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Removal of organic polyelectrolytes and their metal complexes by adsorption onto xonotlite.

Natural organic polyelectrolytes (humic and fulvic acids) and their metal complexes were removed by adsorption onto xonotlite. The removal percentages of humic and fulvic acids by xonotlite were approximately 80% and 30%, respectively. Humic acid removal from solution by adsorption onto xonotlite took place more readily than fulvic acid removal. The molecular weight distributions of the humic substances remaining in solution after adsorption with the xonotlite were measured with size exclusion chromatography. A comparison of molecular weight distributions demonstrated conclusively that large molecular weight components were adsorbed preferentially, indicating that adsorption efficiency depends on the number of functional groups of humic substances. Furthermore, the surface topography of the adsorbent was observed before and after adsorption by scanning electron microscopy. The calculated heat of adsorption was of 330 kJ mol(-1) which was evaluated from the Clapeyron-Clausius equation. Therefore, the adsorption type can be considered chemical. Since xonotlite can be easily synthesized and obtained at low cost, the adsorption method of humic and fulvic acids is superior to their precipitation.

Adsorption↗

Electrical stimulation alters protein adsorption and nerve cell interactions with electrically conducting biomaterials.

Electrical charges have been shown to enhance nerve regeneration; however, the mechanisms for this effect are unclear. One hypothesis is that an electrical stimulus alters the local electrical fields of extracellular matrix molecules, changing protein adsorption. We have investigated this hypothesis--that electrical stimulation increases the adsorption of serum proteins, specifically fibronectin (FN), to the electrically conducting polymer polypyrrole (PP), thereby, increasing neurite extension. PP was used because electrical stimulation of PP has been shown to significantly enhance neurite outgrowth, and more importantly, PP can be formed into conduits to guide nerve regeneration in vivo. Here, we looked at the effects of electrical stimulation on protein adsorption when an electrical current was applied to PP (1) during protein adsorption (immediate stimulation) and (2) several hours after protein adsorption (delayed stimulation). We found that immediate stimulation of PP increases FN adsorption from purified FN and serum-containing solutions. Correspondingly, PC-12 cells grown on PP films that had been previously adsorbed with FN during immediate stimulation expressed longer neurites. However, for delayed stimulation, no significant differences in adsorption or neurite outgrowth were observed. These studies suggest that increased FN adsorption with immediate electrical stimulation may explain enhanced neurite extension on electrically stimulated PP.

Adsorption↗

Effect of several organic acids on phosphate adsorption by variable charge soils of central China.

The effect of several organic acids on phosphate adsorption by acidic soils in subtropical zone of central China was studied. Results showed: (1) citrate and oxalate remarkably reduced the amount of phosphate adsorption, but tartrate, benzoate and acetate had only a very slight influence on phosphate adsorption; (2) the ability of citrate in reducing phosphate adsorption was greater than that of oxalate, moreover, the reduction percentage was dependent on the concentration of organic ligands in the solution; (3) the effect of organic acids on phosphate adsorption was related to the pH value of organic acid solution. The minimum reduction in adsorption of phosphate was present at a specific pH value of organic acid solution which ranged from 2 to 10; (4) a minimum reduction of phosphate adsorption occurred when phosphate was added to the soils before organic acid, whereas a maximum occurred when organic acid was introduced before the addition of phosphate. Meanwhile, the treatment for the mixture of two organic acids resulted in more reduction in phosphate adsorption than each of the organic acids and less than the total of them. Based on these observations, we suggested that the competition between phosphate and organic acids relied on their relatively affinity to soil mineral surface at different conditions.

Adsorption↗

Monitoring for adsorption of human serum albumin and bovine serum albumin onto bare and polystyrene-modified silver electrodes by quartz crystal impedance analysis.

