The Competitive Adsorption of Chromate and Sulfate on Ni-Substituted Magnetite Surfaces: An ATR-FTIR Study

With similar chemical properties and geometrical configurations, sulfate and chromate display interesting competitive adsorption on mineral surfaces. Although such issues have been investigated on several Fe (hydr)oxide surfaces, e.g., ferrihydrite, goethite and hematite, the competitive adsorption on magnetite surfaces and the constraint mechanism have seldom been studied. This impedes the understanding of the transfer and fate of chromate and sulfate on magnetite surfaces, as magnetite is not only a useful adsorbent but also an efficient reductant to decrease the mobility and toxicity of chromium. In the present study, the geometries of the competitive adsorption of chromate and sulfate on Ni-substituted magnetite surfaces over a pH range of 4–9 were investigated using in situ attenuated total reflectance Fourier transform infrared spectroscopy and two-dimensional correlation analysis. In individual adsorption, nonprotonated monodentate mononuclear (NMM) complexes dominated chromate adsorption, accompanied by a few bidentate binuclear (BB) complexes. For sulfate, NMM complexes and outer-sphere (OS) species predominated under acidic and neutral–alkaline conditions, respectively. The above variation in adsorption configuration resulted in the different adsorption competitiveness between chromate and sulfate at different pH values. Specifically, the NMM complexes of chromate were substituted by NMM sulfate complexes under acidic conditions and vice versa. However, under neutral and alkaline conditions, the OS species of sulfate scarcely affected the adsorption of chromate. The adsorption affinity of chromate and sulfate on Ni-substituted magnetite increased in the following order: OS complex (sulfate) < NMM complexes (chromate) < NMM complexes (sulfate).

Fabrication and Evaluation of Cellulose-Alginate-Hydroxyapatite Beads for the Removal of Heavy Metal Ions from Aqueous Solutions

In the present study, the potential of synthesized mixed cellulose, alginate and hydroxyapatite beads for the efficient removal of Ni (II) and Cu (II) ions from aqueous solutions was investigated. Cellulose, alginate and hydroxyapatite are known for their individual adsorption capacity. Beads were prepared in different ratios of these materials. The prepared beads were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscope (SEM) and thermogravimetric analysis (TGA). FTIR and XRD analysis showed characteristic peaks assigned to cellulose, alginate and hydroxyapatite. Thermal stability was observed to increase with increase of hydroxyapatite percentage in beads. SEM images showed increased surface porosity and roughness with the increase of cellulose percentage. The prepared beads were used for the removal of Ni (II) and Cu (II) ions from aqueous solutions and the process was optimized with respect to pH, contact time, adsorbent dose and initial concentration of metal ions. The values of the coefficient of determination (R2) of the Langmuir and Freundlich adsorption model indicated that the adsorbed Cu (II) and Ni (II) ions form monolayer coverage on the adsorbent surface. In kinetic analysis, Pseudo-second-order model fitted the kinetic experimental data well, as it showed high R2 value; above 0.9990.

The Anomalous Influence of Polyelectrolyte Concentration on the Deposition and Nanostructure of Poly(ethyleneimine)/Poly(acrylic acid) Multilayers

The deposition and nanostructure of polyelectrolyte (PEL) multilayers (PEMs) of branched poly(ethyleneimine)/poly(acrylic acid) (PEI/PAA) onto silicon substrates was studied in terms of the dependence of pH and the PEL concentration (cPEL) in the individual adsorption steps z. Both a commercial automatic dipping device and a homebuilt automatic stream coating device (flow cell) were used. Gravimetry, SFM, transmission (TRANS) and in situ attenuated total reflection (ATR) FTIR spectroscopy were used for the quantitative determination of the adsorbed amount, thickness, chemical composition and morphology of deposited PEMs, respectively. Firstly, the combination of pH = 10 for PEI and pH = 4 for PAA, where both PEL were predominantly in the neutral state, resulted in an extraordinarily high PEM deposition, while pH combinations, where one PEL component was charged, resulted in a significantly lower PEM deposition. This was attributed to both PEL conformation effects and acid/base interactions between basic PEI and acidic PAA. Secondly, for that pH combination an exponential relationship between PEM thickness and adsorption step z was found. Thirdly, based on the results of three independent methods, the course of the deposited amount of a PEM-10 (z = 10) versus cPEL in the range 0.001 to 0.015 M at pH = 10/4 was non-monotonous showing a pronounced maximum at cPEL = 0.005 M. Analogously, for cPEL = 0.005 M a maximum of roughness and structure size was found. Fourthly, related to that finding, in situ ATR-FTIR measurements gave evidence for the release of outermost located PEI upon PAA immersion (even step) and of outermost PAA upon PEI immersion (odd step) under formation of PEL complexes in solution. These studies help us to prepare PEL-based films with a defined thickness and morphology for interaction with biofluids in the biomedical and food fields.

