12-15

In current adsorption studies of biotoxins to phyllosilicate clays, multiply weak bonding types regarding these adsorptions are not well known; the major attractive forces, especially for kaolinite and illite, are difficult to be identified as compared to smectite with exchangeable cations. Here, we discriminated the bonding types of aflatoxin B1 (AFB1) contaminant to these clays by combined batch experiment with model computation, expounded their bonding mechanisms which have been not quantitatively described by researchers. The observed adsorbent-to-solution distribution coefficients (K d ) of AFB1 presented in increasing order of 18.5-37.1, 141.6-158.3, and 354.6-484.7L/kg for kaolinite, illite, and smectite, respectively. Normalization of adsorbent-specific surface areas showed that adsorption affinity of AFB1 is mainly dependent on the outside surfaces of clay aggregates. The model computation and test of ionic effect further suggested that weakly electrostatic attractions ((Si/Al-OH) 2 ⋯(OC) 2 ) are responsible for AFB1-kaolinite adsorption (K d , 18.5-37.1L/kg); a moderate electron-donor-acceptor attraction ((CO) 2 ⋯K + ⋯(O-Al) 3 ) is related to AFB1-illite adsorption (K d , 141.6-158.3L/kg); a strong calcium-bridging linkage ((CO) 2 ⋯Ca 2+ ⋯(O-Si) 4 ) is involved in AFB1-smectite adsorption (K d , 354.6-484.7L/kg). Changes in Gibbs free energy (ΔG°) suggested that the computed result is reliable, providing a good reproduction of AFB1-clay interaction. Copyright © 2016 Elsevier B.V. All rights reserved.

Effects of salinity and organic matter on the partitioning of perfluoroalkyl acid (PFAs) to clay particles.

PubMed

Jeon, Junho; Kannan, Kurunthachalam; Lim, Byung J; An, Kwang Guk; Kim, Sang Don

2011-06-01

The influence of salinity and organic matter on the distribution coefficient (K(d)) for perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) in a brackish water-clay system was studied. The distribution coefficients (K(d)) for PFAs onto inorganic clay surfaces increased with salinity, providing evidence for electrostatic interaction for the sorption of PFAs, whereas the relationship between K(d) and organic carbon content (f(oc)) suggested that hydrophobic interaction is the primary driving force for the sorption of PFAs onto organic matter. The organic carbon normalized adsorption coefficient (K(oc)) of PFAs can be slightly overestimated due to the electrostatic interaction within uncoated inorganic surfaces. In addition, the dissolved organic matter released from coated clay particles seemed to solvate PFA molecules in solution, which contributed to a decrease in K(d). A positive relationship between K(d) and salinity was apparent, but an empirical relationship for the 'salting-out' effect was not evident. The K(d) values of PFAs are relatively small compared with those reported for persistent organic pollutants. Thus, sorption may not be a significant route of mass transfer of PFAs from water columns in estuarine environments. However, enhancement of sorption of PFAs to particulate matter at high salinity values could evoke potential risks to benthic organisms in estuarine areas.

Design and development of radioactive xenon gas purification and analysis system based on molecular sieves.

PubMed

Sabzian, M; Nasrabadi, M N; Haji-Hosseini, M

2018-10-01

The dynamic adsorption of xenon on molecular sieve packed columns was investigated. The modified Wheeler-Jonas equation was used to describe adsorption parameters such as adsorption capacity and adsorption rate coefficient. Different experimental conditions were accomplished to study their effects and to touch appropriate adsorbing circumstances. Respectable consistency was reached between experimental and modeled values. A purification and analysis setup was developed for radioactive xenon gas determination. Standard sample analysis results approved acceptable quantification accuracy. Copyright © 2018. Published by Elsevier Ltd.

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

Removal of perfluorinated surfactants from wastewater by adsorption and ion exchange - Influence of material properties, sorption mechanism and modeling.

PubMed

Schuricht, Falk; Borovinskaya, Ekaterina S; Reschetilowski, Wladimir

2017-04-01

Perfluorooctane sulfonate (PFOS) has attracted increasing concern in recent years due to its world-wide distribution, persistence, bioaccumulation and potential toxicity. The influence of sorbent properties on the adsorptive elimination of PFOS from wastewater by activated carbons, polymer adsorbents and anion exchange resins was investigated with regard to their isotherms and kinetics. The batch and column tests were combined with physicochemical characterization methods, e.g., N 2 physisorption, mercury porosimetry, infrared spectroscopy, differential scanning calorimetry, titrations, as well as modeling. Sorption kinetics was successfully modelled applying the linear driving force (LDF) approach for surface diffusion after introducing a load dependency of the mass transfer coefficient β s . The big difference in the initial mass transfer coefficient β s,0 , when non-functionalized adsorbents and ion-exchange resins are compared, suggests that the presence of functional groups impedes the intraparticle mass transport. The more functional groups a resin possesses and the longer the alkyl moieties are the bigger is the decrease in sorption rate. But the selectivity for PFOS sorption is increasing when the character of the functional groups becomes more hydrophobic. Accordingly, ion exchange and hydrophobic interaction were found to be involved in the sorption processes on resins, while PFOS is only physisorptively bound to activated carbons and polymer adsorbents. In agreement with the different adsorption mechanisms, resins possess higher total sorption capacities than adsorbents. Hence, the latter ones are rendered more effective in PFOS elimination at concentrations in the low μg/L range, due to a less pronounced convex curvature of the sorption isotherm in this concentration range. Copyright © 2016. Published by Elsevier B.V.

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.

Characterization of adsorption and desorption of lawn herbicide siduron in heavy metal contaminated soils.

PubMed

Jiang, Rong; Wang, Meie; Chen, Weiping

2018-08-01

Siduron is a widely used herbicide in urban lawn and has been frequently detected in urban and suburban surface water. However, characteristics of its environmental behavior in soil are seldom reported. The combined pollution of heavy metals, especially for Cu, Pb, Cd, Zn and siduron would be common because of the widely existence of heavy metal pollution in urban soils. In this study, four soils with similar physicochemical properties but different levels of preexisting heavy metals were selected to investigate the adsorption and successive desorption of siduron using batch experiments. The results revealed a low sorption of siduron to all the tested soils. The organic carbon normalized distribution coefficient (K oc ) of siduron in the studied soils ranged from 117 to 137 L kg -1 and was not significantly correlated to heavy metal levels. No apparent desorption hysteresis was observed with the hysteresis index (HI) ranging from 0.921 to 1.11. More than 50% of the sorbed siduron was readily released into soil solution. Results suggested that siduron was highly mobile and bioavailable in the studied soils. Significant correlation was found between adsorption/desorption parameters and soil organic carbon (SOC) in four soils. soil organic matter was thus considered as the dominant factor determining the adsorption and desorption of siduron in soils. Different from most of reported studies conducted by laboratory-amended soils, the influence of preexisting heavy metals on the adsorption-desorption of siduron was not significant in this work. Copyright © 2018 Elsevier Ltd. All rights reserved.

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.

Acetylated Lysozyme as Impurity in Lysozyme Crystals: Constant Distribution Coefficient

NASA Technical Reports Server (NTRS)

Thomas, B. R.; Chernov, A. A.

2000-01-01

Hen egg white lysozyme (HEWL) was acetylated to modify molecular charge keeping the molecular size and weight nearly constant. Two derivatives, A and B, more and less acetylated, respectively, were obtained, separated, purified and added to the solution from which crystals of tetragonal HEWL crystals were grown. Amounts of the A or B impurities added were 0.76, 0.38 and 0.1 milligram per millimeter while HEWL concentration were 20, 30 and 40 milligram per milliliter. The crystals grown in 18 experiments for each impurity were dissolved and quantities of A or B additives in these crystals were analyzed by cation exchange high performance liquid chromatography. All the data for each set of 18 samples with the different impurity and regular HEWL concentrations is well described by one distribution coefficient K = 2.15 plus or minus 0.13 for A and K = 3.42 plus or minus 0.25 for B. The observed independence of the distribution coefficient on both the impurity concentration and supersaturation is explained by the dilution model described in this paper. It shows that impurity adsorption and incorporation rate is proportional to the impurity concentration and that the growth rate is proportional to the crystallizing protein in solution. With the kinetic coefficient for crystallization, beta = 5.10(exp -7) centimeters per second, the frequency at which an impurity molecule near the growing interface irreversibly joins a molecular site on the crystal was found to be 3 1 per second, much higher than the average frequency for crystal molecules. For best quality protein crystals it is better to have low microheterogeneous protein impurity concentration and high supers aturation.

Xe adsorption site distributions on Pt(111), Pt(221) and Pt(531)

NASA Astrophysics Data System (ADS)

Gellman, Andrew J.; Baker, L.; Holsclaw, B. S.

2016-04-01

The ideal structures of the Pt(111), Pt(221) and Pt(531) surfaces expose adsorption sites that can be qualitatively described as terrace sites on Pt(111), both step and terrace sites on Pt(221), and kink sites on Pt(531). The real surface structures of these surfaces can be complicated by imperfections such as misorientation, reconstruction and thermal roughening, all of which will influence their distributions of adsorption sites. Xe adsorption sites on the Pt(111), Pt(221) and Pt(531) surfaces have been probed using both photoemission of adsorbed Xe (PAX) and temperature programmed desorption (TPD) of Xe. Both PAX and Xe TPD are sensitive to the adsorption sites of the Xe and serve as complementary means of assessing the distributions of adsorption sites on these three Pt surfaces. The adsorption of Xe is sufficiently sensitive to detect the presence of residual steps on the Pt(111) surface at a density of 1.5% step atoms per Pt atom. On the Pt(221) surface, PAX and Xe TPD reveal adsorption at both terrace and step sites simultaneously. Although the ideal structure of the Pt(531) surface has no well-defined steps or terraces, Xe adsorption indicates that its adsorption sites are best described as a distribution of both step and kink sites with roughly twice as many steps sites as kinks.

Determination of the mass transfer limiting step of dye adsorption onto commercial adsorbent by using mathematical models.

PubMed

Marin, Pricila; Borba, Carlos Eduardo; Módenes, Aparecido Nivaldo; Espinoza-Quiñones, Fernando R; de Oliveira, Silvia Priscila Dias; Kroumov, Alexander Dimitrov

2014-01-01

Reactive blue 5G dye removal in a fixed-bed column packed with Dowex Optipore SD-2 adsorbent was modelled. Three mathematical models were tested in order to determine the limiting step of the mass transfer of the dye adsorption process onto the adsorbent. The mass transfer resistance was considered to be a criterion for the determination of the difference between models. The models contained information about the external, internal, or surface adsorption limiting step. In the model development procedure, two hypotheses were applied to describe the internal mass transfer resistance. First, the mass transfer coefficient constant was considered. Second, the mass transfer coefficient was considered as a function of the dye concentration in the adsorbent. The experimental breakthrough curves were obtained for different particle diameters of the adsorbent, flow rates, and feed dye concentrations in order to evaluate the predictive power of the models. The values of the mass transfer parameters of the mathematical models were estimated by using the downhill simplex optimization method. The results showed that the model that considered internal resistance with a variable mass transfer coefficient was more flexible than the other ones and this model described the dynamics of the adsorption process of the dye in the fixed-bed column better. Hence, this model can be used for optimization and column design purposes for the investigated systems and similar ones.

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.

Adsorption behaviour of methylene blue onto Jordanian diatomite: a kinetic study.

PubMed

Al-Ghouti, Mohammad A; Khraisheh, Majeda A M; Ahmad, Mohammad N M; Allen, Stephen

2009-06-15

The effect of initial concentration, particle size, mass of the adsorbent, pH and agitation speed on adsorption behaviour of methylene blue (MB) onto Jordanian diatomite has been investigated. The maximum adsorption capacity, q, increased from 75 to 105 mg/g when pH of the dye solution increased from 4 to 11. It is clear that the ionisable charge sites on the diatomite surface increased when pH increased from 4 to 11. When the solution pH was above the pH(ZPC), the diatomite surface had a negative charge, while at low pH (pH<5.4) it has a positive charge. The adsorption capacity increased from 88.6 to 143.3mg/g as the initial MB concentrations increased from 89.6 to 225.2mg/dm(3). The experimental results were also applied to the pseudo-first and -second order kinetic models. It is noticed that the whole experimental data of MB adsorption onto diatomite did not follow the pseudo-first order model and had low correlation coefficients (R(2)<0.3). The calculated adsorption capacity, q(e,cal), values obtained from pseudo-first order kinetic model did not give acceptable values, q(e,exp.) The maximum uptake capacity seems to be independent of the particle size of the diatomite when the particle size distribution is less than 250-500 microm. While at larger particle size 250-500 microm, the maximum uptake capacity was dependent on the particle size. It would imply that the MB adsorption is limited by the external surface and that intraparticle diffusion is reduced. The effect of the agitation speeds on the removal of MB from aqueous solution using the diatomite is quite low. The MB removal increased from 43 to 100% when mass of the diatomite increased from 0.3 to 1.7 g.

Theory of chromatography of partially cyclic polymers: Tadpole-type and manacle-type macromolecules.

PubMed

Vakhrushev, Andrey V; Gorbunov, Alexei A

2016-02-12

A theory of chromatography is developed for partially cyclic polymers of tadpole- and manacle-shaped topological structures. We present exact equations for the distribution coefficient K at different adsorption interactions; simpler approximate formulae are also derived, relevant to the conditions of size-exclusion, adsorption, and critical chromatography. Theoretical chromatograms of heterogeneous partially cyclic polymers are simulated, and conditions for good separation by topology are predicted. According to the theory, an effective SEC-radius of tadpoles and manacles is mostly determined by the molar mass M, and by the linear-cyclic composition. In the interactive chromatography, the effect of molecular topology on the retention becomes significant. At the critical interaction point, partial dependences K(Mlin) and K(Mring) are qualitatively different: while being almost independent of Mlin, K increases with Mring. This behavior could be realized in critical chromatography-for separation of partially cyclic polymers by the number and molar mass of cyclic elements. Copyright © 2015 Elsevier B.V. All rights reserved.

Separation and enrichment of trace ractopamine in biological samples by uniformly-sized molecularly imprinted polymers

PubMed Central

Li, Ya; Fu, Qiang; Liu, Meng; Jiao, Yuan-Yuan; Du, Wei; Yu, Chong; Liu, Jing; Chang, Chun; Lu, Jian

2012-01-01

In order to prepare a high capacity packing material for solid-phase extraction with specific recognition ability of trace ractopamine in biological samples, uniformly-sized, molecularly imprinted polymers (MIPs) were prepared by a multi-step swelling and polymerization method using methacrylic acid as a functional monomer, ethylene glycol dimethacrylate as a cross-linker, and toluene as a porogen respectively. Scanning electron microscope and specific surface area were employed to identify the characteristics of MIPs. Ultraviolet spectroscopy, Fourier transform infrared spectroscopy, Scatchard analysis and kinetic study were performed to interpret the specific recognition ability and the binding process of MIPs. The results showed that, compared with other reports, MIPs synthetized in this study showed high adsorption capacity besides specific recognition ability. The adsorption capacity of MIPs was 0.063 mmol/g at 1 mmol/L ractopamine concentration with the distribution coefficient 1.70. The resulting MIPs could be used as solid-phase extraction materials for separation and enrichment of trace ractopamine in biological samples. PMID:29403774

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.

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

Mechanistic Insights from Discrete Molecular Dynamics Simulations of Pesticide-Nanoparticle Interactions.

PubMed

Geitner, Nicholas K; Zhao, Weilu; Ding, Feng; Chen, Wei; Wiesner, Mark R

2017-08-01

Nanoscale particles have the potential to modulate the transport, lifetimes, and ultimate uptake of pesticides that may otherwise be bound to agricultural soils. Engineered nanoparticles provide a unique platform for studying these interactions. In this study, we utilized discrete molecular dynamics (DMD) as a screening tool for examining nanoparticle-pesticide adsorptive interactions. As a proof-of-concept, we selected a library of 15 pesticides common in the United States and 4 nanomaterials with likely natural or incidental sources, and simulated all possible nanoparticle-pesticide pairs. The resulting adsorption coefficients derived from DMD simulations ranged over several orders of magnitude, and in many cases were significantly stronger than pesticide adsorption on clay surfaces, highlighting the significance of specific nanoscale phases as a preferential media with which pesticides may associate. Binding was found to be significantly enhanced by the capacity to form hydrogen bonds with slightly hydroxylated fullerols, highlighting the importance of considering the precise nature of weathered nanomaterials as opposed to pristine precursors. Results were compared to experimental adsorption studies using selected pesticides, with a Pearson correlation coefficient of 0.97.

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

Yu, Z.; Peldszus, S.; Huck, P.M.

The adsorption of two representative PhACs (naproxen and carbamazepine) and one EDC (nonylphenol) were evaluated on two granular activated carbons (GAC) namely coal-based Calgon Filtrasorb 400 and coconut shell-based PICA CTIF TE. 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) relevant for 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 poremore » size distribution had considerably greater NOM loading, resulting in lower adsorption capacity. Different patterns for the change in Freundlich KF 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 that film 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 mass transfer 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. 32 refs., 3 figs., 2 tabs.« less

Chemical processes for the extreme enrichment of tellurium into marine ferromanganese oxides

NASA Astrophysics Data System (ADS)

Kashiwabara, Teruhiko; Oishi, Yasuko; Sakaguchi, Aya; Sugiyama, Toshiki; Usui, Akira; Takahashi, Yoshio

2014-04-01

Tellurium, an element of growing economic importance, is extremely enriched in marine ferromanganese oxides. We investigated the mechanism of this enrichment using a combination of spectroscopic analysis and adsorption/coprecipitation experiments. X-ray Absorption Near-Edge Structure (XANES) analysis showed that in adsorption/coprecipitation systems, Te(IV) was oxidized on δ-MnO2 and not oxidized on ferrihydrite. Extended X-ray Absorption Fine Structure (EXAFS) analysis showed that both Te(IV) and Te(VI) were adsorbed on the surface of δ-MnO2 and ferrihydrite via formation of inner-sphere complexes. In addition, Te(VI) can be structurally incorporated into the linkage of Fe octahedra through a coprecipitation process because of its molecular geometry that is similar to the Fe octahedron. The largest distribution coefficient obtained in the adsorption/coprecipitation experiments was for the Te(VI)/ferrihydrite coprecipitation system, and it was comparable to those calculated from the distribution between natural ferromanganese oxides and seawater. Our XAFS and micro-focused X-ray fluorescence (μ-XRF) mapping of natural ferromanganese oxides showed that Te was structurally incorporated as Te(VI) in Fe (oxyhydr)oxide phases. We conclude that the main process for the enrichment of Te in ferromanganese oxides is structural incorporation of Te(VI) into Fe (oxyhydr)oxide phases through coprecipitation. This mechanism can explain the unique degree of enrichment of Te compared with other oxyanions, which are mainly enriched via adsorption on the surface of the solid structures. In particular, the great contrast in the distributions of Te and Se is caused by their oxidized species: (i) the similar geometry of the Te(VI) molecule to Fe octahedron, and (ii) quite soluble nature of Se(VI). Coexisting Mn oxide phases may promote structural incorporation of Te(VI) by oxidation of Te(IV), although the surface oxidation itself may not work as the critical enrichment process as in the case of some cations. This enrichment mechanism also means that ferromanganese oxides mainly scavenge dominant Te(VI) species from seawater and do not affect its species distribution in seawater, as described in a previous model. The variation in Te abundances and the correlation of Te concentration with the growth rate of natural ferromanganese oxides are consistent with the coprecipitation mechanism.

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.

Chemodynamics of Methyl Parathion and Ethyl Parathion: Adsorption Models for Sustainable Agriculture

PubMed Central

Rafique, Uzaira; Balkhair, Khaled S.; Ashraf, Muhammad Aqeel

2014-01-01

The toxicity of organophosphate insecticides for nontarget organism has been the subject of extensive research for sustainable agriculture. Pakistan has banned the use of methyl/ethyl parathions, but they are still illegally used. The present study is an attempt to estimate the residual concentration and to suggest remedial solution of adsorption by different types of soils collected and characterized for physicochemical parameters. Sorption of pesticides in soil or other porous media is an important process regulating pesticide transport and degradation. The percentage removal of methyl parathion and ethyl parathion was determined through UV-Visible spectrophotometer at 276 nm and 277 nm, respectively. The results indicate that agricultural soil as compared to barren soil is more efficient adsorbent for both insecticides, at optimum batch condition of pH 7. The equilibrium between adsorbate and adsorbent was attained in 12 hours. Methyl parathion is removed more efficiently (by seven orders of magnitude) than ethyl parathion. It may be attributed to more available binding sites and less steric hindrance of methyl parathion. Adsorption kinetics indicates that a good correlation exists between distribution coefficient (Kd) and soil organic carbon. A general increase in Kd is noted with increase in induced concentration due to the formation of bound or aged residue. PMID:24689059

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

Rare earth element scavenging in seawater

NASA Astrophysics Data System (ADS)

Byrne, Robert H.; Kim, Ki-Hyun

1990-10-01

Examinations of rare earth element (REE) adsorption in seawater, using a variety of surface-types, indicated that, for most surfaces, light rare earth elements (LREEs) are preferentially adsorbed compared to the heavy rare earths (HREEs). Exceptions to this behavior were observed only for silica phases (glass surfaces, acid-cleaned diatomaceous earth, and synthetic SiO 2). The affinity of the rare earths for surfaces can be strongly affected by thin organic coatings. Glass surfaces which acquired an organic coating through immersion in Tampa Bay exhibited adsorptive behavior typical of organic-rich, rather than glass, surfaces. Models of rare earth distributions between seawater and carboxylate-rich surfaces indicate that scavenging processes which involve such surfaces should exhibit a strong dependence on pH and carbonate complexation. Scavenging models involving carboxylate surfaces produce relative REE abundance patterns in good general agreement with observed shale-normalized REE abundances in seawater. Scavenging by carboxylate-rich surfaces should produce HREE enrichments in seawater relative to the LREEs and may produce enrichments of lanthanum relative to its immediate trivalent neighbors. Due to the origin of distribution coefficients as a difference between REE solution complexation (which increases strongly with atomic number) and surface complexation (which apparently also increases with atomic number) the relative solution abundance patterns of the REEs produced by scavenging reactions can be quite complex.

Adsorption of enrofloxacin in presence of Zn(II) on a calcareous soil.

PubMed

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

2015-12-01

As a result of their consumption, excretion, disposal and persistence, antibiotics enter the soil environment and may be transported to surface and ground waters. During their transfer through soils, retention processes play a key role in their mobility. Antibiotics often coexist with heavy metals in soils due to agricultural practices and other sources of inputs. In this context, this study deals with the co-adsorption of Zn(II) and enrofloxacin (ENR), a widely-used veterinary antibiotic, on a calcareous soil using batch retention experiments and X-ray Absorption Near Edge Structure (XANES) spectroscopy. To improve our understanding of the interaction of this emerging organic contaminant with metal cations at the water-soil interface, the ternary system containing ENR, Zn(II) and a selected calcareous soil was investigated over a pH range between 7 and 10, at different solid-solution contact times and ENR concentrations. The presence of Zn(II) slightly influenced the retention of the antibiotic, leading to an increase of the adsorbed ENR amounts. The distribution coefficient Kd value increased from 0.66 Lg(-1) for single ENR adsorption to 1.04 Lg(-1) in presence of Zn(II) at a 1/2 ENR/Zn(II) ratio. The combination of adsorption isotherm data, solution speciation diagrams and XANES spectra evidenced a small proportion of Zn(II)-ENR complexes at soil pH leading to the slight increase of ENR adsorption in presence of zinc. These results suggest that it is necessary to consider the interaction between ENR and metal cations when assessing the mobility of ENR in soils. Copyright © 2015 Elsevier Inc. 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.

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.

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.

Assessing Potential Additional PFAS Retention Processes in the Subsurface

NASA Astrophysics Data System (ADS)

Brusseau, M. L.

2017-12-01

Understanding the transport and fate of per- and poly-fluorinated alkyl substances (PFASs) in the subsurface is critical for accurate risk assessments and design of effective remedial actions. Current conceptual and mathematical models are based on an assumption that solid-phase adsorption is the sole source of retention for PFASs. However, additional retention processes may be relevant for PFAS compounds in vadose-zone systems and in source zones that contain trapped immiscible organic liquids. These include adsorption at the air-water interface, partitioning to the soil atmosphere, adsorption at the NAPL-water interface, and absorption by NAPL. A multi-process retention model is proposed to account for these potential additional sources of PFAS retardation. An initial assessment of the relative magnitudes and significance of these retention processes was conducted for three representative PFASs, perfluorooctanoic acid (PFOA), perfluorooctane sulfonate (PFOS), and 8:2 fluorotelomer alcohol (FTOH). Data collected from the literature were used to determine measured or estimated values for the relevant distribution coefficients, which were in turn used to calculate retardation factors for a representative porous medium. Adsorption at the air-water interface was shown to be a primary source of retention for PFOA and PFOS, contributing approximately 80% of total retardation. Adsorption to NAPL-water interfaces and absorption by bulk NAPL were also shown to be significant sources of retention for PFOS and PFOA. The latter process was the predominant source of retention for 8:2 FTOH, contributing 98% of total retardation. These results indicate that we may anticipate significant retention of PFASs by these additional processes. In such cases, retardation of PFASs in source areas may be significantly greater than what is typically estimated based on the standard assumption of solid-phase adsorption as the sole retention mechanism. This has significant ramifications for accurate determination of the migration potential and magnitude of mass flux to groundwater, as well as for calculations of contaminant mass residing in source zones.

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.

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.

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.

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.

Adsorption and desorption for dynamics transport of hexavalent chromium Cr(Ⅵ) in soil column

NASA Astrophysics Data System (ADS)

Tong, J.

2017-12-01

Batch experiments have been carried out to study the adsorption of heavy metals in soils, and the migration and transformation of hexavalent chromium Cr(Ⅵ) in the soil of a vegetable base were studied by dynamic adsorption and desorption soil column experiments. The aim of this study was to investigate the effect of initial concentration and pH value on the adsorption process of Cr(Ⅵ). Breakthrough curve were used to evaluate the capacity of Cr(Ⅵ) adsorption in soil columns. The results show that the higher the initial concentration, the worse the adsorption capacity of Cr(Ⅵ). The adsorption of Cr(Ⅵ) was strongly sensitive to pH value. The capacity of Cr(Ⅵ) adsorption is maximized at very low pH value. This may be due to changes in pH that cause a series of complex reactions in Cr(Ⅵ). In a strongly acidic environment, the reaction of Cr(Ⅵ) with hydrogen ions is accompanied by the formation of Cr3+, which reacts with the soil free iron-aluminum oxide to produce hydroxide in the soil. The results of the desorption experiments indicate that Cr(Ⅵ) is more likely to leach from this soil, but if the eluent is strong acid solution, the leaching process will be slow and persistent. The program CXTFIT was used to fit the breakthrough curve to estimate parameters. The results of the calculation of the dispersion coefficient (D) can be obtained by this program. The two-site model fit the breakthrough curve data of Cr(Ⅵ) well, and the parameters calculated by CXTFIT can be used to explain the behavior of Cr(Ⅵ) migration and transformation in soil columns. When pH=2, the retardation factor (R) reach at 79.71 while the value of the R is generally around 10 in other experiments. The partitioning coefficient β shows that more than half of the adsorption sites are rate-limited in this adsorption process and non-equilibrium effects the Cr(Ⅵ) transport process in this soil.

Importance of the accuracy of experimental data in the nonlinear chromatographic determination of adsorption energy distributions

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

Stanley, B.J.; Guiochon, G.

1994-11-01

Adsorption energy distributions (AEDs) are calculated from the classical, fundamental integral equation of adsorption using adsorption isotherms and the expectation-maximization method of parameter estimation. The adsorption isotherms are calculated from nonlinear elution profiles obtained from gas chromatographic data using the characteristic points method of finite concentration chromatography. Porous layer open tubular capillary columns are used to support the adsorbent. The performance of these columns is compared to that of packed columns in terms of their ability to supply accurate isotherm data and AEDs. The effect of the finite column efficiency and the limited loading factor on the accuracy of themore » estimated energy distributions is presented. This accuracy decreases with decreasing efficiency, and approximately 5000 theoretical plates are needed when the loading factor, L[sub f], equals 0.56 for sampling of a unimodal Gaussian distribution. Increasing L[sub f] further increases the contribution of finite efficiency to the AED and causes a divergence at the low-energy endpoint if too high. This occurs as the retention time approaches the holdup time. Data are presented for diethyl ether adsorption on porous silica and its C-18-bonded derivative. 36 refs., 8 figs., 2 tabs.« less

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

Onishi, Y.; Serne, R.J.; Arnold, E.M.

This report describes the results of a detailed literature review of radionuclide transport models applicable to rivers, estuaries, coastal waters, the Great Lakes, and impoundments. Some representatives sediment transport and water quality models were also reviewed to evaluate if they can be readily adapted to radionuclide transport modeling. The review showed that most available transport models were developed for dissolved radionuclide in rivers. These models include the mechanisms of advection, dispersion, and radionuclide decay. Since the models do not include sediment and radionuclide interactions, they are best suited for simulating short-term radionuclide migration where: (1) radionuclides have small distribution coefficients;more » (2) sediment concentrations in receiving water bodies are very low. Only 5 of the reviewed models include full sediment and radionuclide interactions: CHMSED developed by Fields; FETRA SERATRA, and TODAM developed by Onishi et al, and a model developed by Shull and Gloyna. The 5 models are applicable to cases where: (1) the distribution coefficient is large; (2) sediment concentrations are high; or (3) long-term migration and accumulation are under consideration. The report also discusses radionuclide absorption/desorption distribution ratios and addresses adsorption/desorption mechanisms and their controlling processes for 25 elements under surface water conditions. These elements are: Am, Sb, C, Ce, Cm, Co, Cr, Cs, Eu, I, Fe, Mn, Np, P, Pu, Pm, Ra, Ru, Sr, Tc, Th, {sup 3}H, U, Zn and Zr.« less

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.

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.

Noncompetitive and Competitive Adsorption of Heavy Metals in Sulfur-Functionalized Ordered Mesoporous Carbon.

PubMed

Saha, Dipendu; Barakat, Soukaina; Van Bramer, Scott E; Nelson, Karl A; Hensley, Dale K; Chen, Jihua

2016-12-14

In this work, sulfur-functionalized ordered mesoporous carbons were synthesized by activating the soft-templated mesoporous carbons with sulfur bearing salts that simultaneously enhanced the surface area and introduced sulfur functionalities onto the parent carbon surface. XPS analysis showed that sulfur content within the mesoporous carbons were between 8.2% and 12.9%. The sulfur functionalities include C-S, C═S, -COS, and SO x . SEM images confirmed the ordered mesoporosity within the material. The BET surface areas of the sulfur-functionalized ordered mesoporous carbons range from 837 to 2865 m 2 /g with total pore volume of 0.71-2.3 cm 3 /g. The carbon with highest sulfur functionality was examined for aqueous phase adsorption of mercury (as HgCl 2 ), lead (as Pb(NO 3 ) 2 ), cadmium (as CdCl 2 ), and nickel (as NiCl 2 ) ions in both noncompetitive and competitive mode. Under noncompetitive mode and at a pH greater than 7.0 the affinity of sulfur-functionalized carbons toward heavy metals were in the order of Hg > Pb > Cd > Ni. At lower pH, the adsorbent switched its affinity between Pb and Cd. In the noncompetitive mode, Hg and Pb adsorption showed a strong pH dependency whereas Cd and Ni adsorption did not demonstrate a significant influence of pH. The distribution coefficient for noncompetitive adsorption was in the range of 2448-4000 mL/g for Hg, 290-1990 mL/g for Pb, 550-560 mL/g for Cd, and 115-147 for Ni. The kinetics of adsorption suggested a pseudo-second-order model fits better than other models for all the metals. XPS analysis of metal-adsorption carbons suggested that 7-8% of the adsorbed Hg was converted to HgSO 4 , 14% and 2% of Pb was converted to PbSO 4 and PbS/PbO, respectively, and 5% Cd was converted to CdSO 4 . Ni was below the detection limit for XPS. Overall results suggested these carbon materials might be useful for the separation of heavy metals.