The adsorption of human serum albumin (HSA) and bovine serum albumin (BSA) from PBS (pH 7.4) onto bare and polystyrene (PS)-modified silver electrodes was in situ monitored using quartz crystal impedance analysis. The adsorption characteristics of HSA and BSA were discussed by analyzing piezoelectric parameter simultaneous responses. Experimental results indicated that for both HSA and BSA, the amount adsorbed on bare silver was more than that on PS-modified surface. The BSA amount adsorbed on the two surfaces was more than that of adsorbed HSA. A kinetic model was developed to describe the adsorption process and fitted to the experimental data of frequency shift. It was shown that HSA adsorption could be described by a kinetic equation involving two consecutive reactions. At lower concentration, BSA adsorption only involved the first reaction. At higher concentration, BSA adsorption on PS-modified surface involved two consecutive reactions. All fitted results were well in agreement with the corresponding experimental results. The regression values of reaction rate constants for the HSA and BSA adsorption were obtained. These data exhibited difference in adsorption kinetics under different conditions.

Adsorption↗

Plasma protein adsorption on biodegradable microspheres consisting of poly(D,L-lactide-co-glycolide), poly(L-lactide) or ABA triblock copolymers containing poly(oxyethylene). Influence of production method and polymer composition.

Biodegradable particulate systems have been considered as parenteral drug delivery systems. The adsorption of plasma proteins on micro- and nanoparticles is determined by the surface properties and may, in turn, strongly influence the biocompatibility and biodistribution of both carriers. In the present study the influence of the polymer composition and the production method of microspheres on the in vitro plasma protein adsorption were investigated using two-dimensional electrophoresis (2-DE). Microparticles were prepared from poly(l-lactide) (l-PLA), poly(d,l-lactide-co-glycolide) (PLGA), and ABA triblock copolymers containing hydrophilic poly(oxyethylene) (B-blocks) domains connected to hydrophobic polyesters (A-blocks). Two different microencapsulation methods were employed, namely the w/o/w emulsion solvent evaporation method and the spray-drying technique. It could be demonstrated that the polymer composition and, especially, the encapsulation technique, influenced the interactions with plasma proteins significantly. For example, the percentages of several apolipoproteins in the plasma protein adsorption patterns of spray-dried PLGA- and l-PLA-particles were distinctly higher when compared to the adsorption patterns of the particles produced by the w/o/w-technique. Some adsorbed proteins were found to be characteristic or even specific for particles produced by the same method or consisting of identical polymers. Polyvinyl alcohol used as stabilizer in the w/o/w-technique may decisively influence the surface properties relevant for protein adsorption. The plasma protein adsorption on particles composed of ABA copolymers was drastically reduced when compared to microspheres made from pure polyesters. The adsorption patterns of ABA-particles were dominated by albumin. The plasma protein adsorption patterns detected on the different microspheres are likely to affect their in vivo performance as parenteral drug delivery systems.

Adsorption↗

Development of adsorptive removal process for treatment of explosives contaminated wastewater using activated carbon.

The adsorption characteristics of nitro-organics such as trinitro-toluene (TNT), dinitro-toluene (DNT) and nitrobenzene (NB) on granular activated carbon (GAC) were studied to understand their dynamic adsorption behaviour for dilute aqueous solutions. A model was developed to predict the dynamics of the adsorption process and the effect of various design and operating parameters on adsorption characteristics. The model predictions would provide inputs to design of bench scale and pilot plant scale experiments. Section 2 of the paper describes the assumptions, predictions, development of the model and its validation with experimental data generated during bench scale and pilot plant trials. Section 3 presents the breakthrough characteristics obtained by conducting experimental runs for GAC of different surface areas from 650 to 1500 m(2)/g, hydraulic loading rates (HLR) ranging between 12 and 24 m(3)/h/m(2), feed concentrations from 50 to 130 mg/l and bed heights between 300 and 1000 mm for TNT, DNT and NB solutions. The effect of these independent parameters on the breakthrough time, adsorption capacity and the minimum concentration achieved in the effluent was studied and the results obtained are presented in this paper. These indicate that the adsorption capacity goes though a maximum when studied as a function of HLR and feed concentration. The adsorption capacity per unit surface area also shows a maximum around 1000 m(2)/g. The minimum bed height required for meeting environmental effluent discharge limit of 1 ppm was experimentally found to be about 800 mm. These results compare well with the predictions based on the model developed for column adsorption process. Data from these experimental runs and the model predictions have been used to optimise various parameters for the design of a pilot plant unit with 200 l per hour capacity.

