Quantitative evaluation of the binding of phenylarsenic species to glutathione, isotocin, and thioredoxin by means of electrospray ionization time-of-flight mass spectrometry

An attempt was made to quantitatively describe the binding of phenylarsenic species to thiol-containing biomolecules using electrospray ionization mass spectrometry (ESI-MS). The extent of the reactions of phenylarsine oxide (PAO) with the peptides glutathione and isotocin (ITC) and with the protein thioredoxin resulting in covalent As--S bonds were quantified by deriving the dependence of the corresponding ion signal intensities on the concentration of the reaction products. Problems complicating a quantitative evaluation of the mass spectra, such as signal suppression effects, were critically evaluated. Equilibrium constants for condensation reactions as well as formation constants for noncovalent associations were calculated by means of ESI-MS signal intensities. The comparison of the reaction of PAO with different thiol reactants revealed the highest binding affinity for ITC followed by thioredoxin and a lower affinity to glutathione. Possibly, the intramolecular formation of RS-As(C(6)H(5))-SR occurring in case of ITC and thioredoxin is favored over the intermolecular product involving two molecules glutathione even though the molecular mass of glutathione (307 g mol(-1)) is much smaller than that of ITC (966 g mol(-1)) and thioredoxin (11 688 g mol(-1)). A similar binding affinity for trivalent (K approximately 1.6 x 10(-3) l micromol(-1)) and pentavalent (K approximately 1.6 x 10(-3) and 1.0 x 10(-3) l micromol(-1)) arsenic species was found for the formation of a noncovalent complex of glutathione with different phenylarsenic compounds.     

Characterization and adsorption properties of tetrabutylammonium montmorillonite (TBAM) clay: thermodynamic and kinetic calculations

The montmorillonite has been subjected to modification through ion-exchange reaction by tetrabutylammonium bromide (TBAB). The modified sample was studied by X-ray diffraction (XRD) technique, Fourier transform infrared (FTIR) spectroscopy, and thermogravimetric analysis (TGA) methods. The basal spacing of modified montmorillonite was determined as 14.40 A. The IR spectra of modified montmorillonite showed CH vibrations. The characterization of tetrabutylammonium montmorillonite (TBAM) and the adsorption of p-chlorophenol (p-CP) on organomontmorillonite was studied as a function of the solution concentration and temperature. The observed adsorption rates were found to fit to the pseudo-second-order kinetics. The rate constants were calculated for temperatures ranging between 25.0-35.0 degrees C at constant concentration. The adsorption energy, E, and adsorption capacity, (q(m)), for phenolic compounds adsorbing on organomontmorillonite were estimated using the Dubinin-Radushkevich (D-R) equation. Thermodynamic parameters (delta g(a) = -11.063 and -11.802 kJ/mol, delta h(a) = -30.032 and -30.789 kJ/mol, delta s(a) = -0.0636 and -0.0637 kJ/mol K for 298 and 308 K, respectively) were calculated by a new approximation from the adsorption isotherms of p-CP on organomontmorillonite. These isotherms were modeled according to Freundlich and Dubinin-Radushkevich adsorption isotherms, through which the first-order and second-order coefficients (K(1ads) = 0.0152 and 0.0127 micromol/g min, K(2ads) = 0.0130 and 0.0108 L/min micromol, respectively) were obtained at 298 and 308 K.     

Ellipsometry and Infrared Reflection Absorption Spectroscopy of Adsorbed Layers of Soluble Surfactants at the Air-Water Interface