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

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.

Humic acid transport in saturated porous media: influence of flow velocity and influent concentration.

PubMed

Wei, Xiaorong; Shao, Mingan; Du, Lina; Horton, Robert

2014-12-01

Understanding the transport of humic acids (HAs) in porous media can provide important and practical evidence needed for accurate prediction of organic/inorganic contaminant transport in different environmental media and interfaces. A series of column transport experiments was conducted to evaluate the transport of HA in different porous media at different flow velocities and influent HA concentrations. Low flow velocity and influent concentration were found to favor the adsorption and deposition of HA onto sand grains packed into columns and to give higher equilibrium distribution coefficients and deposition rate coefficients, which resulted in an increased fraction of HA being retained in columns. Consequently, retardation factors were increased and the transport of HA through the columns was delayed. These results suggest that the transport of HA in porous media is primarily controlled by the attachment of HA to the solid matrix. Accordingly, this attachment should be considered in studies of HA behavior in porous media. Copyright © 2014. Published by Elsevier B.V.

Occurrence and fate of pharmaceuticals and personal care products in drinking water in southern China.

PubMed

Qiao, Tiejun; Yu, Zhengrong; Zhang, Xihui; Au, Doris W T

2011-11-01

Occurrence and fate of pharmaceuticals and personal care products (PPCPs) in drinking water was investigated in southern China. Fifteen and twelve PPCPs were detected with concentrations of 0-36 ng L(-1) in source water and of 0-20 ng L(-1) in treated water, respectively. Four PPCPs were detected with concentrations of approximately 1 ng L(-1) in drinking water of distribution network. Conventional water treatment processes removed the types and average concentrations of PPCPs by 30% and above 50%, respectively. Advanced water treatment processes were more efficient in the removal of most PPCPs, with the types and concentrations reduced by 50% and approximately 90%, respectively. Molecular properties of PPCPs had an important influence on their behaviors during water treatment. pK(a) (acidity coefficient) and K(oc) (organic carbon partition coefficient) of PPCPs appeared to have a combined effect on PPCPs removal during coagulation and oxidation. Adsorption and biodegradation were two possible mechanisms responsible for PPCPs removal during sand filtration.

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.

Adsorption and recognition characteristics of surface molecularly imprinted polymethacrylic acid/silica toward genistein.

PubMed

Zhang, Yanyan; Gao, Baojiao; An, Fuqiang; Xu, Zeqing; Zhang, Tingting

2014-09-12

In this paper, on the basis of surface-initiated graft polymerization, a new surface molecular imprinting technique is established by molecular design. And molecularly imprinted polymer MIP-PMAA/SiO2 is successfully prepared with genistein as template. The adsorption and recognition characteristics of MIP-PMAA/SiO2 for genistein are studied in depth by using static method, dynamic method and competitive adsorption experiment. The experimental results show that MIP-PMAA/SiO2 possesses very strong adsorption affinity and specific recognition for genistein. The saturated adsorption capacity could reach to 0.36mmolg(-1). The selectivity coefficients relative to quercetin and rutin are 5.4 and 11.8, respectively. Besides, MIP-PMAA/SiO2 is regenerated easily and exhibits excellent reusability. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

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.

Comparison between different adsorption-desorption kinetics schemes in two dimensional lattice gas

NASA Astrophysics Data System (ADS)

Huespe, V. J.; Belardinelli, R. E.; Pereyra, V. D.; Manzi, S. J.

2017-12-01

Monte Carlo simulation is used to study the adsorption-desorption kinetics in the framework of the kinetic lattice-gas model. Three schemes of the so-called hard dynamics and five schemes of the so called soft dynamics were used for this purpose. It is observed that for the hard dynamic schemes, the equilibrium and non-equilibrium observable, such as adsorption isotherms, sticking coefficients, and thermal desorption spectra, have a normal or physical sustainable behavior. While for the soft dynamics schemes, with the exception of the transition state theory, the equilibrium and non-equilibrium observables have several problems.

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.

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.

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

Yanping Guo; Abhishek Yadav; Tanju Karanfil

Adsorption of trichloroethylene (TCE) and atrazine, two synthetic organic contaminants (SOCs) having different optimum adsorption pore regions, by four activated carbons and an activated carbon fiber (ACF) was examined. Adsorbents included two coconut-shell based granular activated carbons (GACs), two coal-based GACs (F400 and HD4000) and a phenol formaldehyde-based activated carbon fiber. The selected adsorbents had a wide range of pore size distributions but similar surface acidity and hydrophobicity. Single solute and preloading (with a dissolved organic matter (DOM)) isotherms were performed. Single solute adsorption results showed that (i) the adsorbents having higher amounts of pores with sizes about the dimensionsmore » of the adsorbate molecules exhibited higher uptakes, (ii) there were some pore structure characteristics, which were not completely captured by pore size distribution analysis, that also affected the adsorption, and (iii) the BET surface area and total pore volume were not the primary factors controlling the adsorption of SOCs. The preloading isotherm results showed that for TCE adsorbing primarily in pores <10 {angstrom}, the highly microporous ACF and GACs, acting like molecular sieves, exhibited the highest uptakes. For atrazine with an optimum adsorption pore region of 10-20 {angstrom}, which overlaps with the adsorption region of some DOM components, the GACs with a broad pore size distribution and high pore volumes in the 10-20 {angstrom} region had the least impact of DOM on the adsorption. 25 refs., 3 figs., 3 tabs.« less

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.

Reversible adsorption and flushing of arsenic in a shallow, Holocene aquifer of Bangladesh

PubMed Central

Radloff, Kathleen A.; Zheng, Yan; Stute, Martin; Weinman, Beth; Bostick, Benjamin; Mihajlov, Ivan; Bounds, Margaret; Rahman, M. Moshiur; Huq, M. Rezaul; Ahmed, Kazi M.; Schlosser, Peter; van Geen, Alexander

2015-01-01

The spatial heterogeneity of dissolved arsenic (As) concentrations in shallow groundwater of the Bengal Basin has been attributed to transport of As (and reactive carbon) from external sources or to the release of As from within grey sand formations. We explore the latter scenario in this detailed hydrological and geochemical study along a 300 m transect of a shallow aquifer extending from a groundwater recharge area within a sandy channel bar to its discharge into a nearby stream. Within the 10–20 m depth range, groundwater ages along the transect determined by the 3H–3He method increase from <10 yr in the recharge area to a maximum of 40 yr towards the stream. Concentrations of groundwater As within the same grey sands increase from 10 to 100 to ∼500 µg/L along this transect. Evidence of reversible adsorption of As between the groundwater and sediment was obtained from a series of push–pull experiments, traditional batch adsorption experiments, and the accidental flooding of a shallow monitoring well. Assuming reversible adsorption and a distribution coefficient, Kd, of 0.15–1.5 L/kg inferred from these observations, a simple flushing model shows that the increase in As concentrations with depth and groundwater age at this site, and at other sites in the Bengal and Red River Basins, can be attributed to the evolution of the aquifer over 100–1000 years as aquifer sands are gradually flushed of their initial As content. A wide range of As concentrations can thus be maintained in groundwater with increases with depth governed by the history of flushing and local recharge rates, without external inputs of reactive carbon or As from other sources. PMID:28458447

Sorption and biodegradation of sulfonamide antibiotics by activated sludge: experimental assessment using batch data obtained under aerobic conditions.

PubMed

Yang, Sheng-Fu; Lin, Cheng-Fang; Lin, Angela Yu-Chen; Hong, Pui-Kwan Andy

2011-05-01

This study investigated the adsorption, desorption, and biodegradation characteristics of sulfonamide antibiotics in the presence of activated sludge with and without being subjected to NaN(3) biocide. Batch experiments were conducted and the relative contributions of adsorption and biodegradation to the observed removal of sulfonamide antibiotics were determined. Three sulfonamide antibiotics including sulfamethoxazole (SMX), sulfadimethoxine (SDM), and sulfamonomethoxine (SMM), which had been detected in the influent and the activated sludge of wastewater treatment plants (WWTP) in Taiwan, were selected for this study. Experimental results showed that the antibiotic compounds were removed via sorption and biodegradation by the activated sludge, though biodegradation was inhibited in the first 12 h possibly due to competitive inhibition of xenobiotic oxidation by readily biodegradable substances. The affinity of sulfonamides to sterilized sludge was in the order of SDM > SMM > SMX. The sulfonamides existed predominantly as anions at the study pH of 6.8, which resulted in a low level of adsorption to the activated sludge. The adsorption/desorption isotherms were of a linear form, as well described by the Freundlich isotherm with the n value approximating unity. The linear distribution coefficients (K(d)) were determined from batch equilibrium experiments with values of 28.6 ± 1.9, 55.7 ± 2.2, and 110.0 ± 4.6 mL/g for SMX, SMM, and SDM, respectively. SMX, SMM, and SDM desorb reversibly from the activated sludge leaving behind on the solids 0.9%, 1.6%, and 5.2% of the original sorption dose of 100 μg/L. The sorbed antibiotics can be introduced into the environment if no further treatments were employed to remove them from the biomass. Copyright © 2011 Elsevier Ltd. All rights reserved.

Investigation on the reaction of phenolic pollutions to mono-rhamnolipid micelles using MEUF.

PubMed

Liu, Zhifeng; Yu, Mingda; Zeng, Guangming; Li, Min; Zhang, Jiachao; Zhong, Hua; Liu, Yang; Shao, Binbin; Li, Zhigang; Wang, Zhiquan; Liu, Guansheng; Yang, Xin

2017-01-01

Micellar-enhanced ultrafiltration (MEUF) processes of resorcinol, phenol, and 1-Naphthol with rhamnolipid as an anionic biosurfactant were investigated using polysulfone membrane. The effects of retentate/permeate concentration of phenolic pollutants (C R /C P ), distribution coefficient of phenolic pollutions (D), concentration ratios of phenolic pollutions (α P ) and rhamnolipids (α R ) and adsorption capacity of the membrane (N m ) were studied by operating pressure, pH condition, feed surfactant, and phenolic pollution concentrations. Results showed that C R (with pH) increased and ranked in the following order: resorcinol > phenol > 1-Naphthol, which is same with C R (with pressure), C R (with surfactant), C R /C P (with pollution), α, P and D, while C P (with pH), C P (with pressure), and C P (with surfactant) ranked in the reverse order. The operating pressure increased the solubility of phenolic from 0 to 0.1 MPa and then decreased slowly above 0.1 MPa. The concentration ratio of rhamnolipid was nearly at 2.0 and that of phenolic pollution was slightly above 1.0. D of phenolic pollutants reached the maximum at phenolic pollution concentration of 0.1 mM and the feed rhamnolipid concentration at 1 CMC. Moreover, zeta potential in feed stream and retentate stream and membrane adsorption of phenolic pollutions were firstly investigated in this article; the magnitudes of zeta potential with the feed stream of three phenolic pollutions were nearly the same and slightly lower than those with the retentate stream. The adsorption capacity of the membrane (N m ) was calculated and compared to the former research, which showed that rhamnolipid significantly decreases the membrane adsorption of phenolic pollutions at a relatively lower concentration. It was implied that rhamnolipid can be substituted for chemical surfactants.

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.

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.

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.

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.

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.

Successive ion layer adsorption and reaction (SILAR) technique synthesis of Al(III)-8-hydroxy-5-nitrosoquinolate nano-sized thin films: characterization and factors optimization.

PubMed

Haggag, Sawsan M S; Farag, A A M; Abdel Refea, M

2013-02-01

Nano Al(III)-8-hydroxy-5-nitrosoquinolate [Al(III)-(HNOQ)(3)] thin films were synthesized by the rapid, direct, simple and efficient successive ion layer adsorption and reaction (SILAR) technique. Thin film formation optimized factors were evaluated. Stoichiometry and structure were confirmed by elemental analysis and FT-IR. The particle size (27-71 nm) was determined using scanning electron microscope (SEM). Thermal stability and thermal parameters were determined by thermal gravimetric analysis (TGA). Optical properties were investigated using spectrophotometric measurements of transmittance and reflectance at normal incidence. Refractive index, n, and absorption index, k, were determined. Spectral behavior of the absorption coefficient in the intrinsic absorption region revealed a direct allowed transition with 2.45 eV band gap. The current-voltage (I-V) characteristics of [Al(III)-(HNOQ)(3)]/p-Si heterojunction was measured at room temperature. The forward and reverse I-V characteristics were analyzed. The calculated zero-bias barrier height (Φ(b)) and ideality factor (n) showed strong bias dependence. Energy distribution of interface states (N(ss)) was obtained. Copyright © 2012 Elsevier B.V. All rights reserved.

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

Silva, Camila F.N.; Lazarin, Angélica M., E-mail: amlazarin2@uem.br; Sernaglia, Rosana L.

Graphical abstract: Scanning electron microscopy photographs of calcium phosphate (a) and intercalated with p-aminobenzoic acid (b). Highlights: ► Calcium phosphate was intercalated with p-aminobenzoic acid. ► Guest molecule contains nitrogen and oxygen atoms from amine and carboxylic groups. ► These basic centers are potentially useful for cation coordination in ethanol solution. ► Crystal morphology of compounds is lamellar, it agrees with expected structural characteristics. -- Abstract: Crystalline lamellar calcium phosphate retained 4-aminobenzoic acid inside its cavity without leaching. The intense infrared bands in the 1033 and 1010 cm{sup −1} interval confirmed the presence of the phosphonate groups attached to themore » inorganic layer, with sharp and intense peaks in X-ray diffraction patterns, which gave basal distances of 712 and 1578 pm for the original and the intercalated compounds, respectively. Solid-state {sup 31}P nuclear magnetic resonance spectra presented only one peak for the phosphate groups attached to the main inorganic polymeric structure near −2.4 ppm. The adsorption isotherms from ethanol gave the maximum adsorption capacities of 6.44 and 3.34 mmol g{sup −1} for nickel and cobalt, respectively, which stability constant and distribution coefficient followed Co > Ni.« less

Biodegradable metal adsorbent synthesized by graft polymerization onto nonwoven cotton fabric

NASA Astrophysics Data System (ADS)

Sekine, Ayako; Seko, Noriaki; Tamada, Masao; Suzuki, Yoshio

2010-01-01

A fibrous adsorbent for Hg ions was synthesized by radiation-induced emulsion graft polymerization of glycidyl methacrylate (GMA) onto a nonwoven cotton fabric and subsequent chemical modification. The optimal pre-irradiation dose for initiation of the graft polymerization of GMA, which minimized the effects of radiation damage on the mechanical strength of the nonwoven cotton fabric, was found to be 10 kGy. The GMA-grafted nonwoven cotton fabric was subsequently modified with ethylenediamine (EDA) or diethylenetriamine (DETA) to obtain a Hg adsorbent. The resulting amine-type adsorbents were evaluated for batch and continuous adsorption of Hg. In batch adsorption, the distribution coefficients of Hg reached 1.9×10 5 and 1.0×10 5 for EDA- and DETA-type adsorbents, respectively. A column packed with EDA-type adsorbent removed Hg from 1.8 ppm Hg solution at a space velocity of 100 h -1, which corresponds to 16,000 times the volume of the packed adsorbent. The adsorbed Hg on the EDA-type adsorbent could be completely eluted by 1 M HCl solution. A microbial oxidative degradation test revealed that the EDA-type adsorbent is biodegradable.

A novel model for through-silicon via (TSV) filling process simulation considering three additives and current density effect

NASA Astrophysics Data System (ADS)

Wang, Fuliang; Zhao, Zhipeng; Wang, Feng; Wang, Yan; Nie, Nantian

2017-12-01

Through-silicon via (TSV) filling by electrochemical deposition is still a challenge for 3D IC packaging, and three-component additive systems (accelerator, suppressor, and leveler) were commonly used in the industry to achieve void-free filling. However, models considering three additive systems and the current density effect have not been fully studied. In this paper, a novel three-component model was developed to study the TSV filling mechanism and process, where the interaction behavior of the three additives (accelerator, suppressor, and leveler) were considered, and the adsorption, desorption, and consumption coefficient of the three additives were changed with the current density. Based on this new model, the three filling types (seam void, ‘V’ shape, and key hole) were simulated under different current density conditions, and the filling results were verified by experiments. The effect of the current density on the copper ion concentration, additives surface coverage, and local current density distribution during the TSV filling process were obtained. Based on the simulation and experimental results, the diffusion-adsorption-desorption-consumption competition behavior between the suppressor, the accelerator, and the leveler were discussed. The filling mechanisms under different current densities were also analyzed.

Evaluation of PAN-based manganese dioxide composite for the sorptive removal of cesium-137 from aqueous solutions.

PubMed

Nilchi, A; Saberi, R; Garmarodi, S Rasouli; Bagheri, A

2012-02-01

Hydrous manganese dioxide-polyacrylonitrile (MnO(2)-PAN) was chemically synthesized and evaluated, as an organic-inorganic composite material, for the removal of radio-contaminant cesium-137 from aqueous solutions. The physico-chemical characterization was carried out by Fourier transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), CHN elemental analysis, scanning electron microscopy (SEM), nitrogen adsorption-desorption studies and thermogravimetry-differential scanning calorimetry (TGA-DSC). Batch experiments were carried out as a function of contact time, interference of the coexisting ions and initial pH of adsorptive solution applying a radiotracer technique. The effect of temperature on the distribution coefficient of cesium has been utilized in order to evaluate the changes in the standard thermodynamic parameters. The results indicated that Cs(+) ions could be efficiently removed using MnO(2)-PAN composite in the pH range of 4-9 from aqueous solutions and the uptake of cesium is affected to varying degrees by the presence of some diverse co-ions. The equilibrium isotherms have been determined and the sorption data were successfully modeled using Freundlich model. Copyright © 2011 Elsevier Ltd. All rights reserved.

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.

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.

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

[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

[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.

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.

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.

Adsorption properties for urokinase on local diatomite surface

NASA Astrophysics Data System (ADS)

Yang, Yuxiang; Zhang, Jianbo; Yang, Weimin; Wu, Jieda; Chen, Rongsan

2003-02-01

In this paper, adsorption isotherm of urokinase on two typical local diatomites were determined at 25 °C and their surface electrical potentials (ζ), isoelectrical point values (IEP) were determined. The properties of diatomites, the relationship among diatomite structure, pore-size distribution, surface ζ and adsorption isotherm were discussed. The adsorption equation of urokinase was calculated from the adsorption isotherm. The adsorption mode of urokinase on diatomite surface was judged by the configuration function α. The relationship between the amount of adsorbed urokinase and IEP value was also discussed.

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.

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.

Adsorption of finite semiflexible polymers and their loop and tail distributions

NASA Astrophysics Data System (ADS)

Kampmann, Tobias A.; Kierfeld, Jan

2017-07-01

We discuss the adsorption of semiflexible polymers to a planar attractive wall and focus on the questions of the adsorption threshold for polymers of finite length and their loop and tail distributions using both Monte Carlo simulations and analytical arguments. For the adsorption threshold, we find three regimes: (i) a flexible or Gaussian regime if the persistence length is smaller than the adsorption potential range, (ii) a semiflexible regime if the persistence length is larger than the potential range, and (iii) for finite polymers, a novel crossover to a rigid rod regime if the deflection length exceeds the contour length. In the flexible and semiflexible regimes, finite size corrections arise because the correlation length exceeds the contour length. In the rigid rod regime, however, it is essential how the global orientational or translational degrees of freedom are restricted by grafting or confinement. We discuss finite size corrections for polymers grafted to the adsorbing surface and for polymers confined by a second (parallel) hard wall. Based on these results, we obtain a method to analyze adsorption data for finite semiflexible polymers such as filamentous actin. For the loop and tail distributions, we find power laws with an exponential decay on length scales exceeding the correlation length. We derive and confirm the loop and tail power law exponents for flexible and semiflexible polymers. This allows us to explain that, close to the transition, semiflexible polymers have significantly smaller loops and both flexible and semiflexible polymers desorb by expanding their tail length. The tail distribution allows us to extract the free energy per length of adsorption for actin filaments from experimental data [D. Welch et al., Soft Matter 11, 7507 (2015)].

Fabrication and evaluation of low-cost agarose-zinc nanoporous composite matrix: influence of adsorbent density and size distribution on the performance of expanded beds.

PubMed

Asghari, Fateme; Jahanshahi, Mohsen

2012-09-28

Expanded bed adsorption (EBA), a promising and practical separation technique for adsorption of nanobioproduct/bioproduct, has been widely studied in the past two decades. The development of adsorbent with the special design for expanded bed process is a challenging course. To reduce the costs of adsorbent preparation, fine zinc powder was used as the inexpensive densifier. A series of matrices named Ag-Zn were prepared by water-in-oil emulsification method. The structure and morphology of the prepared matrix were studied by the optical microscope (OM) and scanning electron microscopy (SEM). The physical properties as a function of zinc powder ratio to agarose slurry were measured. The prepared matrices had regular spherical shape, and followed logarithmic normal size distribution with the range of 75-330 μm, mean diameter of 140.54-191.11 μm, wet density of 1.33-2.01 g/ml, water content of 0.45-0.75, porosity of 0.86-0.97 and pore size of about 40-90 nm. The bed expansion factor at the range of 2-3 was examined. The obtained results indicated that the expansion factor was decreased with increasing of matrix density. In addition, it was found that matrices with large particle size were suitable for high operation flow rate. The hydrodynamic properties were determined in expanded bed by the residence time distribution method (RTD). The effects of flow velocity, expansion factor and density of matrix on the hydrodynamic properties were also investigated. Moreover, the influence of particle size distribution on the performance of expanded bed has been studied. Therefore, three different particle size fractions (65-140, 215-280 and 65-280 μm) were assessed. The results indicated that dispersion in liquid-solid expanded beds increased with increasing flow rate and expansion factor; and matrix with a wide particle size distribution leaded to a reduced axial dispersion compared to matrices with a narrow size distribution. The axial dispersion coefficient also enhanced with the increasing of matrix density. It was found that flow rate was the most essential factor to effect on the hydrodynamic characteristics in the bed. For all the prepared matrices, the values of axial mixing coefficients (D(axl)) were smaller than 1.0 × 10⁻⁵ m²/s when flow velocities in expanded bed were less than 700 cm/h. All the results indicate that the prepared matrix show good expansion and stability in expanded bed; and it is suitable for expanded bed processes as an economical adsorbent. Copyright © 2012 Elsevier B.V. All rights reserved.

The source apportionment of polycyclic aromatic hydrocarbons (PAHs) in the topsoil in Xiaodian sewage irrigation area, North of China.

PubMed

Li, Jia-Le; Wang, Yan-Xin; Zhang, Cai-Xiang; Dong, Yi-Hui; Du, Bin; Liao, Xiao-Ping

2014-12-01

31 topsoil samples were collected by grid method in Xiaodian sewage irrigation area, Taiyuan City, North of China. The concentrations of 16 kinds of polycyclic aromatic hydrocarbons (PAHs) were determined by gas chromatograph coupled with mass spectrum. Generally speaking, the distribution order of PAHs in the area is: those with five and six rings > those with four rings > those with two and three rings. Source apportionment shows a significant zonation of the source of PAHs: the civil coal pollution occurred in the north part, the local and far factory pollution happened in the middle area and the mixed pollution sources from coal and wood combustion, automotive emission, presented in the south area. The distribution of PAHs has a definite relationship with the sewage water flow and soil adsorption. The related coefficient between PAHs and physicochemical property showed there was a negative correlation between pH, silt, clay and PAHs while there was a positive correlation between total organic carbon, sand and PAHs.

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 nicotine from aqueous solution onto hydrophobic zeolite type USY

NASA Astrophysics Data System (ADS)

Lazarevic, Natasa; Adnadjevic, Borivoj; Jovanovic, Jelena

2011-07-01

The isothermal adsorption of nicotine from an aqueous solution onto zeolite type USY was investigated. The adsorption isotherms of nicotine onto the zeolite at different temperatures ranging from 298 to 322 K were determined. It was found that the adsorption isotherms can be described by the model of Freundlich adsorption isotherm. Based on the adsorption isotherms the changes of adsorption heat, free energy and entropy with adsorption degree were determined. The determined decrease of adsorption heat with adsorption degree can be explained by the presence of the adsorption centers of different energy and concentration on interface of zeolite-nicotine solution. It was found that the probability function of density distribution of the heat of adsorption (DDF) has exponential form. It was concluded that the possibility of fitting the adsorption isotherms of nicotine onto the zeolite by Freundlich adsorption isotherm was a direct consequence of that. The determined increase in entropy with the increase in adsorption degree can be explained with the change of phase state of adsorbed nicotine.

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.

Process for the removal of radium from acidic solutions containing same

DOEpatents

Scheitlin, F.M.

The invention is a process for the removal of radium from acidic aqueous solutions. In one aspect, the invention is a process for removing radium from an inorganic-acid solution. The process comprises contacting the solution with coal fly ash to effect adsorption of the radium on the ash. The radium-containing ash then is separated from the solution. The process is simple, comparatively inexpensive, and efficient. High radium-distribution coefficients are obtained even at room temperature. Coal fly ash is an inexpensive, acid-resistant, high-surface-area material which is available in large quantities throughout the United States. The invention is applicable, for example, to the recovery of /sup 226/Ra from nitric acid solutions which have been used to leach radium from uranium-mill tailings.

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.

Hard versus soft dynamics for adsorption-desorption kinetics: Exact results in one-dimension.

PubMed

Manzi, S J; Huespe, V J; Belardinelli, R E; Pereyra, V D

2009-11-01

The adsorption-desorption kinetics is discussed in the framework of the kinetic lattice-gas model. The master equation formalism has been introduced to describe the evolution of the system, where the transition probabilities are written as an expansion of the occupation configurations of all neighboring sites. Since the detailed balance principle determines half of the coefficients that arise from the expansion, it is necessary to introduce ad hoc, a dynamic scheme to get the rest of them. Three schemes of the so-called hard dynamics, in which the probability of transition from single site cannot be factored into a part which depends only on the interaction energy and one that only depends on the field energy, and five schemes of the so-called soft dynamics, in which this factorization is possible, were introduced for this purpose. It is observed that for the hard dynamic schemes, the equilibrium and nonequilibrium observables, such as adsorption isotherms, sticking coefficients, and thermal desorption spectra, have a normal or physical sustainable behavior. While for the soft dynamics schemes, with the exception of the transition state theory, the equilibrium and nonequilibrium observables have several problems. Some of them can be regarded as abnormal behavior.

Reaction-Mediated Desorption of Macromolecules: Novel Phenomenon Enabling Simultaneous Reaction and Separation.

PubMed

Isakari, Yu; Kishi, Yuhi; Yoshimoto, Noriko; Yamamoto, Shuichi; Podgornik, Aleš

2018-02-02

Combining chemical reaction with separation offers several advantages. In this work possibility to induce spontaneous desorption of adsorbed macromolecules, once being PEGylated, through adjustment of the reagent composition is investigated. Bovine serum albumin (BSA) and activated oligonucleotide, 9T, are used as the test molecules and 20 kDa linear activated PEG is used for their PEGylation. BSA solid-phase PEGylation is performed on Q Sepharose HP. Distribution coefficient of BSA and PEG-BSA as a function of NaCl is determined using linear gradient elution (LGE) experiments and Yamamoto model. According to the distribution coefficient the selectivity between BSA and PEG - BSA of around 15 is adjusted by using NaCl. Spontaneous desorption of PEG - BSA is detected with no presence of BSA. However, due to a rather low selectivity, also desorption of BSA occurred at high elution volume. A similar procedure is applied for activated 9T oligonucleotide, this time using monolithic CIM QA disk monolithic column for adsorption. Selectivity of over 2000 is obtained by proper adjustment of PEG reagent composition. High selectivity enables spontaneous desorption of PEG-9T without any desorption of activated 9T. Both experiments demonstrates that reaction-mediated desorption of macromolecules is possible when the reaction conditions are properly tuned. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermodynamic parameters of U (VI) sorption onto soils in aquatic systems.

PubMed

Kumar, Ajay; Rout, Sabyasachi; Ghosh, Malay; Singhal, Rakesh Kumar; Ravi, Pazhayath Mana

2013-01-01

The thermodynamic parameters viz. the standard free energy (∆Gº), Standard enthalpy change (∆Hº) and standard entropy change (∆Sº) were determined using the obtained values of distribution coefficient (kd) of U (VI) in two different types of soils (agricultural and undisturbed) by conducting a batch equilibrium experiment with aqueous media (groundwater and deionised water) at two different temperatures 25°C and 50°C. The obtained distribution coefficients (kd) values of U for undisturbed soil in groundwater showed about 75% higher than in agricultural soil at 25°C while in deionised water, these values were highly insignificant for both soils indicating that groundwater was observed to be more favorable for high surface sorption. At 50°C, the increased kd values in both soils revealed that solubility of U decreased with increasing temperature. Batch adsorption results indicated that U sorption onto soils was promoted at higher temperature and an endothermic and spontaneous interfacial process. The high positive values of ∆Sº for agricultural soil suggested a decrease in sorption capacity of U in that soil due to increased randomness at solid-solution interface. The low sorption onto agricultural soil may be due to presence of high amount of coarse particles in the form of sand (56%). Geochemical modeling predicted that mixed hydroxo-carbonato complexes of uranium were the most stable and abundant complexes in equilibrium solution during experimental.

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.

Drag coefficient Variability and Thermospheric models

NASA Astrophysics Data System (ADS)

Moe, Kenneth

Satellite drag coefficients depend upon a variety of factors: The shape of the satellite, its altitude, the eccentricity of its orbit, the temperature and mean molecular mass of the ambient atmosphere, and the time in the sunspot cycle. At altitudes where the mean free path of the atmospheric molecules is large compared to the dimensions of the satellite, the drag coefficients can be determined from the theory of free-molecule flow. The dependence on altitude is caused by the concentration of atomic oxygen which plays an important role by its ability to adsorb on the satellite surface and thereby affect the energy loss of molecules striking the surface. The eccentricity of the orbit determines the satellite velocity at perigee, and therefore the energy of the incident molecules relative to the energy of adsorption of atomic oxygen atoms on the surface. The temperature of the ambient atmosphere determines the extent to which the random thermal motion of the molecules influences the momentum transfer to the satellite. The time in the sunspot cycle affects the ambient temperature as well as the concentration of atomic oxygen at a particular altitude. Tables and graphs will be used to illustrate the variability of drag coefficients. Before there were any measurements of gas-surface interactions in orbit, Izakov and Cook independently made an excellent estimate that the drag coefficient of satellites of compact shape would be 2.2. That numerical value, independent of altitude, was used by Jacchia to construct his model from the early measurements of satellite drag. Consequently, there is an altitude dependent bias in the model. From the sparce orbital experiments that have been done, we know that the molecules which strike satellite surfaces rebound in a diffuse angular distribution with an energy loss given by the energy accommodation coefficient. As more evidence accumulates on the energy loss, more realistic drag coefficients are being calculated. These improved drag coefficients help evaluate the biases in present models. Moreover, they make possible the derivation of accurate densities from accelerometer measurements.

