Mesostructured iron oxyhydroxide (FeO x ) and iron oxyhydroxide-phosphate (FeO x P) composites were organized using dodecylsulfate surfactant as a template. X-ray diffraction studies depicted a lamellar structure of the product. Ion exchange and solvent extraction methods were employed for the removal of the surfactant. Carboxylate ions exchanged lamellar type mesostructured material reorganized to a wormhole-like mesoporous material when heated under N₂ atmosphere. Surfactant was completely removed by carboxylate ions as observed by the Fourier transform infrared spectra. High surface area acetate-exchanged FeO x (230 m² g⁻¹) was obtained after the surfactant removal from the composite (2.8 m² g⁻¹). Surface area of acetate-exchanged FeO x P was the highest (240 m²g⁻¹) after the removal of the surfactant. Local structure of iron species of FeO x was investigated by X-ray absorption fine structure spectroscopy. Further, Fe···Fe bond appeared at 3.21-3.25 Å with coordination number 2-3, showing a high degree of un-saturation of Fe···Fe bonds. As compared with bulk iron oxyhydroxide and iron-intercalated montmorillonite, the mesoporous iron materials were highly effective for arsenic removal from low concentrations of aqueous solutions. Furthermore, mesoporous iron materials were stable in aqueous phase.

Background, aim, and scope Dye pollutants are a major class of environmental contaminants. Over 100,000 dyes have been synthesized worldwide and more than 700,000 tons are produced annually and over 5% are discharged into aquatic environments. The adsorption or sorption is one of the most efficient methods to remove dye and heavy metal pollutants from wastewater. However, most of the present sorbents often bear some disadvantages, e.g. low sorption capacity, difficult separation of spoil, complex reproduction, or secondary pollution. Development of novel sorbents that can overcome these limitations is desirable. Materials and methods On the basis of the chemical coprecipitation of calcium oxalate (CaC₂O₄), bromopyrogallol red (BPR) was embedded during the growing of CaC₂O₄ particles. The ternary C₂O₄ ²⁻-BPR-Ca²⁺ sorbent was yielded by the centrifugation. Its composition was determined by spectrophotometry and AAS, and its structure and morphology were characterized by powder X-ray diffraction (XRD), laser particle-size analysis, and scanning electron microscopy (SEM). The adsorption of ethyl violet (EV) and heavy metals, e.g. Cu(II), Cd(II), Ni(II), Zn(II), and Pb(II) were carried out and their removal rate determined by spectrophotometry and ICP-OES. The adsorption performance of the sorbent was compared with powder activated carbon. The Langmuir isothermal model was applied to fit the embedment of BPR and adsorption of EV. Results The saturation number of BPR binding to CaC₂O₄ reached 0.0105 mol/mol and the adsorption constant of the complex was 4.70 x 10⁵ M⁻¹. Over 80% of the sorbent particles are between 0.7 and 1.02 μm, formed by the aggregation of the global CaC₂O₄/BPR inclusion grains of 30-50 nm size. Such a material was found to adsorb cationic dyes selectively and sensitively. Ethyl violet (EV) was used to investigate the adsorption mechanism of the material. One BPR molecule may just bind with one EV molecule. The CaC₂O₄/BPR inclusion material adsorbed EV over two times more efficiently than the activated carbon. The adsorption of EV on the CaC₂O₄/BPR inclusion sorbent was complete in only 5 min and the sedimentation complete in 1 h. However, those of EV onto activated carbon took more than 1.5 and 5 h, respectively. The treatment of methylene blue and malachite green dye wastewaters indicated that only 0.4% of the sorbent adsorbed over 80% of color substances. Besides, the material can also adsorb heavy metals by complexation with BPR. Over 90% of Pb²⁺, and approximately 50% of Cd²⁺ and Cu²⁺, were removed in a high Zn²⁺-electroplating wastewater when 3% of the material was added. Eighty-six percent of Cu²⁺, and 60% of Ni²⁺ and Cd²⁺, were removed in a high Cd²⁺-electroplating wastewater. Discussion The embedment of BPR into CaC₂O₄ particles responded to the Langmuir isothermal adsorption. As the affinity ligand of Ca²⁺, BPR with sulfonic groups may be adsorbed into the temporary electric double layer during the growing of CaC₂O₄ particles. Immediately, C₂O₄ ²⁻ captured the Ca²⁺ to form the CaC₂O₄ outer enclosed sphere. Thus, BPR may be released and embedded as a sandwich between CaC₂O₄ layers. The adsorption of EV on the sorbent obeyed the Langmuir isothermal equation and adsorption is mainly due to the ion-pair attraction between EV and BPR. Different from the inclusion sorbent, the activated carbon depended on the specific surface area to adsorb organic substances. Therefore, the adsorption capacity, equilibrium, and sedimentation time of the sorbent are much better than activated carbon. The interaction of heavy metals with the inclusion sorbent responded to their coordination. Conclusions By characterizing the C₂O₄ ²⁻-BPR-Ca²⁺ inclusion material using various modern instruments, the ternary in situ embedment particle, [(CaC₂O₄)₉₅(BPR)] n ²n⁻, an electronegative, micron-sized adsorbent was synthesized. It is selective, rapid, and highly effective for adsorbing cationic dyes and heavy metals. Moreover, the adsorption is hardly subject to the impact of electrolytes. Recommendations and perspectives The present work provides a simple and valuable method for preparing the highly effective adsorbent. If a concentrated BPR wastewater was reused as the inclusion reactant, the sorbent will be low cost. By selecting the inclusion ligand with a special structure, we may prepare some particular functional materials to recover the valuable substances from seriously polluted wastewaters. The recommended method will play a significant role in development of advanced adsorption materials.

