Bioadsorption of a reactive dye from aqueous solution by municipal solid waste.

The biosorbent was obtained from municipal solid waste (MSW) of the Mostaganem city. Before use the MSW was dried in air for three days and washed several times. The sorption of yellow procion reactive dye MX-3R onto biomass from aqueous solution was investigated as function of pH, contact time and temperature. The adsorption capacity of MX-3R was 45.84 mg/g at pH 2-3 and room temperature. MX-3R adsorption decreases with increasing temperature. The Langmuir, Freundlich and Langmuir-Freundlich adsorption models were applied to describe the related isotherms. Langmuir-Freundlich equation has shown the best fitting with the experimental data. The pseudo first-order, pseudo second-order and intra-particle diffusion kinetic models were used to describe the kinetic sorption. The results clearly showed that the adsorption of MX-3R onto biosorbent followed the pseudo second-order model. The enthalpy (ΔH°), entropy (ΔS°) and Gibbs free energy (ΔG°) changes of adsorption were calculated. The results indicated that the adsorption of MX-3R occurs spontaneously as an exothermic process.

The dissolution rates of SiO2 nanoparticles as a function of particle size.

There is a critical need to better define the relationship among particle size, surface area, and dissolution rate for nanoscale materials to determine their role in the environment, their toxicity, and their technological utility. Although some previous studies concluded that nanoparticles dissolve faster than their bulk analogs, contradictory evidence suggests that nanoparticles dissolve more slowly. Furthermore, insufficient characterization of the nanoparticulate samples and the solution chemistry in past studies obscures the relationship between particle size, surface area, and dissolution rate. Here we report amorphous SiO(2) dissolution rates in aqueous solutions determined from complementary mixed-flow and closed reactor experiments at 6.9 ≥ pH ≥ 11.2 and 25 °C as a function of particle diameter from 25 to 177 nm. Experiments were performed at far-from-equilibrium conditions to isolate kinetic effects from those of changing the reaction driving force on overall dissolution rates. Measured far-from-equilibrium mass normalized dissolution rates are nearly independent of particle size, but corresponding BET surface area normalized rates decrease substantially with decreasing particle size. Combining these observations with existing established kinetic rate equations allows the prediction of nanoparticle dissolution rates as a function of both particle size and aqueous fluid saturation state.

Cu(II) adsorption by halloysites intercalated with sodium acetate.

Intercalated halloysites with sodium acetate at various contact time were prepared. The resulting materials were characterised by X-ray powder diffraction, Fourier transformed infrared spectroscopy, scanning electronic microscopy, and specific surface area evaluation. The modified halloysites were employed as Cu(II) adsorbents from aqueous solutions. Various parameters were studied through the batch method. Kinetic data, equilibrium isotherms, and thermodynamic parameters were evaluated by considering several models. The fraction of halloysite intercalated with sodium acetate remained low, up to 7 days, then linearly increased with contact time. Thirty days were required to achieve a ratio of 91%. For this sample, a proliferation of small tubes (nanotubes) was evidenced. The best results were achieved with the pseudo-second-order kinetic model associated with intraparticle diffusion and with the Redlich-Peterson isotherm, for the equilibrium data. The thermodynamic data show that adsorption would be spontaneous at low temperatures, of exothermic nature, resulting in an adsorbate-adsorbent system much more ordered. The insertion of CH(3)COONa into halloysite significantly affects the Cu(II) adsorption. The magnitude in enhancement of copper adsorption on solid phase thus depends on the content of the carboxylic functional groups, which increases with the insertion of CH(3)COONa into the halloysitic matrix. The involved mechanism is quite complex. It implies electrostatic considerations and a cationic exchange process. The most intercalated sample was found to be very effective as adsorbent of copper(II) from aqueous solutions.

Acid-base behavior of the gaspeite (NiCO3(s)) surface in NaCl solutions.

Gaspeite is a low reactivity, rhombohedral carbonate mineral and a suitable surrogate to investigate the surface properties of other more ubiquitous carbonate minerals, such as calcite, in aqueous solutions. In this study, the acid-base properties of the gaspeite surface were investigated over a pH range of 5 to 10 in NaCl solutions (0.001, 0.01, and 0.1 M) at near ambient conditions (25 +/- 3 degrees C and 1 atm) by means of conventional acidimetric and alkalimetric titration techniques and microelectrophoresis. Over the entire experimental pH range, surface protonation and electrokinetic mobility are strongly affected by the background electrolyte, leading to a significant decrease of the pH of zero net proton charge (PZNPC) and the pH of isoelectric point (pH(iep)) at increasing NaCl concentrations. This challenges the conventional idea that carbonate mineral surfaces are chemically inert to background electrolyte ions. Multiple sets of surface complexation reactions (i.e., ionization and ion adsorption) were formulated within the framework of three electrostatic models (CCM, BSM, and TLM) and their ability to simulate proton adsorption and electrokinetic data was evaluated. A one-site, 3-pK, constant capacitance surface complexation model (SCM) reproduces the proton adsorption data at all ionic strengths and qualitatively predicts the electrokinetic behavior of gaspeite suspensions. Nevertheless, the strong ionic strength dependence exhibited by the optimized SCM parameters reveals that the influence of the background electrolyte on the surface reactivity of gaspeite is not fully accounted for by conventional electrostatic and surface complexation models and suggests that future refinements to the underlying theories are warranted.