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.

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.

[Adsorption characteristics of proteins on membrane surface and effect of protein solution environment on permeation behavior of berberine].

PubMed

Li, Yi-Qun; Xu, Li; Zhu, Hua-Xu; Tang, Zhi-Shu; Li, Bo; Pan, Yong-Lan; Yao, Wei-Wei; Fu, Ting-Ming; Guo, Li-Wei

2017-10-01

In order to explore the adsorption characteristics of proteins on the membrane surface and the effect of protein solution environment on the permeation behavior of berberine, berberine and proteins were used as the research object to prepare simulated solution. Low field NMR, static adsorption experiment and membrane separation experiment were used to study the interaction between the proteins and ceramic membrane or between the proteins and berberine. The static adsorption capacity of proteins, membrane relative flux, rejection rate of proteins, transmittance rate of berberine and the adsorption rate of proteins and berberine were used as the evaluation index. Meanwhile, the membrane resistance distribution, the particle size distribution and the scanning electron microscope (SEM) were determined to investigate the adsorption characteristics of proteins on ceramic membrane and the effect on membrane separation process of berberine. The results showed that the ceramic membrane could adsorb the proteins and the adsorption model was consistent with Langmuir adsorption model. In simulating the membrane separation process, proteins were the main factor to cause membrane fouling. However, when the concentration of proteins was 1 g•L⁻¹, the proteins had no significant effect on membrane separation process of berberine. Copyright© by the Chinese Pharmaceutical Association.

Competitive adsorption of As(III), As(V), Sb(III) and Sb(V) onto ferrihydrite in multi-component systems: Implications for mobility and distribution.

PubMed

Qi, Pengfei; Pichler, Thomas

2017-05-15

The simultaneous adsorption behavior and competitive interactions between As(III), As(V), Sb(III) and Sb(V) by ferrihydrite were evaluated in multi-component (binary, ternary, quaternary) systems. In binary systems, Sb(III) had a stronger inhibitory influence on As(III) adsorption than Sb(V) did, and As(V) had a stronger inhibitory effect on Sb(V) adsorption than As(III) did. In ternary systems, NO 3 - , PO 4 3- and SO 4 2- did not compete with the adsorption of As(III) and Sb(III). NO 3 - and SO 4 2- also had no distinct effect on the adsorption of As(V) and Sb(V), while PO 4 3- competed with As(V) and Sb(V) for surface sites. In quaternary systems, the simultaneous adsorption behavior of the four redox species was pH dependent. Sb(III) always showed the strongest adsorption affinity regardless of pH. At pH 3.5 As(III) showed the lowest affinity could be due to the presence and negative effect of Sb(III) and As(V). The Freundlich model provided a good fit for the simultaneous adsorption data under quaternary conditions. The study of competitive/simultaneous adsorption of the four possible redox species onto ferrihydrite contributed to a better understanding of their distribution, mobility and fate in the environment. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

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.

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.

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.

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.

Effects of topology on the adsorption of singly tethered ring polymers to attractive surfaces.

PubMed

Li, Bing; Sun, Zhao-Yan; An, Li-Jia

2015-07-14

We investigate the effect of topology on the equilibrium behavior of singly tethered ring polymers adsorbed on an attractive surface. We focus on the change of square radius of gyration Rg(2), the perpendicular component Rg⊥(2) and the parallel component Rg‖(2) to the adsorbing surface, the mean contacting number of monomers with the surface , and the monomer distribution along z-direction during transition from desorption to adsorption. We find that both of the critical point of adsorption εc and the crossover exponent ϕ depend on the knot type when the chain length of ring ranges from 48 to 400. The behaviors of Rg(2), Rg⊥(2), and Rg‖(2) are found to be dependent on the topology and the monomer-surface attractive strength. At weak adsorption, the polymer chains with more complex topology are more adsorbable than those with simple topology. However, at strong adsorption, the polymer chains with complex topology are less adsorbable. By analyzing the distribution of monomer along z-direction, we give a possible mechanism for the effect of topology on the adsorption behavior.

Predicting CH4 adsorption capacity of microporous carbon using N2 isotherm and a new analytical model

USGS Publications Warehouse

Sun, Jielun; Chen, S.; Rostam-Abadi, M.; Rood, M.J.

1998-01-01

A new analytical pore size distribution (PSD) model was developed to predict CH4 adsorption (storage) capacity of microporous adsorbent carbon. The model is based on a 3-D adsorption isotherm equation, derived from statistical mechanical principles. Least squares error minimization is used to solve the PSD without any pre-assumed distribution function. In comparison with several well-accepted analytical methods from the literature, this 3-D model offers relatively realistic PSD description for select reference materials, including activated carbon fibers. N2 and CH4 adsorption data were correlated using the 3-D model for commercial carbons BPL and AX-21. Predicted CH4 adsorption isotherms, based on N2 adsorption at 77 K, were in reasonable agreement with the experimental CH4 isotherms. Modeling results indicate that not all the pores contribute the same percentage Vm/Vs for CH4 storage due to different adsorbed CH4 densities. Pores near 8-9 A?? shows higher Vm/Vs on the equivalent volume basis than does larger pores.

Sorption of noble gases by solids, with reference to meteorites. II - Chromite and carbon. III - Sulfides, spinels, and other substances; on the origin of planetary gases

NASA Technical Reports Server (NTRS)

Yang, J.; Anders, E.

1982-01-01

The trapping of noble gases by chromite and carbon, two putative carriers of primordial noble gases in meteorites, was studied by synthesizing 19 samples in a Ne-Ar-Kr-Xe atmosphere at 440-720 K. Noble gas contents are found to approximately obey Henry's Law, but only slight correlations are found with composition, surface area, or adsorption temperature. Geometric mean distribution coefficients for bulk samples and HCl residues in 10 cu cm STP/g atm are: Xe 100, Kr 15, Ar 3.5, and Ne 0.62. Elemental fractionation data support the suggestion of Lewis et al. (1977) that chromite and carbon in C2 and C3 chondrites were formed by the reaction: Fe, Cr + 4CO yields (Fe, Cr)3O4 + 4C + carbides. In contrast to meteoritic minerals, the synthetic specimens show no isotopic fractionation of noble gases. In a subsequent study, attention is given to the cases of sulfides and spinels, on the way to consideration of the origin of planetary gases. Sulfides showed three distinctive trends relative to chromite or magnetite. The elemental fractionation pattern of Ar, Kr and Xe in meteorites, terrestrial rocks and planets resembles the adsorption patterns on the carbons, spinels, sulfides, and other solids studied. The high release temperature of meteoritic noble gases may be explained by transformation of the physisorbed or chemisorbed gas. The ready loss of meteoritic heavy gases on surficial oxidation is consistent with adsorption, as is the high abundance.

Ion-imprinted polymethacrylic microbeads as new sorbent for preconcentration and speciation of mercury.

PubMed

Dakova, Ivanka; Karadjova, Irina; Georgieva, Ventsislava; Georgiev, George

2009-04-30

Metal ion-imprinted polymer particles have been prepared by copolymerization of methacrylic acid as monomer, trimethylolpropane trimethacrylate as cross-linking agent and 2,2'-azobisisobutyronitrile as initiator, in the presence of Hg(II)-1-(2-thiazolylazo)-2-naphthol complex. The separation and preconcentration characteristics of the Hg-ion-imprinted microbeads for inorganic mercury have been investigated by batch procedure. The optimal pH value for the quantitative sorption is 7. The adsorbed inorganic mercury is easily eluted by 2 mL 4M HNO(3). The adsorption capacity of the newly synthesized Hg ion-imprinted microbeads is 32.0 micromol g(-1) for dry copolymer. The selectivity of the copolymer toward inorganic mercury (Hg(II)) ion is confirmed through the comparison of the competitive adsorptions of Cd(II), Co(II), Cu(II), Ni(II), Pb(II), Zn(II)) and high values of the selectivity and distribution coefficients have been calculated. Experiments performed for selective determination of inorganic mercury in mineral and sea waters showed that the interfering matrix does not influence the extraction efficiency of Hg ion-imprinted microbeads. The detection limit for inorganic mercury is 0.006 microg L(-1) (3 sigma), determined by cold vapor atomic adsorption spectrometry. The relative standard deviation varied in the range 5-9 % at 0.02-1 microg L(-1) Hg levels. The new Hg-ion-imprinted microbeads have been tested and applied for the speciation of Hg in river and mineral waters: inorganic mercury has been determined selectively in nondigested sample, while total mercury e.g. sum of inorganic and methylmercury, has been determined in digested sample.

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.

Adsorption and Dissociation of Molecular Hydrogen on the (0001) Surface of DHCP Americium

NASA Astrophysics Data System (ADS)

Dholabhai, Pratik; Ray, Asok

2009-03-01

Hydrogen molecule adsorption on the (0001) surface of double hexagonal closed packed americium has been studied in detail within the framework of density functional theory. Weak molecular hydrogen adsorptions were observed. The most stable configuration corresponded to a Hor2 approach molecular adsorption at the one-fold top site where the molecule's approach is perpendicular to a lattice vector. Adsorption energies and adsorption geometries for different adsorption sites will be discussed. The change in work functions, magnetic moments, partial charges inside muffin-tins, difference charge density distributions and density of states for the bare Am slab and the Am slab after adsorption of the hydrogen molecule will be discussed. Reaction barrier for the dissociation of hydrogen molecule will be presented. The implications of adsorption on Am 5f electron localization-delocalization will be summarized.

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.

Application of Freeze-Dried Powders of Genetically Engineered Microbial Strains as Adsorbents for Rare Earth Metal Ions.

PubMed

Moriwaki, Hiroshi; Masuda, Reiko; Yamazaki, Yuki; Horiuchi, Kaoru; Miyashita, Mari; Kasahara, Jun; Tanaka, Tatsuhito; Yamamoto, Hiroki

2016-10-12

The adsorption behaviors of the rare earth metal ions onto freeze-dried powders of genetically engineered microbial strains were compared. Cell powders obtained from four kinds of strains, Bacillus subtilis 168 wild type (WT), lipoteichoic acid-defective (ΔLTA), wall teichoic acid-defective (ΔWTA), and cell wall hydrolases-defective (EFKYOJLp) strains, were used as an adsorbent of the rare earth metal ions at pH 3. The adsorption ability of the rare earth metal ions was in the order of EFKYOJLp > WT > ΔLTA > ΔWTA. The order was the same as the order of the phosphorus quantity of the strains. This result indicates that the main adsorption sites for the ions are the phosphate groups and the teichoic acids, LTA and WTA, that contribute to the adsorption of the rare earth metal ions onto the cell walls. The contribution of WTA was clearly greater than that of LTA. Each microbial powder was added to a solution containing 16 kinds of rare earth metal ions, and the removals (%) of each rare earth metal ion were obtained. The scandium ion showed the highest removal (%), while that of the lanthanum ion was the lowest for all the microbial powders. Differences in the distribution coefficients between the kinds of lanthanide ions by the EFKYOJLp and ΔWTA powders were greater than those of the other strains. Therefore, the EFKYOJLp and ΔWTA powders could be applicable for the selective extraction of the lanthanide ions. The ΔLTA powder coagulated by mixing with a rare earth metal ion, although no sedimentation of the WT or ΔWTA powder with a rare earth metal ion was observed under the same conditions. The EFKYOJLp powder was also coagulated, but its flocculating activity was lower than that of ΔLTA. The ΔLTA and EFKYOJLp powders have a long shape compared to those of the WT or ΔWTA strain. The shapes of the cells will play an important role in the sedimentation of the microbial powders with rare earth metal ions. As the results, three kinds of the genetically engineered microbial powders revealed unique adsorption behaviors of the rare earth metal ions.

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 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

An experimental and theoretical study of the adsorption removal of toluene and chlorobenzene on coconut shell derived carbon.

PubMed

Zhao, Xiaoyan; Zeng, Xiaolan; Qin, Yu; Li, Xiang; Zhu, Tianle; Tang, Xiaolong

2018-04-26

The adsorption performance of toluene and chlorobenzene on prepared coconut shell derived carbon (CDC) is investigated and compared with commercial activated carbon (CAC) by experiment and theory calculation. Textural properties of prepared adsorbents are characterized by N 2 adsorption, infrared spectra (FT-IR), Raman spectra and X-ray photoelectron spectra (XPS). Adsorption isotherms of toluene and chlorobenzene are obtained and fitted using structure optimizations, Grand Canonical Monte Carlo (GCMC) simulation and thermodynamic models. The results indicate that CDC shows better volatile organic compounds (VOCs) removal performance than CAC, and chlorobenzene is easily adsorbed than toluene. On the aspect of textural characteristics, CDC possesses more micropores ratio and narrower pore size distribution than CAC. Furthermore, amounts of electron-withdrawing carbonyl groups on the CAC surface reduce the electron density of adsorbents, thus weakening the interaction between VOCs and adsorbents. On the aspect of model fitting, the Yoon and Nelson (Y-N) and Dubinin-Astakhov (D-A) models can well describe the dynamic adsorption and the adsorption equilibrium of toluene and chlorobenzene on CDC respectively. It is believed that substituent groups of adsorbates, making the charge distribution deviate, lead to adsorption potentials of chlorobenzene larger than toluene. In general, both the pore structure and the surface property of adsorbents affect the VOCs adsorption behaviors on CDC. Copyright © 2018. Published by Elsevier Ltd.

Pore size distribution and supercritical hydrogen adsorption in activated carbon fibers

NASA Astrophysics Data System (ADS)

Purewal, J. J.; Kabbour, H.; Vajo, J. J.; Ahn, C. C.; Fultz, B.

2009-05-01

Pore size distributions (PSD) and supercritical H2 isotherms have been measured for two activated carbon fiber (ACF) samples. The surface area and the PSD both depend on the degree of activation to which the ACF has been exposed. The low-surface-area ACF has a narrow PSD centered at 0.5 nm, while the high-surface-area ACF has a broad distribution of pore widths between 0.5 and 2 nm. The H2 adsorption enthalpy in the zero-coverage limit depends on the relative abundance of the smallest pores relative to the larger pores. Measurements of the H2 isosteric adsorption enthalpy indicate the presence of energy heterogeneity in both ACF samples. Additional measurements on a microporous, coconut-derived activated carbon are presented for reference.

Pore size distribution and supercritical hydrogen adsorption in activated carbon fibers.

PubMed

Purewal, J J; Kabbour, H; Vajo, J J; Ahn, C C; Fultz, B

2009-05-20

Pore size distributions (PSD) and supercritical H2 isotherms have been measured for two activated carbon fiber (ACF) samples. The surface area and the PSD both depend on the degree of activation to which the ACF has been exposed. The low-surface-area ACF has a narrow PSD centered at 0.5 nm, while the high-surface-area ACF has a broad distribution of pore widths between 0.5 and 2 nm. The H2 adsorption enthalpy in the zero-coverage limit depends on the relative abundance of the smallest pores relative to the larger pores. Measurements of the H2 isosteric adsorption enthalpy indicate the presence of energy heterogeneity in both ACF samples. Additional measurements on a microporous, coconut-derived activated carbon are presented for reference.

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.

Removal of Radionuclides from Waste Water at Fukushima Daiichi Nuclear Power Plant: Desalination and Adsorption Methods - 13126

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

Kani, Yuko; Kamosida, Mamoru; Watanabe, Daisuke

Waste water containing high levels of radionuclides due to the Fukushima Daiichi Nuclear Power Plant accident, has been treated by the adsorption removal and reverse-osmosis (RO) desalination to allow water re-use for cooling the reactors. Radionuclides in the waste water are collected in the adsorbent medium and the RO concentrate (RO brine) in the water treatment system currently operated at the Fukushima Daiichi site. In this paper, we have studied the behavior of radionuclides in the presently applied RO desalination system and the removal of radionuclides in possible additional adsorption systems for the Fukushima Daiichi waste water treatment. Regarding themore » RO desalination system, decontamination factors (DFs) of the elements present in the waste water were obtained by lab-scale testing using an RO unit and simulated waste water with non-radioactive elements. The results of the lab-scale testing using representative elements showed that the DF for each element depended on its hydrated ionic radius: the larger the hydrated ionic radius of the element, the higher its DF is. Thus, the DF of each element in the waste water could be estimated based on its hydrated ionic radius. For the adsorption system to remove radionuclides more effectively, we studied adsorption behavior of typical elements, such as radioactive cesium and strontium, by various kinds of adsorbents using batch and column testing. We used batch testing to measure distribution coefficients (K{sub d}s) for cesium and strontium onto adsorbents under different brine concentrations that simulated waste water conditions at the Fukushima Daiichi site. For cesium adsorbents, K{sub d}s with different dependency on the brine concentration were observed based on the mechanism of cesium adsorption. As for strontium, K{sub d}s decreased as the brine concentration increased for any adsorbents which adsorbed strontium by intercalation and by ion exchange. The adsorbent titanium oxide had higher K{sub d}s and it was used for the column testing to obtain breakthrough curves under various conditions of pH and brine concentration. The breakthrough point had a dependency on pH and the brine concentration. We found that when the pH was higher or the brine concentration was lower, the longer it took to reach the breakthrough point. The inhibition of strontium adsorption by alkali earth metals would be diminished for conditions of higher pH and lower brine concentration. (authors)« less

Removal and attenuation of sewage effluent combined tracer signals of phosphorus, caffeine and saccharin in soil.

PubMed

Richards, Samia; Withers, Paul J A; Paterson, Eric; McRoberts, Colin W; Stutter, Marc

2017-04-01

Contaminants in septic tank effluent (STE) are expected to be removed by the soil system before discharging to the environment. However, potential contaminants such as phosphorus (P), caffeine and artificial sweeteners do find their way to watercourses impacting aquatic eco systems. In this study, the attenuation of STE P, caffeine and saccharin were investigated in untreated soil and in soil with reduced microbial activity, in aqueous solutions and in the complex matrix of STE. Time series sorption and desorption experiments using batch equilibrium and a column experiment of STE P attenuation were conducted. The results revealed that the soil distribution coefficients (K d ) were: P 81.57 > caffeine 22.16 > saccharin 5.98 cm 3 /g, suggesting greater soil affinity to P adsorption. The data revealed that 80% of saccharin and 33% of caffeine attenuation was associated with microbial activities rather than adsorption processes. However, a complete removal of saccharin and caffeine did not occur during the equilibration period, suggesting their leaching potential. The dominant mechanism of P attenuation was adsorption (chemical and physical), yielding P retention of >73% and 35% for P in aqueous solution and in STE matrix, respectively, for batch equilibrium. The soil in the column acted as effluent P sink retaining 125 μg P/g soil of effluent P. The attenuation of P, caffeine and saccharin in the aqueous solution was greater than in STE, suggesting that the complex composition of STE reduced soil adsorption ability, and that other substances present in STE may be competing for soil binding sites. The data revealed that caffeine and P had similarities in the interaction with soils and thus caffeine may be considered as a STE tracer of anthropogenic source of P in receiving waters. Copyright © 2017 Elsevier Ltd. All rights reserved.

Potential contributions of smectite clays and organic matter to pesticide retention in soils.

PubMed

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

2001-06-01

Soil organic matter (SOM) is often considered the dominant sorptive phase for organic contaminants and pesticides in soil-water systems. This is evidenced by the widespread use of organic-matter-normalized sorption coefficients (K(OM)) to predict soil-water distribution of pesticides, an approach that ignores the potential contribution of soil minerals to sorption. To gain additional perspective on the potential contributions of clays and SOM to pesticide retention in soils, we measured sorption of seven pesticides by a K-saturated reference smectite clay (SWy-2) and SOM (represented by a muck soil). In addition, we measured the adsorption of atrazine by five different K-saturated smectites and Ca-saturated SWy-2. On a unit mass basis, the K-SWy-2 clay was a more effective sorbent than SOM for 4,6-dinitro-o-cresol (DNOC), dichlobenil, and carbaryl of the seven pesticides evaluated, of which, DNOC was sorbed to the greatest extent. Atrazine was sorbed to a similar extent by K-SWy-2 and SOM. Parathion, diuron, and biphenyl were sorbed to a greater extent by SOM than by K-SWy-2. Atrazine was adsorbed by Ca-SWy-2 to a much lesser extent than by K-SWy-2. This appears to be related to the larger hydration sphere of Ca(2+) (compared to that of K(+)) which shrinks the effective size of the adsorption domains between exchangeable cations, and which expands the clay layers beyond the apparently optimal spacing of approximately 12.2 A for sorption of aromatic pesticide structures. Although a simple relation between atrazine adsorption by different K-smectites and charge properties of clay was not observed, the highest charge clay was the least effective sorbent; a higher charge density would result in a loss of adsorption domains. These results indicate that for certain pesticides, expandable soil clays have the potential to be an equal or dominant sorptive phase when compared to SOM for pesticide retention in soil.

Comparison of nitrogen adsorption and transmission electron microscopy analyses for structural characterization of carbon nanotubes

NASA Astrophysics Data System (ADS)

Abbaslou, Reza Malek; Vosoughi, Vahid; Dalai, Ajay K.

2017-10-01

Carbon nanotubes (CNTs) are different from other porous substrates such as activated carbon due to their high external surfaces. This structural feature can lead in some uncertainties in the results of nitrogen adsorption analysis for characterization of CNTs. In this paper, the results of microscopic analyses and nitrogen adsorption method for characterization of carbon nanotubes were compared. Five different types of CNTs with different structures were either synthesized or purchased. The CNT samples were characterized by high resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM) and N2 adsorption analysis. The comparisons between the results from the microscopic analyses and N2 adsorption showed that the total pore volume and BET surface measurements include the internal and external porosity of CNTs. Therefore, the interpretation of N2 adsorption data required accurate TEM analysis. In addition, the evaluation of pore size distribution curves from all CNT samples in this study and several instances in the literature revealed the presence of a common peak in the range of 2-5 nm. This peak does not explain the inner pore size distribution. The presence of this common peak can be attributed to the strong adsorption of N2 on the junction of touched and crossed nanotubes.

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.

[Effects of Fulvic Acid on Absorption and Form Distribution of Heavy Metals on Sediments].

PubMed

Li, Yu-qing; He, Jiang; Lü, Chang-wei; Fan, Ming-de; Wang, Wei; Zhang, Rui-qing; Xie, Zhi- lei; Wang, Jing-hua; Yu, Bo; En, He; Ding, Tao

2016-03-15

Based on the extracted fulvic acid (FA) from Lake Wuliangsuhai sediments by sequential alkali extraction, this work studied the effects of FA on the adsorption and fraction distribution of heavy metals (HM) on sediments using original sediments and sediments treated with 30% H₂O₂ as adsorbents. The results showed both organic matter and FA had effects on the HM adsorption onto sediments; The treatments of FA-free conditions and the sediments treated by H₂O₂ showed relatively strong influence on Cu²⁺ adsorption, which decreased the Cu²⁺ adsorption by 17.85%. With the increasing FA addition, the adsorption percentage of HM on both types of sediments showed gradually decreasing trends, with the order of Cu²⁺ > Cd²⁺ > Zn²⁺ > Pb²⁺; when the FA content was more than 5% , FA became the governing factor on the decreasing adsorption percentage of HM. With increasing FA addition, forms distribution of HM showed significant changes in both types of sediments; i. e. FA additions showed significant negative and positive correlations with percentages of metals bound to carbonates and organic matter, respectively, since the FA addition increased the H⁺ concentration of the system, in which H⁺ could activate the metals bound to carbonate from the sediments. As an organophilic weak element, the fraction percentage of Cd bound to organic matter was the lowest with the minimal changes.

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.

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.

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.

Adsorption dynamics of methyl violet onto granulated mesoporous carbon: Facile synthesis and adsorption kinetics.

PubMed

Kim, Yohan; Bae, Jiyeol; Park, Hosik; Suh, Jeong-Kwon; You, Young-Woo; Choi, Heechul

2016-09-15

A new and facile one-step synthesis method for preparing granulated mesoporous carbon (GMC) with three-dimensional spherical mesoporous symmetry is prepared to remove large molecular weight organic compounds in aqueous phase. GMC is synthesized in a single step using as-synthesized mesoporous carbon particles and organic binders through a simple and economical synthesis approach involving a simultaneous calcination and carbonization process. Characterization results obtained from SEM, XRD, as well as surface and porosity analysis indicate that the synthesized GMC has similar physical properties to those of the powdered mesoporous carbon and maintains the Brunauer-Emmett-Teller (BET) surface area and pore volume because the new synthesis method prevents the collapse of the pores during the granulation process. Batch adsorption experiments revealed GMC showed a substantial adsorption capacity (202.8 mg/g) for the removal of methyl violet as a target large molecular contaminant in aqueous phase. The mechanisms and dynamics modeling of GMC adsorption were also fully examined, which revealed that surface diffusion was rate limiting step on adsorption process of GMC. Adsorption kinetics of GMC enables 3 times faster than that of granular activated carbon in terms of surface diffusion coefficient. This is the first study, to the best of our knowledge, to synthesize GMC as an adsorbent for water purification by using facile granulation method and to investigate the adsorption kinetics and characteristics of GMC. This study introduces a new and simple method for the synthesis of GMC and reveals its adsorption characteristics for large molecular compounds in a water treatment. Copyright © 2016 Elsevier Ltd. 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.

Efficiency of fly ash belite cement and zeolite matrices for immobilizing cesium.

PubMed

Goñi, S; Guerrero, A; Lorenzo, M P

2006-10-11

The efficiency of innovative matrices for immobilizing cesium is presented in this work. The matrix formulation included the use of fly ash belite cement (FABC-2-W) and gismondine-type Na-P1 zeolite, both of which are synthesized from fly ash of coal combustion. The efficiency for immobilizing cesium is evaluated from the leaching test ANSI/ANS 16.1-1986 at the temperature of 40 degrees C, from which the apparent diffusion coefficient of cesium is obtained. Matrices with 100% of FABC-2-W are used as a reference. The integrity of matrices is evaluated by porosity and pore-size distribution from mercury intrusion porosimetry, X-ray diffraction and nitrogen adsorption analyses. Both matrices can be classified as good solidify systems for cesium, specially the FABC-2-W/zeolite matrix in which the replacement of 50% of belite cement by the gismondine-type Na-P1 zeolite caused a decrease of two orders of magnitude of cesium mean Effective Diffusion Coefficient (D(e)) (2.8e-09 cm(2)/s versus 2.2e-07 cm(2)/s, for FABC-2-W/zeolite and FABC-2-W matrices, respectively).

Assessing the combined influence of TOC and black carbon in soil-air partitioning of PBDEs and DPs from the Indus River Basin, Pakistan.

PubMed

Ali, Usman; Mahmood, Adeel; Syed, Jabir Hussain; Li, Jun; Zhang, Gan; Katsoyiannis, Athanasios; Jones, Kevin C; Malik, Riffat Naseem

2015-06-01

Levels of polybrominated diphenyl ethers (PBDEs) and dechlorane plus (DPs) were investigated in the Indus River Basin from Pakistan. Concentrations of ∑PBDEs and ∑DPs were ranged between 0.05 and 2.38 and 0.002-0.53 ng g(-1) in the surface soils while 1.43-22.1 and 0.19-7.59 pg m(-3) in the passive air samples, respectively. Black carbon (fBC) and total organic carbon (fTOC) fractions were also measured and ranged between 0.73 and 1.75 and 0.04-0.2%, respectively. The statistical analysis revealed strong influence of fBC than fTOC on the distribution of PBDEs and DPs in the Indus River Basin soils. BDE's congener profile suggested the input of penta-bromodiphenylether (DE-71) commercial formulation in the study area. Soil-air partitioning of PBDEs were investigated by employing octanol-air partition coefficients (KOA) and black carbon-air partition coefficients (KBC-A). The results of both models suggested the combined influence of total organic carbon (absorption) and black carbon (adsorption) in the studied area. Copyright © 2015 Elsevier Ltd. All rights reserved.

Correlating N2 and CH4 adsorption on microporous carbon using a new analytical model

USGS Publications Warehouse

Sun, Jielun; Chen, S.; Rood, M.J.; Rostam-Abadi, M.

1998-01-01

A new pore size distribution (PSD) model is developed to readily describe PSDs of microporous materials with an analytical expression. Results from this model can be used to calculate the corresponding adsorption isotherm to compare the calculated isotherm to the experimental isotherm. This aspect of the model provides another check on the validity of the model's results. The model is developed on the basis of a 3-D adsorption isotherm equation that is derived from statistical mechanical principles. Least-squares error minimization is used to solve the PSD without any preassumed distribution function. In comparison with several well-accepted analytical methods from the literature, this 3-D model offers a relatively realistic PSD description for select reference materials, including activated-carbon fibers. N2 and CH4 adsorption is correlated using the 3-D model for commercial carbons BPL and AX-21. Predicted CH4 adsorption isotherms at 296 K based on N2 adsorption at 77 K are in reasonable agreement with experimental CH4 isotherms. Use of the model is also described for characterizing PSDs of tire-derived activated carbons and coal-derived activated carbons for air-quality control applications.

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.

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

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.

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.

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.

A fundamental study of the impact of pressure on the adsorption mechanism in reversed-phase liquid chromatography.

PubMed

Åsberg, Dennis; Samuelsson, Jörgen; Fornstedt, Torgny

2016-07-29

A fundamental investigation of the pressure effect on individual adsorption sites was undertaken based on adsorption energy distribution and adsorption isotherm measurements. For this purpose, we measured adsorption equilibrium data at pressures ranging from 100 to 1000bar at constant flow and over a wide concentration range for three low-molecular-weight solutes, antipyrine, sodium 2-naphthalenesulfonate, and benzyltriethylammonium chloride, on an Eternity C18 stationary phase. The adsorption energy distribution was bimodal for all solutes, remaining clearly so at all pressures. The bi-Langmuir model best described the adsorption in these systems and two types of adsorption sites were identified, one with a low and another with a high energy of interaction. Evidence exists that the low-energy interactions occur at the interface between the mobile and stationary phases and that the high-energy interactions occur nearer the silica surface, deeper in the C18 layer. The contribution of each type of adsorption site to the retention factor was calculated and the change in solute molar volume from the mobile to stationary phase during the adsorption process was estimated for each type of site. The change in solute molar volume was 2-4 times larger at the high-energy site, likely because of the greater loss of solute solvation layer when penetrating deeper into the C18 layer. The association equilibrium constant increased with increasing pressure while the saturation capacity of the low-energy site remained almost unchanged. The observed increase in saturation capacity for the high-energy site did not affect the column loading capacity, which was almost identical at 50- and 950-bar pressure drops over the column. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

Surface structural ion adsorption modeling of competitive binding of oxyanions by metal (hydr)oxides

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

Hiemstra, T.; Riemsdijk, W.H. van

1999-02-01

An important challenge in surface complexation models (SCM) is to connect the molecular microscopic reality to macroscopic adsorption phenomena. This study elucidates the primary factor controlling the adsorption process by analyzing the adsorption and competition of PO{sub 4}, AsO{sub 4}, and SeO{sub 3}. The authors show that the structure of the surface-complex acting in the dominant electrostatic field can be ascertained as the primary controlling adsorption factor. The surface species of arsenate are identical with those of phosphate and the adsorption behavior is very similar. On the basis of the selenite adsorption, The authors show that the commonly used 1pKmore » models are incapable to incorporate in the adsorption modeling the correct bidentate binding mechanism found by spectroscopy. The use of the bidentate mechanism leads to a proton-oxyanion ratio and corresponding pH dependence that are too large. The inappropriate intrinsic charge attribution to the primary surface groups and the condensation of the inner sphere surface complex to a point charge are responsible for this behavior of commonly used 2pK models. Both key factors are differently defined in the charge distributed multi-site complexation (CD-MUSIC) model and are based in this model on a surface structural approach. The CD-MUSIC model can successfully describe the macroscopic adsorption phenomena using the surface speciation and binding mechanisms as found by spectroscopy. The model is also able to predict the anion competition well. The charge distribution in the interface is in agreement with the observed structure of surface complexes.« less

Modeling of adsorption dynamics at air-liquid interfaces using statistical rate theory (SRT).