Optical techniques play an increasingly important role in the characterization of microstructure and surface densities of thin films at various interfaces. In this study, ellipsometry and infrared reflection absorption spectroscopy (IRRAS) were used for determining the surface densities of adsorbed layers of cationic surfactants in situ at the air-water interface. The surfactants were N(alpha)-lauroyl-arginine methyl ester (LAM) and N(alpha), N(omega)-bis(N(alpha)-lauroyl-arginine)-alpha,omega-alkylidenediamide (C(6)(LA)(2)). In ellipsometry, the ellipsometric phase angle Delta was obtained at various surfactant concentrations and was referenced to that of the solvent. Three algorithms were used for analyzing the data. The surface densities are 3.3+/-0.3x10(-6) mol/m(2) at 1 mM for LAM and 1.5+/-0.3x10(-6) mol/m(2) at 0.1 mM for C(6)(LA)(2) by using an algorithm for which the monolayer thickness was estimated from molecular modeling. The corresponding surface densities from literature surface tension data and the Gibbs adsorption isotherm procedure are 2.2+/-0.4x10(-6) mol/m(2) and 1.2+/-0.2x10(-6) mol/m(2), respectively. In addition, IRRAS spectra were obtained from monolayers of LAM and C(6)(LA)(2) at the air-water interface. The frequencies of the methylene stretching vibration bands indicate that the monolayers are liquid-like. The surface densities were determined from the reflectance-absorbance data by using the model of either an isotropic film or an anisotropic film on the aqueous subphase. The IRRAS-based surface densities from either model, by using DPPC monolayers for calibration, are 2.4+/-0.7x10(-6) mol/m(2) at 1 mM for LAM and 1.5+/-0.6x10(-6) mol/m(2) at 0.1 mM for C(6)(LA)(2), which are in fair agreement with the ellipsometry- and the surface-tension-based surface densities. Copyright 2001 Academic Press.     

Impedance analysis of an electrode-separated piezoelectric sensor as a surface monitoring technique for surfactant adsorption on quartz surface

This paper describes the measurement of the kinetics of adsorption of sodium dodecyl sulfate (SDS), an anionic surfactant, onto a quartz surface with a pre-adsorbed layer of Ca2+ as an ion bridge, using an electrode-separated piezoelectric sensor (ESPS). An impedance analysis method was employed to characterize the responses of the ESPS. The impedance and frequency parameters of the ESPS were examined as functions of the conductivity, permittivity, viscosity and density of the liquid. The adsorption process of SDS onto the quartz surface resulted in an increase in both the mass and energy dissipation of the oscillating quartz crystal. The adsorption densities could be estimated by the ESPS method after taking into consideration the effects of surface viscosity and roughness. The adsorption and desorption rate constants of SDS onto the quartz surface were calculated as ka = (88.1 +/- 0.26) mol(-1) L s(-1) and kd = (4.92 +/- 0.53) x 10(-3) s(-1), respectively, based on the Langmuir model. ESPS was shown to be a powerful means of examining anionic surfactant adsorption to the solid/liquid interface.     

Adsorption mechanism in reversed-phase liquid chromatography. Effect of the surface coverage of a monomeric C18-silica stationary phase

The effect of the bonding density of the octadecyl chains onto the same silica on the adsorption and retention properties of low molecular weight compounds (phenol, caffeine, and sodium 2-naphthalene sulfonate) was investigated. The same mobile phase (methanol:water, 20:80, v/v) and temperature (T = 298 K) were applied and two duplicate columns (A and B) from each batch of packing material (neat silica, simply endcapped or C1 phase, 0.42, 1.01, 2.03, and 3.15 micromol/m2 of C18 alkyl chains) were tested. Adsorption data of the three compounds were acquired by frontal analysis (FA) and the adsorption energy distributions (AEDs) were calculated using the expectation-maximization method. Results confirmed earlier findings in linear chromatography of a retention maximum at an intermediate bonding density. From a general point of view, the saturation capacity of the adsorbent tends to decrease with increasing bonding density, due to the vanishing space intercalated between the C18 bonded chains and to the decrease of the specific surface area of the stationary phase. The equilibrium constants are maximum for an intermediary bonding density (approximately 2 micromol/m2). An enthalpy-entropy compensation was found for the thermodynamic parameters of the isotherm data. Weak equilibrium constants (small deltaH) and high saturation capacities (large deltaS) were observed at low bonding densities, higher equilibrium constants and lower saturation capacities at high bonding densities, the combinations leading to similar apparent retention in RPLC. The use of a low surface coverage column is recommended for preparative purposes.     