Adsorption↗

Adsorption and removal of arsenic(V) from drinking water by aluminum-loaded Shirasu-zeolite.

The demand for effective and inexpensive adsorbents is to increase in response to the widespread recognition of the deleterious health effects of arsenic exposure through drinking water. A novel adsorbent, aluminum-loaded Shirasu-zeolite P1 (Al-SZP1), was prepared and employed for the adsorption and removal of arsenic(V) (As(V)) ion from aqueous system. The process of adsorption follows first-order kinetics and the adsorption behavior is fitted with a Freundlich isotherm. The adsorption of As(V) is slightly dependent on the initial pH over a wide range (3-10). Al-SZP1 was found with a high As(V) adsorption ability, equivalent to that of activated alumina, and seems to be especially suitable for removal of As(V) in low concentration. The addition of arsenite, chloride, nitrate, sulfate, chromate, and acetate ions hardly affected the As(V) adsorption, whereas the coexisting phosphate greatly interfered with the adsorption. The adsorption mechanism is supposed as a ligand-exchange process between As(V) ions and the hydroxide groups present on the surface of Al-SZP1. The adsorbed As(V) ions were desorbed effectively by a 40 mM NaOH solution. Continuous operation was demonstrated in a column packed with Al-SZP1. The feasibility of this technique to practical utilization was also assessed by adsorption/desorption multiple cycles with in situ desorption/regeneration operation.

Adsorption↗

Comparative study of adsorption properties of Turkish fly ashes. I. The case of nickel(II), copper(II) and zinc(II).

The objective of this study was to compare two different Turkish fly ashes (Afsin-Elbistan and Seyitomer) for their ability to remove nickel [Ni(II)], copper [Cu(II)] and zinc [Zn(II)] from an aqueous solution. The effect of contact time, pH, initial metal concentration and fly ash origin on the adsorption process at 20+/-2 degrees C were studied. Batch kinetic studies showed that an equilibrium time of 2h was required for the adsorption of Ni(II), Cu(II) and Zn(II) on both the fly ashes. The maximum metal removal was found to be dependent on solution pH (7.0-8.0 for Ni(II), 5.0-6.0 for Cu(II) and 6.0-7.0 for Zn(II)) for each type of fly ash. With an increase in the concentrations of these metals, the adsorption of Ni(II) and Zn(II) increased while the Cu(II) adsorption decreased on both the fly ashes. Adsorption densities for the metal ions were Zn(II)>Cu(II)>Ni(II) for both the fly ashes. The effectiveness of fly ash as an adsorbent improved with increasing calcium (CaO) content. Adsorption data in the range of pH values (3.0-8.0) using Ni(II) and Cu(II) concentrations of 25+/-2mg/l and Zn(II) concentration of 30+/-2mg/l in solution were correlated using the linear forms of the Langmuir and Freundlich equations. The adsorption data were better fitted to the Langmuir isotherm since the correlation coefficients for the Langmuir isotherm were higher than that for the Freundlich isotherm. The fly ash with high calcium content (Afsin-Elbistan) was found to be a metal adsorbent as effective as activated carbon and, therefore, there are good prospects for the adsorptions of these metals on fly ash with high calcium content in practical applications in Turkey.

Adsorption↗

Thermodynamic and kinetic investigations of uranium adsorption on amberlite IR-118H resin.