PubMed

Biswas, M E; Chatzis, I; Ioannidis, M A; Chen, P

2005-06-01

A large number of natural and technological processes involve mass transfer at interfaces. Interfacial properties, e.g., adsorption, play a key role in such applications as wetting, foaming, coating, and stabilizing of liquid films. The mechanistic understanding of surface adsorption often assumes molecular diffusion in the bulk liquid and subsequent adsorption at the interface. Diffusion is well described by Fick's law, while adsorption kinetics is less understood and is commonly described using Langmuir-type empirical equations. In this study, a general theoretical model for adsorption kinetics/dynamics at the air-liquid interface is developed; in particular, a new kinetic equation based on the statistical rate theory (SRT) is derived. Similar to many reported kinetic equations, the new kinetic equation also involves a number of parameters, but all these parameters are theoretically obtainable. In the present model, the adsorption dynamics is governed by three dimensionless numbers: psi (ratio of adsorption thickness to diffusion length), lambda (ratio of square of the adsorption thickness to the ratio of adsorption to desorption rate constant), and Nk (ratio of the adsorption rate constant to the product of diffusion coefficient and bulk concentration). Numerical simulations for surface adsorption using the proposed model are carried out and verified. The difference in surface adsorption between the general and the diffusion controlled model is estimated and presented graphically as contours of deviation. Three different regions of adsorption dynamics are identified: diffusion controlled (deviation less than 10%), mixed diffusion and transfer controlled (deviation in the range of 10-90%), and transfer controlled (deviation more than 90%). These three different modes predominantly depend on the value of Nk. The corresponding ranges of Nk for the studied values of psi (10(-2)

[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.

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.

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.

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.

Marine Chemistry in the People’s Republic of China.

DTIC Science & Technology

1984-08-01

Eh, Fe, Al, Mn, Cu, Pb, Zn, Cd, Hg, Cr, and also the sedimentation rate by Pb- 210 method. (2) The effects of flow rate, eddy diffusion, axial length of...sediments, distribution, determination, radium-226, uranium-238, radon-222, polonium - 210 , bismuth- 210 , lead-206, particulates, adsorption, polonium ...sediments, distribution, radium-226, uranium-238, radon-222, polonium - 210 , bismuth- 210 , lead-206, particulates, adsorption, polonium , dating, Zhujiang

Fabrication and properties of multilayer structures

NASA Astrophysics Data System (ADS)

Tiller, W. A.

1983-09-01

The synthesis of SiC films and Pd2Si films via single source and dual source sputtering, respectively, has been experimentally investigated while the reactive sputter deposition of SiO sub x films has been theoretically analyzed. The SiO sub x film data requires a mobile precursor adsorption process to be operative for the oxygen and an oxygen sticking coefficient of between 1.56 x 10 to the minus 3rd power and 4.17 x 10 to the minus 3rd power. An analysis of in-situ electrical diagnostics of the films via a non-contact technique shows the method to be of marginal accuracy for the example selected. An important new formulation of the stress and elastic constant tensors in the vicinity of interfaces has been developed and applied to the simple example of adsorbed layer/substrate interactions via a parametric analysis. Atomic modeling of the SiO system yields peroxide bond formation for oxygen-rich (100) alpha-cristobalite surfaces. Radial distribution function and angular distribution function data have been calculated for bulk alpha-quartz and bulk alpha-cristobalite in good agreement with experiment.

Effects of topography and soil properties on soil selenium distribution and bioavailability (phosphate extraction): A case study in Yongjia County, China.

PubMed

Xu, Yuefeng; Li, Yonghua; Li, Hairong; Wang, Li; Liao, Xiaoyong; Wang, Jing; Kong, Chang

2018-08-15

Selenium (Se) is an essential trace element for humans. In order to investigate how soil Se is influenced by topography and soil properties, we selected Yongjia County, an area with mountainous topography, as a study area. This study used cultivated soil data to comprehensively analyze the effects of topography and soil properties on Se mobility and bioavailability and to identify the key factors influencing Se distribution in the environment. Factors considered in this study were elevation, slope, topographic wetness index, the coefficient of weathering and eluviation, pH, organic matter, and Fe 2 O 3 . The concentration of total soil Se (0.382±0.123mgkg -1 ) was far higher than the background value of soil in China, and 98% of the soil samples were classified as having moderate Se levels (>0.175mgkg -1 ), indicating Yongjia County is a Se-rich region in China. Phosphate extracted Se accounted for an average of 9% of the total Se and was significantly associated with soil total Se, Fe 2 O 3 , pH, and the coefficient of weathering and eluviation. Fe 2 O 3 primarily controlled Se adsorption, fixation, and availability in soil. Under the geo-environmental conditions in the study area, the total Se in the soil increased first and then decreased with increases in elevation, slope, and the topographic wetness index, and the phosphate extracted Se showed similar patterns except for the elevation. The findings showed that topographical attributes and soil physicochemical properties synthetically influenced the distribution and bioavailability of Se in soil. Copyright © 2018 Elsevier B.V. All rights reserved.

Study of Cs/NF3 adsorption on GaN (0 0 1) surface

NASA Astrophysics Data System (ADS)

Diao, Yu; Liu, Lei; Xia, Sihao; Kong, Yike

2017-03-01

To investigate the optoelectronics properties of Cs/NF3 adsorption on GaN (0 0 1) photocathode surface, different adsorption models of Cs-only, Cs/O, Cs/NF3 adsorption on GaN clean surface were established, respectively. Atomic structures, work function, adsorption energy, E-Mulliken charge distribution, density of states and optical properties of all these adsorption systems were calculated using first principles. Compared with Cs/O co-adsorption, Cs/NF3 co-adsorption show better stability and more decline of work function, which is more beneficial for photoemission efficiency. Besides, surface band structures of Cs/NF3 co-adsorption system exhibit metal properties, implying good conductivity. Meanwhile, near valence band minimum of Cs/NF3 co-adsorption system, more acceptor levels emerges to form a p-type emission surface, which is conductive to the escape of photoelectrons. In addition, imaginary part of dielectric function curve and absorption curve of Cs/NF3 co-adsorption system both move towards lower energy side. This work can direct the optimization of activation process of NEA GaN photocathode.

Influence of Polyvinyl Alcohol (PVA) Addition on Silica Membrane Performance Prepared from Rice Straw

NASA Astrophysics Data System (ADS)

Wahyuningsih, S.; Ramelan, A. H.; Wardoyo, D. T.; Ichsan, S.; Kristiawan, Y. R.

2018-03-01

The utilization and modification of silica from rice straw as the main ingredient of adsorbent has been studied. The aim of this study was to determine the optimum composition of PVA (polyvinyl alcohol): silica to produce adsorbents with excellent pore characteristics, optimum adsorption efficiency and optimum pH for methyl yellow adsorptions. X-Ray Fluorescence (XRF) analysis results showed that straw ash contains 82.12 % of silica (SiO2). SAA (Surface Area Analyzer) analysis showed optimum composition ratio 5:5 of PVA: silica with surface area of 1.503 m2/g. Besides, based on the pore size distribution of PVA: silica (5:5) showed the narrow pore size distribution with the largest pore cumulative volume of 2.8 x 10-3 cc/g. The optimum pH for Methanyl Yellow adsorption is pH 2 with adsorption capacity = 72.1346%.

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.

Heterogeneity of activated carbons in adsorption of phenols from aqueous solutions—Comparison of experimental isotherm data and simulation predictions

NASA Astrophysics Data System (ADS)

Podkościelny, P.; Nieszporek, K.

2007-01-01

Surface heterogeneity of activated carbons is usually characterized by adsorption energy distribution (AED) functions which can be estimated from the experimental adsorption isotherms by inverting integral equation. The experimental data of phenol adsorption from aqueous solution on activated carbons prepared from polyacrylonitrile (PAN) and polyethylene terephthalate (PET) have been taken from literature. AED functions for phenol adsorption, generated by application of regularization method have been verified. The Grand Canonical Monte Carlo (GCMC) simulation technique has been used as verification tool. The definitive stage of verification was comparison of experimental adsorption data and those obtained by utilization GCMC simulations. Necessary information for performing of simulations has been provided by parameters of AED functions calculated by regularization method.

The role of beaded activated carbon's pore size distribution on heel formation during cyclic adsorption/desorption of organic vapors.

PubMed

Jahandar Lashaki, Masoud; Atkinson, John D; Hashisho, Zaher; Phillips, John H; Anderson, James E; Nichols, Mark

2016-09-05

The effect of activated carbon's pore size distribution (PSD) on heel formation during adsorption of organic vapors was investigated. Five commercially available beaded activated carbons (BAC) with varying PSDs (30-88% microporous) were investigated. Virgin samples had similar elemental compositions but different PSDs, which allowed for isolating the contribution of carbon's microporosity to heel formation. Heel formation was linearly correlated (R(2)=0.91) with BAC micropore volume; heel for the BAC with the lowest micropore volume was 20% lower than the BAC with the highest micropore volume. Meanwhile, first cycle adsorption capacities and breakthrough times correlated linearly (R(2)=0.87 and 0.93, respectively) with BAC total pore volume. Micropore volume reduction for all BACs confirmed that heel accumulation takes place in the highest energy pores. Overall, these results show that a greater portion of adsorbed species are converted into heel on highly microporous adsorbents due to higher share of high energy adsorption sites in their structure. This differs from mesoporous adsorbents (low microporosity) in which large pores contribute to adsorption but not to heel formation, resulting in longer adsorbent lifetime. Thus, activated carbon with high adsorption capacity and high mesopore fraction is particularly desirable for organic vapor application involving extended adsorption/regeneration cycling. Copyright © 2016 Elsevier B.V. All rights reserved.

Functionalized layered double hydroxide with nitrogen and sulfur co-decorated carbondots for highly selective and efficient removal of soft Hg2+ and Ag+ ions.

PubMed

Asiabi, Hamid; Yamini, Yadollah; Shamsayei, Maryam; Molaei, Karam; Shamsipur, Mojtaba

2018-05-28

A facile composite was fabricated via direct assembly of nitrogen and sulfur co-decorated carbon dots with abundant oxygen-containing functional groups on the surface of the positively charged layered double hydroxide (N,S-CDs-LDH). The novel N,S-CDs-LDH demonstrates highly selective bindings (M-S) and an extremely efficient removal capacity for soft metal ions such as Ag + and Hg 2+ ions. N,S-CDs-LDH displayed a selectivity order of Ag + > Hg 2+ > Cu 2+ > Pb 2+ > Zn 2+ > Cd 2+ for their adsorption. The enormous capacities for Hg 2+ (625.0 mg g -1 ) and Ag + (714.3 mg g -1 ) and very high distribution coefficients (K d ) of 9.9 × 10 6 mL g -1 (C 0  = 20 mg L -1 ) and 2.0 × 10 7 mL g -1 (C 0  = 20 mg L -1 ) for Hg 2+ and Ag + , respectively, place the N,S-CDs-LDH at the top of LDH based materials known for such removal. The adsorption kinetic curves for Hg 2+ and Ag + fitted well with the pseudo-second order model. For Hg 2+ and Ag + , an exceptionally rapid capture with removal ∼100% within 80 min was observed (C ions  = 30 mg L -1 and V/m ratio of 1000). The adsorption isotherms were well described using Langmuir isotherm. The N,S-CDs-LDH was successfully applied to highly efficient removal of Hg 2+ and Ag + from aqueous solutions. Copyright © 2018 Elsevier B.V. All rights reserved.

Pesticide leaching from two Swedish topsoils of contrasting texture amended with biochar

NASA Astrophysics Data System (ADS)

Larsbo, Mats; Löfstrand, Elisabeth; de Veer, David van Alphen; Ulén, Barbro

2013-04-01

The use of biochar as a soil amendment has recently increased because of its potential for long-term soil carbon sequestration and its potential for improving soil fertility. The objective of this study was to quantify the effects of biochar soil incorporation on pesticide adsorption and leaching for two Swedish topsoils, one clay soil and one loam soil. We used the non-reactive tracer bromide and the pesticides sulfosulfuron, isoproturon, imidacloprid, propyzamid and pyraclostrobin, substances with different mobility in soil. Adsorption was studied in batch experiments and leaching was studied in experiments using soil columns (20 cm high, 20 cm diameter) where 0.01 kg kg- 1 dw biochar powder originating from wheat residues had been mixed into the top 10 cm. After solute application the columns were exposed to simulated rain three times with a weekly interval and concentrations were measured in the effluent water. The biochar treatment resulted in significantly larger adsorption distribution coefficients (Kd) for the moderately mobile pesticides isoproturon and imidacloprid for the clay soil and for imidacloprid only for the loam soil. Relative leaching of the pesticides ranged from 0.0035% of the applied mass for pyraclostrobin (average Kd = 360 cm3 g- 1) to 5.9% for sulfosulfuron (average Kd = 5.6 cm3 g- 1). There were no significant effects of the biochar amendment on pesticide concentrations in column effluents for the loam soil. For the clay soil concentrations were significantly reduced for isoproturon, imidacloprid and propyzamid while they were significantly increased for the non-mobile fungicide pyraclostrobin suggesting that the transport was facilitated by material originating from the biochar amendment.

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.

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

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.

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.

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.

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.

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.

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.

Supported Intrinsically Porous Oligomers as Hybrid Materials for Separations, Storage, and Sensing

NASA Astrophysics Data System (ADS)

Thompson, Anthony Boone

Adsorption-desorption phenomena are often difficult to study at the molecular level because the surfaces on which they occur can be heterogeneous, giving a wide distribution of adsorption sites and associated energies. Considering that these phenomena underlie an incredibly wide variety of industrially important processes, a better understanding could aid in the development of more efficient methods. In this work, we describe an approach to designing materials with well-defined adsorption sites by covalently attaching intrinsically porous molecules to solid surfaces by a rigid multidentate linker. These cup-shaped molecules are intended to act as adsorption sites on the material, whereas the rigid attachment to the solid support serves to prevent movement and conformational changes of the sites, leading to better understanding of adsorption phenomena. As a proof-of-concept application, materials were used for adsorption of n-butanol biofuel and related compounds from dilute aqueous solution. The materials were thermally and hydrolytically stable, and adsorption phenomena were reversible. Adsorption sites containing more hydrophobic molecular area led to stronger adsorption, suggesting that it is driven by weak van der Waals forces. Likewise, adsorption sites that were strongly polarized performed poorly, possibly reflecting a greater energy penalty of removing water molecules from the cavity. Upon placing a Lewis acidic metal at the bottom of the cavity, an enhancement was seen only with the most acidic metal, which may indicate weak guest coordination. Observing that hydrophobic interactions dominate adsorption on these materials, efforts were made to develop hybrid materials with large hydrophobic area for adsorption. Glaser coupling of diethynylbenzene was used to grow oligo(phenylene butadiynylene)s from the surface of silica, resulting in materials that were more than 25% organic by weight. In addition to their potential use as adsorbents, these materials may be promising for hydrogen storage via spillover. Finally, to demonstrate other potential uses of supported intrinsically porous oligomers, a TiO2-supported calixarene material was synthesized and used as a simple molecular sensor, opening up the possibility of using these materials for sensing. Overall, the methods used here result in robust hybrid materials with narrow adsorption site distributions and therefore are of potential use in many future applications.

Aspects of droplet and particle size control in miniemulsions

NASA Astrophysics Data System (ADS)

Saygi-Arslan, Oznur

Miniemulsion polymerization has become increasingly popular among researchers since it can provide significant advantages over conventional emulsion polymerization in certain cases, such as production of high-solids, low-viscosity latexes with better stability and polymerization of highly water-insoluble monomers. Miniemulsions are relatively stable oil (e.g., monomer) droplets, which can range in size from 50 to 500 nm, and are normally dispersed in an aqueous phase with the aid of a surfactant and a costabilizer. These droplets are the primary locus of the initiation of the polymerization reaction. Since particle formation takes place in the monomer droplets, theoretically, in miniemulsion systems the final particle size can be controlled by the initial droplet size. The miniemulsion preparation process typically generates broad droplet size distributions and there is no complete treatment in the literature regarding the control of the mean droplet size or size distribution. This research aims to control the miniemulsion droplet size and its distribution. In situ emulsification, where the surfactant is synthesized spontaneously at the oil/water interface, has been put forth as a simpler method for the preparation of miniemulsions-like systems. Using the in situ method of preparation, emulsion stability and droplet and particle sizes were monitored and compared with conventional emulsions and miniemulsions. Styrene emulsions prepared by the in situ method do not demonstrate the stability of a comparable miniemulsion. Upon polymerization, the final particle size generated from the in situ emulsion did not differ significantly from the comparable conventional emulsion polymerization; the reaction mechanism for in situ emulsions is more like conventional emulsion polymerization rather than miniemulsion polymerization. Similar results were found when the in situ method was applied to controlled free radical polymerizations (CFRP), which have been advanced as a potential application of the method. Molecular weight control was found to be achieved via diffusion of the CFRP agents through the aqueous phase owing to limited water solubilities. The effects of adsorption rate and energy on the droplet size and size distribution of miniemulsions using different surfactants (sodium lauryl sulfate (SLS), sodium dodecylbenzene sulfonate (SDBS), Dowfax 2A1, Aerosol OT-75PG, sodium n-octyl sulfate (SOS), and sodium n-hexadecyl sulfate (SHS)) were analyzed. For this purpose, first, the dynamics of surfactant adsorption at an oil/water interface were examined over a range of surfactant concentrations by the drop volume method and then adsorption rates of the different surfactants were determined for the early stages of adsorption. The results do not show a direct relationship between adsorption rate and miniemulsion droplet size and size distribution. Adsorption energies of these surfactants were also calculated by the Langmuir adsorption isotherm equation and no correlation between adsorption energy and miniemulsion droplet size was found. In order to understand the mechanism of miniemulsification process, the effects of breakage and coalescence processes on droplet size distributions were observed at different surfactant concentrations, monomer ratios, and homogenization conditions. A coalescence and breakup mechanism for miniemulsification is proposed to explain the size distribution of droplets. The multimodal droplet size distribution of ODMA miniemulsions was controlled by the breakage mechanism. The results also showed that, at a surfactant concentration when 100% surface coverage was obtained, the droplet size distribution became unimodal.

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.

Analyzing adsorption characteristics of CO2, N2 and H2O in MCM-41 silica by molecular simulation

NASA Astrophysics Data System (ADS)

Chang, Shing-Cheng; Chien, Shih-Yao; Chen, Chieh-Li; Chen, Cha'o.-Kuang

2015-03-01

The adsorption characteristics of carbon dioxide, nitrogen and water molecules in MCM-41 mesoporous molecular sieve have been investigated by the molecular simulation. We evaluate the pressure-adsorption isotherms and adsorption density profiles under variant gas pressure, operating temperature and mesopore radius of MCM-41 by the grand canonical Monte Carlo simulation. According to the calculated adsorption energy distributions, the adsorption mechanisms of gas in MCM-41 are mainly divided into three types, namely "surface adsorption" on the pore wall, "multilayer adsorption" on the adsorbed gas molecules and "molecular self-aggregation" near the pore center. In addition, the adsorption characteristics of water molecules in MCM-41 are found to be quite different from those of carbon dioxide and nitrogen due to the hydrogen bonds effect. The results indicate that the MCM-41 is practicable in engineering application for the capture, storage, and re-use of water molecules, since it is temperature-sensitive and can achieve significant adsorption loadings within a small range of pressure values via the capillary condensation phenomena.

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.

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.

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.

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.

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.

A Universal Isotherm Model to Capture Adsorption Uptake and Energy Distribution of Porous Heterogeneous Surface.

PubMed

Ng, Kim Choon; Burhan, Muhammad; Shahzad, Muhammad Wakil; Ismail, Azahar Bin

2017-09-06

The adsorbate-adsorbent thermodynamics are complex as it is influenced by the pore size distributions, surface heterogeneity and site energy distribution, as well as the adsorbate properties. Together, these parameters defined the adsorbate uptake forming the state diagrams, known as the adsorption isotherms, when the sorption site energy on the pore surfaces are favorable. The available adsorption models for describing the vapor uptake or isotherms, hitherto, are individually defined to correlate to a certain type of isotherm patterns. There is yet a universal approach in developing these isotherm models. In this paper, we demonstrate that the characteristics of all sorption isotherm types can be succinctly unified by a revised Langmuir model when merged with the concepts of Homotattic Patch Approximation (HPA) and the availability of multiple sets of site energy accompanied by their respective fractional probability factors. The total uptake (q/q*) at assorted pressure ratios (P/P s ) are inextricably traced to the manner the site energies are spread, either naturally or engineered by scientists, over and across the heterogeneous surfaces. An insight to the porous heterogeneous surface characteristics, in terms of adsorption site availability has been presented, describing the unique behavior of each isotherm type.

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.

Adsorption of octylamine on titanium dioxide

NASA Astrophysics Data System (ADS)

Siwińska, Daria; Kołodziejczak-Radzimska, Agnieszka; Krysztafkiewicz, Andrzej; Jesionowski, Teofil

2009-05-01

Processes of adsorption and desorption of a model active substance (octylamine) on the surface of unmodified titanium dioxide (E 171) have been performed. The effects of concentration of octylamine and time of the process on the character of adsorption have been studied and the efficiency of the adsorption/desorption has been determined. The samples obtained have been studied by X-ray diffraction. The nitrogen adsorption/desorption isotherms, particle size distribution and absorption capacities of water, dibutyl phthalate and paraffin oil have been determined. The efficiency of octylamine adsorption on the surface of the titanium dioxide has been found positively correlated with the concentration of octylamine in the initial solution. The desorption of octylamine has decreased with increasing concentration of this compound adsorbed. For octylamine in low concentrations the physical adsorption has been found to dominate, which is desirable when using TiO 2 in the production of pharmaceuticals.

The electronic and optical properties of Cs adsorbed GaAs nanowires via first-principles study

NASA Astrophysics Data System (ADS)

Diao, Yu; Liu, Lei; Xia, Sihao; Feng, Shu; Lu, Feifei

2018-07-01

In this study, we investigate the Cs adsorption mechanism on (110) surface of zinc-blende GaAs nanowire. The adsorption energy, work function, dipole moment, geometric structure, Mulliken charge distribution, charge transfer index, band structures, density of state and optical properties of Cs adsorption structures are calculated utilizing first-principles method based on density function theory. Total-energy calculations show that all the adsorption energies are negative, indicating that Cs adsorption process is exothermic and Cs covered GaAs nanowires are stable. The work function of nanowire surface has an obvious decrease after Cs adsorption. Besides, the ionization of nanowire surface is enhanced as well. More importantly, Cs adsorption contributes to a lower side shift of bands near Fermi level, and the corresponding band gap disappears. Additionally, the absorption peak and energy loss function after Cs adsorption are far higher than those before adsorption, implying better light absorption characteristic of nanowire surface after Cs adsorption. These theoretical calculations can directly guide the Cs activation experiment for negative electron affinity GaAs nanowire, and also lay a foundation for the further study of Cs/O co-adsorption on the nanowire surface.

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).

Thin film assembly of nano-sized Zn(II)-8-hydroxy-5,7-dinitroquinolate by using successive ion layer adsorption and reaction (SILAR) technique: characterization and optical-electrical-photovoltaic properties.

PubMed

Farag, A A M; Haggag, Sawsan M S; Mahmoud, Mohamed E

2012-07-01

A method is described for thin film assembly of nano-sized Zn(II)-8-hydroxy-5,7-dinitroquinolate complex, Zn[((NO(2))(2)-8HQ)(2)] by using successive ion layer adsorption and reaction (SILAR) technique. Highly homogeneous assembled nano-sized metal complex thin films with particle size distribution in the range 27-47nm was identified by using scanning electron microscopy (SEM). Zn[((NO(2))(2)-8HQ)(2)] and [(NO(2))(2)-8HQ] ligand were studied by thermal gravimetric analysis (TGA). Graphical representation of temperature dependence of the dark electrical conductivity produced two distinct linear parts for two activation energies at 0.377eV and 1.11eV. The analysis of the spectral behavior of the absorption coefficient in the intrinsic absorption region reveals a direct allowed transition with a fundamental band gap of 2.74eV. The dark current density-voltage (J-V) characteristics showed the rectification effect due to the formation of junction barrier of Zn[((NO(2))(2)-8HQ)(2)] complex film/n-Si interface. The photocurrent in the reverse direction is strongly increased by photo-illumination and the photovoltaic characteristics were also determined and evaluated. Copyright © 2012 Elsevier B.V. All rights reserved.

Impact of kerogen heterogeneity on sorption of organic pollutants. 2. Sorption equilibria

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

Yang, C.; Yu, Z.Q.; Xiao, B.H.

2009-08-15

Phenanthrene and naphthalene sorption isotherms were measured for three different series of kerogen materials using completely mixed batch reactors. Sorption isotherms were nonlinear for each sorbate-sorbent system, and the Freundlich isotherm equation fit the sorption data well. The Freundlich isotherm linearity parameter n ranged from 0.192 to 0.729 for phenanthrene and from 0.389 to 0.731 for naphthalene. The n values correlated linearly with rigidity and aromaticity of the kerogen matrix, but the single-point, organic carbon-normalized distribution coefficients varied dramatically among the tested sorbents. A dual-mode sorption equation consisting of a linear partitioning domain and a Langmuir adsorption domain adequately quantifiedmore » the overall sorption equilibrium for each sorbent-sorbate system. Both models fit the data well, with r{sup 2} values of 0.965 to 0.996 for the Freundlich model and 0.963 to 0.997 for the dual-mode model for the phenanthrene sorption isotherms. The dual-mode model fitting results showed that as the rigidity and aromaticity of the kerogen matrix increased, the contribution of the linear partitioning domain to the overall sorption equilibrium decreased, whereas the contribution of the Langmuir adsorption domain increased. The present study suggested that kerogen materials found in soils and sediments should not be treated as a single, unified, carbonaceous sorbent phase.« less

Interaction of inorganic anions with iron-mineral adsorbents in aqueous media--a review.

PubMed

Kumar, Eva; Bhatnagar, Amit; Hogland, William; Marques, Marcia; Sillanpää, Mika

2014-01-01

A number of inorganic anions (e.g., nitrate, fluoride, bromate, phosphate, and perchlorate) have been reported in alarming concentrations in numerous drinking water sources around the world. Their presence even in very low concentrations may cause serious environmental and health related problems. Due to the presence and significance of iron minerals in the natural aquatic environment and increasing application of iron in water treatment, the knowledge of the structure of iron and iron minerals and their interactions with aquatic pollutants, especially inorganic anions in water are of great importance. Iron minerals have been known since long as potential adsorbents for the removal of inorganic anions from aqueous phase. The chemistry of iron and iron minerals reactions in water is complex. The adsorption ability of iron and iron minerals towards inorganic anions is influenced by several factors such as, surface characteristics of the adsorbent (surface area, density, pore volume, porosity, pore size distribution, pHpzc, purity), pH of the solution, and ionic strength. Furthermore, the physico-chemical properties of inorganic anions (pore size, ionic radius, bulk diffusion coefficient) also significantly influence the adsorption process. The aim of this paper is to provide an overview of the properties of iron and iron minerals and their reactivity with some important inorganic anionic contaminants present in water. It also summarizes the usage of iron and iron minerals in water treatment technology. © 2013.

A field, laboratory and modeling study of reactive transport of groundwater arsenic in a coastal aquifer

PubMed Central

Jung, Hun Bok; Charette, Matthew A.; Zheng, Yan

2009-01-01

A field, laboratory, and modeling study of As in groundwater discharging to Waquoit Bay, MA, shed light on coupled control of chemistry and hydrology on reactive transport of As in a coastal aquifer. Dissolved Fe(II) and As(III) in a reducing groundwater plume bracketed by an upper and a lower redox interface are oxidized as water flows towards the bay. This results in precipitation of Fe(III) oxides, along with oxidation and adsorption of As to sediment at the redox interfaces where concentrations of sedimentary HCl-leachable Fe (80~90% Fe(III)) are 734±232 mg kg-1, sedimentary phosphate extractable As (90~100% As(V)) are 316±111 μg kg-1, and are linearly correlated. Batch adsorption of As(III) onto orange, brown and gray sediments follows Langmuir isotherms, and can be fitted by a surface complexation model (SCM) assuming a diffuse layer for ferrihydrite. The sorption capacity and distribution coefficient for As increase with decreasing sediment Fe(II)/Fe. To allow accumulation of the amount of sediment As, similar hydrogeochemical conditions would have been operating for thousands of years at Waquoit Bay. The SCM simulated the observed dissolved As concentration better than a parametric approach based on Kd. Site specific isotherms should be established for Kd or SCM based models. PMID:19708362

Surface complexation modeling calculation of Pb(II) adsorption onto the calcined diatomite

NASA Astrophysics Data System (ADS)

Ma, Shu-Cui; Zhang, Ji-Lin; Sun, De-Hui; Liu, Gui-Xia

2015-12-01

Removal of noxious heavy metal ions (e.g. Pb(II)) by surface adsorption of minerals (e.g. diatomite) is an important means in the environmental aqueous pollution control. Thus, it is very essential to understand the surface adsorptive behavior and mechanism. In this work, the Pb(II) apparent surface complexation reaction equilibrium constants on the calcined diatomite and distributions of Pb(II) surface species were investigated through modeling calculations of Pb(II) based on diffuse double layer model (DLM) with three amphoteric sites. Batch experiments were used to study the adsorption of Pb(II) onto the calcined diatomite as a function of pH (3.0-7.0) and different ionic strengths (0.05 and 0.1 mol L-1 NaCl) under ambient atmosphere. Adsorption of Pb(II) can be well described by Freundlich isotherm models. The apparent surface complexation equilibrium constants (log K) were obtained by fitting the batch experimental data using the PEST 13.0 together with PHREEQC 3.1.2 codes and there is good agreement between measured and predicted data. Distribution of Pb(II) surface species on the diatomite calculated by PHREEQC 3.1.2 program indicates that the impurity cations (e.g. Al3+, Fe3+, etc.) in the diatomite play a leading role in the Pb(II) adsorption and dominant formation of complexes and additional electrostatic interaction are the main adsorption mechanism of Pb(II) on the diatomite under weak acidic conditions.

Formation patterns of water clusters in CMK-3 and CMK-5 mesoporous carbons: a computational recognition study.