Adsorption and thermodynamic characteristics of Hg(II)-SCN complex onto polyurethane foam

The sorption of Hg(II) in the presence of sodium thiocyanate solution onto polyurethane (PUR) foam, an excellent sorbent, has been investigated in detail. Maximum sorption of Hg(II) is achieved from 0.1 M hydrochloric acid solution containing 7.5x10(-2) M sodium thiocyanate in 5 min. The sorption data followed both Freundlich and Langmuir adsorption isotherms. The Freundlich constants 1/n and sorption capacity, C(m), are evaluated to be 0.44+/-0.02 and (3.86+/-0.89)x10(-3) mol g(-1). The saturation capacity and adsorption constant derived from Langmuir isotherm are (6.88+/-0.28)x10(-5) mol g(-1) and (5.6+/-0.37)x10(4) dm(3) mol(-1) respectively. The mean free energy (E) of Hg(II)-SCN sorption onto PUR foam computed from D-R isotherm is 12.4+/-0.3 kJ mol(-1) indicating ion-exchange type mechanism of chemisorption. The variation of sorption with temperature yields thermodynamic parameters of DeltaH=-30.7+/-1.2 kJ mol(-1), DeltaS=-70.1+/-4.1 J mol(-1) K(-1) and DeltaG=-9.86+/-0.77 kJ mol(-1) at 298 K. The negative value of enthalpy and free energy reflects the exothermic and spontaneous nature of sorption. On the basis of the sorption data, sorption mechanism has been proposed.     

Methanation of CO over nickel: Mechanism and kinetics at high H2/CO ratios

The CO methanation reaction over nickel was studied at low CO concentrations and at hydrogen pressures slightly above ambient pressure. The kinetics of this reaction is well described by a first-order expression with CO dissociation at the nickel surface as the rate-determining step. At very low CO concentrations, adsorption of CO molecules and H atoms compete for the sites at the surface, whereas the coverage of CO is close to unity at higher CO pressures. The ratio of the equilibrium constants for CO and H atom adsorption, K(CO)/K(H), was obtained from the rate of CO methanation at various CO concentrations. K(H) was determined independently from temperature programmed adsorption/desorption of hydrogen to be K(H) = 7.7 x 10(-4) (bar(-0.5)) exp[43 (kJ/mol)/RT] and hence the equilibrium constants for adsorption of CO molecules may be calculated to be K(CO) = 3 x 10(-7) (bar(-1)) exp[122 (kJ/mol)/RT]. Furthermore, the rate of dissociation of CO at the catalyst surface was determined to be 5 x 10(9) (s(-1)) exp[-96.7 (kJ/mol)/RT] assuming that 5% of the surface nickel atoms are active for CO dissociation. The results are compared to equilibrium and rate constants reported in the literature.     

Modeling Pb(II) adsorption onto sandy loam soil

The adsorption of Pb(II) onto hydrous sandy loam soil was investigated with batch equilibrium adsorption experiments. Results show that the amount of Pb(II) adsorbed increases with increasing pH and surface loading. It was demonstrated that the surface acidity of the soil could be determined using electrophoretic mobility measurements. The surface acidity constants, pK(a1)(int) and pK(a2)(int), were 1.57 and 3.43, respectively. A surface complex formation model (SCFM) was employed to describe the adsorption. The intrinsic stability constants, pK(i)(s), for the surface reaction between the Pb species and the ionized soil surface hydroxyl groups were determined from SCFM fitting. The adsorption free energy of Pb2+ and Pb(OH)+ ions ranges from -5.74 to -6.48 kcal/mol and from -9.68 to -10.00 kcal/mol, respectively, for surface loadings between 1.21 x 10(-5) and 2.41 x 10(-4) mol/g. The adsorption binding calculation indicated that the specific chemical interaction is the major mechanism responsible for the adsorption process.     

Surface adsorption and transfer of organomercaptans to colloidal gold and direct identification by matrix assisted laser desorption/ionization mass spectrometry

The adsorption characteristics of two different organomercaptan adsorbates, 5-((2-(and-3)-S-(acetylmercapto)succinoyl)amino)fluorescein (SAMSA) and the peptide Cys-Lys-Trp-Ala-Lys-Trp-Ala-Trp (CKWAKWAK), on colloidal Au were studied, and the conjugates produced were characterized by UV-vis spectroscopy, transmission electron microscopy, and matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). Fluorescence difference measurements of free thiols in solution were used to assemble surface adsorption isotherms on Au colloid revealing surface coverages of 1.0 x 10(14) molecules cm(-2) for SAMSA and 3.1 x 10(14) molecules cm(-2) for CKWAKWAK. The free energies of adsorption were calculated to be -48.4 kJ/mol for SAMSA and -49.2 kJ/mol for CKWAKWAK. UV-visible absorption spectroscopy and transmission electron microscopy reveal that the thiol/colloid conjugates flocculate under conditions where the net charge per colloid is small or neutral and that flocculated colloids can be resuspended by a change in pH to more basic for the acidic SAMSA/Au conjugates or to more acidic for the basic CKWAKWAK/Au conjugates. The reversible flocculation allows the conjugates to be readily separated from free adsorbate in solution and thereby prepared for further characterization. CKWAKWAK/colloid conjugates were analyzed by MALDI-MS, and the mass spectra show (M + H)(+), (M + Na)(+), and (M + K)(+) ions attributable to the peptide. The manipulations studied here constitute a powerful complement to microfluidic-based separation and analysis methods. Conjugating mass-limited analytes to Au colloids makes it possible to sequester and transfer small quantities of analytes with high efficiency.     