The adsorption behavior of uranium(VI) on a strongly acidic cation exchanger amberlite IR-118H has been studied as a function of the solution concentration and temperature. Results have been analyzed by Langmuir and Dubinin-Radushkevich (D-R) adsorption isotherms. The mean energy of adsorption 7.14kJmol(-1) was calculated from the D-R adsorption isotherm. In order to understand the significance of the diffusion mechanisms and to accurately estimate the diffusivities inside the adsorbent particles, a model for uranium(VI) adsorption on amberlite IR-118H was used. The rate constants have been calculated for 293, 313 and 333K using Lagergren equation and the activation energy (E(a)) was derived using the Arhenius equation. The thermodynamic quantities for the process of adsorption have been estimated by plotting Ln K(D) versus 1/T. The DeltaH(o) and DeltaG(o) values of uranium(VI) adsorption on amberlite IR-118H show endothermic heat of adsorption; higher temperatures favor the process.

Adsorption↗

Controlling nonspecific protein adsorption in a plug-based microfluidic system by controlling interfacial chemistry using fluorous-phase surfactants.

Control of surface chemistry and protein adsorption is important for using microfluidic devices for biochemical analysis and high-throughput screening assays. This paper describes the control of protein adsorption at the liquid-liquid interface in a plug-based microfluidic system. The microfluidic system uses multiphase flows of immiscible fluorous and aqueous fluids to form plugs, which are aqueous droplets that are completely surrounded by fluorocarbon oil and do not come into direct contact with the hydrophobic surface of the microchannel. Protein adsorption at the aqueous-fluorous interface was controlled by using surfactants that were soluble in fluorocarbon oil but insoluble in aqueous solutions. Three perfluorinated alkane surfactants capped with different functional groups were used: a carboxylic acid, an alcohol, and a triethylene glycol group that was synthesized from commercially available materials. Using complementary methods of analysis, adsorption was characterized for several proteins (bovine serum albumin (BSA) and fibrinogen), including enzymes (ribonuclease A (RNase A) and alkaline phosphatase). These complementary methods involved characterizing adsorption in microliter-sized droplets by drop tensiometry and in nanoliter plugs by fluorescence microscopy and kinetic measurements of enzyme catalysis. The oligoethylene glycol-capped surfactant prevented protein adsorption in all cases. Adsorption of proteins to the carboxylic acid-capped surfactant in nanoliter plugs could be described by using the Langmuir model and tensiometry results for microliter drops. The microfluidic system was fabricated using rapid prototyping in poly(dimethylsiloxane) (PDMS). Black PDMS microfluidic devices, fabricated by curing a suspension of charcoal in PDMS, were used to measure the changes in fluorescence intensity more sensitively. This system will be useful for microfluidic bioassays, enzymatic kinetics, and protein crystallization, because it does not require surface modification during fabrication to control surface chemistry and protein adsorption.

Adsorption↗

beta-Casein adsorption at the silicon oxide--aqueous solution interface.

Neutron reflectometry was used to investigate the time-dependent beta-casein adsorption at the silica-aqueous solution interface. The transient and steady-state structural characteristics of the adsorbed layer were determined from reflectivity curves, fitted to three-layer and two-layer models. The results show that the beta-casein adsorption to silica is very slow. The adsorption process involves the formation of an inner dense protein layer with a mean thickness of about 30 A onto which a more hydrated outer layer is self-associated. The surface excess and the total layer thickness of the asymmetric bilayer were, after 5 h adsorption time, estimated to be about 6.5 mg/m2 and 105 A, respectively. The adsorption behavior observed on silica contrasts with that previously reported for hydrophobic substrates, where beta-casein adsorption is much more rapid and the final surface excess is less than half of that observed for silica. Rinsing the silica surface with protein-free buffer resulted in a substantial desorption; much more pronounced than observed for hydrophobic substrates. This behavior suggests a weak adsorption affinity for a fraction of the adsorbed casein molecules; most likely the outer self-associated casein molecules in the adsorbed bilayer. The comparative desorption from hydrophobic surfaces was shown to be marginal. The difference between the layer structures adopted on hydrophobic and hydrophilic surfaces is also mirrored in the effects that the addition of a specific proteolytic enzyme (endoproteinase Asp-N) has on the adsorbed layer properties. The rinsing and endoproteinase cleavage processes result together in more than 80% reduction of the originally adsorbed mass at the silica surface. Only a thin but dense adsorbed layer remains after these treatments. The corresponding reduction reported for the hydrophobic adsorbent system was only about 20%. It is concluded that beta-casein adsorption on silica results in the formation of an asymmetric surface bound bilayer that stands in strong contrast to the monolayer structure formed at hydrophobic surfaces. This finding support the previous results obtained by using ellipsometry. The study also shows that neutron reflection, despite its limitations in time resolution, can be used for studying dynamic interfacial phenomena in protein systems.