PubMed

Peng, Xuan; Jain, Surendra Kumar; Singh, Jayant Kumar; Liu, Anqi; Jin, Qibing

2018-06-13

Grand canonical Monte Carlo simulations are performed to study the adsorption of water in realistic CMK-3 and CMK-5 models at 300 K. The adsorption isotherms are characterized by negligible uptake at lower chemical potentials and complete pore filling once the threshold chemical potential is increased. Results for the isosteric heat of adsorption, radial distribution function (O-O and O-H), hydrogen bond statistics and the cluster size distribution of water molecules are presented. The snapshots of GCMC simulations in CMK-3 and CMK-5 models show that the adsorption happens via the formation of water clusters. For the CMK-3 model, it was found that the pore filling occurred via the formation of a single water cluster and a few very small clusters. The water cluster size increased with an increase in pore size of the CMK-3 model. For the CMK-5 model, it was found that the adsorption first occurred in the inner porosity (via cluster formation). There was no adsorption of water in the outer porosity during the filling of the inner porosity. After the inner porosity was completely filled, the water begins to fill the outer porosity. Snapshots from GCMC simulations of the CMK-5 model clearly show that the water adsorption in the outer porosity occurs via the formation and growth of clusters and there was no formation of layers of water in the porosity as seen for nonpolar fluids like nitrogen.

Enhanced adsorption of humic acids on ordered mesoporous carbon compared with microporous activated carbon.

PubMed

Liu, Fengling; Xu, Zhaoyi; Wan, Haiqin; Wan, Yuqiu; Zheng, Shourong; Zhu, Dongqiang

2011-04-01

Humic acids are ubiquitous in surface and underground waters and may pose potential risk to human health when present in drinking water sources. In this study, ordered mesoporous carbon was synthesized by means of a hard template method and further characterized by X-ray diffraction, N2 adsorption, transition electron microscopy, elemental analysis, and zeta-potential measurement. Batch experiments were conducted to evaluate adsorption of two humic acids from coal and soil, respectively, on the synthesized carbon. For comparison, a commercial microporous activated carbon and nonporous graphite were included as additional adsorbents; moreover, phenol was adopted as a small probe adsorbate. Pore size distribution characterization showed that the synthesized carbon had ordered mesoporous structure, whereas the activated carbon was composed mainly of micropores with a much broader pore size distribution. Accordingly, adsorption of the two humic acids was substantially lower on the activated carbon than on the synthesized carbon, because of the size-exclusion effect. In contrast, the synthesized carbon and activated carbon showed comparable adsorption for phenol when the size-exclusion effect was not in operation. Additionally, we verified by size-exclusion chromatography studies that the synthesized carbon exhibited greater adsorption for the large humic acid fraction than the activated carbon. The pH dependence of adsorption on the three carbonaceous adsorbents was also compared between the two test humic acids. The findings highlight the potential of using ordered mesoporous carbon as a superior adsorbent for the removal of humic acids. Copyright © 2011 SETAC.

Adsorption and Photodesorption of CO from Charged Point Defects on TiO 2 (110)

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

Mu, Rentao; Dahal, Arjun; Wang, Zhi-Tao

Adsorption and photodesorption of weakly-bound carbon monoxide, CO, from reduced and hydroxylated rutile TiO2(110) (r- and h- TiO2(110)) at sub-monolayer coverages is studied with atomically-resolved scanning tunneling microscopy (STM) along with ensemble-averaged temperature-programmed desorption (TPD) and angle-resolved photon-stimulated desorption (PSD) at low temperatures ( 50 K). STM data weighted by the concentration of each kind of adsorption sites on r-TiO2(110) give an adsorption probability which is the highest for the bridging oxygen vacancies (VO) and very low for the Ti5c sites closest to VO. Occupancy of the remaining Ti5c sites with CO is significant, but smaller than for VO. Themore » probability distribution for the different adsorption sites corresponds to a very small difference in CO adsorption energies: < 0.02 eV. We also find that UV irradiation stimulates both diffusion and desorption of CO at low temperature. CO photodesorbs primarily from the vacancies with a bi-modal angular distribution. In addition to a major, normal to the surface component, there is a broader cosine component indicating scattering from the surface which likely also leads to photo-stimulated diffusion. Hydroxylation of VO’s does not significantly change the CO PSD yield and angular distribution, indicating that not atomic but rather electronic surface defects are involved in the site-specific PSD process. We suggest that photodesorption can be initiated by recombination of photo-generated holes with excess unpaired electrons localized near the surface point-defect (either VO or bridging hydroxyl), leading to the surface atoms rearrangement and ejection of the weakly-bound CO molecules.« less

Assessing the potential contributions of additional retention processes to PFAS retardation in the subsurface.

PubMed

Brusseau, Mark L

2018-02-01

A comprehensive understanding of the transport and fate of per- and poly-fluoroalkyl substances (PFAS) in the subsurface is critical for accurate risk assessments and design of effective remedial actions. A multi-process retention model is proposed to account for potential additional sources of retardation for PFAS transport in source zones. These include partitioning to the soil atmosphere, adsorption at air-water interfaces, partitioning to trapped organic liquids (NAPL), and adsorption at NAPL-water interfaces. An initial assessment of the relative magnitudes and significance of these retention processes was conducted for two PFAS of primary concern, perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), and an example precursor (fluorotelomer alcohol, FTOH). The illustrative evaluation was conducted using measured porous-medium properties representative of a sandy vadose-zone soil. Data collected from the literature were used to determine measured or estimated values for the relevant distribution coefficients, which were in turn used to calculate retardation factors for the model system. The results showed that adsorption at the air-water interface was a primary source of retention for both PFOA and PFOS, contributing approximately 50% of total retention for the conditions employed. Adsorption to NAPL-water interfaces and partitioning to bulk NAPL were also shown to be significant sources of retention. NAPL partitioning was the predominant source of retention for FTOH, contributing ~98% of total retention. These results indicate that these additional processes may be, in some cases, significant sources of retention for subsurface transport of PFAS. The specific magnitudes and significance of the individual retention processes will depend upon the properties and conditions of the specific system of interest (e.g., PFAS constituent and concentration, porous medium, aqueous chemistry, fluid saturations, co-contaminants). In cases wherein these additional retention processes are significant, retardation of PFAS in source areas would likely be greater than what is typically estimated based on the standard assumption of solid-phase adsorption as the sole retention mechanism. This has significant ramifications for accurate determination of the migration potential and magnitude of mass flux to groundwater, as well as for calculations of contaminant mass residing in source zones. Both of which have critical implications for human-health risk assessments. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

Comparative study on the copper activation and xanthate adsorption on sphalerite and marmatite surfaces

NASA Astrophysics Data System (ADS)

Liu, Jian; Wang, Yu; Luo, Deqiang; Chen, Luzheng; Deng, Jiushuai

2018-05-01

The copper activation and potassium butyl xanthate (PBX) adsorption on sphalerite and marmatite surfaces were comparatively investigated using in situ local electrochemical impedance spectroscopy (LEIS), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and surface adsorption tests. Comparing the LEIS and surface adsorption results, it was found that the activation time is a key factor influencing the copper activation and PBX adsorption on marmatite surface, but it has a negligible influence on sphalerite. For a short activation time within 10 min, the Fe impurity in marmatite shows an adverse influence on the speed of Cu adsorption and ion exchange as well as on the subsequent PBX adsorption. For a long activation time of 30 min, the LEIS, ToF-SIMS and surface adsorption results suggested that the Fe impurity in marmatite enhances the copper adsorption, whereas such enhanced copper adsorption of marmatite cannot result in corresponding enhancing of PBX adsorption. DFT result showed that the Fe impurity in marmatite has harmful influence on the PBX interaction with the Cu-activated surface by increasing the interaction energy. ToF-SIMS result further indicated that the Cu distribution in the outermost surface of marmatite is less than that of the sphalerite, which also results in the less PBX adsorption for the marmatite.

Regeneration of acid orange 7-exhausted granular activated carbons with microwave irradiation.

PubMed

Quan, Xie; Liu, Xitao; Bo, Longli; Chen, Shuo; Zhao, Yazhi; Cui, Xinyi

2004-12-01

An investigation was performed for the regeneration of three granular activated carbons (GACs) exhausted with acid orange 7 (AO7). The three GACs were made from different materials, i.e. coconut shells, almond nucleus and coal. The AO7 adsorption process was carried out in a continuous-flow adsorption column. After adsorption, the AO7-saturated GAC was dried at 120 degrees C, then regenerated in a quartz reactor by 2450 MHz microwave (MW) irradiation at 850 W for 5 min. The efficacy of this procedure was analyzed by determining the rates and amounts of AO7 adsorbed in successive adsorption-MW regeneration cycles. Effects of this regeneration on the structural properties, surface chemistry and the AO7 adsorption capacities of GAC samples were examined. It was found that after several adsorption-MW regeneration cycles, the adsorption rates and capacities of GACs could maintain relatively high levels, even higher than those of virgin GACs, as indicated by AO7 breakthrough curves and adsorption isotherms. The improvement of GAC adsorption properties resulted from the modification of pore size distribution and surface chemistry by MW irradiation.

Microscopic modeling of gas-surface scattering: II. Application to argon atom adsorption on a platinum (111) surface

NASA Astrophysics Data System (ADS)

Filinov, A.; Bonitz, M.; Loffhagen, D.

2018-06-01

A new combination of first principle molecular dynamics (MD) simulations with a rate equation model presented in the preceding paper (paper I) is applied to analyze in detail the scattering of argon atoms from a platinum (111) surface. The combined model is based on a classification of all atom trajectories according to their energies into trapped, quasi-trapped and scattering states. The number of particles in each of the three classes obeys coupled rate equations. The coefficients in the rate equations are the transition probabilities between these states which are obtained from MD simulations. While these rates are generally time-dependent, after a characteristic time scale t E of several tens of picoseconds they become stationary allowing for a rather simple analysis. Here, we investigate this time scale by analyzing in detail the temporal evolution of the energy distribution functions of the adsorbate atoms. We separately study the energy loss distribution function of the atoms and the distribution function of in-plane and perpendicular energy components. Further, we compute the sticking probability of argon atoms as a function of incident energy, angle and lattice temperature. Our model is important for plasma-surface modeling as it allows to extend accurate simulations to longer time scales.

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.

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.

How realistic is the pore size distribution calculated from adsorption isotherms if activated carbon is composed of fullerene-like fragments?

PubMed

Terzyk, Artur P; Furmaniak, Sylwester; Harris, Peter J F; Gauden, Piotr A; Włoch, Jerzy; Kowalczyk, Piotr; Rychlicki, Gerhard

2007-11-28

A plausible model for the structure of non-graphitizing carbon is one which consists of curved, fullerene-like fragments grouped together in a random arrangement. Although this model was proposed several years ago, there have been no attempts to calculate the properties of such a structure. Here, we determine the density, pore size distribution and adsorption properties of a model porous carbon constructed from fullerene-like elements. Using the method proposed recently by Bhattacharya and Gubbins (BG), which was tested in this study for ideal and defective carbon slits, the pore size distributions (PSDs) of the initial model and two related carbon models are calculated. The obtained PSD curves show that two structures are micro-mesoporous (with different ratio of micro/mesopores) and the third is strictly microporous. Using the grand canonical Monte Carlo (GCMC) method, adsorption isotherms of Ar (87 K) are simulated for all the structures. Finally PSD curves are calculated using the Horvath-Kawazoe, non-local density functional theory (NLDFT), Nguyen and Do, and Barrett-Joyner-Halenda (BJH) approaches, and compared with those predicted by the BG method. This is the first study in which different methods of calculation of PSDs for carbons from adsorption data can be really verified, since absolute (i.e. true) PSDs are obtained using the BG method. This is also the first study reporting the results of computer simulations of adsorption on fullerene-like carbon models.

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.

Distribution of some organochlorine compounds (PCB, CBz, and DDE) in beeswax and honey

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

Jan, J.; Cerne, K.

Organochlorines are ranked among the class of prevalent and environmentally persistent synthetic chemicals. Honey bees, beeswax, and honey could be indicators for monitoring environmental pollution by organochlorines such as polychlorobiphenyls (PCBs) and organochloro pesticides. Scarcely any data were reported on the distribution of organochloro compounds between beeswax and honey. Physicochemical factors such as adsorption, volatilization, lipophilicity (octanol-water partition coefficient) and metabolic stability can influence the level of individual organochlorine compounds in beeswax and honey. During wax and honey formation metabolic attack by different enzymes can degrade pollutants. In the PCB and chlorobenzene (CBz) series, biodegradation decreases and bioconcentration increases withmore » increasing degree of chlorine substitution. Regarding the composition of honey (sugars, water, and some organic material and particles such as pollen, organic acid and essential oils in traces), and of beeswax (esters, hydrocarbons, acids and some natural wax from plants as minor components), it is expected that beeswax is more lipophilic and organochlorines could be more enriched in beeswax. However, the presence of particulate matters (e.g., pollen) in honey can increase the level of nonpolar compounds in honey due to sorption processes. This effect has been demonstrated in a similar system where suspended particles can influence the partition coefficient. In this contribution (i) the partition between beeswax and honey of some organochlorine compounds (PCB and CBz isomers, DDE) and (ii) bioconcentration in beeswax and honey from a feeding experiment by administration to honey bees of feed fortified with these compounds is presented and discussed. 17 refs., 3 figs., 1 tab.« less

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.

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.

Enhancement of the dissolution rate and bioavailability of fenofibrate by a melt-adsorption method using supercritical carbon dioxide

PubMed Central

Cha, Kwang-Ho; Cho, Kyung-Jin; Kim, Min-Soo; Kim, Jeong-Soo; Park, Hee Jun; Park, Junsung; Cho, Wonkyung; Park, Jeong-Sook; Hwang, Sung-Joo

2012-01-01

Background: The aim of this study was to enhance the bioavailability of fenofibrate, a poorly water-soluble drug, using a melt-adsorption method with supercritical CO2. Methods: Fenofibrate was loaded onto Neusilin® UFL2 at different weight ratios of fenofibrate to Neusilin UFL2 by melt-adsorption using supercritical CO2. For comparison, fenofibrate-loaded Neusilin UFL2 was prepared by solvent evaporation and hot melt-adsorption methods. The fenofibrate formulations prepared were characterized by differential scanning calorimetry, powder x-ray diffractometry, specific surface area, pore size distribution, scanning electron microscopy, and energy-dispersive x-ray spectrometry. In vitro dissolution and in vivo bioavailability were also investigated. Results: Fenofibrate was distributed into the pores of Neusilin UFL2 and showed reduced crystal formation following adsorption. Supercritical CO2 facilitated the introduction of fenofibrate into the pores of Neusilin UFL2. Compared with raw fenofibrate, fenofibrate from the prepared powders showed a significantly increased dissolution rate and better bioavailability. In particular, the area under the drug concentration-time curve and maximal serum concentration of the powders prepared using supercritical CO2 were 4.62-fold and 4.52-fold greater than the corresponding values for raw fenofibrate. Conclusion: The results of this study highlight the usefulness of the melt-adsorption method using supercritical CO2 for improving the bioavailability of fenofibrate. PMID:23118538

Crystal Face Distributions and Surface Site Densities of Two Synthetic Goethites: Implications for Adsorption Capacities as a Function of Particle Size.

PubMed

Livi, Kenneth J T; Villalobos, Mario; Leary, Rowan; Varela, Maria; Barnard, Jon; Villacís-García, Milton; Zanella, Rodolfo; Goodridge, Anna; Midgley, Paul

2017-09-12

Two synthetic goethites of varying crystal size distributions were analyzed by BET, conventional TEM, cryo-TEM, atomic resolution STEM and HRTEM, and electron tomography in order to determine the effects of crystal size, shape, and atomic scale surface roughness on their adsorption capacities. The two samples were determined by BET to have very different site densities based on Cr VI adsorption experiments. Model specific surface areas generated from TEM observations showed that, based on size and shape, there should be little difference in their adsorption capacities. Electron tomography revealed that both samples crystallized with an asymmetric {101} tablet habit. STEM and HRTEM images showed a significant increase in atomic-scale surface roughness of the larger goethite. This difference in roughness was quantified based on measurements of relative abundances of crystal faces {101} and {201} for the two goethites, and a reactive surface site density was calculated for each goethite. Singly coordinated sites on face {210} are 2.5 more dense than on face {101}, and the larger goethite showed an average total of 36% {210} as compared to 14% for the smaller goethite. This difference explains the considerably larger adsorption capacitiy of the larger goethite vs the smaller sample and points toward the necessity of knowing the atomic scale surface structure in predicting mineral adsorption processes.

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.

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.

Distribution of atrazine and its phytoremediation by submerged macrophytes in lake sediments.

PubMed

Qu, Mengjie; Li, Huidong; Li, Na; Liu, Guanglong; Zhao, Jianwei; Hua, Yumei; Zhu, Duanwei

2017-02-01

We investigated sediments with high atrazine accumulation capability from 6 eutrophic lakes in Hubei Province of central China. Almost all lakes have atrazine in their sediments because of human activities. Honghu Lake and Liangzihu Lake were found to have higher levels of atrazine in sediment: 0.171 and 0.114 mg kg -1 , respectively. The results showed that lake sediments could adsorb atrazine six times faster than soils. The equilibrium partition coefficient of atrazine desorption (K Pd ) is much larger than the adsorption equilibrium partition coefficient (K Pa ) of atrazine, indicating that the residue of atrazine in water is easily immobilized by the sediments. Meanwhile, the incubation experiment showed that the removal rateof atrazine in Potamogeton crispus-planted and Myriophyllum spicatum-planted sediments reached >90%, while the rate in unplanted sediments was 77.2 ± 2.12% over 45 d. In unplanted sediment, the half-life of atrazine dissipation was 14.30 d, which was strongly enhanced by P. crispus and M. spicatum, greatly reducing the half-life to 8.60 and 9.72 d, respectively. These two submerged macrophytes are considered to be potential tools in the remediation of atrazine-contaminated sediments. Copyright © 2016 Elsevier Ltd. All rights reserved.

Highly Selective and Efficient Removal of Heavy Metals by Layered Double Hydroxide Intercalated with the MoS4(2-) Ion.

PubMed

Ma, Lijiao; Wang, Qing; Islam, Saiful M; Liu, Yingchun; Ma, Shulan; Kanatzidis, Mercouri G

2016-03-02

The MoS4(2-) ion was intercalated into magnesium-aluminum layered double hydroxide (MgAl-NO3-LDH) to produce a single phase material of Mg0.66Al0.34(OH)2(MoS4)0.17·nH2O (MgAl-MoS4-LDH), which demonstrates highly selective binding and extremely efficient removal of heavy metal ions such as Cu(2+), Pb(2+), Ag(+), and Hg(2+). The MoS4-LDH displays a selectivity order of Co(2+), Ni(2+), Zn(2+) < Cd(2+) ≪ Pb(2+) < Cu(2+) < Hg(2+) < Ag(+) for the metal ions. The enormous capacities for Hg(2+) (∼500 mg/g) and Ag(+) (450 mg/g) and very high distribution coefficients (Kd) of ∼10(7) mL/g place the MoS4-LDH at the top of materials known for such removal. Sorption isotherm for Ag(+) agrees with the Langmuir model suggesting a monolayer adsorption. It can rapidly lower the concentrations of Cu(2+), Pb(2+), Hg(2+), and Ag(+) from ppm levels to trace levels of ≤1 ppb. For the highly toxic Hg(2+) (at ∼30 ppm concentration), the adsorption is exceptionally rapid and highly selective, showing a 97.3% removal within 5 min, 99.7% removal within 30 min, and ∼100% removal within 1 h. The sorption kinetics for Cu(2+), Ag(+), Pb(2+), and Hg(2+) follows a pseudo-second-order model suggesting a chemisorption with the adsorption mechanism via M-S bonding. X-ray diffraction patterns of the samples after adsorption demonstrate the coordination and intercalation structures depending on the metal ions and their concentration. After the capture of heavy metals, the crystallites of the MoS4-LDH material retain the original hexagonal prismatic shape and are stable at pH ≈ 2-10. The MoS4-LDH material is thus promising for the remediation of heavy metal polluted water.

Adsorption of dissolved organics in lake water by aluminum oxide. Effect of molecular weight

USGS Publications Warehouse

Davis, J.A.; Gloor, R.

1981-01-01

Dissolved organic compounds in a Swiss lake were fractionated into three molecular size classes by gel exclusion chromatography, and adsorption of each fraction on colloidal alumina was studied as a function of pH. Organic compounds with molecular weight (Mr) greater than 1000 formed strong complexes with the alumina surface, but low molecular weight compounds were weakly adsorbed. Electrophoretic mobility measurements indicated that alumina particles suspended in the original lake water were highly negatively charged because of adsorbed organic matter. Most of the adsorbed organic compounds were in the Mr range 1000 < Mr < 3000. Adsorption of these compounds during the treatment of drinking water by alum coagulation may be responsible for the preferential removal of trihalomethane precursors. Adsorption may also influence the molecular-weight distribution of dissolved organic material in lakes. surface, the present work will focus on the influence of molecular size and pH on the adsorption behavior of dissolved organic material of a Swiss lake. From a geochemical point of view, it is important to know the molecular-weight distribution of adsorbed organic matter so that we may better assess its reactivity with trace elements. The study also serves as a first step in quantifying the role of adsorption in the geochemical cycle of organic carbon in lacustrine environments. For water-treatment practice, we need to determine whether molecular weight fractionation occurs during adsorption by aluminum oxide. Such a fractionation could be significant in the light of recent reports that chloroform and other organochlorine compounds are preferentially produced by particular molecular-weight fractions (25-27). ?? 1981 American Chemical Society.

Method transfer from high-pressure liquid chromatography to ultra-high-pressure liquid chromatography. I. A thermodynamic perspective.

PubMed

Åsberg, Dennis; Leśko, Marek; Samuelsson, Jörgen; Kaczmarski, Krzysztof; Fornstedt, Torgny

2014-10-03

This is the first investigation in a series that aims to enhance the scientific knowledge needed for reliable analytical method transfer between HPLC and UHPLC using the quality by design (QbD) framework. Here, we investigated the differences and similarities from a thermodynamic point of view between RP-LC separations conducted with 3.5μm (HPLC) and 1.7μm (UHPLC) C18 particles. Three different model solutes and one pharmaceutical compound were used: the uncharged cycloheptanone, the cationic benzyltriethylammonium chloride, the anionic sodium 2-naphatlene sulfonate and the pharmaceutical compound omeprazole, which was anionic at the studied pH. Adsorption data were determined for the four solutes at varying fractions of organic modifier and in gradient elution in both the HPLC and UHPLC system, respectively. From the adsorption data, the adsorption energy distribution of each compound was calculated and the adsorption isotherm model was estimated. We found that the adsorption energy distribution was similar, with only minor differences in degree of homogeneity, for HPLC and UHPLC stationary phases. The adsorption isotherm model did not change between HPLC and UHPLC, but the parameter values changed considerably especially for the ionic compounds. The dependence of the organic modifier followed the same trend in HPLC as in UHPLC. These results indicates that the adsorption mechanism of a solute is the same on HPLC and UHPLC stationary phases which simplifies design of a single analytical method applicable to both HPLC and UHPLC conditions within the QbD framework. Copyright © 2014. Published by Elsevier B.V.

A Density Functional Study of Atomic Hydrogen and Oxygen Chemisorptions on the (0001) Surface of Double Hexagonal Close Packed Americium

NASA Astrophysics Data System (ADS)

Dholabhai, Pratik; Atta-Fynn, Raymond; Ray, Asok

2008-03-01

Ab initio total energy calculations within the framework of density functional theory have been performed for atomic hydrogen and oxygen chemisorptions on the (0001) surface of double hexagonal packed americium using a full-potential all-electron linearized augmented plane wave plus local orbitals (FLAPW+lo) method. The three-fold hollow hcp site was found to be the most stable site for H adsorption, while the two-fold bridge adsorption site was found to be the most stable site for O adsorption. Chemisorption energies and adsorption geometries for different adsorption sites will be discussed. The change in work functions, magnetic moments, partial charges inside muffin-tins, difference charge density distributions and density of states for the bare Am slab and the Am slab after adsorption of the adatom will be discussed. The implications of chemisorption on Am 5f electron localization-delocalization will also be discussed.

Adsorption of humic acids and trace metals in natural waters

NASA Technical Reports Server (NTRS)

Leung, W. H.

1982-01-01

Studies concerning the interactions between suspended hydrous iron oxide and dissolved humic acids and trace metals are reported. As a major component of dissolved organic matters and its readiness for adsorption at the solid/water interface, humic acids may play a very important role in the organometallic geochemistry of suspended sediments and in determining the fate and distribution of trace metals, pesticides and anions in natural water systems. Most of the solid phases in natural waters contain oxides and hydroxides. The most simple promising theory to describe the interactions of hydrous iron oxide interface is the surface complex formation model. In this model, the adsorptions of humic acids on hydrous iron oxide may be interpreted as complex formation of the organic bases (humic acid oxyanions) with surface Fe ions. Measurements on adsorptions were made in both fresh water and seawater. Attempts have been made to fit our data to Langmuir adsorption isotherm. Adsorption equilibrium constants were determined.

Binary gas mixture adsorption-induced deformation of microporous carbons by Monte Carlo simulation.

PubMed

Cornette, Valeria; de Oliveira, J C Alexandre; Yelpo, Víctor; Azevedo, Diana; López, Raúl H

2018-07-15

Considering the thermodynamic grand potential for more than one adsorbate in an isothermal system, we generalize the model of adsorption-induced deformation of microporous carbons developed by Kowalczyk et al. [1]. We report a comprehensive study of the effects of adsorption-induced deformation of carbonaceous amorphous porous materials due to adsorption of carbon dioxide, methane and their mixtures. The adsorption process is simulated by using the Grand Canonical Monte Carlo (GCMC) method and the calculations are then used to analyze experimental isotherms for the pure gases and mixtures with different molar fraction in the gas phase. The pore size distribution determined from an experimental isotherm is used for predicting the adsorption-induced deformation of both pure gases and their mixtures. The volumetric strain (ε) predictions from the GCMC method are compared against relevant experiments with good agreement found in the cases of pure gases. Copyright © 2018 Elsevier Inc. All rights reserved.

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.

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.

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.

Tunable gas adsorption in graphene oxide framework

NASA Astrophysics Data System (ADS)

Razmkhah, Mohammad; Moosavi, Fatemeh; Taghi Hamed Mosavian, Mohammad; Ahmadpour, Ali

2018-06-01

Effect of length of linker inter-space was studied on the adsorption capacity of CO2 by graphene oxide framework (GOF). Effect of linker inter-space of 14, 11, and 8 Å was studied here. The linker inter-space of 11 Å showed the highest CO2 adsorption capacity. A dual-site Langmuir model was observed for adsorption of CO2 and CH4 into the GOF. According to radial distribution function (RDF), facial and central atoms of linker are the dual-site predicted by Langmuir model. Two distinguishable sites of adsorption and parallel orientation of CO2 are the main reasons of high adsorption capacity in 11 Å linker inter-space. Gas-adsorbent affinity obtains the orientation of CO2 near the linker. The affinity in the 11 Å linker inter-space is the highest. Thus, it forces the CO2 to lay parallel and orient more localized than the other GOFs. In addition, CH4 resulted higher working capacity than CO2 in 14 Å. This occurs because of the change in gas-adsorbent affinity by changing pressure. An entrance adsorption occurs out of the pore of the GOF. This adsorption is not as stable as deep adsorption.

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.

Production of Concentrated Pickering Emulsions with Narrow Size Distributions Using Stirred Cell Membrane Emulsification.

PubMed

Manga, Mohamed S; York, David W

2017-09-12

Stirred cell membrane emulsification (SCME) has been employed to prepare concentrated Pickering oil in water emulsions solely stabilized by fumed silica nanoparticles. The optimal conditions under which highly stable and low-polydispersity concentrated emulsions using the SCME approach are highlighted. Optimization of the oil flux rates and the paddle stirrer speeds are critical to achieving control over the droplet size and size distribution. Investigating the influence of oil volume fraction highlights the criticality of the initial particle loading in the continuous phase on the final droplet size and polydispersity. At a particle loading of 4 wt %, both the droplet size and polydispersity increase with increasing of the oil volume fraction above 50%. As more interfacial area is produced, the number of particles available in the continuous phase diminishes, and coincidently a reduction in the kinetics of particle adsorption to the interface resulting in larger polydisperse droplets occurs. Increasing the particle loading to 10 wt % leads to significant improvements in both size and polydispersity with oil volume fractions as high as 70% produced with coefficient of variation values as low as ∼30% compared to ∼75% using conventional homogenization techniques.

Influence of preozonation on the adsorptivity of humic substances onto activated carbon.

PubMed

Rodríguez, Francisco J; García-Valverde, María

2016-11-01

This research aims to study the influence of preozonation on the adsorptivity of humic substances onto activated carbon, which are usual stages in drinking water treatment. Three different types of humic substances were used in this study: natural fulvic and humic acids extracted from the Úzquiza Reservoir (Burgos, Spain) and a commercially supplied humic acid. The fractionation of the humic substances by ultrafiltration showed a very different molecular weight (MW) distribution for them: the lowest fraction of <1 kDa comprises the vast majority of the fulvic acids (around 86 %), whereas the main fraction for the commercial humic acids was the highest one of >30 kDa (around 40 %). The natural humic acids show an intermediate distribution between the two aforementioned humic substances. The 1-5-kDa fraction turned out to be the most reactive toward trihalomethane formation for the commercial humic acids. The adsorptive capacity of activated carbon for the humic substances was in the following order: natural fulvic acids > natural humic acids > commercial humic acids. The most adsorbable fraction was that of <1 kDa for the fulvic acids, whereas the 5-10-kDa fraction was the most adsorbable for both humic acids. Preozonation changes the MW distribution of the humic substances, decreasing the abundance of the high MW fractions and generating smaller molecules within the low to medium MW range. Adsorption isotherms show that preozonation has a beneficial effect on the adsorptivity of the commercial humic acids onto activated carbon, whereas no appreciable effect was observed for the case of the fulvic acids.

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.

Surface study and sensing activity of nanotubular indium trioxide to NH3, H2S, NO2 and CO environmental pollutants

NASA Astrophysics Data System (ADS)

Zamani, Mehdi

2016-02-01

Molecular and electronic structures of nanotubular indium trioxide were studied using B3LYP and CAM-B3LYP density functional methods. Three nanotube models including nanotubes with closed ends (CENT), one opened end (OOENT) and two opened ends (TOENT) were considered. The highest occupied molecular orbital (HOMO) of CENT is distributed over the entire nanotube; while it is distributed on the end cap of OOENT. In both CENT and OOENT, the distribution of the lowest unoccupied molecular orbital (LUMO) is on the end caps. HOMO and LUMO of TOENT are distributed on the center of nanotube. The sensing activity of OOENT to environmental pollutants was evaluated regarding the interaction of nanotube with NH3, H2S, NO2 and CO molecules. Adsorptions over different positions of OOENT are exothermic and the NH3 adsorption is thermodynamically more favorable. The selectivity of OOENT toward gaseous pollutants is investigated as NH3 > H2S > CO > NO2. Interaction of NO2 and CO over the closed end (end cap) of nanotube is preferred; while adsorption of NH3 and H2S on the opened end is more favorable.

An Investigation of the Sampling Distribution of the Congruence Coefficient.

ERIC Educational Resources Information Center

Broadbooks, Wendy J.; Elmore, Patricia B.

This study developed and investigated an empirical sampling distribution of the congruence coefficient. The effects of sample size, number of variables, and population value of the congruence coefficient on the sampling distribution of the congruence coefficient were examined. Sample data were generated on the basis of the common factor model and…

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.

