Brilliant red X-3B uptake by a novel polycyclodextrin-modified magnetic cationic hydrogel: Performance, kinetics and mechanism

A novel polycyclodextrin-modified magnetic cationic hydrogel (PCD-MCH) was developed and its performance, kinetics and mechanism for the removal of reactive brilliant red X-3B (X-3B) were studied. The results showed that the zeta-potential of PCD-MCH was 32.8 to 16.7 mV at pH 3.0–10.5. The maximum X-3B adsorption capacity of PCD-MCH was 2792.3 mg/g. The adsorption kinetics could be well-described by the Weber–Morris model and the homogeneous surface diffusion model (HSDM). Diffusion stages corresponding to surface or film diffusion, intra-particle or wide mesopore diffusion, and narrow mesopore/micropore diffusion occurred at 0–120, 120–480 and 480–1200 min, respectively. The latter two diffusion stages were rate-controlling for X-3B adsorption kinetics. At the initial X-3B concentration of 600 mg/L, the diffusion coefficient (D_s) and external mass transfer coefficient in the liquid phase (k_F) were 3 × 10^?11 cm²/min and 4.68 × 10^?6 cm/min, respectively. X-3B approaching the center of PCD-MCH particles could be observed at 360 min. At the end of the third diffusion stage, the C_p at q/q_e = 0 was 45.20 mg/L, which was close to the homogeneous C_p value of 46 mg/L along the radius of PCD-MCH particles. At pH 3.0–10.0, PCD-MCH showed stable X-3B adsorption capacities. After five regeneration-reuse cycles, the residual adsorption capacity of regenerated PCD-MCH was higher than 892.7 mg/g. The corresponding adsorption mechanism was identified as involving electrostatic interactions, cyclodextrin cavities and hydrogen bonds, of which cyclodextrin cavities showed prominent capture performance towards dye molecules through the formation of inclusion complexes.     

Predicting heavy metals'' adsorption edges and adsorption isotherms on MnO2 with the parameters determined from Langmuir kinetics

Although surface complexation models have been widely used to describe the adsorption of heavy metals, few studies have verified the feasibility of modeling the adsorption kinetics, edge, and isotherm data with one pH-independent parameter. A close inspection of the derivation process of Langmuir isothermrevealed that the equilibriumconstant derived from the Langmuir kinetic model, K_S-kinetic, is theoretically equivalent to the adsorption constant in Langmuir isotherm, K_S-Langmuir. The modified Langmuir kinetic model (MLK model) and modified Langmuir isothermmodel (MLImodel) incorporating pH factor were developed. The MLKmodel was employed to simulate the adsorption kinetics of Cu(II), Co(II), Cd(II), Zn(II) and Ni(II) on MnO₂ at pH 3.2 or 3.3 to get the values of K_S-kinetic. The adsorption edges of heavy metals could be modeled with the modified metal partitioning model (MMP model), and the values of K_S-Langmuirwere obtained. The values of K_S-kinetic and K_S-Langmuir are very close to each other, validating that the constants obtained by these two methods are basically the same. The MMP model with K_S-kinetic constants could predict the adsorption edges of heavy metals on MnO₂ very well at different adsorbent/adsorbate concentrations. Moreover, the adsorption isotherms of heavy metals on MnO₂ at various pH levels could be predicted reasonably well by the MLI model with the K_S-kinetic constants.     

TiO2/Ag modified penta-bismuth hepta-oxide nitrate and its adsorption performance for azo dye removal

A modified hydrophilic penta-bismuth hepta-oxide nitrate (Bi₅O₇NO₃) surface was synthesized via a precipitation method using TiO₂ and Ag as modified agents. The synthesized product was characterized by different analytical techniques. The removal efficiency was evaluated using mono-and di-sulphonated azo dyes as model pollutants. Different kinetic, isotherm and diffusion models were chosen to describe the adsorption process. X-ray photoelectron spectroscopy (XPS) results revealed no noticeable differences in the chemical states of modified adsorbent when compared to pure Bi₅O₇NO₃;however, the presence of hydrophilic centres such as TiO₂ and Ag developed positively charged surface groups and improved its adsorption performance to a wide range of azo dyes. Dyes removal was found to be a function of adsorbent dosage, initial dye concentration, solution pH and temperature. The reduction of Langmuir 1,2-mixed order kinetics to the second or first-order kinetics could be successfully used to describe the adsorption of dyes onto the modified adsorbent. Mass transfer can be described by intra-particle diffusion at a certain stage, but it was not the rate limiting step that controlled the adsorption process. Homogenous behavior of adsorbent surface can be explored by applying Langmuir isotherm to fit the adsorption data.     