New ligand, N-(2-pyridylmethyl)aminoacetate, for use in the immobilised metal ion affinity chromatographic separation of proteins.

A new chelating compound has been developed for use in the immobilised metal ion affinity chromatographic separation of proteins. The tridentate ligand, sodium N-(2-pyridylmethyl)aminoacetate (carbpyr), 1, was prepared via a one-step synthesis from 2-picolylamine, 3 and then immobilised onto Sepharose CL-4B through the epoxide coupling procedure. The binding behaviour of the resulting IMAC sorbent, following chelation with Cu2+ ions to a density of 152 micromol Cu2+ ions/g gel was characterised by frontal analysis experiments using horse heart myoglobin (HMYO) at pH 7.0 and pH 9.0. From the derived isotherms, the adsorption capacity, q(m), for the binding of HMYO to immobilised Cu2+-N-(2-pyridylmethyl)aminoacetate (im-Cu2+-carbpyr)-Sepharose CL-4B at these pH values was found to be 1.92 and 1.91 micromol/g sorbent, respectively, whilst the dissociation constants K(D) were 0.0092 x 10(-6) M and 0.0062 x 10(-6) M at pH 7.0 and pH 9.0, respectively, indicating that the HMYO-im-Cu2+-N-(2-pyridylmethyl)aminoacetate complex was more stable under alkaline conditions, although the binding capacity in terms of micromol protein/g gel remained essentially unchanged. The selectivity features of the im-Cu2+-carbpyr-Sepharose CL-4B sorbent were further characterised in terms of the binding properties with several human serum proteins at pH 5.0, pH 7.0 and pH 9.0.     

Complexation of cadmium and copper by fluvial humic matter and effects on their toxicity

The effects of humic acids and fulvic acids isolated from the River Arno (Italy) on the bioavailability and toxicity of cadmium and copper were assessed in relation to changes in their speciation. Measurements of the complexing capacity of solutions containing these organic ligands were carried out by a titration procedure followed by DPASV and toxicity tests were carried out using lysosomes isolated from rat liver. The complexing capacity of the physiological medium containing about 13 mg/L of humic acids, expressed as ligand concentrations, was 0.30 and 0.072 micromol/L for cadmium and copper respectively; the corresponding conditional stability constants were 4.2 x 10(11) and 1.3 x 10(8) (mol/L)-1. The complexing capacities of the solution containing the same amount of fulvic acids were 0.33 and 0.164 micromol/L for cadmium and copper respectively, the conditional stability constants were 3.2 x 10(11) and 2.4 x 10(7) (mol/L)-1. The humic acids reduced the toxicity of cadmium by about 5 times: the EC50 changed from 4.4 to 20.4 micromol/L. The dose effect curve of copper presented a bi-sigmoid trend and two EC50 values can be determined: The EC50(1) in the presence of humic acids changed from 2.0 to 3.1 micromol/L, while the EC50(2) increased from 22.3 to 45.3 micromol/L. The fulvic acids reduced the cadmium toxicity by about the same amount as humic acids, from 4.4 to 18.6 micromol/L, but they had no effect on copper toxicity. Analysing the chemical speciation of cadmium and copper in the presence of humic components and under toxicity test conditions we can say that the appreciable decrease of EC50 is not related to changes in their speciation; we can hypothesize that this is due to different processes, as well as to blocking of the lysosomal membrane. On the basis of the shape of the dose-effect curves obtained for cadmium and copper respectively, we can say that the toxic effects of the two metals are different and we can hypothesize that copper could exercise its toxic activity by inhibiting the ATP-driven proton pump and the function of the Cl- selective channel.     