Adsorption and desorption characteristics of gradient distributed Bragg reflector porous silicon layers.

PubMed

Um, Sungyong; Lee, Sung Gi; Woo, Hee-Gweon; Cho, Sungdong; Sohn, Honglae

2013-01-01

Adsorption and desorption characteristics of gradient distributed Bragg reflector (DBR) porous silicon (PSi) were investigated under the exposure of organic vapors. Gradient DBR PSi whose average pore size decreased as the lateral distance from the Pt electrode increased was generated by using an asymmetric etching configuration. The reflection resonances were measured as a function of lateral distance from a point closest to the plate Pt electrode to a position on the silicon surface. Two types of gradient DBR PSi (H- and HO-terminated gradient DBR PSi) were used in this study. The detection of volatile organic compounds (VOCs) using the gradient DBR PSi had been achieved. When the vapor of VOCs condensed in the nanopores, the gradient DBR PSi modified with hydrophobic and hydrophilic functionality exhibited different pore adsorption and desorption characteristics.

Adsorption, Desorption, and Diffusion of Nitrogen in a Model Nanoporous Material: II. Diffusion Limited Kinetics in Amorphous Solid Water

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

Zubkov, Tykhon; Smith, R. Scott; Engstrom, Todd R.

2007-11-14

Tykhon Zubkov, R. Scott Smith, Todd R. Engstrom, and Bruce D. Kay The adsorption, desorption, and diffusion kinetics of N2 on thick (up to ~9 mm) porous films of amorphous solid water (ASW) films were studied using molecular beam techniques and temperature programmed desorption (TPD). Porous ASW films were grown on Pt(111) at low temperature (<30 K) from a collimated H2O beam at glancing incident angles. In thin films (<1 mm), the desorption kinetics are well described by a model that assumes rapid and uniform N2 distribution throughout the film. In thicker films, (>1 mm), N2 adsorption at 27 Kmore » results in a non-uniform distribution where most of N2 is trapped in the outer region of the film. Redistribution of N2 can be induced by thermal annealing. The apparent activation energy for this process is ~7 kJ/mol, which is approximately half of the desorption activation energy at the corresponding coverage. Blocking adsorption sites near the film surface facilitates transport into the film. Despite the onset of limited diffusion, the adsorption kinetics are efficient, precursor-mediated and independent of film thickness. An adsorption mechanism is proposed, in which a high-coverage N2 front propagates into a pore by the rapid transport of physisorbed 2nd layer N2 species on top of the 1st layer chemisorbed layer.« less

Occurrence and carcinogenic potential of airborne polycyclic aromatic hydrocarbons in some large-scale enclosed/semi-enclosed vehicle parking areas.

PubMed

Li, Huiru; Zeng, Xiangying; Zhang, Delin; Chen, Pei; Yu, Zhiqiang; Sheng, Guoying; Fu, Jiamo; Peng, Ping'an

2014-06-15

Polycyclic aromatic hydrocarbons (PAHs) originating from vehicle exhaust have aroused much attention due to their potential healthy effect. In this study, air samples were collected from three representative parking lots in a metropolitan area, analyzed for PAHs and evaluated for inhalation risk. Atmospheric PAH levels of these parking areas ranged between 1,178-4,793 ng m(-3), one order of magnitude higher than general urban areas. Their benzo[a]pyrene equivalent (BaPeq) values varied in 11.0-98.0 ng m(-3), far exceeding the air quality standard of WHO (1.0 ng m(-3)). Monte Carlo simulation (100,000 trials) results suggest that the potential lifetime inhalation cancer risks of PAHs were 0.27 × 10(-5) to 7.11 × 10(-5) for park employees, which are in the acceptable range acknowledged by US EPA (1.0 × 10(-6) to 1.0 × 10(-4)). Several source diagnostic methods proved that vehicle exhaust was the dominant PAH contributor of these parks with the contribution percentages being >53%; oil combustion and/or coal combustion were other important sources. Logarithms of gas-particle distribution coefficients (Kps) of PAHs in all studied parks were linearly correlated with those of both their sub-cooled vapor pressures (pLs) and octanol-air partition coefficients (KOAs). The correlation coefficients indicated that both adsorption onto black carbon and absorption into organic matter were involved in the partition process, but the latter was dominant. Copyright © 2014 Elsevier B.V. All rights reserved.

Rigorous Mathematical Modeling of Adsorption System with Electrothermal Regeneration of the Used Adsorbent

DTIC Science & Technology

2006-12-01

DISTRIBUTION STATEMENT. ________//signature//________________ ________//signature//________________ PATRICK D. SULLIVAN, Ph.D., P.E. SANDRA R ...adsorber, at r =1.24 cm: (a) gas phase; (b) solid phase..................................................................................... 30 46 The...34 57 Axial profiles of the gas velocity during adsorption in the 2-cartridge adsorber at r =1.25cm..... 34 60

Multisite adsorption of cadmium on goethite

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

Venema, P.; Hiemstra, T.; Riemsdijk, W.H. van

1996-11-10

Recently a new general ion adsorption model has been developed for ion binding to mineral surfaces (Hiemstra and van Riemsdijk, 1996). The model uses the Pauling concept of charge distribution (CD) and is an extension of the multi-site complexation (MUSIC) approach. In the CD-MUSIC model the charge of an adsorbing ion that forms an inner sphere complex is distributed over its ligands, which are present in two different electrostatic planes. In this paper the authors have applied the CD-MUSIC model to the adsorption of metal cations, using an extended data set for cadmium adsorbing on goethite. The adsorption of cadmiummore » and the cadmium-proton exchange ratio were measured as function of metal ion concentration, pH, and ionic strength. The data could be described well, taking into account the surface heterogeneity resulting from the presence of two different crystal planes (the dominant 110 face and the minor 021 face). The surface species used in the model are consistent with recent EXAFS data. In accordance with the EXAFS results, high-affinity complexes at the 021 face were used in the model.« less

Ion distribution in dry polyelectrolyte multilayers: a neutron reflectometry study

DOE PAGES

Ghoussoub, Yara E.; Zerball, Maximilian; Fares, Hadi M.; ...

2018-02-09

Counterions were found to be uniformly distributed in polycation-terminated films of poly(diallyldimethylammonium) and poly(styrenesulfonate) prepared on silicon wafers using layer-by-layer adsorption.

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.

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

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.

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.

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.

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.

Interactions of satellite-speed helium atoms with satellite surfaces. 3: Drag coefficients from spatial and energy distributions of reflected helium atoms

NASA Technical Reports Server (NTRS)

Sharma, P. K.; Knuth, E. L.

1977-01-01

Spatial and energy distributions of helium atoms scattered from an anodized 1235-0 aluminum surface as well as the tangential and normal momentum accommodation coefficients calculated from these distributions are reported. A procedure for calculating drag coefficients from measured values of spatial and energy distributions is given. The drag coefficient calculated for a 6061 T-6 aluminum sphere is included.

Distribution coefficients of rare earth ions in cubic zirconium dioxide

NASA Astrophysics Data System (ADS)

Romer, H.; Luther, K.-D.; Assmus, W.

1994-08-01

Cubic zirconium dioxide crystals are grown with the skull melting technique. The effective distribution coefficients for Nd(exp 3+), Sm(exp 3+) and Er(sup 3+) as dopants are determined experimentally as a function of the crystal growth velocity. With the Burton-Prim-Slichter theory, the equilibrium distribution coefficients can be calculated. The distribution coefficients of all other trivalent rare earth ions can be estimated by applying the correlation towards the ionic radii.

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.

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.

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.

The adsorption of copper in a packed-bed of chitosan beads: modeling, multiple adsorption and regeneration.

PubMed

Osifo, Peter O; Neomagus, Hein W J P; Everson, Raymond C; Webster, Athena; vd Gun, Marius A

2009-08-15

In this study, exoskeletons of Cape rock lobsters were used as raw material in the preparation of chitin that was successively deacetylated to chitosan flakes. The chitosan flakes were modified into chitosan beads and the beads were cross-linked with glutaraldehyde in order to study copper adsorption and regeneration in a packed-bed column. Five consecutive adsorption and desorption cycles were carried out and a chitosan mass loss of 25% was observed, after the last cycle. Despite the loss of chitosan material, an improved efficiency in the second and third cycles was observed with the adsorbent utilizing 97 and 74% of its adsorbent capacity in the second and third cycles, respectively. The fourth and fifth cycles, however, showed a decreased efficiency, and breakage of the beads was observed after the fifth cycle. In the desorption experiments, 91-99% of the adsorbed copper was regenerated in the first three cycles. It was also observed that the copper can be regenerated at a concentration of about a thousand fold the initial concentration. The first cycle of adsorption could be accurately described with a shrinking core particle model combined with a plug flow column model. The input parameters for this model were determined by batch characterization methods, with as only fitting parameter, the effective diffusion coefficient of copper in the bead.

The Impact of Iron Adsorption on the Electronic and Photocatalytic Properties of the Zinc Oxide (0001) Surface: A First-Principles Study.

PubMed

Cheng, Jingsi; Wang, Ping; Hua, Chao; Yang, Yintang; Zhang, Zhiyong

2018-03-12

The structural stability, electronic structure, and optical properties of an iron-adsorbed ZnO (0001) surface with three high-symmetry adsorption sites are investigated with first-principle calculations on the basis of density functional theory and the Hubbard-U method. It is found that the iron adatom in the H₃ adsorption site of ZnO (0001) surface has the lowest adsorption energy of -5.665 eV compared with T₄ and Top sites. For the Top site, compared with the pristine ZnO (0001) surface, the absorption peak located at 1.17 eV has a red shift, and the elevation of the absorption coefficient is more pronounced in the visible-light region, because the Fe-related levels are introduced in the forbidden band and near the Fermi level. The electrostatic potential computation reveals that the work function of the ZnO (0001) surface is significantly decreased from 2.340 to 1.768 eV when iron is adsorbed on the Top site. Furthermore, the degradation mechanism based on the band structure is analyzed. It can be concluded that the adsorption of iron will promote the separation of photoinduced carriers, thus improving the photocatalytic activity of ZnO (0001) surface. Our study benefits research on the photocatalytic activity of ZnO and the utilization rate of solar energy.

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.

[Removal of DON in micro-polluted raw water by coagulation and adsorption using activated carbon].

PubMed

Liu, Bing; Yu, Guo-Zhong; Gu, Li; Zhao, Cheng-Mei; Li, Qing-Fei; Zhai, Hui-Min

2013-04-01

Dissolved organic nitrogen as a precursor of new type nitrogenous disinfection by-products in drinking water attracted gradually the attention of scholars all over the world. In order to explore the mechanism of DON removal in micro-polluted raw water by coagulation and adsorption, water quality parameters, such as DON, DOC, NH4(+) -N, UV254, pH and dissolved oxygen, were determined in raw water and the molecular weight distribution of the DON and DOC was investigated. The variations in DON, DOC and UV254 in the coagulation and adsorption tests were investigated, and the changes of DON in raw water were characterized using three-dimensional fluorescence spectroscopy. The results showed that DON, DOC and UV254 were 1.28 mg x L(-1), 8.56 mg x L(-1), 0.16 cm(-1), and DOC/DON and SUVA were 6.69 mg x mg(-1), 1.87 m(-1) x (mg x L(-1))(-1) in raw water, respectively. The molecular weight distribution of the DON in raw water showed a bimodal distribution. The small molecular weight (< 6 000) fractions accounted for a high proportion of 68% and the large (> 20 000) fractions accounted for about 22%. The removal of DON, DOC and UV254 was about 20%, 26% and 70%, respectively, in the coagulation test and the dosage of coagulant was 10 mg x L(-1). The removal of DON, DOC and UV254 was about 60%, 35% and 100%, respectively, in the adsorption test and the dosage of activated carbon was 1.0 g. In the combination of coagulation and adsorption, the removal of DON and DOC reached approximately 82% and 64%, respectively. 3DEEM revealed that the variation of DON in the coagulation and adsorption tests depended intimately on tryptophan protein-like substances, aromatic protein-like substances and fulvic acid-like substances.

Water Saturation Relations and Their Diffusion-Limited Equilibration in Gas Shale: Implications for Gas Flow in Unconventional Reservoirs

NASA Astrophysics Data System (ADS)

Tokunaga, Tetsu K.; Shen, Weijun; Wan, Jiamin; Kim, Yongman; Cihan, Abdullah; Zhang, Yingqi; Finsterle, Stefan

2017-11-01

Large volumes of water are used for hydraulic fracturing of low permeability shale reservoirs to stimulate gas production, with most of the water remaining unrecovered and distributed in a poorly understood manner within stimulated regions. Because water partitioning into shale pores controls gas release, we measured the water saturation dependence on relative humidity (rh) and capillary pressure (Pc) for imbibition (adsorption) as well as drainage (desorption) on samples of Woodford Shale. Experiments and modeling of water vapor adsorption into shale laminae at rh = 0.31 demonstrated that long times are needed to characterize equilibrium in larger (5 mm thick) pieces of shales, and yielded effective diffusion coefficients from 9 × 10-9 to 3 × 10-8 m2 s-1, similar in magnitude to the literature values for typical low porosity and low permeability rocks. Most of the experiments, conducted at 50°C on crushed shale grains in order to facilitate rapid equilibration, showed significant saturation hysteresis, and that very large Pc (˜1 MPa) are required to drain the shales. These results quantify the severity of the water blocking problem, and suggest that gas production from unconventional reservoirs is largely associated with stimulated regions that have had little or no exposure to injected water. Gravity drainage of water from fractures residing above horizontal wells reconciles gas production in the presence of largely unrecovered injected water, and is discussed in the broader context of unsaturated flow in fractures.

[Microwave In-situ Regeneration of Cu-Mn-Ce/ZSM Catalyst Adsorbed Toluene and Distribution of Bed Temperature].

PubMed

Hu, Xue-jiao; Bo, Long-li; Liang, Xin-xin; Meng, Hai-long

2015-08-01

Microwave in-situ regeneration of Cu-Mn-Ce/ZSM catalyst adsorbed toluene, distribution of fixed bed temperature, adsorption breakthrough curves of the catalyst after several regenerations and characterizations of the catalyst by BET and SEM were investigated in this study. The research indicated that regeneration effect of the catalyst adsorbed was excellent under conditions of microwave power 117 W, air flow 0.5 m3 x h(-1) and catalyst dosage of 800 g. Toluene desorbed was oxidized onto the surface of the catalyst, and the adsorption capacity of the catalyst was recovered simultaneously. Under microwave irradiation, bed temperature decreased slowly from inside to outside in horizontal level, and increased gradually from down to up in vertical level so that the highest temperature reached 250-350 degrees C at the upper sites of the bed. Sintering and agglomeration occurred on the surface of the catalyst in the course of regeneration so that the special surface area and micropore volume of the catalyst were reduced and breakthrough time was shortened, which was verified by six adsorption breakthrough curves and related characteristics of the catalyst. However, the structure of the catalyst was steady after two regenerations, and adsorption breakthrough time was kept at 70 min. The result showed that the changes of surface morphology and pore structure were positively correlated with the distribution of bed temperature.

The Relationship Between DOC Partition Coefficient and Mineral Soil C:N Ratio

NASA Astrophysics Data System (ADS)

Aitkenhead-Peterson, J. A.; McDowell, W. H.

2001-12-01

Since our recent publication showing that soil C:N predicts DOC flux at local and global scales, an effort has been made to understand mechanisms controlling the relationship between the two variables. We have approached this at multiple scales, using soil batch experiments, soil column experiments, and long-term field manipulations. We present here the results from our batch adsorption experiment. Mineral soils from tropical (wet and moist) and temperate (coniferous and hardwood) forests were used to assess DOC adsorption by the initial mass isotherm approach. We found that the DOC partition co-efficient (m) which represents a soil's tendency to adsorb DOC is strongly and inversely related to mineral soil C:N ratio (R2 = 0.99 n = 10 p < 0.001). The intercept of the mass isotherm, or the desorption term, was positively related to mineral soil C:N ratio (R2 = 0.80 n = 10 p < 0.01), but we found that desorption of DOC was more closely correlated with equilibrium DOC concentration (R2 = 0.97 n = 10 p < 0.001) than with mineral soil C:N. The mass isotherm approach is also useful in calculating the reactive soil pool (RSP), the fraction of the soil pool of organic carbon that may be lost to leaching. The RSP was not significantly related to mineral soil C:N, but tropical soils tended to have a larger RSP than temperate soils. Although some of the tropical soils came from areas where the natural forest had been cleared, used for plantations and then abandoned, the relationship between DOC adsorption and mineral soil C:N was not compromised. Watershed soil C:N ratio is an excellent predictor of DOC export because soil C:N is related to physiochemical adsorption processes in mineral soils and biotic production of DOC in organic soil horizons. It appears that soil C:N is a relatively robust predictor of soil solution DOC concentration and surface water DOC export for ecosystems undergoing environmental stress.

Physical parameters of Fluvisols on flooded and non-flooded terraces

NASA Astrophysics Data System (ADS)

Kercheva, Milena; Sokołowska, Zofia; Hajnos, Mieczysław; Skic, Kamil; Shishkov, Toma

2017-01-01

The heterogeneity of soil physical properties of Fluvisols, lack of large pristine areas, and different moisture regimes on non-flooded and flooded terraces impede the possibility to find a soil profile which can serve as a baseline for estimating the impact of natural or anthropogenic factors on soil evolution. The aim of this study is to compare the pore size distribution of pristine Fluvisols on flooded and non-flooded terraces using the method of the soil water retention curve, mercury intrusion porosimetry, nitrogen adsorption isotherms, and water vapour sorption. The pore size distribution of humic horizons of pristine Fluvisols on the non-flooded terrace differs from pore size distribution of Fluvisols on the flooded terrace. The peaks of textural and structural pores are higher in the humic horizons under more humid conditions. The structural characteristics of subsoil horizons depend on soil texture and evolution stage. The peaks of textural pores at about 1 mm diminish with lowering of the soil organic content. Structureless horizons are characterized by uni-modal pore size distribution. Although the content of structural pores of the subsoil horizons of Fluvisols on the non-flooded terrace is low, these pores are represented by biopores, as the coefficient of filtration is moderately high. The difference between non-flooded and flooded profiles is well expressed by the available water storage, volume and mean radius of pores, obtained by mercury intrusion porosimetry and water desorption, which are higher in the surface horizons of frequently flooded Fluvisols.

Sorption of metolachlor and atrazine in fly ash amended soils: comparison of optimized isotherm models.

PubMed

Ghosh, Rakesh K; Singh, Neera

2012-01-01

Adsorption of metolachlor and atrazine was studied in the fly ash (Inderprastha and Badarpur)- amended Inceptisol and Alfisol soils using batch method. Results indicated that sorption of both the herbicides in soil+fly ash mixtures was highly nonlinear and sorption decreased with a higher herbicide concentration in the solution. Also, nonlinearity increased with an increase in the level of fly ash amendment from 0-5%. Three two-parameter monolayer isotherms viz. Langmuir, Temkin, Jovanovic and one imperical Freundlich models were used to fit the experimental data. Data analysis and comparison revealed that the Temkin and the Freundlich isotherms were best-suited to explain the sorption results and the observed and the calculated adsorption coefficient values showed less variability. The study suggested that sorption mechanism of metolachlor and atrazine involved the physical association at the sorbate surface and the nonlinearity in the sorption at higher pesticide or fly ash concentration was due to a decrease in the heat of adsorption and higher binding energy.

Eggshell membrane as a novel bio sorbent for remediation of boron from desalinated water.

PubMed

Al-Ghouti, Mohammad A; Khan, Mariam

2018-02-01

This study investigated the use of eggshell membrane (ESM) as a bio-sorbent and the effect of temperature, pH, and initial concentration on its efficiency. Furthermore, by altering the chemical composition, modified eggshell membrane (MESM) was prepared, and its efficiency was compared with the ESM. Results showed that the adsorption of boron preferred an acidic condition; pH 6 at 35 °C. In addition, the positive value of ΔH° suggested that the reaction favored endothermic pathway, while the negative value for ΔG° further suggested that the adsorption process was spontaneous. Furthermore, the ESM could adsorb 97% of boron, while MESM was able to adsorb 95%. From the Fourier transform infrared (FTIR), different functional groups were recorded on the surface of the ESM and MESM, and they played key role in the boron adsorption mechanisms. Linear Freundlich model was suggested to best describe the experimental data with 99.4% correlation coefficient. Copyright © 2017 Elsevier Ltd. All rights reserved.

Adsorption of trace metals to plastic resin pellets in the marine environment.

PubMed

Holmes, Luke A; Turner, Andrew; Thompson, Richard C

2012-01-01

Plastic production pellets collected from beaches of south west England contain variable concentrations of trace metals (Cr, Co, Ni, Cu, Zn, Cd and Pb) that, in some cases, exceed concentrations reported for local estuarine sediments. The rates and mechanisms by which metals associate with virgin and beached polyethylene pellets were studied by adding a cocktail of 5 μg L(-1) of trace metals to 10 g L(-1) pellet suspensions in filtered seawater. Kinetic profiles were modelled using a pseudo-first-order equation and yielded response times of less than about 100 h and equilibrium partition coefficients of up to about 225 ml g(-1) that were consistently higher for beached pellets than virgin pellets. Adsorption isotherms conformed to both the Langmuir and Freundlich equations and adsorption capacities were greater for beached pellets than for virgin pellets. Results suggest that plastics may represent an important vehicle for the transport of metals in the marine environment. Copyright © 2011 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.

Chromatography of Penicillins, Penicilloates, and Penicilloylamides on Dextran Gels

PubMed Central

Hyslop, Newton E.; Milligan, Richard J.

1974-01-01

The factors influencing the chromatographic behavior on dextran gels of penicillins and their derivatives were investigated by comparing elution profiles and partition coefficients (KD and KAV) of penicillins differing in side-chain structure and among penicillin derivatives of identical side-chain but different nuclear structure. Under the conditions of pH and ionic strength employed (pH 7.4, 0.145 M NaCl, 0.05 M PO4), side-chain adsorptive effects best explained the anomalous behavior of benzylpenicillin and of oxacillin and its chlorine-substituted analogues. Polar side-chain substituents, such as the amino group of ampicillin and the carboxyl group of carbenicillin, and cleavage of the β-lactam ring, exemplified by penicilloates and penicilloylamines, both appeared to interfere with side-chain-directed adsorption. The differential adsorption of penicillins and their derivatives to dextran gels is not only of theoretical interest relative to the mechanism of chromatography but of practical application to analytical and preparative procedures in penicillin chemistry. PMID:15825415

Adsorption of Pb(II) from aqueous solution using a magnetic chitosan/graphene oxide composite and its toxicity studies.

PubMed

Samuel, Melvin S; Shah, Sk Sheriff; Bhattacharya, Jayanta; Subramaniam, Kalidass; Pradeep Singh, N D

2018-05-02

This study involves the adsorption of lead using magnetic chitosan/graphene oxide (MCGO) composite material in batch mode. The MCGO composite material was synthesized via modified Hummers method. The MCGO composite material was characterized by powder x-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), Tunnelling electron microscopy (TEM), thermogravimetric analysis (TGA), Brunauer-Emmett-Teller (BET) and UV-vis diffusive reflectance spectra. The adsorption mechanism of MCGO composite material was well described by Langmuir isotherm and pseudo second order kinetic model, with a high regression coefficient (<0.99). The MCGO composite material was applied for the removal of lead metal from aqueous solution. We have also evaluated toxicity of synthesized MCGO composite material by examining on A549 cells. The results have shown that MCGO material showed viable cell percentage of 53.7% at 50 μg and 44.8% at 100 μg. Copyright © 2018 Elsevier B.V. All rights reserved.

Adsorption behavior and mechanism of chloramphenicols, sulfonamides, and non-antibiotic pharmaceuticals on multi-walled carbon nanotubes.

PubMed

Zhao, Heng; Liu, Xue; Cao, Zhen; Zhan, Yi; Shi, Xiaodong; Yang, Yi; Zhou, Junliang; Xu, Jiang

2016-06-05

The adsorption behavior of different emerging contaminants (3 chloramphenicols, 7 sulfonamides, and 3 non-antibiotic pharmaceuticals) on five types of multi-walled carbon nanotubes (MWCNTs), and the underlying factors were studied. Adsorption equilibriums were reached within 12h for all compounds, and well fitted by the Freundlich isotherm model. The adsorption affinity of pharmaceuticals was positively related to the specific surface area of MWCNTs. The solution pH was an important parameter of pharmaceutical adsorption on MWCNTs, due to its impacts on the chemical speciation of pharmaceuticals and the surface electrical property of MWCNTs. The adsorption of ionizable pharmaceuticals decreased in varying degrees with the increased ionic strength. MWCNT-10 was found to be the strongest adsorbent in this study, and the Freundlich constant (KF) values were 353-2814mmol(1-n)L(n)/kg, 571-618mmol(1-n)L(n)/kg, and 317-1522mmol(1-n)L(n)/kg for sulfonamides, chloramphenicols, and non-antibiotic pharmaceuticals, respectively. The different adsorption affinity of sulfonamides might contribute to the different hydrophobic of heterocyclic substituents, while chloramphenicols adsorption was affected by the charge distribution in aromatic rings via substituent effects. Copyright © 2016 Elsevier B.V. All rights reserved.

Counterion adsorption and desorption rate of a charged macromolecule

NASA Astrophysics Data System (ADS)

Shi, Yu; Yang, Jingfa; Zhao, Jiang

The rate constant of counterion adsorption to and desorption from a synthetic polyelectrolyte, polystyrene sulfonate (PSS-), is measured in aqueous solution by single molecule fluorescence spectroscopy. The results show that both adsorption and desorption rate of counterions have strong dependence on polymer concentration, salt concentration as well as the molecular weight of polyelectrolytes. The results clearly demonstrate that the contribution of electrostatic interaction and the translational entropy to the distribution of counterions of a polyelectrolyte molecule. The information is helpful to the understanding of polyelectrolyte physics. National Natural Science Foundation of China.

Adsorption of SO2 on bituminous coal char and activated carbon fiber

USGS Publications Warehouse

DeBarr, Joseph A.; Lizzio, Anthony A.; Daley, Michael A.

1997-01-01

The SO2 adsorption behaviors of activated carbons produced from Illinois coal and of commercially prepared activated carbon fibers (ACFs) were compared. There was no relation between surface area of coal-based carbons and SO2 adsorption, whereas adsorption of SO2 on the series of ACFs was inversely proportional to N2 BET surface area. Higher surface area ACFs had wider pores and adsorbed less SO2; thus, pore size distribution is thought to play a significant role in SO2 adsorption for these materials. Oxidation with HNO3 and/or H2SO4, followed by heat treatment at 700−925°C to remove carbon−oxygen complexes, resulted in increased SO2 adsorption for both coal chars and ACFs. This behavior was explained by an increase in the available number of free sites, previously occupied by oxygen and now available for SO2 adsorption. The use of nitrogen-containing functional groups on ACFs of proper pore size shows promise for further increasing SO2 adsorption capacities. Knowledge of the relationship among the number of free sites, pore size, and surface chemistry on corresponding SO2 adsorption should lead to the development of more efficient adsorbents prepared from either coal or ACFs.

A solid-phase extraction method for rapidly determining the adsorption coefficient of pharmaceuticals in sewage sludge.

PubMed

Berthod, Laurence; Roberts, Gary; Whitley, David C; Sharpe, Alan; Mills, Graham A

2014-12-15

The partitioning of pharmaceuticals in the environment can be assessed by measuring their adsorption coefficients (Kd) between aqueous and solid phases. Measuring this coefficient in sewage sludge gives an indication of their partitioning behaviour in a wastewater treatment plant and hence contributes to an understanding of their subsequent fate. The regulatory approved method for measuring Kd in sewage sludge is the US Environmental Protection Agency's Office of Prevention, Pesticides and Toxic Substances (OPPTS) guideline 835.1110, which is labour intensive and time consuming. We describe an alternative method for measuring the Kd of pharmaceuticals in sewage sludge using a modified solid-phase extraction (SPE) technique. SPE cartridges were packed at different sludge/PTFE ratios (0.4, 6.0, 24.0 and 40.0% w/w sludge) and eluted with phosphate buffer at pH 7.4. The approach was tested initially using three pharmaceuticals (clofibric acid, diclofenac and oxytetracycline) that covered a range of Kd values. Subsequently, the sorption behaviour of ten further pharmaceuticals with varying physico-chemical properties was evaluated. Results from the SPE method were comparable to those of the OPPTS test, with a correlation coefficient of 0.93 between the two approaches. SPE cartridges packed with sludge and PTFE were stable for up to one year; use within one month reduced variability in measurements (to a maximum of 0.6 log units). The SPE method is low-cost, easy to use and enables the rapid measurement of Kd values for a large number of chemicals. It can be used as an alternative to the more laborious full OPPTS test in environmental fate studies and risk assessments. Copyright © 2014 The Authors. Published by Elsevier Ltd.. All rights reserved.

A solid-phase extraction method for rapidly determining the adsorption coefficient of pharmaceuticals in sewage sludge

PubMed Central

Berthod, Laurence; Roberts, Gary; Whitley, David C.; Sharpe, Alan; Mills, Graham A.

2014-01-01

The partitioning of pharmaceuticals in the environment can be assessed by measuring their adsorption coefficients (Kd) between aqueous and solid phases. Measuring this coefficient in sewage sludge gives an indication of their partitioning behaviour in a wastewater treatment plant and hence contributes to an understanding of their subsequent fate. The regulatory approved method for measuring Kd in sewage sludge is the US Environmental Protection Agency's Office of Prevention, Pesticides and Toxic Substances (OPPTS) guideline 835.1110, which is labour intensive and time consuming. We describe an alternative method for measuring the Kd of pharmaceuticals in sewage sludge using a modified solid-phase extraction (SPE) technique. SPE cartridges were packed at different sludge/PTFE ratios (0.4, 6.0, 24.0 and 40.0% w/w sludge) and eluted with phosphate buffer at pH 7.4. The approach was tested initially using three pharmaceuticals (clofibric acid, diclofenac and oxytetracycline) that covered a range of Kd values. Subsequently, the sorption behaviour of ten further pharmaceuticals with varying physico-chemical properties was evaluated. Results from the SPE method were comparable to those of the OPPTS test, with a correlation coefficient of 0.93 between the two approaches. SPE cartridges packed with sludge and PTFE were stable for up to one year; use within one month reduced variability in measurements (to a maximum of 0.6 log units). The SPE method is low-cost, easy to use and enables the rapid measurement of Kd values for a large number of chemicals. It can be used as an alternative to the more laborious full OPPTS test in environmental fate studies and risk assessments. PMID:25299795

[Effect of humic acids on migration and transformation of NH4(+) -N in saturated aquifer].

