Synergistic adsorption of Cd(II) with sulfate/phosphate on ferrihydrite: An in situ ATR-FTIR/2D-COS study

Elucidation of the co-adsorption characteristics of heavy metal cations and oxyanions on (oxyhydr)oxides can help to better understand their distribution and transformation in many geological settings. In this work, batch adsorption experiments in combination with in situ attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) were applied to explore the interaction mechanisms of Cd(II) with sulfate or phosphate at the ferrihydrite (Fh)–water interface, and the two-dimensional correlation spectroscopic analysis (2D–COS) was used to enhance the resolution of ATR-FTIR bands and the accuracy of analysis. The batch adsorption experiments showed enhanced adsorption of both sulfate (S) and phosphate (P) on Fh when co-adsorbed with Cd(II); additionally, the desorbed percentages of Cd(II) were much lower in the P + Cd adsorption systems than those in the S + Cd adsorption systems. The spectroscopic results suggested that in the single adsorption systems, sulfate primarily adsorbed as outer-sphere complexes with a small amount of bidentate inner-sphere complexes, while the dominant adsorbed species of phosphate were largely the bidentate nonprotonated inner-sphere complexes, although there was significant pH-dependence. In the co-adsorption systems, the synergistic adsorption of Cd(II) and sulfate was dominantly attributed to the electrostatic interaction, as well as the formation of Fe–Cd–S (i.e., Cd-bridged) ternary complexes. In contrast, Fe–P–Cd (i.e., phosphate-bridged) ternary complexes were found in all of the co-adsorption systems of phosphate and Cd(II); furthermore, electrostatic interaction should also contribute to the co-adsorption process. Our results show that in situ ATR-FTIR in combination with 2D–COS can be an efficient tool in analyzing the co-adsorption mechanisms of anions and heavy metal cations on iron (oxyhydr)oxides in ternary adsorption systems. The co-existence of Cd(II) with sulfate or phosphate can be beneficial for their accumulations on Fh, and phosphate is more efficient than sulfate for the long-term immobilization of Cd(II)

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)

Synthesis of organoclays: A critical review and some unresolved issues

The synthesis of organoclays (OC) by intercalation of quaternary ammonium cation (QAC) into expanding clay minerals, notably montmorillonite (Mt), has attracted a great deal of attention during the past two decades. The OC have also found applications in the manufacture of clay polymer nanocomposites (CPN) and environmental remediation. Despite the wealth of information that exists on the formation and properties of OC, some problems remain to be resolved. The present contribution is an attempt at clarifying two outstanding issues, based on the literature and experimental data obtained by the authors over the past years. The first issue concerns the relationship between the cation exchange capacity (CEC) of the Mt and the basal spacing of the OC which, in turn, is dependent on the concentration and the nature of the added QAC. At a concentration less than 1 CEC, organo-Mt (OMt) formed using the QAC with a short alkyl chain length with nc < 16 (e.g., dodecyl trimethylammonium) gives basal spacings of 1.4–1.6 nm that are essentially independent of the CEC. However, for long-chain QAC with nc ≥ 16 (e.g., hexadecyl trimethylammonium), the basal spacing varies with the QAC concentration. For Mt with a CEC of 80–90 meq/100 g, the basal spacing of the OC increases gradually with the CEC and shows a sudden (stepwise) increase to 3.2–3.8 nm at a QAC concentration of 1.5 CEC and to 3.5–4.0 nm at a concentration of 2.0 CEC. The second issue pertains to the “locking” effect in QAC- and silane-modified pillared interlayered clays (PILC) and Mt. For silylated Mt, the “locking” effect results from the covalent bonding of silane to two adjacent layers within a single clay mineral particle. The same mechanism can operate in silane-grafted PILC but in this case, the “locking” effect may primarily be ascribed to the pillaring of adjacent basal surfaces by metal hydr(oxides)