Influence of the structure and composition of Fe–Mn binary oxides on rGO on As(III) removal from aquifers

Fe–Mn binary oxide (FMBO) possesses high efficiency for As(III) abatement based on the good adsorption affinity of iron oxide and the oxidizing capacity of Mn(IV), and the composition and structure of FMBO play important roles in this process. To compare the removal performance and determine the optimum formula for FMBO, magnetic graphene oxide (MRGO)–FMBO and MRGO–MnO₂ were synthesized with MRGO as a carrier to improve the dispersity of the adsorbents in aquifers and achieve magnetic recycling. Results indicated that MRGO–FMBO had higher As(III) removal than that of MRGO–MnO₂, although the ratios of Fe and Mn were similar, because the binary oxide of Fe and Mn facilitated electron transfer from Mn(IV) to As(III), while the separation of Mn and Fe on MRGO–MnO₂ restricted the process. The optimal stoichiometry x for MRGO–FMBO (Mn_xFe_3-xO₄) was 0.46, and an extraordinary adsorption capacity of 24.38 mg/g for As(III) was achieved. MRGO–FMBO showed stable dispersive properties in aquifers, and exhibited excellent practicability and reusability, with a saturation magnetization of 7.6 emu/g and high conservation of magnetic properties after 5 cycles of regeneration and reuse. In addition, the presence of coexisting ions would not restrict the practical application of MRGO–FMBO in groundwater remediation. The redox reactions of As(III) and Mn(IV) on MRGO–FMBO were also described. The deprotonated aqueous As(III) on the surface of MRGO–FMBO transferred electrons to Mn(IV), and the formed As(V) oxyanions were bound to ferric oxide as inner-sphere complexes by coordinating their “–OH” groups with Mn(IV) oxides at the surface of MRGO–FMBO. This work could provide new insights into high-performance removal of As(III) in aquifers.     

A mechanistic study of ciprofloxacin adsorption by goethite in the presence of silver and titanium dioxide nanoparticles

The adsorption behaviors of ciprofloxacin (CIP), a fluoroquinolone antibiotic, onto goethite (Gt) in the presence of silver and titanium dioxide nanoparticles (AgNPs and TiO₂NPs) were investigated. Results showed that CIP adsorption kinetics in Gt with or without NPs both followed the pseudo-second-order kinetic model. The presence of AgNPs or TiO₂NPs inhibited the adsorption of CIP by Gt. The amount of inhibition of CIP sorption due to AgNPs was decreased with an increase of solution pH from 5.0 to 9.0. In contrast, in the presence of TiO₂NPs, CIP adsorption by Gt was almost unchanged at pHs of 5.0∼6.5 but was decreased with an increase of pH from 6.5 to 9.0. The mechanisms of AgNPs and TiO₂NPs in inhibiting CIP adsorption by Gt were different, which was attributed to citrate coating of AgNPs resulting in competition with CIP for adsorption sites on Gt, while TiO₂NPs could compete with Gt for CIP adsorption. Additionally, CIP was adsorbed by Gt or TiO₂NPs through a tridentate complex involving the bidentate inner-sphere coordination of the deprotonated carboxylic group and hydrogen bonding through the adjacent carbonyl group on the quinoline ring. These findings advance our understanding of the environmental behavior and fate of fluoroquinolone antibiotics in the presence of NPs.     

Flower-, wire-, and sheet-like MnO2-deposited diatomites: Highly efficient absorbents for the removal of Cr(VI)

Flower-, wire-, and sheet-like MnO₂-deposited diatomites have been prepared using a hydrothermal method with Mn(Ac)₂, KMnO₄ and/or MnSO₄ as Mn source and diatomite as support. Physical properties of the materials were characterized by means of numerous analytical techniques, and their behaviors in the adsorption of chromium(VI) were evaluated. It is shown that the MnO₂-deposited diatomite samples with different morphologies possessed high surface areas and abundant surface hydroxyl groups (especially the wire-like MnO₂/diatomite sample). Thewire-like MnO₂/diatomite sample showed the best performance in the removal of Cr(VI), giving the maximum Cr(VI) adsorption capacity of 101 mg/g.     