PubMed

Meng, Qing-Jun; Zhang, Yan; Feng, Qi-Yan; Zhang, Shuang-Sheng

2011-11-01

Isothermal adsorption experiment was used to study the adsorbing process of NH4(+) -N in quartz sands under the conditions with and without humic acid; the Langmuir and Freundlich equations were used to fit the absorption result and the maximum adsorption capacity of NH4(+) -N by quarts sands was calculated. Through the soil column experiments, the concentration of NH4(+) -N, NO3(-) -N and NO2(-) -N in effluent water in the tested soil column was investigated, and the effect of humic acid on migration and transformation of NH4(+) -N in saturated aquifer was analyzed, and Pseudo-second-order Kinetics Equation and Two-step Adsorption Kinetics Rate Equation were applied to fit the kinetic processes. The results showed that both Langmuir and Freundlich models can well describe the isothermal adsorption process of NH4(+) -N on the surface of quartz sands, which means that NH4(+) -N adsorbed by the quartz sand was mainly in the form of monolayer adsorption. The humic acid could increase the adsorption capacity of NH4(+) -N on quartz sand, and the saturated adsorption capacity was 0.354 mg x g(-1) under the condition with humic acid and 0.205 mg x g(-1) with the absence of humic acid. The experiment indicated that humic acid increased the adsorption capacity of NH4(+) -N on the surface of quartz sand by increasing adsorption space in the initial stage. After saturation, humic acid influenced the migration and transformation of NH4(+) -N to NO3(-) -N and NO2(-) -N probably through providing carbon source and energy for microorganisms such as nitrifying bacteria and then resulting in lower NH4(+) -N concentration in effluent water. Both Pseudo-second-order Kinetics Equation and Two-step Adsorption Kinetics Rate Equations can well describe the process of NH4(+) -N adsorption kinetics on quartz sand (R2 = 0.997 7 and R2 = 0.998 1 with humic acid; R2 = 0.992 3 and R2 = 0.994 4 without humic acid), indicating that this process was chemical adsorption. By comparing the adsorption rate coefficient of Two-step Adsorption Kinetics Rate Equation k3 (0.247 and 0.143, respectively) and k4 (0.006 27 and 0.001 7) between the treatments with and without humic acid, it can be referred that NH4(+) -N was non-orientated adsorption on active points of the quartz sand at the initial stage, and the humic acid could increase the equilibrium adsorption quantity(q(e)) of NH4(+) -N on quartz sands.

[Influence of Three Low-Molecular-Weight Organic Acids on the Adsorption of Phenanthrene in Purple Soil].

PubMed

Xie, Li; Chen, Ben-shou; Zhang, Jin-zhong; Lu, Song; Jiang, Tao

2016-03-15

The effects of three low-molecular-weight organic acids (citric acid, malic acid and oxalic acid) on the adsorption of phenanthrene in purple soil were studied by static adsorption experiment. The results showed that the adsorption kinetic process of phenanthrene in purple soil could be described by the second-order kinetic model, and the adsorption rate constant would significantly decrease in the presence of the three low-molecular-weight organic acids ( LMWOAs). The adsorption thermodynamic process could be well described by linear adsorption model, which was dominated by distribution role. The three LMWOAs could promote the adsorption of phenantherene in purple soil when their concentrations were less than 5 mmol · L⁻¹, whereas inhibit the adsorption when their concentrations were more than 10 mmol · L⁻¹, and the inhibition would increase with increasing concentrations. Moreover, the inhibitory ability displayed a decreasing order of citric acid, oxalic acid, and malic acid when their concentrations were 20 mmol · L⁻¹, which is related to the molecular structure and acidity of the three LMWOAs. Compared with the control, the content of dissolved organic matter (DOM) released from purple soil showed a trend of first decrease and then increase with increasing LMWOAs concentration, and the adsorption capacity of phenanthrene in purple soil was negatively related to DOM content.

Adsorption characteristics of siloxanes in landfill gas by the adsorption equilibrium test.

PubMed

Nam, Sangchul; Namkoong, Wan; Kang, Jeong-Hee; Park, Jin-Kyu; Lee, Namhoon

2013-10-01

Due to the increase in energy cost by constantly high oil prices and the obligation to reduce greenhouse effect gases, landfill gas is frequently used as an alternative energy source for producing heat and electricity. Most of landfill gas utility facilities, however, are experiencing problems controlling siloxanes from landfill gas as their catalytic oxidizers are becoming fouled by silicon dioxide dust. To evaluate adsorption characteristics of siloxanes, an adsorption equilibrium test was conducted and parameters in the Freundlich and Langmuir isotherms were analyzed. Coconut activated carbon (CA1), coal activated carbon (CA2), impregnated activated carbon (CA3), silicagel (NCA1), and activated alumina (NCA2) were used for the adsorption of the mixed siloxane which contained hexamethyldisiloxane (L2), octamethylcyclotetrasiloxane (D4), and decamethylcyclopentasiloxane (D5). L2 had higher removal efficiency in noncarbon adsorbents compared to carbon adsorbents. The application of Langmuir and Freundlich adsorption isotherm demonstrated that coconut based CA1 and CA3 provided higher adsorption capacity on L2. And CA2 and NCA1 provided higher adsorption capacity on D4 and D5. Based on the experimental results, L2, D4, and D5 were converted by adsorption and desorption in noncarbon adsorbents. Adsorption affinity of siloxane is considered to be affect by the pore size distribution of the adsorbents and by the molecular size of each siloxane. Copyright © 2013 Elsevier Ltd. All rights reserved.

Using supramolecular binding motifs to provide precise control over the ratio and distribution of species in multiple component films grafted on surfaces: demonstration using electrochemical assembly from aryl diazonium salts.

PubMed

Gui, Alicia L; Yau, Hon Man; Thomas, Donald S; Chockalingam, Muthukumar; Harper, Jason B; Gooding, J Justin

2013-04-16

Supramolecular interactions between two surface modification species are explored to control the ratio and distribution of these species on the resultant surface. A binary mixture of aryl diazonium salts bearing oppositely charged para-substituents (either -SO3(-) or -N(+)(Me)3), which also reduce at different potentials, has been examined on glassy carbon surfaces using cyclic voltammetry and X-ray photoelectron spectroscopy (XPS). Striking features were observed: (1) the two aryl diazonium salts in the mixed solution undergo reductive adsorption at the same potential which is distinctively less negative than the potential required for the reduction of either of the two aryl diazonium salts alone; (2) the surface ratio of the two phenyl derivatives is consistently 1:1 regardless of the ratio of the two aryl diazonium salts in the modification solutions. Homogeneous distribution of the two oppositely charged phenyl species on the modified surface has also been suggested by XPS survey spectra. Diffusion coefficient measurements by DOSY NMR and DFT based computation have indicated the association of the two aryl diazonium species in the solution, which has led to changes in the molecular orbital energies of the two species. This study highlights the potential of using intermolecular interactions to control the assembly of multicomponent thin layers.

The effects of cations and anions on hydrogen chemisorption at Pt

NASA Technical Reports Server (NTRS)

Huang, J. C.; Ogrady, W. E.; Yeager, E.

1977-01-01

Experimental evidence based on linear sweep voltammetry is presented to substantiate the view that ionic adsorption substantially shifts electrode potentials in addition to the relative heights of the hydrogen adsorption peaks. HClO4 and HF are chosen as better reference electrolytes for anion studies. The voltammetry curves for 0.1M HF and 0.1M HClO4 as well as the effect of adding successively increasing amounts of H2SO4 to these electrolytes are discussed. The measurements are also extended to alkaline solutions. Mechanisms whereby the addition of various cations and anions to electrolytes such as HF and HClO4 can induce changes in the structure of the hydrogen adsorption region in the voltammetry curves are identified: (1) blocking of sites by anion adsorption and coupling of hydrogen adsorption and anion desorption, (2) modification in the hydrogen adsorption energies for sites adjacent to adsorbed anions, (3) changes in the potential distribution across the interface, and (4) surface restructuring.

Removal of Heavy Metals by Adsorption onto Activated Carbon Derived from Pine Cones of Pinus roxburghii.

PubMed

Saif, Muhammad Jawwad; Zia, Khalid Mahmood; Fazal-ur-Rehman; Usman, Muhammad; Hussain, Abdullah Ijaz; Chatha, Shahzad Ali Shahid

2015-04-01

Activated carbon derived from cones of Pinus roxburghii (Himalayan Pine) was used as an adsorbent for the removal of copper, nickel and chromium ions from waste water. Surface analysis was carried out to determine the specific surface area and pore size distribution of the pine cone derived activated carbon. Optimal parameters, effect of adsorbent quantity, pH, equilibrium time, agitation speed and temperature were studied. Equilibrium data were evaluated by Langmuir and Freundlich isotherm models. Langmuir isotherm afforded the best fit to the equilibrium data with a maximum adsorption capacity of 14.2, 31.4 and 29.6 mg/g for Cu(II), Ni(II) and Cr(VI) respectively. Maximum adsorption of Cu(II), Ni(II) was observed in the pH range 4.0 to 4.5, whereas the best adsorption of Cr(VI) was observed at pH 2.5. It was found that 180 minutes was sufficient to gain adsorption equilibrium. The adsorption process follows a pseudo-second-order kinetic model.

Removals of pesticides and pesticide transformation products during drinking water treatment processes and their impact on mutagen formation potential after chlorination.

PubMed

Matsushita, Taku; Morimoto, Ayako; Kuriyama, Taisuke; Matsumoto, Eisuke; Matsui, Yoshihiko; Shirasaki, Nobutaka; Kondo, Takashi; Takanashi, Hirokazu; Kameya, Takashi

2018-07-01

Removal efficiencies of 28 pesticide transformation products (TPs) and 15 parent pesticides during steps in drinking water treatment (coagulation-sedimentation, activated carbon adsorption, and ozonation) were estimated via laboratory-scale batch experiments, and the mechanisms underlying the removal at each step were elucidated via regression analyses. The removal via powdered activated carbon (PAC) treatment was correlated positively with the log K ow at pH 7. The adjusted coefficient of determination (r 2 ) increased when the energy level of the highest occupied molecular orbital (HOMO) was added as an explanatory variable, the suggestion being that adsorption onto PAC particles was largely governed by hydrophobic interactions. The residual error could be partly explained by π-π electron donor-acceptor interactions between the graphene surface of the PAC particles and the adsorbates. The removal via ozonation correlated positively with the energy level of the HOMO, probably because compounds with relatively high energy level HOMOs could more easily transfer an electron to the lowest unoccupied molecular orbital of ozone. Overall, the TPs tended to be more difficult to remove via PAC adsorption and ozonation than their parent pesticides. However, the TPs that were difficult to remove via PAC adsorption did not induce strong mutagenicity after chlorination, and the TPs that were associated with strong mutagenicity after chlorination could be removed via PAC adsorption. Therefore, PAC adsorption is hypothesized to be an effective method of treating drinking water to reduce the possibility of post-chlorination mutagenicity associated with both TPs and their parent pesticides. Copyright © 2018 Elsevier Ltd. All rights reserved.

Biosorption of copper ions from aqueous solution using rape straw powders: Optimization, equilibrium and kinetic studies.

PubMed

Liu, Xin; Chen, Zhao-Qiong; Han, Bin; Su, Chun-Li; Han, Qin; Chen, Wei-Zhong

2018-04-15

In this paper, the adsorption behaviors of Cu(II) from the aqueous solution using rape straw powders were studied. The effects of initial Cu(II) concentration, pH range and absorbent dosage on the adsorption efficiency of Cu(II) by rape straw powder were investigated by Box-Behnken Design based on response surface methodology. The values of coefficient constant of the nonlinear models were 0.9997, 0.9984 and 0.9944 for removal Cu(II) from aqueous solution using rape straw shell, seed pods and straw pith core, respectively, which could navigate the design space for various factors on effects of biosorption Cu(II) from aqueous solution. The various factors of pH and biosorbents dosage were the key factors that affecting the removal efficiency of Cu(II) from aqueous solution. The biosorption equilibrium data presented its favorable monolayer adsorption Cu(II) onto shell, seed pods and straw pith core, respectively. The pseudo-second order kinetic model was the proper approach to determine the adsorption kinetics. The biosorption of Cu(II) onto surfaces of rape straw powders were confirmed and ion-exchanged in the adsorption process by energy dispersive spectrometer. The critical groups, -OH, -CH, -NH 3 + , -CH 3 , -NH and -C-O, exhibited by the infrared spectra results, changed to suggest that these groups played critical roles, especially -CH 3 in the adsorption of copper ions onto rape straw powders. The study provided evidences that rape straw powders can be used for removing Cu(II) from aqueous water. Copyright © 2017 Elsevier Inc. All rights reserved.

Microwave-assisted RAFT polymerization of well-constructed magnetic surface molecularly imprinted polymers for specific recognition of benzimidazole residues

NASA Astrophysics Data System (ADS)

Chen, Fangfang; Wang, Jiayu; Chen, Huiru; Lu, Ruicong; Xie, Xiaoyu

2018-03-01

Magnetic nanoparticles have been widely used as support core for fast separation, which could be directly separated from complicated matrices using an external magnet in few minutes. Surface imprinting based on magnetic core has shown favorable adsorption and separation performance, including good adsorption capacity, fast adsorption kinetics and special selectivity adsorption. Reversible addition-fragmentation chain transfer (RAFT) is an ideal choice for producing well-defined complex architecture with mild reaction conditions. We herein describe the preparation of well-constructed magnetic molecularly imprinted polymers (MMIPs) for the recognition of benzimidazole (BMZ) residues via the microwave-assisted RAFT polymerization. The merits of RAFT polymerization assisting with microwave heating allowed successful and more efficient preparation of well-constructed imprinted coats. Moreover, the polymerization time dramatically shortened and was just 1/24th of the time taken by conventional heating. The results indicated that a uniform nanoscale imprinted layer was formed on the Fe3O4 core successfully, and enough saturation magnetization of MMIPs (16.53 emu g-1) was got for magnetic separation. The desirable adsorption capacity (30.18 μmol g-1) and high selectivity toward template molecule with a selectivity coefficient (k) of 13.85 of MMIPs were exhibited by the adsorption isothermal assay and competitive binding assay, respectively. A solid phase extraction enrichment approach was successfully established for the determination of four BMZ residues from apple samples using MMIPs coupled to HPLC. Overall, this study provides a versatile approach for highly efficient fabrication of well-constructed MMIPs for enrichment and determination of target molecules from complicated samples.

First-principles calculation of adsorption of shale gas on CaCO3 (100) surfaces.

PubMed

Luo, Qiang; Pan, Yikun; Guo, Ping; Wang, Zhouhua; Wei, Na; Sun, Pengfei; Liu, Yuxiao

2017-06-16

To demonstrate the adsorption strength of shale gas to calcium carbonate in shale matrix, the adsorption of shale gas on CaCO3 (100) surfaces was studied using the first-principles method, which is based on the density functional theory (DFT). The structures and electronic properties of CH4, C2H6, CO2 and N2 molecules were calculated by the generalized gradient approximation (GGA), for a coverage of 1 monolayer (ML). Under the same conditions, the density of states (DOS) of CaCO3 (100) surfaces before and after the adsorption of shale gas molecules at high-symmetry adsorption sites were compared. The results showed that the adsorption energies of CH4, C2H6, CO2 and N2 on CaCO3 (100) surfaces were between 0.2683 eV and -0.7388 eV. When a CH4 molecule was adsorbed at a hollow site and its 2 hydrogen atoms were parallel to the long diagonal (H3) on the CaCO3 (100) surface, it had the most stable adsorption, and the adsorption energy was only -0.4160 eV. The change of adsorption energy of CH4 was no more than 0.0535 eV. Compared with the DOS distribution of CH4 before adsorption, it shifted to the left overall after adsorption. At the same time, the partial density of states (PDOS) curves of CaCO3 (100) surfaces before and after adsorption basically overlapped. This work showed that the adsorption effect of shale gas on calcium carbonate is very weak, and the adsorption is physisorption at the molecular level.

Coal lithotypes before and after saturation with CO2; insights from micro- and mesoporosity, fluidity, and functional group distribution

USGS Publications Warehouse

Mastalerz, Maria; Drobniak, A.; Walker, R.; Morse, D.

2010-01-01

Four lithotypes, vitrain, bright clarain, clarain, and fusain, were hand-picked from the core of the Pennsylvanian Springfield Coal Member (Petersburg Formation) in Illinois. These lithotypes were analyzed petrographically and for meso- and micropore characteristics, functional group distribution using FTIR techniques, and fluidity. High-pressure CO2 adsorption isotherm analyses of these lithotypes were performed and, subsequently, all samples were reanalyzed in order to investigate the effects of CO2. After the high-pressure adsorption isotherm analysis was conducted and the samples were reanalyzed, there was a decrease in BET surface area for vitrain from 31.5m2/g in the original sample to 28.5m2/g, as determined by low-pressure nitrogen adsorption. Bright clarain and clarain recorded a minimal decrease in BET surface area, whereas for fusain there was an increase from 6.6m2/g to 7.9m2/g. Using low-pressure CO2 adsorption techniques, a small decrease in the quantity of the adsorbed CO2 is recorded for vitrain and bright clarain, no difference is observed for clarain, and there is an increase in the quantity of the adsorbed CO2 for fusain. Comparison of the FTIR spectra before and after CO2 injection for all lithotypes showed no differences with respect to functional group distribution, testifying against chemical nature of CO2 adsorption. Gieseler plastometry shows that: 1) softening temperature is higher for the post-CO2 sample (389.5??C vs. 386??C); 2) solidification temperature is lower for the post-CO2 sample (443.5??C vs. 451??C); and 3) the maximum fluidity is significantly lower for the post-CO2 sample (4 ddpm vs. 14 ddpm). ?? 2010 Elsevier B.V.

Distribution and possible immobilization of lead in a forest soil (Luvisol) profile.

PubMed

Sipos, Péter; Németh, Tibor; Mohai, Ilona

2005-02-01

Geochemical analyses using a sequential extraction method and lead adsorption studies were carried out in order to characterize the distribution and adsorption of lead on each genetic horizon of a Luvisol profile developed on a pelagic clayey aleurolite. Clay illuviation is the most important pedogenic process in the profile studied. Its clay mineralogy is characterized by chlorite/vermiculite species with increasing chlorite component downward. The amount of carbonate minerals strongly increases in the lower part of the profile resulting in an abrupt rise in soil pH within a small distance. The Pb content of the soil profile exceeds the natural geochemical background only in the Ao horizon, and its amount decreases with depth in the profile without correcting for differences in bulk density, suggesting the binding of Pb to soil organic matter. According to the sequential extraction analysis the organic matter and carbonate content of the soil have the most significant effect on lead distribution. This effect varies in the different soil horizons. Lead adsorption experiments were carried out on whole soil samples, soil clay fractions, as well as on their carbonate and organic matter free variant. The different soil horizons adsorb lead to different extents depending on their organic matter, clay mineral and carbonate content; and the mineralogical features of soil clays significantly affect their lead adsorption capacity. The clay fraction adsorbs 25% more lead than the whole soil, while in the calcareous subsoil a significant proportion of lead is precipitated due to the alkaline conditions. 10 and 5% of adsorbed Pb can be leached with distilled water in the organic matter and clay mineral dominated soil horizons, respectively. These results suggest that soil organic matter plays a decisive role in the adsorption of Pb, but the fixation by clay minerals is stronger.

Numerical analysis of field-scale transport of bromacil

NASA Astrophysics Data System (ADS)

Russo, David; Tauber-Yasur, Inbar; Laufer, Asher; Yaron, Bruno

Field-scale transport of bromacil (5-bromo-3- sec-butyl-6-methyluracil) was analyzed using two different model processes for local description of the transport. The first was the classical, one-region convection dispersion equation (CDE) model while the second was the two-region, mobile-immobile (MIM) model. The analyses were performed by means of detailed three-dimensional, numerical simulations of the flow and the transport [Russo, D., Zaidel, J. and Laufer, A., Numerical analysis of flow and transport in a three-dimensional partially saturated heterogeneous soil. Water Resour. Res., 1998, in press], employing local soil hydraulic properties parameters from field measurements and local adsorption/desorption coefficients and the first-order degradation rate coefficient from laboratory measurements. Results of the analyses suggest that for a given flow regime, mass exchange between the mobile and the immobile regions retards the bromacil degradation, considerably affects the distribution of the bromacil resident concentration, c, at relatively large travel times, slightly affects the spatial moments of the distribution of c, and increases the skewing of the bromacil breakthrough and the uncertainty in its prediction, compared with the case in which the soil contained only a single (mobile) region. Mean and standard deviation of the simulated concentration profiles at various elapsed times were compared with measurements from a field-scale transport experiment [Tauber-Yasur, I., Hadas, A., Russo, D. and Yaron, B., Leaching of terbuthylazine and bromacil through field soils. Water, Air Soil Poln., 1998, in press] conducted at the Bet Dagan site. Given the limitations of the present study (e.g. the lack of detailed field data on the spatial variability of the soil chemical properties) the main conclusion of the present study is that the field-scale transport of bromacil at the Bet Dagan site is better quantified with the MIM model than the CDE model.

Effect of Solution Concentration on Magnetic Ni0.5Zn0.5Fe₂O₄ Nanoparticles and Their Adsorption Behavior of Neutral Red.

PubMed

Li, Shasha; Liu, Qifeng; Lu, Rongzhu; Wu, Xiaoyang; Chen, Jian

2018-07-01

Magnetic Ni0.5Zn0.5Fe2O4 nanoparticles were prepared via the methanol combustion process, the morphology, chemical composition, microstructure and magnetic properties of them were investigated by SEM, EDX, TEM, XRD, VSM, and BET. The experimental data revealed that the solution concentration was a key factor to the Ni0.5Zn0.5Fe2O4 nanoparticles, with the solution concentration of ferric nitrate decreasing from 3.37 to 1.12 mol/L, the saturation magnetization decreased from 69.3 Am2/kg to 37.2 Am2/kg, and the average crystalline size of Ni0.5Zn0.5Fe2O4 nanoparticles decreased from 32 to 25 nm. While, with the solution concentration of ferric nitrate decreasing from 1.12 to 0.56 mol/L, the saturation magnetization increased from 37.2 Am2/kg to 104.6 Am2/kg, and the average crystalline size increased from 25 to 44 nm. The adsorption behavior of neutral red (NR) onto magnetic Ni0.5Zn0.5Fe2O4 nanoparticles was investigated by UV spectroscopy at room temperature; the adsorption kinetics data related to the adsorption of NR from aqueous solutions were in good agreement with the pseudo-second-order kinetic model in a range of initial concentration of 50-300 mg/L. By comparison of the Langmuir and Freundlich models for adsorption isotherm of NR, the Langmuir model (correlation coefficient R2 = 0.9918) could be used to evaluate the adsorption isotherm of NR onto magnetic Ni0.5Zn0.5Fe2O4 nanoparticles at room temperature, which suggested that the adsorption of NR onto magnetic Ni0.5Zn0.5Fe2O4 nanoparticles was monolayer, and the adsorption energy was constant.

CO2 adsorption on diatomaceous earth modified with cetyltrimethylammonium bromide and functionalized with tetraethylenepentamine: Optimization and kinetics.

PubMed

Pornaroonthama, Phuwadej; Thouchprasitchai, Nutthavich; Pongstabodee, Sangobtip

2015-07-01

The carbon dioxide (CO2) adsorbent diatomaceous earth (DE) was modified with cetyltrimethylammonium bromide (CTAB) and functionalized with varying levels of tetraethylenepentamine (TEPA). The CO2 absorption at atmospheric pressure was optimized by varying the TEPA-loading level (0-40% (w/w)), operating temperature (40-80 °C) and water vapor concentration (0-16% (v/v)) in a 10% (v/v) CO2 feed stream in helium balance using a full 2(3) factorial design. The TEPA/CTAB-DE adsorbents were characterized by X-ray diffractometry, Fourier transform infrared spectrometry and thermogravimetric analyses. The CO2 adsorption capacity increased as each of these three factors increased. The TEPA loading level-water concentration interaction had a positive influence on the CO2 adsorption while the operating temperature-water concentration interaction was antagonistic. The optimal condition for CO2 adsorption on 40%TEPA/CTAB-DE, evaluated via a factorial design response surface method (RSM), was a temperature of 58-68 °C and a water vapor concentration of 9.5-14% (v/v), with a maximum CO2 adsorption capacity of 149.4 mg g(-1) at 63.5 °C and 12% (v/v) water vapor concentration in the feed. Validation and sensitivity tests revealed that the estimated CO2 adsorption capacity was within ±4% of the experimental values, suggesting that the RSM model was satisfied and acceptable. From three kinetic models (pseudo-first-order, pseudo-second-order model and Avrami's equation), assessed using an error function (Err) and the coefficient of determination (R(2)), Avrami's equation was the most appropriate to describe the kinetics of CO2 adsorption on the 40%TEPA/CTAB-DE adsorbent and suggested that more than one reaction pathway occurred in the CO2 adsorption. Copyright © 2015 Elsevier Ltd. All rights reserved.

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.

Simulations and experiments on gas adsorption in novel microporous polymers

NASA Astrophysics Data System (ADS)

Larsen, Gregory Steven

Microporous materials represent a fascinating class of materials with a broad range of applications. The work presented here focuses on the use of a novel class of microporous material known as polymers of intrinsic micrioporosity, or PIMs, for use in gas separation and storage technologies. The aim of this research is to develop a detailed understanding of the relationship between the monomeric structure and the adsorptive performance of PIMs. First, a generalizable structure generation technique was developed such that simulation samples of PIM-1 recreated experimental densities, scattering, surface areas, pore size distributions, and adsorption isotherms. After validation, the simulations were applied as virtual experiments on several new PIMs with the intent to screen their capabilities as adsorbent materials and elucidate design principles for linear PIMs. The simulations are useful in understanding the unique properties such as pore size distribution and scattering observed experimentally.

Microplastics as vector for heavy metal contamination from the marine environment

NASA Astrophysics Data System (ADS)

Brennecke, Dennis; Duarte, Bernardo; Paiva, Filipa; Caçador, Isabel; Canning-Clode, João

2016-09-01

The permanent presence of microplastics in the marine environment is considered a global threat to several marine animals. Heavy metals and microplastics are typically included in two different classes of pollutants but the interaction between these two stressors is poorly understood. During 14 days of experimental manipulation, we examined the adsorption of two heavy metals, copper (Cu) and zinc (Zn), leached from an antifouling paint to virgin polystyrene (PS) beads and aged polyvinyl chloride (PVC) fragments in seawater. We demonstrated that heavy metals were released from the antifouling paint to the water and both microplastic types adsorbed the two heavy metals. This adsorption kinetics was described using partition coefficients and mathematical models. Partition coefficients between pellets and water ranged between 650 and 850 for Cu on PS and PVC, respectively. The adsorption of Cu was significantly greater in PVC fragments than in PS, probably due to higher surface area and polarity of PVC. Concentrations of Cu and Zn increased significantly on PVC and PS over the course of the experiment with the exception of Zn on PS. As a result, we show a significant interaction between these types of microplastics and heavy metals, which can have implications for marine life and the environment. These results strongly support recent findings where plastics can play a key role as vectors for heavy metal ions in the marine system. Finally, our findings highlight the importance of monitoring marine litter and heavy metals, mainly associated with antifouling paints, particularly in the framework of the Marine Strategy Framework Directive (MSFD).

Facilitated Bioaccumulation of Perfluorooctanesulfonate in Common Carp (Cyprinus carpio) by Graphene Oxide and Remission Mechanism of Fulvic Acid.

PubMed

Qiang, Liwen; Chen, Meng; Zhu, Lingyan; Wu, Wei; Wang, Qiang

2016-11-01

As one of the most popular carbon-based nanomaterials, graphene oxide (GO) has the potential to be released in aquatic environment and interact with some coexistent organic pollutants, such as perfluorooctanesulfonate (PFOS), which is an emerging persistent organic pollutant. In this study, the adsorption of PFOS on GO in the presence of fulvic acid (FA), the impacts of GO and FA on PFOS toxicokinetics in carp (Cyprinus carpio), and in vitro digestion behaviors were examined. The results indicated that PFOS could be strongly adsorbed on GO with a Freundlich affinity coefficient K F of 580 ± 205 (mg/g)/(mg/L) n , while the adsorption was suppressed by FA due to competitive adsorption. GO significantly enhanced the bioaccumulation of PFOS in blood, kidney, liver, gill, intestine, and muscle of carp, and the corresponding bioaccumulation factor (BAF) was in the range of 2026-53513 L/kg. The enhancement was greatest for liver and intestine, which was 10.3 and 9.33 times of that without GO, respectively. In vivo toxicokinetic and in vitro digestion-absorption experiments indicated that GO could carry PFOS to penetrate the intestine cells. There herein, PFOS absorption, especially via intestine, and the uptake rate coefficient (k u ) were greatly enhanced, leading to distinctly promoted bioaccumulation of PFOS in fish. However, FA could facilitate the flocculation of GO in the intestine and also accelerate excretion of GO-PFOS complex. Thus, in the presence of FA, PFOS absorption was reduced and the promotion effect of GO on PFOS accumulation was remitted.

An Investigation of the Sampling Distributions of Equating Coefficients.

ERIC Educational Resources Information Center

Baker, Frank B.

1996-01-01

Using the characteristic curve method for dichotomously scored test items, the sampling distributions of equating coefficients were examined. Simulations indicate that for the equating conditions studied, the sampling distributions of the equating coefficients appear to have acceptable characteristics, suggesting confidence in the values obtained…

Controlling the electrophoretic mobility of single-walled carbon nanotubes: a comparison of theory and experiment.

PubMed

Usrey, Monica L; Nair, Nitish; Agnew, Daniel E; Pina, Cesar F; Strano, Michael S

2007-07-03

The electrophoretic mobilities of single-walled carbon nanotubes (SWNTs) in agarose gels subjected to negatively charged covalent functionalization and noncovalent anionic surfactant adsorption are compared using a simplified hydrodynamic model. Net charges are calculated on the basis of estimated friction coefficients for cylindrical rodlike particles. The effects of functionalization with negatively charged 4-hydroxybenzene diazonium and anionic sodium cholate are quantified and compared with model predictions. The adsorption of Na+ counterions into the nonionic surfactant layer adsorbed on SWNTs (Triton-X-405) is shown to induce a positive charge and reverse the mobility under select conditions. This effect has not been identified or quantified for nanoparticle systems and may be important in the processing of these systems.

Effect of seawater salinity on pore-size distribution on a poly(styrene)-based HP20 resin and its adsorption of diarrhetic shellfish toxins.