Background, aim, and scope Pesticides and heavy metals pollution in soil environment has become a serious problem in many countries including China. Repeated applications of bordeaux mixture (a blend of copper sulfate and calcium hydroxide) and pyrethroid (Pys) insecticides have led to elevated copper (Cu) and Pys concentrations in vineyard surface soils. However, few studies focused on the interaction of Pys and heavy metals in the soil environment. Our previous studies had indicated the combined effect of cypermethrin (CPM) and Cu on soil catalase activity. Also, we had suggested that the addition of Cu could catalyze photo-degradation of CPM and lambda-cyhalothrin (λ-CHT) in aqueous solution and restrain their degradation in soil. To better understand the potential influence of Cu on the fate of Pys in the soil environment, the aim of the present work was to examine the effect of Cu on the adsorption of λ-CHT and CPM on two typical Chinese soils with different soil characteristics, which was one of the key processes controlling the fate of Pys, and to provide more information about the potential ecological risk of chemicals on the soil ecosystem. Fourier transform infrared and point charges analysis using the MOPAC program of the Gaussian system were also used to reveal the probable adsorption mechanism of λ-CHT and CPM on soils. Materials and methods Two vineyard soils with different properties were chosen as experimental samples. They were sampled from 0 to 10 cm, dried, and sieved to 2 mm. Each soil was spiked with copper sulfate solution to obtain the following total soil Cu concentrations: 100, 200, 400, 800, and 1,600 mg·kg⁻¹. The treated soils were incubated for 2 weeks and then dried at 20°C. For each soil sample and at each soil Cu concentration, the adsorption of λ-CHT and CPM was measured using a batch equilibrium method. The concentration of λ-CHT was determined by HPLC, and the amount of λ-CHT and CPM adsorbed by the soil sample at equilibrium was determined by the difference between the initial and equilibrium concentrations in solution corrected by the blank adsorption measurement. Results Without the addition of Cu, the adsorption of λ-CHT and CPM on Black soil is greater than that on Red soil, while the adsorption of λ-CHT on both soils is significantly stronger than that of CPM. As the soil Cu concentration increased from 19 (or 18; background) to 1,600 mg·kg⁻¹, the adsorption coefficient (K d) of λ-CHT decreased from 12.2 to 5.9 L·kg⁻¹ for Red soil, and from 26.1 to 16.8 L·kg⁻¹ for Black soil, whereas the CPM adsorption coefficient in both soils decreased nearly by 100% (K d decreased from 9.4 to 0.2 L·kg⁻¹ for Red soil and from 16.2 to 0.5 L·kg⁻¹ for Black soil). Discussion Pys adsorption is a surface phenomenon which depends on the surface area and the organic matter content. Thus, the Black soil, having higher organic matter and greater surface area than that of the Red soil, show greater adsorption affinity to λ-CHT and CPM. In our study, the different adsorption affinity of the two Pys was obtained, which was probably attributed to differences with respect to their physical-chemical properties. Further comparison upon the two Pys was conducted. The point charges of halogen atoms in the λ-CHT and CPM were calculated, the differences of which probably lead to the fact that λ-CHT has a stronger binding capacity to soils than CPM. Also, FTIR spectra show that competitive adsorption occurs between CPM and Cu for the same adsorption sites, which is responsible for the obtained suppression of CPM adsorption affected by Cu. Conclusions Lambda-cyhalothrin shows a significantly stronger adsorption than cypermethrin on both soils. This phenomenon may be due to several reasons: (1) λ-CHT has lower solubility and a higher octanol-water partition coefficient value than CPM; (2) λ-CHT consists of specific isomers, whereas CPM is mixtures of eight different isomers; (3) the chlorine and fluorine atoms in the λ-CHT have a negative point charge, whereas the chlorine atoms in the CPM have a positive point charge. As the soil Cu concentrations increased from 19 (or 18) mg·kg⁻¹ to 1,600 mg·kg⁻¹, the adsorption coefficient of λ-CHT and CPM decreased on both soils. This is mainly due to a competition between Cu and Pys for occupying the adsorption sites on soils. The information from this study have important implications for vineyard and orchard soils, which often contain elevated levels of Cu and Pys. These results are also useful in assessing the environmental fate and health effect of λ-CHT and CPM. Recommendations and perspectives It is important for environmental scientists and engineers to get a better understanding of soil-metal-organic contaminant interactions. However, pesticide adsorption involves complex processes, and shortcomings in understanding them still restrict the ability to predict the fate and behavior of pesticide. Therefore, considerable research should be carried out to understand the mechanism of interaction between Pys and heavy metal on soils clearly.