Thermodynamic and kinetic characterization of nitrogen-containing polycyclic aromatic hydrocarbons in reversed-phase liquid chromatography

A series of five nitrogen-containing polycyclic aromatic hydrocarbons (NPAHs) was studied on polymeric octadecylsilica using methanol and acetonitrile as the mobile phase. The thermodynamic and kinetic behavior was examined as a function of ring number, annelation structure, and position of the nitrogen atom. The retention factors for the NPAHs are smaller than those for the parent PAHs in methanol, while the converse is true in acetonitrile. The changes in molar enthalpy are relatively comparable in both mobile phases with 1-aminopyrene having values of -5.0 +/- 0.2 kcal/mol in methanol and -6.3 +/- 0.7 kcal/mol in acetonitrile (1 cal = 4.184 J). However, the rate constants from mobile to stationary phase (k(sm)) and from stationary to mobile phase (k(ms)) demonstrate large differences as a function of mobile phase. For example, the rate constants k(ms) for 1-aminopyrene and 4-azapyrene are 675 and 62 s(-1), respectively, in methanol at 303 K. In contrast, the same solutes demonstrate rate constants of 3.47 and 3.9 x 10(-3) s(-1), respectively, in acetonitrile. The activation energies for transfer from mobile phase to transition state (deltaE(double dagger(m)) and from stationary phase to transition state (deltaE(double dagger(s)) also differ as a function of mobile phase. For example, the activation energies deltaE(double dagger(s)), for 1-aminopyrene are 21 and approximately 0 kcal/mol, whereas those for 4-azapyrene are 19 and 23 kcal/mol, in methanol and acetonitrile, respectively. Based on these thermodynamic and kinetic results, the relative contributions from the partition and adsorption mechanisms are discussed.     

New alpha-amino phenylalanine tetrazole ligand for immobilized metal affinity chromatography of proteins

A new chelating compound has been developed for use in the immobilized metal affinity chromatographic (IMAC) separation of proteins. The bidentate ligand, alpha-amino phenylalanine tetrazole, 4, was synthesized via a five-step synthesis from N-fluorenylmethoxycarbonyl phenylalanine and then immobilized onto silica through the epoxide coupling procedure. The binding behavior of the resulting IMAC sorbent, following chelation with Zn2+ to a density of 183 micromol Zn2+ ions/g silica, was characterized by the retention of proteins in the pH range of 5.0-8.0, and by the adsorption behavior of lysozyme with frontal chromatography at pH 6.0 and 8.0. The prepared column showed the separation ability to four test proteins and the retention time of these proteins increased with an increase in pH. From the derived isotherms, the adsorption capacity, qm, for the binding of lysozyme to immobilized Zn2+-alpha-amino phenylalanine tetrazole-silica was found to be 1.21 micromol/g at pH 6.0 and 1.20 micromol/g sorbent at pH 8.0, respectively, whilst the dissociation constants KD at these pH values were 5.22x10(-6) and 3.49x10(-6) M, respectively, indicating that the lysozyme was retained more stable under alkaline conditions, although the binding capacity in terms of micromole protein per gram sorbent remained essentially unchanged.     

Unburned carbon as a low-cost adsorbent for treatment of methylene blue-containing wastewater

Fly ash, natural zeolite, and unburned carbon separated from fly ash have been employed as low-cost adsorbents for dye adsorption in methylene blue-containing wastewater. It is found that the unburned carbon exhibits a much higher adsorption capacity than raw fly ash and natural zeolite. The adsorption capacities of fly ash, natural zeolite, and unburned carbon for methylene blue are 2 x 10(-5), 5 x 10(-5), and 2.5 x 10(-4) mol/g, respectively. Investigation also indicates that adsorption is influenced by initial dye concentration, particle size, dye solution pH, and adsorption temperature. Adsorption on unburned carbon increases with the initial dye concentration, solution pH, and temperature, but reduces with the increasing particle size. Kinetic studies show that adsorption of methylene blue on fly ash, natural zeolite, and unburned carbon can be best described by the pseudo-second-order adsorption model and that adsorption is a two-step diffusion process. The apparent activation energies for methylene blue adsorption on unburned carbon in the first and second diffusion processes are 12.4 and 39.3 kJ/mol, respectively.     