Removal of Colored Organic Pollutants from Wastewaters by Magnetite/Carbon Nanocomposites: Single and Binary Systems

This work develops a methodology for selective removal of industrial dyes from wastewaters using adsorption technology based on magnetic adsorbents. The magnetic nanoparticles embedded within a matrix of activated carbon were tested as adsorbents for removal of industrial dyes from aqueous solutions. The effects of four independent variables, solution pH, initial concentration of pollutant, adsorbent dose, contact time, and their interactions on the adsorption capacity of the nanocomposite were investigated in order to optimize the process. The removal efficiency of pollutants depends on solution pH and increases with increasing the carbon content, with initial concentration of the pollutants, the temperature, and the dose of magnetite/carbon nanocomposites. Pseudo-second-order kinetic model was fitted to the kinetic data, and adsorption isotherm analysis and thermodynamics were used to elucidate the adsorption mechanism. The maximum adsorption capacities were 223.82 mg g−1 for Nylosan Blue, 114.68 mg g−1 for Chromazurol S, and 286.91 mg g−1 for Basic Red 2. The regeneration and reuse of the sorbent were evaluated in seven adsorption/desorption cycles. The optimum conditions obtained for individual adsorption were selected as starting conditions for simultaneous adsorption of dyes. In binary systems, in normal conditions, selectivity decreases in the order: Red Basic 2 > Nylosan Blue > Chromazurol S.

Simultaneous adsorption of Cd2+ and reactive dye on mesoporous nanocarbons

The presence of the dye facilitated the elimination of the heavy metal. Moreover a synergic effect was observed: simultaneous adsorption enhanced each individual adsorption.

Surface/bulk partitioning and acid/base speciation of aqueous decanoate: direct observations and atmospheric implications

Dilute aqueous solutions of the atmospheric organic surfactant sodium decanoate have been studied using surface sensitive X-ray photoelectron spectroscopy combined with synchrotron radiation. We studied the decanoate/decanoic acid speciation and preferential adsorption at the vapor–liquid interface, and the responses to mixing in solution with some of the most common atmospheric inorganic ions, Na+, NH4+, Cl−, and SO42−. We observe little or no influence of Na+, Cl−, or SO42− ions, on neither the relative speciation nor the individual adsorption properties of decanoate and decanoic acid. In particular, no significant salting-out effect due to common Na+ cations of the organic and inorganic salts was observed for these solutions. On the other hand, mixing with NH4+ cations resulted in a pronounced surface enhancement of decanoic acid, which is attributed to surface specific acid–base chemistry. These changes in surface/bulk partitioning and surface speciation may significantly affect properties of aqueous droplets containing decanoate/decanoic acid, and potential implications for several processes critical to the climate effects of atmospheric aerosols are discussed.

Surface/bulk partitioning and acid/base speciation of aqueous decanoate: direct observations and atmospheric implications

Dilute aqueous solutions of the atmospheric organic surfactant sodium decanoate have been studied using surface sensitive X-ray photoelectron spectroscopy combined with synchrotron radiation. We studied the decanoate/decanoic acid speciation and preferential adsorption at the vapor–liquid interface, and the responses to mixing in solution with some of the most common atmospheric inorganic ions, Na+, NH4+, Cl−, and O42−. We observe no influence of Na+, Cl−, or SO42− ions on neither the relative speciation nor the individual adsorption properties of decanoate and decanoic acid. In particular, the anticipated salting-out effect due to common Na+ cations of the organic and inorganic salts was not observed. On the other hand, mixing with NH4+ cations resulted in a pronounced surface enhancement of decanoic acid, which is attributed to surface specific acid–base chemistry. These changes in surface/bulk partitioning and speciation may significantly affect properties of aqueous droplets containing decanoate/decanoic acid, and potential implications for several processes critical to the climate effects of atmospheric aerosols are discussed.

Differences in adsorption mechanisms of heavy metal by two different plant biomasses: reed and brown seaweed

The adsorption of Pb(II) by two different biomaterials, reed (Phragmites australis) and brown seaweed (Sargassum horneri) biomass pretreated with CaCl2, were compared in an attempt to explain the differences in adsorption performance between the two biosorbents. A very interesting characteristic was found in their individual adsorption performances; the Pb(II) adsorption capacity of brown seaweed (Qmax=0.45 mmol/g) was much higher than that of reed (Qmax=0.05 mmol/g), but its adsorption affinity (b=112 L/mmol) was much lower compared with that of reed (b=471 L/mmol). To elucidate the mechanism, the elemental components, ion exchange phenomenon and roles of functional groups of these two biosorbents were compared. The higher Pb(II) adsorption by brown seaweed could be due to its richness in total functional groups and calcium contents on its surface. In contrast, the functional complexity, higher zeta potential and pKa value (deprotonation state) of reed are believed to lead to its high adsorption affinity.