On the effect of Fe(III) on proliferation of Microcystis aeruginosa at high nitrate and low chlorophyll condition

The impact of Fe concentrations on the growth of Microcystisaeruginosa in aquatic systems under high nitrate and low chlorophyll conditions was studied. The responses of cell density, total and cell chlorophyll-a intracellular Fe content and organic elemental composition of M. aeruginosa to different concentration gradients of Fe(III) in the solutions were analysed. The results showed that the proliferation speeds of M. aeruginosa were: (1) decelerated when the Fe(III) concentration was lower than 50 μg/L in the solutions, (2) promoted and positively related to the increase of Fe(III) concentration from 100 to 500 μg/L in the solutions over the experimental period, and (3) promoted in the early stage but decelerated in later stages by excess adsorption of Fe by cells when the Fe(III) concentration was higher than 500 μg/L in the solutions. The maximum cell density, total and cell chlorophyll-a were all observed at 500 μg Fe(III)/L concentration. The organic elemental composition of M. aeruginosa was also affected by the concentration of Fe(III) in the solutions, and the molecular formula of M. aeruginosa should be expressed as C_7–7.5H₁₄O_0.8–1.3N_3.5–5 according to the functions for different Fe(III) concentrations. Cell carbon and oxygen content appeared to increase slightly, while cell nitrogen content appeared to decrease as Fe(III) concentrations increased from 100 to 500 μg/L in the solutions. This was attributed to the competition of photosynthesis and nitrogen adsorption under varying cell Fe content.     

Enhanced adsorption of arsenate by spinel zinc ferrite nano particles: Effect of zinc content and site occupation

In this work, zinc ferrite spinel with different zinc contents (Zn_xFe_3-xO₄) was synthesized by a hydrothermal method and used for removing As(V) in aqueous solution. X-ray diffraction (XRD) results indicated that in the crystal structure of Zn_xFe_3-xO₄, the zinc atoms tended to occupy the octahedral sites for x?<?0.6 and diffused into the tetrahedral sites gradually with x?>?0.6. The size of Zn_xFe_3-xO₄ crystallites increased with the increasing zinc content. Batch adsorption experiments showed that the adsorption isotherms could be well described by the Langmuir model, while the adsorption kinetics followed the pseudo-second-order kinetic model. Zinc ferrite exhibited the highest adsorption capacity towards As(V) when x?=?0.6. Study of the mechanism indicated that doping with zinc increased the number of surface hydroxyl groups on ferrite spinel, and thus enhanced the adsorption capacity when x?=?0.6. This work revealed the effects of doping site and content of metal atoms on the adsorption ability of ferrite spinel towards As(V).     

Adsorption kinetics of the herbicide safeners, benoxacor and furilazole, to activated carbon and agricultural soils

Chloroacetamide herbicides, namely acetochlor and metolachlor, are common herbicides used on corn and soybean fields. Dichloroacetamide safeners, namely benoxacor and furilazole, are commonly used in formulations containing chloroacetamide herbicides. Extensive reports on adsorption of chloroacetamide herbicides are available, yet little information exists regarding adsorption potential of co-applied safeners. Herein, the adsorption and desorption characteristics of selected herbicide safeners to granular activated carbon (GAC) and in agricultural soils are reported. Further, soil column studies were performed to understand the leaching behaviour of the herbicide Dual II Magnum. Equilibrium sorption experiments of safeners to three agricultural soils and one GAC showed that adsorption was best fitted by the Freundlich isotherm. The Freundlich adsorption constant, K_f, for benoxacor and furilazole sorption onto three agricultural soils ranged from 0.1 to 0.27 and 0.1 to 0.13 (mg/g) × (mg/L)?(1/n), respectively. The K_f for benoxacor and furilazole to GAC was 6.4 and 3.4 (mg/g) × (mg/L)?(1/n), respectively, suggesting more favorable sorption of benoxacor to GAC than furilazole to GAC. The sorption to soils was reversible as almost 40%–90% of both safeners was desorbed from three soils. These results were validated in four replicated soil column studies, where S-metolachlor was shown to leach similarly to the safener benoxacor, originating from the herbicide formulation. The leaching of S-metolachlor and benoxacor was influenced by soil texture. Cumulatively, these results show that safeners will move through the environment to surface waters similarly to the active ingredients in herbicides, but may be removed during drinking water treatment via GAC.     

氧化铝表面处理对吸附腐殖酸的影响

采用酸、碱和金属盐表面修饰处理,影响氧化铝表面结构和成份分布,以达到提高吸附性能的目的。研究表明,经酸处理和酸性条件下的钙镁修饰处理的氧化铝,其对腐殖酸的吸附能力比Al-500分别提高32.3％和23.8％。同时,就改性氧化铝去除腐殖酸的影响条件、动力学、热力学性能进行了讨论。     