Effect of Temperature on Interfacial Adsorption of Cr(VI) on Wollastonite

An extensive study on the effect of temperature on interfacial adsorption of Cr(VI) on wollastonite has been carried out. Adsorption on the wollastonite surface increased from 69.5 to 91.7% by increasing the temperature from 30 to 50 degrees C under optimum conditions. Kinetic modeling of the process of adsorption of Cr(VI) was done and various parameters were determined. The process follows a first-order kinetic equation and the rate of uptake was found to be 2.40x10(-2) min(-1) at 30 degrees C, 2.5 pH, 0.5x10(-4) M Cr(VI) concentration, and 0.01 M NaClO(4) ionic strength. Kinetic and equilibrium modeling of the process of adsorption was undertaken and the equilibrium parameters were determined. The process of adsorption follows pore diffusion and the value of the rate constant of pore diffusion was found to be 5.00x10(-3) mg g(-1) min(-1/2) at 30 degrees C and optimum conditions. The values of the coefficient of mass transfer, beta(L), were determined at different temperatures. Thermodynamic studies of the removal process were performed. The study suggests that the process is a typical example of endothermic adsorption. Copyright 2001 Academic Press.     

Polymer fractionation using chromatographic column packed with novel regenerated cellulose beads modified with silane

Novel microporous beads with the particle size of about 90 microm were prepared, for the first time, from cellulose and konjac glucomannan (RC/KGM3) in 1.5 M NaOH/0.65 M thiourea aqueous solution by emulsification method. The microporous beads were then modified with silane to avoid the adsorption of polymers containing hydroxyl groups, coded as RC/KGM3-Si. A preparative size-exclusion chromatographic (SEC) column (500 mm x 20 mm) was packed with RC/KGM3-Si, and its exclusion limit and fractionation range of the stationary phase were, respectively, weight-average molecular masses (Mw) of 4.8 x 10(5) g/mol and 5.3 x 10(3)-4.8 x 10(5) g/mol for polystyrene in tetrahydrofuran. The preparative SEC column was used to fractionate poly(epsilon-caprolactone) (PCL, Mw = 8.31 x 10(4) g/mol polydispersity index d= 1.55) in tetrahydrofuran and a polysaccharide PC3-2 (Mw = 1.21 x 10(5) g/mol, d= 1.70) in 0.05 M NaOH aqueous solution, respectively. The Mw values of the fractions determined by analytical SEC combined with laser light scattering were from 1.2 x 10(4) to 1.84 x 10(5) for PCL and from 8.5 x 10(4) to 2.13 x 10(5) for PC3-2, as well as d from 1.2 to 1.5. The results indicated that the preparative SEC has good fractionation efficiency in both organic solvent and alkaline aqueous solution for the various polymers.     

Interaction of 2-chloronaphthalene with high carbon iron filings (HCIF): adsorption, dehalogenation and mass transfer limitations

Interaction of 2-chloronaphthalene (2-CN) with high-carbon iron filings (HCIF) was studied in anaerobic batch systems, both under well-mixed and poorly-mixed conditions. In well-mixed conditions, partitioning of 2-CN between solid and aqueous phases was fast, resulting in rapid attainment of equilibrium. Equilibrium partitioning could be described by a Freundlich isotherm, C(s)=K x [C(a)](m), where C(s) (micromoles g(-1) iron) and C(a) (micromoles L(-1)) were the solid and aqueous phase 2-CN concentrations, respectively. Isotherm parameters, m and K were determined to be 0.76 and 5.6 x 10(-2) (micromole g(-1) iron)/(micromole L(-1)), respectively. Sorption (k(2)) and desorption (k(3)) rate constants were determined to be 5.60 x 10(-1) h(-1) g(-1) iron L and 10 h(-1), respectively. Reductive dehalogenation of aqueous phase 2-CN occurred concurrently but at a slower rate, and could be described by the expression (dC(T)//dt)= -k(1) x M x (C(a))(N), where C(T) (micromoles L(-1)) was the total 2-CN concentration and M (g iron L(-1)) the concentration of HCIF. The values of k(1) and N were determined to be 1.09 x 10(-2) h(-1) g(-1) iron L and 1.647, respectively. In poorly mixed conditions, adsorption (k(2)) and desorption (k(3)) rate constants were 3.92 x 10(-5) h(-1) g(-1) iron L and 7 x 10(-4) h(-1), respectively, i.e., several orders of magnitude less than in well-mixed systems. The dehalogenation rate parameters, k(1) and N were determined to be 2.22 x 10(-4) h(-1) g(-1) iron L and 0.986, respectively, suggesting slower dehalogenation. These results highlight how mass-transfer limitations during the interaction between HCIF and 2-CN in poorly mixed systems, such as permeable reactive barriers (PRBs), can potentially impact the dehalogenation process.     