Adsorption↗

Thermodynamic measurements and predictions of the adsorption of short-chain peptides on nanothin polymer films.

This contribution describes experimental measurements of submolecular-level interaction energies involved in the process of peptide adsorption on polymer films. The objective of this study was to use surface plasmon resonance (SPR) spectroscopy to measure the Gibbs energy change on adsorption (DeltaG(ad)) for pairs of various homopeptides on highly uniform, nanothin polymer films and to use these data, along with the principle of additivity, to predict DeltaG(ad) for homologous homopeptides, as well as for a mixed-residue peptide. By using a graft polymerization methodology, a nanothin poly(2-vinylpyridine) film was prepared and adsorption energies were measured first for a homologous series of tyrosine (Y) homopeptides on this film to determine submolecular-level interaction energies. By using SPR, adsorption isotherms were measured for YY and YYY peptides; analysis of these isotherms provided DeltaG(ad) data for a midchain tyrosine unit and a set of chain-end tyrosine units; values were -0.75 +/- 0.07 kcal/mol and -2.12 +/- 0.04 kcal/mol, respectively. Combining the thermodynamic contributions for adsorption of individual tyrosine units allowed a predictive estimate of -5.12 +/- 0.32 kcal/mol for the adsorption energy for YYYYYY; this estimate deviated by only 2.3% from its measured value of -5.24 +/- 0.06 kcal/mol. Similarly, adsorption energies were found for phenylalanine, glycine, and tyrosine-leucine peptides. Combining the thermodynamic contributions for adsorption of individual residue units allowed a predictive estimate of -3.24 +/- 0.38 kcal/mol for a pentapeptide, leucine enkephalin; this estimate deviated by only 3.0% from its measured value of -3.34 +/-0.11 kcal/mol.

Adsorption↗

An investigation of the adsorption of C5-C12 hydrocarbons in the ppmv and ppbv ranges on Carbotrap B.

The effects of concentration and temperature on the breakthrough volumes (Vb) of 23 volatile organic compounds on Carbotrap B have been determined using the frontal chromatography method. From the measured Vb, original isotherms have been produced and adsorption parameters based on the Langmuir, Freundlich, and Dubinin-Polyani adsorption models have been calculated. The calculated adsorption parameters describe the behavior of these VOC on Carbotrap B under the experimental conditions and are useful data for VOC sampling applications including adsorption modeling of pumped and diffusive sampling. Each of the adsorption models give similar results and are in good agreement with the experimental data in the ppmv concentration range. It will be shown that contrary to previous assumptions the Langmuir adsorption parameters obtained at ppmv concentrations cannot be used to predict Vb at ppbv concentrations and the calculated parameter mmax does not represent the maximum adsorbent capacity. The Freundlich and Dubinin-Polyani models are shown to be more successful in describing the adsorption behavior of the VOC at ppbv levels where Vb is independent of concentration. The isosteric heats of adsorption (-delta Hst) for some of the compounds have been determined using the Van't Hoff equation which can be used to predict the effect of temperature on Vb.