Adsorption of REEs on kaolinite and halloysite: A link to the REE distribution on clays in the weathering crust of granite

The clay minerals, kaolinite and halloysite are dominant hosts for rare earth elements (REEs) in the weathered crust elution-deposited REE deposits. However, the accumulation of REEs on kaolinite and halloysite has not been systematically compared. In this study, the adsorption of complete REE series on kaolinite and halloysite was investigated under different pH levels and ionic strengths, which was linked to the enrichment and fractionation of REEs within the clay fraction of a typical weathered crust elution-deposited REE deposit. At low ionic strength, the adsorption of REEs on kaolinite and halloysite increased with increase in pH, with some noticeable fluctuation observed on halloysite at high pH. All the REEs were adsorbed to a similar extent without apparent fractionation, except for the slight enrichment of heavy REEs (HREEs) at high pH. At high ionic strength, REE adsorption exhibited a linear increase with the increase in pH, particularly at high pH, with HREEs being preferentially adsorbed. Compared to halloysite, kaolinite possessed a higher specific surface area (SSA) normalized adsorption capacity towards REEs. These observed adsorption characteristics could possibly explain the distribution of REEs in the clay fraction along the REE deposit. The decrease of ion-exchangeable REE content with depth was significant for kaolinite, while the REE fractionation was ascribed to the selective adsorption of HREEs on both kaolinite and halloysite. The enrichment and fractionation mechanism of REEs on kaolinite and halloysite were also discussed in terms of the surface chemistry and morphology of the clay minerals and the variations of chemical properties across the REE group

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)

Efficiency of Fe-montmorillonite on the removal of Rhodamine B and hexavalent chromium from aqueous solution

Fe-montmorillonite (Fe-Mt) was prepared and tested for its potential application in the simultaneous removal of hexavalent chromium (Cr(VI)) and rhodamine B (RhB) from aqueous solution. The adsorption kinetics and capacities of Fe-Mt toward Cr(VI) and RhB were determined in relation to the initial contaminant concentration, pH of the solution and concentration of coexist contaminant. The adsorption kinetics of Cr(VI) or/and RhB in both single and simultaneous systems were investigated, which showed that an equilibrium time of a few hours was needed for the adsorption of Cr(VI) and RhB on Fe-Mt. The pseudo-second order model offers a better fit than pseudo-first order model for the Cr(VI) and RhB adsorption. Compared with the single adsorption systems, adsorption rates and quantities of Cr(VI) and RhB adsorbed on Fe-Mt were slightly enhanced in the simultaneous adsorption system. The most effective pH range for the removal of Cr(VI) and RhB was found to be 3.0–4.0. Cr(VI) adsorption isotherms were best represented by the two-site Langmuir model while RhB isotherms followed the Freundlich model. For both contaminants, the adsorption of one contaminant increases with increase in the initial concentration of the other one. Therefore, Fe-Mt could simultaneously remove Cr(VI) and RhB from water. The properties of Fe-Mt were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), and thermogravimetric analysis (TG). The findings of this study provide novel information for the development of clay-based adsorbents toward dyes and heavy metals

Bisphenol A degradation by a new acidic nano zero-valent iron diatomite composite

A new nano zero-valent iron (nZVI) material that generates acidic conditions in situ was prepared by grafting acid precursor onto diatomite. This new material was used in the evaluation of Bisphenol A (BPA) degradation by a Fenton-like process. The prepared material (M-nZVI-Da) exhibited a high removal efficiency (100%) of BPA under the natural pH conditions of the solution (pH ~ 5.75). The degradation of BPA using this new catalyst material follows a reaction pathway modelled on Fermi’s equation with predictable kinetic outcomes for increased temperature of reaction. Experiments demonstrate that the optimum starting concentration ratio of H₂O₂/sample is 200 mM/g^-1 for efficient catalyst use. This study shows that nZVI materials with acid precursor are efficient catalysts for removal of BPA in solution