Surface charge and zeta-potential of metabolically active and dead cyanobacteria.

Zeta potential and acid-base titrations of active, inactivated, and dead Planktothrix sp. and Synechococcus sp. cyanobacteria were performed to determine the degree to which cell surface electric potential and proton/hydroxyl adsorption are controlled by metabolism or cell membrane structure. Surface OH(-) excess from potentiometric data, showed differences in surface charge between active and dead cyanobacteria from pH 3 to 10. Average zero salt effect pH (pH(pzse)) of 5.8+/-0.1 and 6.3+/-0.1 were obtained for active Planktothrix sp. and Synechococcus sp., respectively. Similarly for dead cyanobacteria pH(pzse) values of 5.8+/-0.1 and 4.6+/-0.1 were obtained. Zeta potentials of active Planktothrix sp. and Synechococcus sp. were positive at alkaline conditions, with a maximum of +13.7+/-1.5 mV at a pH of 9.0+/-0.1 for both species. This positive potential diminished in the presence of 1 mM HCO(-)(3). The zeta potential of Planktothrix sp. and Synechococcus sp. cells was negative at alkaline pH following their exposure to NaN(3), a metabolic inhibitor. The zeta potential of dead cyanobacteria was negative for Planktothrix sp., from pH 2.5 to 10.5, at -30 to -20 mV. Dead Synechococcus sp. exposed to a pH 2.5 solution recorded negative potentials to a minimum of -30 mV at pH 8, but positive potentials were found at higher pH reaching a maximum of +10 mV at pH 9.1. Zeta potentials for dead, but non-acidified Synechococcus sp. remained negative at -30 mV from an initial pH of 5.6 to 10.5, reflecting differences in cell wall structure between these species. These results indicate that Planktothrix sp. and Synechococcus sp. may metabolically control their surface charge to electrostatically attract bicarbonate anions at alkaline pH, required for photosynthesis.

Removal of pentachlorophenol from aqueous solutions by dolomitic sorbents.

The partial decomposition of dolomite carried out within the temperature range 600-1000 degrees C provides new sorbents, called dolomitic sorbents. Their surface properties and identification by X-ray diffraction are discussed. The lowest specific surface area value was found for the raw dolomite, while the highest value was achieved by the D-1000 sample. The adsorption equilibrium of pentachlorophenol from aqueous solutions on the examined sorbents was investigated at 30, 40, and 50 degrees C via a bath process. Langmuir, Freundlich, Langmuir-Freundlich, and Redlich-Petersen models were fitted to experimental equilibrium data, and their goodnesses of fit are compared. The adjustable parameters of Langmuir-Freundlich and Redlich-Petersen isotherms were estimated by nonlinear least-squares analysis. Langmuir and Freundlich models were found insufficient to explain the adsorption equilibrium, while Langmuir-Freundlich and Redlich-Petersen isotherms provide the best correlation of the pentachlorophenol adsorption onto dolomitic sorbents.

Speciation of Zn associated with diatoms using X-ray absorption spectroscopy.

The long- and short-term interactions between zinc, an essential but also toxic element, and freshwater and marine diatoms are not well understood partly because of a lack of information on Zn speciation on the surface and inside the cells. In this work, interactions of aqueous Zn2+ with marine (Skeletonema costatum) and freshwater (Achnanthidium minutissimum, Navicula minima, and Melosira varians) diatoms were studied using conventional macroscopic techniques, while the local atomic structure of metal ions adsorbed on their surface or incorporated into the cells was characterized by in-situ Zn K-edge X-ray absorption fine structure (XAFS) spectroscopy on both intact and liophylized samples. At the cell surface for all diatom species studied, Zn was tetrahedrally coordinated with oxygen at approximately 2.00 +/- 0.02 A and monodentately bonded to one or two carboxylate groups; these results are consistent with the surface speciation model developed from macroscopic adsorption experiments. The atomic environment of Zn incorporated into freshwater diatoms during long-term growth in normal nutrient media was distinctly differentfrom that of adsorbed Zn: it was dominated by O (and/or N) neighbors in a tetrahedral arrangement at 1.97 +/- 0.02 A in the first atomic shell, with the presence of 1 phosphorus and 2 carbons in the Zn second shell. Contrasting speciation of intracellular zinc was revealed for the marine species Skeletonema costatum in which Zn was coordinated to 2 O/N atoms and 2 sulfur groups in the form of cysteine-histidine complexes and/or zinc thiolate clusters. These new structural data strongly suggest: (i) the predominant > R-COO- ligand binding of Zn atthe diatom surface; (ii) the nonspecific storage of Zn in the form of carboxylate/phosphate groups inside the cell of freshwater species; and (iii) the highly specific thiol-ligand coordination of intracellular zinc for marine S. costatum species.