Adsorption↗

Gas/solid partitioning of semivolatile organic compounds (SOCs) to air filters. 3. An analysis of gas adsorption artifacts in measurements of atmospheric SOCs and organic carbon (OC). WHen using teflon membrane filters and quartz fiber filters.

Adsorption of gaseous semivolatile organic compounds (SOCs) onto the filter(s) of a filter/sorbent sampler is a potential source of measurement error when determining specific SOCs as well as organic carbon (OC) levels in the atmosphere. This work examines partitioning to both Teflon membrane filters (TMFs) and quartz fiber filters (QFFs) for purposes of predicting the magnitude of the compound-dependent gas adsorption artifact as a function of various sampling parameters. The examination is based on values of Kp,face (m3 cm(-2)), the gas/filter partition coefficient expressed as [ng sorbed per cm2 of filter face]/[ng per m3 in the gas phase]. Values of Kp,face were calculated based on literature values of the gas/solid partition coefficient Kp,s [ng sorbed per m2 of filter]/[ng per m3 in gas phase] for the adsorption of various polycyclic aromatic hydrocarbons (PAHs), polychlorinated dibenzodioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs) to TMFs, and for the adsorption of PAHs to QFFs. At relative humidity (RH) values below approximately 50%, the Kp,face values for PAHs are lower on TMFs than on ambient-backup QFFs. The gas adsorption artifact will therefore be lower for PAHs with TMFs than with QFFs under these conditions. In the past, corrections for the gas/filter adsorption artifact have been made by using a backup filter, and subtracting the mass amount of each compound found on the backup filter from the total (particle phase + sorbed on filter) amount found on the front filter. This procedure assumes that the ng cm(-2) amounts of each SOC sorbed on the front and backup filters are equal. That assumption will only be valid after both filters have reached equilibrium with each of the gaseous SOCs in the incoming sample air. The front filter will reach equilibrium first. The minimum air sample volume Vmin,f+b required to reach gas/filter sorption equilibrium with a pair of filters is 2Kp,face Afilter where Afilter (cm2) is the per-filter face area. Kp,face values, and therefore Vmin,f+b values, depend on the compound, relative humidity (RH), temperature, and filter type. Compound-dependent Vmin,f+b values are presented for PAHs and PCDD/Fs on both TMFs and QFFs. Compound-dependent equations which give the magnitude of the filter adsorption artifact are presented for a range of different sampling arrangements and circumstances. The equations are not intended for use in actually correcting field data because of uncertainties in actual field values of relevant parameters such as the compound-dependent Kp,face and gas/particle Kp values, and because of the fact that the equations assume ideal step-function chromatographic movement of gas-phase compounds through the adsorbing filter. Rather, the main utility of the equations is as guidance tools in designing field sampling efforts that utilize filter/sorbent samplers and in evaluating prior work. The results indicate that some backup-filter-based corrections described in the literature were carried out using sample volumes that were too small to allow proper correction for the gas adsorption artifactfor some specific SOCs of interest. Similar conclusions are reached regarding artifacts associated with the measurement of gaseous and particulate OC.

Adsorption↗

Mechanisms for the adsorption of substituted nitrobenzenes by smectite clays.

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.

Adsorption↗

U(VI) adsorption to heterogeneous subsurface media: application of a surface complexation model.