Biosorption of Cd(II), Cr(III), and Cr(VI) by saltbush (Atriplex canescens) biomass: thermodynamic and isotherm studies

The biosorption data of Cd(II), Cr(III), and Cr(VI) by saltbush leaves biomass were fit on the Freundlich and Langmuir adsorption isotherms at 297 K. The Cd(II) and Cr(III) solutions were adjusted to pH 5.0 and the Cr(VI) solution was adjusted to pH 2.0. The correlation coefficient values indicated that the data fit better the Freundlich model. The maximal capacities (K(F)) were found to be 5.79 x 10(-2), 3.25 x 10(-2), and 1.14 x 10(-2) mol/g for Cr(III), Cd(II), and Cr(VI), respectively. Similar results were obtained using the Langmuir and the Dubinin-Radushkevick equations. Thermodynamic parameters calculated from the Khan and Singh equation and from the q(e) vs C(e) plot show that the equilibrium constants for the biosorption of the metals follow the same order of the maximal capacities. The negative Gibbs free energy values obtained for Cd(II) and Cr(III) indicated that these ions were biosorbed spontaneously. The mean free energy values calculated from the Dubinin-Radushkevick equation (10.78, 9.45, and 9.05 for Cr(III), Cr(VI), and Cd(II), respectively) suggest that the binding of Cd(II), Cr(III), and Cr(VI) by saltbush leaves biomass occurs through an ionic exchange mechanism.     

Flocculation mechanism induced by cationic polymers investigated by light scattering

Three cationic polymers with molecular weights and charge densities of 3.0 x 10(5) g/mol and 10%, 1.1 x 10(5) g/mol and 40%, and 1.2 x 10(5) g/mol and 100% were chosen as flocculants to aggregate silica particles (90 nm), under various conditions, including change in polymer dosage, particle concentration, background electrolyte concentration, and shear rate. The size and structure of flocs produced were determined using the static light scattering technique. On the basis of measurements of polymer adsorption and its effect on the zeta potential and floc properties, it has been found that the polymer charge density plays an important role in determining the flocculation mechanism. Polymers with a 10% charge density facilitate bridging, 40% charged polymers bring about either a combination of charge neutralization and bridging or bridging, depending on the polymer dosage, and polymers with the charge density of 100% induce electrostatic patch flocculation mechanism at the optimum polymer dosage and below but bring about bridging mechanism at the polymer dosage approaching the adsorption plateau value. Bridging aggregation can readily be affected by the particle concentration, and an increase in particle concentration results in the formation of larger but looser aggregates, whereas electrostatic patch aggregation is independent of particle concentration. The addition of a background electrolyte aids in bridging aggregation while it is detrimental to electrostatic patch aggregation. It has also been found that the effect of shear rate on the mass fractal dimension depends on polymer charge density.     

Carbon paste electrode based on surface activation for trace adriamycin determination by a preconcentration and voltammetric method.

A voltammetric determination of adriamycin (ADM) at a carbon paste electrode (CPE) in the presence of cetyltrimethylammonium bromide (CTAB) is described. ADM strongly adsorbs on the surface of the electrode by the adsorption of CTAB, thereby affecting the reduction current. This method provides a detection limit below 10(-10) mol/L for ADM. The experimental parameters, which influence the voltammetric responses of ADM, e.g. the pH value, variety and concentration of surfactants and the scan rate, were optimized. The reduction peak current changes linearly with the ADM concentration over the range from 2.5 x 10(-8) mol/L to 5 x 10(-6) mol/L. The detection limit is 4 x 10(-10) mol/L for an accumulation time of 3 min. The coefficient of variation, determined at 4 x 10(-6) mol/L ADM, is 3.0% (n = 8). Using this method, ADM in the patient's urine samples, which undergoes active ADM chemotherapy, was determined.