PubMed

Fan, Lin; Sun, Geng; Qiu, Jiangbing; Ma, Qimin; Hess, Philipp; Li, Aifeng

2014-12-19

In the present study, okadaic acid (OA) and dinophysistoxin-1 (DTX1) were spiked into artificial seawater at low, medium and high estuarine salinities (9‰, 13.5‰ and 27‰). Passive samplers (HP20 resin) used for solid phase adsorption toxin tracking (SPATT) technology were exposed in these seawaters for 12-h periods. Adsorption curves well fitted a pseudo-secondary kinetics model. The highest initial sorption rates of both toxins occurred in the seawater of medium salinity, followed by seawater of low and high estuarine salinity. Pore volumes of micropores (<2 nm) and small mesopores (2 nm

Adsorption Properties of Lignin-derived Activated Carbon Fibers (LACF)

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

Contescu, Cristian I.; Gallego, Nidia C.; Thibaud-Erkey, Catherine

The object of this CRADA project between Oak Ridge National Laboratory (ORNL) and United Technologies Research Center (UTRC) is the characterization of lignin-derived activated carbon fibers (LACF) and determination of their adsorption properties for volatile organic compounds (VOC). Carbon fibers from lignin raw materials were manufactured at Oak Ridge National Laboratory (ORNL) using the technology previously developed at ORNL. These fibers were physically activated at ORNL using various activation conditions, and their surface area and pore-size distribution were characterized by gas adsorption. Based on these properties, ORNL did down-select five differently activated LACF materials that were delivered to UTRC formore » measurement of VOC adsorption properties. UTRC used standard techniques based on breakthrough curves to measure and determine the adsorption properties of indoor air pollutants (IAP) - namely formaldehyde and carbon dioxide - and to verify the extent of saturated fiber regenerability by thermal treatments. The results are summarized as follows: (1) ORNL demonstrated that physical activation of lignin-derived carbon fibers can be tailored to obtain LACF with surface areas and pore size distributions matching the properties of activated carbon fibers obtained from more expensive, fossil-fuel precursors; (2) UTRC investigated the LACF potential for use in air cleaning applications currently pursued by UTRC, such as building ventilation, and demonstrated their regenerability for CO2 and formaldehyde, (3) Both partners agree that LACF have potential for possible use in air cleaning applications.« less

Surface complexation modeling of Cd(II) sorption to montmorillonite, bacteria, and their composite

NASA Astrophysics Data System (ADS)

Wang, Ning; Du, Huihui; Huang, Qiaoyun; Cai, Peng; Rong, Xingmin; Feng, Xionghan; Chen, Wenli

2016-10-01

Surface complexation modeling (SCM) has emerged as a powerful tool for simulating heavy metal adsorption processes on the surface of soil solid components under different geochemical conditions. The component additivity (CA) approach is one of the strategies that have been widely used in multicomponent systems. In this study, potentiometric titration, isothermal adsorption, zeta potential measurement, and extended X-ray absorption fine-structure (EXAFS) spectra analysis were conducted to investigate Cd adsorption on 2 : 1 clay mineral montmorillonite, on Gram-positive bacteria Bacillus subtilis, and their mineral-organic composite. We developed constant capacitance models of Cd adsorption on montmorillonite, bacterial cells, and mineral-organic composite. The adsorption behavior of Cd on the surface of the composite was well explained by CA-SCM. Some deviations were observed from the model simulations at pH < 5, where the values predicted by the model were lower than the experimental results. The Cd complexes of X2Cd, SOCd+, R-COOCd+, and R-POCd+ were the predominant species on the composite surface over the pH range of 3 to 8. The distribution ratio of the adsorbed Cd between montmorillonite and bacterial fractions in the composite as predicted by CA-SCM closely coincided with the estimated value of EXAFS at pH 6. The model could be useful for the prediction of heavy metal distribution at the interface of multicomponents and their risk evaluation in soils and associated environments.

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

Grand canonical Monte Carlo simulation of the adsorption isotherms of water molecules on model soot particles

NASA Astrophysics Data System (ADS)

Moulin, F.; Picaud, S.; Hoang, P. N. M.; Jedlovszky, P.

2007-10-01

The grand canonical Monte Carlo method is used to simulate the adsorption isotherms of water molecules on different types of model soot particles. The soot particles are modeled by graphite-type layers arranged in an onionlike structure that contains randomly distributed hydrophilic sites, such as OH and COOH groups. The calculated water adsorption isotherm at 298K exhibits different characteristic shapes depending both on the type and the location of the hydrophilic sites and also on the size of the pores inside the soot particle. The different shapes of the adsorption isotherms result from different ways of water aggregation in or/and around the soot particle. The present results show the very weak influence of the OH sites on the water adsorption process when compared to the COOH sites. The results of these simulations can help in interpreting the experimental isotherms of water adsorbed on aircraft soot.

A novel surface imprinted polymer/magnetic hydroxyapatite nanocomposite for selective dibenzothiophene scavenging

NASA Astrophysics Data System (ADS)

Ali, Hager R.; El-Maghrabi, Heba H.; Zahran, Fouad; Moustafa, Yasser Mohamed

2017-12-01

Highly selective adsorbent for dibenzothiophene (DBT) was successfully designed and prepared. Molecularly imprinted polymer (MIP) and magnetic hydroxyapatite (MHAP) were used as building blocks for the novel nanocomposite adsorbent. MIP/MHAP was synthesized by grafting polymerization and surface molecular imprinting using DBT as a template molecule. The microstructure and morphology of the designed nanoadsorbent were examined via FTIR, SEM and VSM. Specific surface area and pore size distribution were determined by Quantachrome Nova 3200S automated gas sorption apparatus. Additionally, static adsorption experiments, isotherms and selective recognition adsorption studies were carried out. Reversed-phase high performance liquid chromatography (RP-HPLC) was used to determine DBT. The experimental data exhibits excellent adsorption capacity for DBT reaches 247 mg/g within 60 min. Competitive adsorption results proved that MIP/MHAP have a greater affinity towards DBT molecules than benzothiophene analogues. Pseudo-second-order model and the Langmuir isotherm were used to describe the adsorption process.

Recent studies on activated carbons and fly ashes from Turkish resources

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

Ayhan Demirbas; Gulsin Arslan; Erol Pehlivan

2006-05-15

This article deals with adsorptive properties of activated carbons (ACs) and fly ashes from Turkish coal and biomass resources. ACs because of their high surface area, microporous character and the chemical nature of their surface have been considered potential adsorbents for the removal of heavy metals from industrial wastewater. Pyrolysis is an established process method for preparation of activated carbon from biomass. The bio-char is can be used as AC. The adsorption properties of ACs were strictly defined by the physicochemical nature of their surface and their texture, i.e., pore volume, pore size distribution, surface area. It is well knownmore » that the pH of the solution-adsorbant mixture is an important variable in the adsorption process. Fly ash has the highest adsorption capacity (198.2 mg/g for Cd(II)). Almond shell AC has the lowest adsorption capacity (2.7 mg/g).« less

Heterogeneity of activated carbons in adsorption of aniline from aqueous solutions

NASA Astrophysics Data System (ADS)

Podkościelny, P.; László, K.

2007-08-01

The heterogeneity of activated carbons (ACs) prepared from different precursors is investigated on the basis of adsorption isotherms of aniline from dilute aqueous solutions at various pH values. The APET carbon prepared from polyethyleneterephthalate (PET), as well as, commercial ACP carbon prepared from peat were used. Besides, to investigate the influence of carbon surface chemistry, the adsorption was studied on modified carbons based on ACP carbon. Its various oxygen surface groups were changed by both nitric acid and thermal treatments. The Dubinin-Astakhov (DA) equation and Langmuir-Freundlich (LF) one have been used to model the phenomenon of aniline adsorption from aqueous solutions on heterogeneous carbon surfaces. Adsorption-energy distribution (AED) functions have been calculated by using an algorithm based on a regularization method. Analysis of these functions for activated carbons studied provides important comparative information about their surface heterogeneity.

Effect of different analyte diffusion/adsorption protocols on SERS signals

NASA Astrophysics Data System (ADS)

Li, Ruoping; Petschek, Rolfe G.; Han, Junhe; Huang, Mingju

2018-07-01

The effect of different analyte diffusion/adsorption protocols was studied which is often overlooked in surface-enhanced Raman scattering (SERS) technique. Three protocols: highly concentrated dilution (HCD) protocol, half-half dilution (HHD) protocol and layered adsorption (LA) protocol were studied and the SERS substrates were monolayer films of 80 nm Ag nanoparticles (NPs) which were modified by polyvinylpyrrolidone. The diffusion/adsorption mechanisms were modelled using the diffusion equation and the electromagnetic field distribution of two adjacent Ag NPs was simulated by the finite-different time-domain method. All experimental data and theoretical analysis suggest that different diffusion/adsorption behaviour of analytes will cause different SERS signal enhancements. HHD protocol could produce the most uniform and reproducible samples, and the corresponding signal intensity of the analyte is the strongest. This study will help to understand and promote the use of SERS technique in quantitative analysis.

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.

A simple thermodynamic approach to predict responses from polymer-coated quartz crystal microbalance sensors exposed to organic vapors.

PubMed

Palmas, P; Klingenfus, J; Vedeau, B; Girard, E; Montmeat, P; Hairault, L; Pradier, C M; Méthivier, C

2013-10-15

As of lately, the demand for developing artificial sensors with improved capabilities for the detection of explosives, toxics or drugs has increased. Ideally, sensor devices should provide high sensitivity and give a response that is specific to a given target molecule without being influenced by possible interfering molecules in the atmosphere. These properties strongly depend on the structure of the chemical compound used as a sensitive material. It is thus crucial to select the right compound and this step would be facilitated with the aid of predictive tools. The present investigations have been focused on a family of functionalized polysiloxane polymers deposited on a QCM device, producing only weak interactions compatible with reversible sensors. The quartz frequency variation at equilibrium has been linked to the partition coefficient that was evaluated using a thermodynamic description of the adsorption process. We have shown that the relative responses of two polymers can be directly determined from the Gibbs free enthalpy of mixing as determined from NMR measurements performed on neat liquid mixtures. An equivalence of this term-including both enthalpy and entropy contributions-to the energy interaction term calculated using Hansen solubility coefficients, has been demonstrated previously. These results constitute a basis for the development of a numerical program for calculating equilibrium sensor responses. For small molecules, the adsorption kinetics can be easily accounted for by a Fick diffusion coefficient estimated from the Van der Waals volume. Copyright © 2013 Elsevier B.V. All rights reserved.

Structure and Dynamics of Confined Alcohol-Water Mixtures.

PubMed

Bampoulis, Pantelis; Witteveen, Jorn P; Kooij, E Stefan; Lohse, Detlef; Poelsema, Bene; Zandvliet, Harold J W

2016-07-26

The effect of confinement between mica and graphene on the structure and dynamics of alcohol-water mixtures has been studied in situ and in real time at the molecular level by atomic force microscopy (AFM) at room temperature. AFM images reveal that the adsorbed molecules are segregated into faceted alcohol-rich islands on top of an ice layer on mica, surrounded by a pre-existing multilayer water-rich film. These faceted islands are in direct contact with the graphene surface, revealing a preferred adsorption site. Moreover, alcohol adsorption at low relative humidity (RH) reveals a strong preference of the alcohol molecules for the ordered ice interface. The growth dynamics of the alcohol islands is governed by supersaturation, temperature, the free energy of attachment of molecules to the island edge and two-dimensional (2D) diffusion. The measured diffusion coefficients display a size dependence on the molecular size of the alcohols, and are about 6 orders of magnitude smaller than the bulk diffusion coefficients, demonstrating the effect of confinement on the behavior of the alcohols. These experimental results provide new insights into the behavior of multicomponent fluids in confined geometries, which is of paramount importance in nanofluidics and biology.

Adsorption of Phthalates on Impervious Indoor Surfaces.

PubMed

Wu, Yaoxing; Eichler, Clara M A; Leng, Weinan; Cox, Steven S; Marr, Linsey C; Little, John C

2017-03-07

Sorption of semivolatile organic compounds (SVOCs) onto interior surfaces, often referred to as the "sink effect", and their subsequent re-emission significantly affect the fate and transport of indoor SVOCs and the resulting human exposure. Unfortunately, experimental challenges and the large number of SVOC/surface combinations have impeded progress in understanding sorption of SVOCs on indoor surfaces. An experimental approach based on a diffusion model was thus developed to determine the surface/air partition coefficient K of di-2-ethylhexyl phthalate (DEHP) on typical impervious surfaces including aluminum, steel, glass, and acrylic. The results indicate that surface roughness plays an important role in the adsorption process. Although larger data sets are needed, the ability to predict K could be greatly improved by establishing the nature of the relationship between surface roughness and K for clean indoor surfaces. Furthermore, different surfaces exhibit nearly identical K values after being exposed to kitchen grime with values that are close to those reported for the octanol/air partition coefficient. This strongly supports the idea that interactions between gas-phase DEHP and soiled surfaces have been reduced to interactions with an organic film. Collectively, the results provide an improved understanding of equilibrium partitioning of SVOCs on impervious surfaces.

Thermo-osmosis in Membrane Systems: A Review

NASA Astrophysics Data System (ADS)

Barragán, V. María; Kjelstrup, Signe

2017-06-01

We give a first review of experimental results for a phenomenon little explored in the literature, namely thermal osmosis or thermo-osmosis. Such systems are now getting increased attention because of their ability to use waste heat for separation purposes. We show that this volume transport of a solution or a pure liquid caused by a temperature difference across a membrane can be understood as a property of the membrane system, i. e. the membrane with its adjacent solutions. We present experimental values found in the literature of thermo-osmotic coefficients of neutral and hydrophobic as well as charged and hydrophilic membranes, with water and other permeant fluids as well as electrolyte solutions. We propose that the coefficient can be qualitatively explained by a formula that contains the entropy of adsorption of permeant into the membrane, the hydraulic permeability, and a factor that depends on the interface resistance to heat transfer. A variation in the entropy of adsorption with hydrophobic/hydrophilic membranes and structure breaking/structure making cations could then explain the sign of the permeant flux. Systematic experiments in the field are lacking and we propose an experimental program to mend this situation.

Confidence bounds and hypothesis tests for normal distribution coefficients of variation

Treesearch

Steve Verrill; Richard A. Johnson

2007-01-01

For normally distributed populations, we obtain confidence bounds on a ratio of two coefficients of variation, provide a test for the equality of k coefficients of variation, and provide confidence bounds on a coefficient of variation shared by k populations.

The role of particle-size soil fractions in the adsorption of heavy metals

NASA Astrophysics Data System (ADS)

Mandzhieva, Saglara; Minkina, Tatiana; Pinsky, David; Batukaev, Abdulmalik; Kalinitchenko, Valeriy; Sushkova, Svetlana; Chaplygin, Viktor; Dikaev, Zaurbek; Startsev, Viktor; Bakoev, Serojdin

2014-05-01

Ion-exchange adsorption phenomena are important in the immobilization of heavy metals (HMs) by soils. Numerous works are devoted to the study of this problem. However, the interaction features of different particle-size soil fractions and their role in the immobilization of HMs studied insufficiently. Therefore, the assessment of the effect of the particle-size distribution on the adsorption properties of soils is a vital task. The parameters of Cu2+, Pb2+ and Zn2+ adsorption by chernozems of the south of Russia and their particle-size fractions were studied. In the particle-size fractions separated from the soils, the concentrations of Cu2+, Pb2+, and Zn2 decreased with the decreasing particle size. The parameters of the adsorption values of k (the constant of the affinity)and Cmax.(the maximum adsorption of the HMs) characterizing the adsorption of HMs by the southern chernozem and its particle-size fractions formed the following sequence: silt > clay > entire soil. The adsorption capacity of chernozems for Cu2+, Pb2+, and Zn2+ depending on the particle-size distribution decreased in the following sequence: clay loamy ordinary chernozem clay loamy southern chernozem> loamy southern chernozem> loamy sandy southern chernozem. According to the parameters of the adsorption by the different particle-size fractions, the heavy metal cations form a sequence analogous to that obtained for the entire soils: Cu2+ ≥ Pb2+ > Zn2+. The parameters of the heavy metal adsorption by similar particle-size fractions separated from different soils decreased in the following order: clay loamy chernozem> loamy chernozem> loamy sandy chernozem. The analysis of the changes in the parameters of the Cu2+, Pb2+, and Zn2+ adsorption by the studied soils and their particle-size fractions showed that the extensive adsorption characteristic - the maximum adsorption (Cmax.) - is a less sensitive parameter characterizing the adsorption capacity of the soils than the intensive characteristic of the process - the adsorption equilibrium constant (k).The ratio between the content of exchangeable cations displaced from the soil adsorbing complex (SAC) into the solution and the content of adsorbed HMs decreased with the increasing concentration of adsorbed HMs. These values could be higher (for Cu2+ and Pb2+), equal, or lower than 1 (for Zn2+) and depend on the properties of HMs. At the first case, this was due to the dissolution of readily soluble salts at low HM concentrations in the SAC. In the latter case, this was related to the adsorption of associated forms HMs and the formation of new phases localized on the surface of soil particles at high HM concentrations in the SAC. Soil solution equilibrium (SSE) accords to the soil fine fraction composition. SSE thermodynamics causes the ratio of free and associated forms of ions and ion's activity in soil solution influencing composition, concentration and adsorption of HMs salts by SAC. This study was supported by the Russian Foundation for Basic Research, project no. 12-05-33078,14-05-00586_a, grant of President of MK-6448.2014.4

Deposition on disordered substrates with precursor layer diffusion

NASA Astrophysics Data System (ADS)

Filipe, J. A. N.; Rodgers, G. J.; Tavassoli, Z.

1998-09-01

Recently we introduced a one-dimensional accelerated random sequential adsorption process as a model for chemisorption with precursor layer diffusion. In this paper we consider this deposition process on disordered or impure substrates. The problem is solved exactly on both the lattice and continuum and for various impurity distributions. The results are compared with those from the standard random sequential adsorption model.

Adsorption Study on Moringa Oleifera Seeds and Musa Cavendish as Natural Water Purification Agents for Removal of Lead, Nickel and Cadmium from Drinking Water

NASA Astrophysics Data System (ADS)

Aziz, N. A. A.; Jayasuriya, N.; Fan, L.

2016-07-01

The effectiveness of plant based materials Moringa oleifera (Moringa) seeds and Musa cavendish (banana peel) for removing heavy metals namely lead (Pb), nickel (Ni) and cadmium (Cd) from contaminated groundwater was studied. Tests were carried out with individual and combined biomass at neutral pH condition on synthetic groundwater samples. The optimum biomass doses were determined as 200 mg/L for single biomass and 400 mg/L (in the ratio of 200 mg/L: 200 mg/L) for combined biomasses and used for adsorption isotherm studies with contact time of 30 minutes. Results showed that combined biomasses was able to met the Pb, Ni and Cd WHO standards from higher Pb, Ni and Cd initial concentrations which were up to 40 µg/L, 50 µg/L 9 µg/L, respectively compared to individual biomass of Moringa seed and banana peel. Moringa seeds exhibited the highest removal of Pb (81%) while the combined biomasses was most effective in removing Ni (74%) and Cd (97%) over wider their initial concentration ranges. The experimental data were linearized with Langmuir and Freundlich adsorption isotherm models. Freundlich model described the Pb adsorption better than the Langmuir model for all the tested biomasses. However, the Langmuir model fit better with the experimental data of Ni adsorption by Moringa seeds. Both models showed negligible differences in the coefficient of determination (R2) when applied for Ni and Cd adsorption on banana peel and combined biomasses, suggesting that there were multiple layers on the biomass interacting with the metals. Chemisorption is suggested to be involved in Pb adsorption for all tested biomasses as the value of nF calculated was lower than one. This type of adsorption could explain the phenomenon of different behavior of Pb removal and the higher Pb adsorption capacity (represented by KF values) compared to Ni and Cd. The study demonstrates that Moringa seeds, banana peel and their combination have the potential to be used as a natural alternative to the other water treatment agents for removing the Pb, Ni and Cd from drinking water.

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.

Effects of Lewis acidity of metal oxide promoters on the activity and selectivity of Co-based Fischer–Tropsch synthesis catalysts

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

Johnson, Gregory R.; Bell, Alexis T.

2016-06-17

Metal oxides of Ce, Gd, La, Mn, and Zr were investigated as promoters for improving the activity and selectivity of Co-based FTS catalysts. The extent to which these promoters decrease the selectivity toward CH 4 and increase the selectivity toward C 5+ hydrocarbons was found to depend on both the loading and the composition of the oxide promoter. Elemental mapping by STEM–EDS revealed that the propensity for a given metal oxide to associate with Co affects the sensitivity of the product distribution to changes in promoter loading. For all promoters, a sufficiently high loading resulted in the product distributions becomingmore » insensitive to further increases in promoter loading, very likely due to the formation of a half monolayer of promoter oxide over the Co surface. Simulations suggest that the fraction of Co active sites that are adjacent to the promoter moieties approaches unity at this degree of coverage. The oxidation state of the promoter metal cation under reaction conditions, determined by in situ XANES measurements, was used to calculate relative Lewis acidity of the promoter metal cation. A strong positive correlation was found between the C 5+ product selectivity and the Lewis acidity of the promoter metal cations, suggesting that the promotional effects are a consequence of Lewis acid–base interactions between the reaction intermediates and the promoter metal cations. Rate data obtained at different pressures were used to estimate the apparent rate coefficient and the CO adsorption constant appearing in the Langmuir–Hinshelwood expression that describes the CO consumption kinetics for both unpromoted and the metal oxide-promoted catalysts. Both parameters exhibited positive correlations with the promoter Lewis acidity. In conclusion, these results are consistent with the hypothesis that the metal cations of the promoter act as Lewis acids that interact with the O atom of adsorbed CO to facilitate CO adsorption and dissociation.« less

Effects of Lewis acidity of metal oxide promoters on the activity and selectivity of Co-based Fischer–Tropsch synthesis catalysts

DOE PAGES

Johnson, Gregory R.; Bell, Alexis T.

2016-03-31

Metal oxides of Ce, Gd, La, Mn, and Zr were investigated as promoters for improving the activity and selectivity of Co-based FTS catalysts. The extent to which these promoters decrease the selectivity toward CH 4 and increase the selectivity toward C 5+ hydrocarbons was found to depend on both the loading and the composition of the oxide promoter. Elemental mapping by STEM-EDS revealed that the propensity for a given metal oxide to associate with Co affects the sensitivity of the product distribution to changes in promoter loading. For all promoters, a sufficiently high loading resulted in the product distributions becomingmore » insensitive to further increases in promoter loading, very likely due to the formation of a half monolayer of promoter oxide over the Co surface. Simulations suggest that the fraction of Co active sites that are adjacent to the promoter moieties approaches unity at this degree of coverage. The oxidation state of the promoter metal cation under reaction conditions, determined by in situ XANES measurements, was used to calculate relative Lewis acidity of the promoter metal cation. We found a strong positive correlation between the C 5+ product selectivity and the Lewis acidity of the promoter metal cations, suggesting that the promotional effects are a consequence of Lewis acid-base interactions between the reaction intermediates and the promoter metal cations. Rate data obtained at different pressures were used to estimate the apparent rate coefficient and the CO adsorption constant appearing in the Langmuir-Hinshelwood expression that describes the CO consumption kinetics for both unpromoted and the metal oxide-promoted catalysts. Both parameters exhibited positive correlations with the promoter Lewis acidity. Our results are consistent with the hypothesis that the metal cations of the promoter act as Lewis acids that interact with the O atom of adsorbed CO to facilitate CO adsorption and dissociation.« less

Predicting membrane flux decline from complex mixtures using flow-field flow fractionation measurements and semi-empirical theory.

PubMed

Pellegrino, J; Wright, S; Ranvill, J; Amy, G

2005-01-01

Flow-Field Flow Fractionation (FI-FFF) is an idealization of the cross flow membrane filtration process in that, (1) the filtration flux and crossflow velocity are constant from beginning to end of the device, (2) the process is a relatively well-defined laminar-flow hydrodynamic condition, and (3) the solutes are introduced as a pulse-input that spreads due to interactions with each other and the membrane in the dilute-solution limit. We have investigated the potential for relating FI-FFF measurements to membrane fouling. An advection-dispersion transport model was used to provide 'ideal' (defined as spherical, non-interacting solutes) solute residence time distributions (RTDs) for comparison with 'real' RTDs obtained experimentally at different cross-field velocities and solution ionic strength. An RTD moment analysis based on a particle diameter probability density function was used to extract "effective" characteristic properties, rather than uniquely defined characteristics, of the standard solute mixture. A semi-empirical unsteady-state, flux decline model was developed that uses solute property parameters. Three modes of flux decline are included: (1) concentration polarization, (2) cake buildup, and (3) adsorption on/in pores, We have used this model to test the hypothesis-that an analysis of a residence time distribution using FI-FFF can describe 'effective' solute properties or indices that can be related to membrane flux decline in crossflow membrane filtration. Constant flux filtration studies included the changes of transport hydrodynamics (solvent flux to solute back diffusion (J/k) ratios), solution ionic strength, and feed water composition for filtration using a regenerated cellulose ultrafiltration membrane. Tests of the modeling hypothesis were compared with experimental results from the filtration measurements using several correction parameters based on the mean and variance of the solute RTDs. The corrections used to modify the boundary layer mass transfer coefficient and the specific resistance of cake or adsorption layers demonstrated that RTD analysis is potentially useful technique to describe colloid properties but requires improvements.

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.

The surface characteristics of hyperbranched polyamide modified corncob and its adsorption property for Cr(VI)

NASA Astrophysics Data System (ADS)

Lin, Hai; Han, Shaoke; Dong, Yingbo; He, Yinhai

2017-08-01

A low-cost anion adsorbent for Cr(VI) effectively removing was synthesized by hyperbranched polyamide modified corncob (HPMC). Samples were characterized by Brunauer-Emmett-Teller (BET) surface area analysis, field-emission scanning electron microscopy (FE-SEM) with energy-dispersive X-ray spectroscopy, Fourier transform infrared (FTIR) and zeta potential analysis. Kinetics, isotherms and thermodynamics studies of HPMC for Cr(VI) adsorption were investigated in batch static experiments, in the temperature range of 25-45 °C, pH = 2.0. Results showed that the adsorption was rapid and stable, with the uptake capacity higher than 80% after 30 min. Adsorption behavior and rate-controlling mechanisms were analyzed using three kinetic models (pseudo-first order, pseudo-second order, intra-particle kinetic model). Kinetic studies showed that the adsorption of HPMC to Cr(VI) relied the pseudo-second-order model, and controlled both by the intra-particle diffusion and film diffusion. Equilibrium data was tested by Langmuir and Freundlich adsorption isotherm models. Langmuir model was more suitable to indicate a homogeneous distribution of active sites on HPMC and monolayer adsorption. The maximum adsorption capacity from the Langmuir model, qmax, was 131.6 mg/g at pH 2.0 and 45 °C for HPMC. Thermodynamic parameters revealed spontaneous and endothermic nature of the Cr(VI) adsorption onto HPMC.

Adsorptive removal of Cr3+ from aqueous solutions using chitosan microfibers immobilized with plant polyphenols as biosorbents with high capacity and selectivity

NASA Astrophysics Data System (ADS)

Zhang, Ting; Wang, Yujia; Kuang, Yiwen; Yang, Ruilin; Ma, Jun; Zhao, Shilin; Liao, Yang; Mao, Hui

2017-05-01

A novel biosorbent was facilely prepared by immobilizing bayberry tannin (BT, a typical natural polyphenols) onto chitosan microfiber (CM). The as-prepared CM-BT adsorbent featured to a well-defined microfibrous morphology and highly distributed adsorption sites, which was highly efficient and selective for the adsorptive removal of Cr3+ from aqueous solutions. Based on batch experiments, the adsorption of Cr3+ on CM-BT was pH-dependent, and the optimized adsorption pH was determined to be 5.5. The adsorption capacity of CM-BT to Cr3+ was high up to 20.90 mg/g. The co-existing cations, such as Mg2+, Ca2+, Fe3+ and Cu2+, exhibited no significant influences on the adsorption of Cr3+ on CM-BT. The adsorption kinetics were well fitted by the pseudo-second-order rate model (R2 > 0.99) while the adsorption isotherms were well described by the Langmuir model (R2 > 0.98). Importantly, CM-BT was effective for the continues treatment of low concentration Cr3+ (2.0 mg/L) contaminated wastewater. Before reached the breakthrough point (5% of the initial Cr3+ concentration, 0.1 mg/L), the treated volume was as high as 894 bed volume, manifesting the great potential of CM-BT in practical treatment of Cr3+ contaminated wastewater.

Protein adsorption at charged surfaces: the role of electrostatic interactions and interfacial charge regulation.

PubMed

Hartvig, Rune A; van de Weert, Marco; Østergaard, Jesper; Jorgensen, Lene; Jensen, Henrik

2011-03-15

The understanding of protein adsorption at charged surfaces is important for a wide range of scientific disciplines including surface engineering, separation sciences and pharmaceutical sciences. Compared to chemical entities having a permanent charge, the adsorption of small ampholytes and proteins is more complicated as the pH near a charged surface can be significantly different from the value in bulk solution. In this work, we have developed a phenomenological adsorption model which takes into account the combined role of interfacial ion distribution, interfacial charge regulation of amino acids in the proximity of the surface, electroneutrality, and mass balance. The model is straightforward to apply to a given set of experimental conditions as most model parameters are obtained from bulk properties and therefore easy to estimate or are directly measurable. The model provides a detailed understanding of the importance of surface charge on adsorption and in particular of how changes in surface charge, concentration, and surface area may affect adsorption behavior. The model is successfully used to explain the experimental adsorption behavior of the two model proteins lysozyme and α-lactalbumin. It is demonstrated that it is possible to predict the pH and surface charge dependent adsorption behavior from experimental or theoretical estimates of a preferred orientation of a protein at a solid charged interface.

Adsorption of aromatic compounds by carbonaceous adsorbents: a comparative study on granular activated carbon, activated carbon fiber, and carbon nanotubes.

PubMed

Zhang, Shujuan; Shao, Ting; Kose, H Selcen; Karanfil, Tanju

2010-08-15

Adsorption of three aromatic organic compounds (AOCs) by four types of carbonaceous adsorbents [a granular activated carbon (HD4000), an activated carbon fiber (ACF10), two single-walled carbon nanotubes (SWNT, SWNT-HT), and a multiwalled carbon nanotube (MWNT)] with different structural characteristics but similar surface polarities was examined in aqueous solutions. Isotherm results demonstrated the importance of molecular sieving and micropore effects in the adsorption of AOCs by carbonaceous porous adsorbents. In the absence of the molecular sieving effect, a linear relationship was found between the adsorption capacities of AOCs and the surface areas of adsorbents, independent of the type of adsorbent. On the other hand, the pore volume occupancies of the adsorbents followed the order of ACF10 > HD4000 > SWNT > MWNT, indicating that the availability of adsorption site was related to the pore size distributions of the adsorbents. ACF10 and HD4000 with higher microporous volumes exhibited higher adsorption affinities to low molecular weight AOCs than SWNT and MWNT with higher mesopore and macropore volumes. Due to their larger pore sizes, SWNTs and MWNTs are expected to be more efficient in adsorption of large size molecules. Removal of surface oxygen-containing functional groups from the SWNT enhanced adsorption of AOCs.

Features of the adsorption of naproxen enantiomers on weak chiral anion-exchangers in nonlinear chromatography

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

Asnin, Leonid; Kaczmarski, Krzysztof; Guiochon, Georges A

The retention mechanism of the enantiomers of naproxen on a Pirkle-type chiral stationary phase (CSP) was studied. This CSP is made of a porous silica grafted with quinidine carbamate. It can interact with the weak organic electrolyte naproxen either by adsorbing it or by ion-exchange. Using frontal chromatography, we explored the adsorption equilibrium under such experimental conditions that naproxen dissociates or cannot dissociate. Under conditions preventing ionic dissociation, the adsorption isotherms were measured, the adsorption energy distributions determined, and the chromatographic profiles calculated. Three different types of the adsorption sites were found for both enantiomers. The density and the bindingmore » energy of these sites depend on the nature of the organic modifier. Different solute species, anions, neutral molecules, solvent-ion associates, and solute dimers can coexist in solution, giving rise to different forms of adsorption. This study showed the unexpected occurrence of secondary steps in the breakthrough profiles of S-naproxen in the adsorption mode at high concentrations. Being enantioselective, this phenomenon was assumed to result from the association of solute molecules involving a chiral selector moiety. A multisite Langmuir adsorption model was used to calculate band profiles. Although this model accounts excellently for the experimental adsorption isotherms, it does not explain all the features of the breakthrough profiles. A comparison between the calculated and experimental profiles allowed useful conclusions concerning the effects of the adsorbate-adsorbate and adsorbate-solvent interactions on the adsorption mechanism.« less