The pH-dependent adsorption of U(VI) onto three heterogeneous, subsurface media from the Department of Energy (DOE) Oak Ridge Reservation, Savannah River Site, and Hanford Reservation was investigated. The three materials contained significant quantities of iron and manganese oxides with nearly identical extractable iron oxide contents (25.3-25.8 g/kg). A model independently developed for the adsorption of U(VI) to synthetic ferrihydrite (Waite, T. D.; Davis, J. A.; Payne, T. E.; Waychunas, G. A.; Xu, N. Geochim. Cosmochim. Acta 1994, 58, 5465-5478) was able to predict the major features of the pH-dependent U(VI) adsorption to the materials under the assumption that all the dithionite-citrate-bicarbonate extractable iron oxide was present as ferrihydrite. Further experiments with the Oak Ridge soil as a function of carbonate and U(VI) concentration indicated that the model could predict pH-dependent U(VI) adsorption to within a root mean square error of 0.163-0.408, even under conditions outside of those for which the model was developed. These results indicate that this model could be used as a first approximation in predicting U(VI) adsorption and transport in the subsurface. U(VI) adsorption also decreased at pH >10, even in the absence of carbonate, which is of potential importance to U(VI) mobility in extreme environments present in the subsurface at some DOE facilities. The pH-dependent adsorption of U(VI) was fundamentally different in systems with a constant CO2 partial pressure as compared to a constant total carbonate concentration. Experiments at constant CO2 partial pressure may not be representative of the conditions present in the subsurface, and a constant carbonate concentration does not always result in decreased U(VI) adsorption at higher pH values.

Adsorption↗

Kinetics and mechanisms of H2S adsorption by alkaline activated carbon.

Activated carbon adsorption is widely used to remove hydrogen sulfide (H2S), one of the major odorous compounds, from gas streams. In this study, the mechanisms of H2S adsorption by alkaline activated carbon were systematically studied. Two brands of commercial activated carbons were used as H2S adsorbents. A series of designed experiments were carried outto understand on a fundamental basis the differences in H2S removal capacity observed for the two types of carbons and samples for the same carbon obtained from different batches. The physicochemical and structural characteristics of the original and exhausted activated carbons were identified using several analytical approaches (i.e., XRF, SEM, XRD, and BET). The relationships between the adsorption performances of activated carbon for H2S and its physicochemical characteristics were discussed. The kinetics of the H2S adsorption was also studied using TGA/DSC system. Both physical adsorption and chemisorption played an important role in the H2S adsorption mechanisms with the studied carbons. Chemisorption was rapid and occurred mostly at the carbon surface whereas physical adsorption was relatively slow and mostly took place at the inner pores of carbon. Carbon II demonstrated the best performance of H2S removal due to its high capacity of both physical adsorption and chemisorption. Catalytic effects of transition metals might also contribute to enhancing the H2S oxidation.

Adsorption↗

Three-component competitive adsorption model for flow-through PAC systems. 1. Model development and verification with a PAC/membrane system.

Natural organic matter (NOM) interferes with the adsorption of trace organic compounds on porous adsorbents such as powdered activated carbon (PAC) by pore blockage and direct competition for adsorption sites. The competitive effect of NOM in flow-through systems in which the retention time of the PAC is greater than the hydraulic retention time of the system can be magnified because NOM from the influent water can continue to adsorb on the PAC retained in the system. As a result, the adsorption capacity and the diffusion coefficient of trace compounds can decrease as NOM from the influent water accumulates. In this study, a dynamic three-component adsorption model was developed to quantitatively describe the removal of a trace compound from water in flow-through PAC processes. The system was simplified by using p-dichlorobenzene (p-DCB) to represent the NOM fraction that competes directly with the target trace organic atrazine for adsorption sites and by using poly(styrene sulfonate) (PSS-1.8k) to represent large, pore-blocking NOM. The model was based on the homogeneous surface diffusion assumption with the adsorption capacity of atrazine being gradually adjusted using a simplified version of the ideal adsorbed solution theory model developed in this study. The surface diffusion coefficients of atrazine and p-DCB were modeled as a function of the surface concentration of the pore-blocking compound, PSS-1.8k. The model was verified experimentally with a PAC/microfiltration (MF) system. The use of single-solute adsorption parameters obtained from batch isotherm and kinetic tests resulted in good model predictions for the adsorption of atrazine and the two model compounds under operating conditions typical of PAC/MF systems. The model will be applied to study various operating conditions and other system parameters of PAC/membrane systems in part 2 of this study.

Adsorption↗