Adsorption of VOCs on reduced graphene oxide

A modified Hummer's method was adopted for the synthesis of graphene oxide(GO) and reduced graphene oxide(rGO). It was revealed that the modified method is effective for the production of GO and rGO from graphite. Transmission electron microscopy(TEM) images of GO and rGO showed a sheet-like morphology. Because of the presence of oxygenated functional groups on the carbon surface, the interlayer spacing of the prepared GO was higher than that of rGO. The presence of \OH and C_O groups in the Fourier transform infrared spectra(FTIR) spectrum and G-mode and 2D-mode in Raman spectra confirmed the synthesis of GO and rGO. rGO(292.6 m~2/g) showed higher surface area than that of GO(236.4 m~2/g). The prepared rGO was used as an adsorbent for benzene and toluene(model pollutants of volatile organic compounds(VOCs)) under dynamic adsorption/desorption conditions. rGO showed higher adsorption capacity and breakthrough times than GO. The adsorption capacity of rGO for benzene and toluene was 276.4 and 304.4 mg/g, respectively.Desorption experiments showed that the spent rGO can be successfully regenerated by heating at 150.0°C. Its excellent adsorption/desorption performance for benzene and toluene makes rGO a potential adsorbent for VOC adsorption.     

活性氧化铁/石英砂吸附剂去除水体中的重金属

介绍了活性氧化铁／石英砂吸附剂的特点和制备方法。该吸附能有效去除水体中的重金属，包括阳离子、阴离子、重金属颗粒物及一些络离子，且容易再生，被吸附的金属可以回收。     

Carbon dioxide adsorption and cycloaddition reaction of epoxides using chitosan–graphene oxide nanocomposite as a catalyst

One of today's major challenges is to provide green materials for a cleaner environment. We have conducted studies on carbon dioxide(CO2) adsorption and conversion to valuable products by an ecofriendly approach based in chitosan/graphene oxide(CSGO) nanocomposite film. Rheological behavior indicates that the CSGO has a better solvation property than the pure chitosan. An adsorption capacity of 1.0152 mmol CO_2/g of CSGO nanocomposite at4.6 bar was observed. The catalytic behavior of the CSGO nanocomposite in the presence of tetra-n-butylammonium iodide(n-Bu4 NI) as co-catalyst was evaluated for the cycloaddition of CO_2 to epoxides, to give cyclic carbonates, in the absence of any solvent. These results strongly suggest that the CSGO nanocomposite may open new vistas towards the development of ecofriendly material for catalytic conversion and adsorption of CO_2 on industrial scale.     

Removal of Cs from water and soil by ammonium-pillared montmorillonite/Fe3O4 composite

To remove cesium ions from water and soil, a novel adsorbent was synthesized by following a one-step co-precipitation method and using non-toxic raw materials. By combining ammonium-pillared montmorillonite (MMT) and magnetic nanoparticles (Fe₃O₄), an MMT/Fe₃O₄ composite was prepared and characterized. The adsorbent exhibited high selectivity of Cs⁺ and could be rapidly separated from the mixed solution under an external magnetic field. Above all, the adsorbent had high removal efficiency in cesium-contaminated samples (water and soil) and also showed good recycling performance, indicating that the MMT/Fe₃O₄ composite could be widely applied to the remediation of cesium-contaminated environments. It was observed that the pH, solid/liquid ratio and initial concentration affected adsorption capacity. In the presence of coexisting ions, the adsorption capacity decreased in the order of Ca^2 + > Mg^2 + > K⁺ > Na⁺, which is consistent with our theoretical prediction. The adsorption behavior of this new adsorbent could be expressed by the pseudo-second-order model and Freundlich isotherm. In addition, the adsorption mechanism of Cs⁺ was NH₄⁺ ion exchange and surface hydroxyl group coordination, with the former being more predominant.     

Fast and efficient aqueous arsenic removal by functionalized MIL-100(Fe)/rGO/δ-MnO2 ternary composites: Adsorption performance and mechanism

Because of its significant toxicological effects on the environment and human health,arsenic(As) is a major global issue.In this study,an Fe-based metal-organic framework(MOF)(Materials of Institut Lavoisier:MIL-100(Fe)) which was impregnated with reduced graphene oxide(rGO) by using a simple hydrothermal method and coated with birnessitetype manganese oxide(δ-MnO_2) using the one-pot reaction process(MIL-100(Fe)/rGO/δ-MnO_2 nanocomposites) was synthesized and applied successfully in As removal.The removal efficiency was rapid,the equilibrium was achieved in 40 min and 120 min for As(Ⅲ) and As(Ⅴ),respectively,at a level of 5 mg/L.The maximum adsorption capacities of As(Ⅲ) and As(Ⅴ) at pH 2 were 192.67 mg/g and 162.07 mg/g,respectively.The adsorbent revealed high stability in pH range 2-9 and saturated adsorbent can be fully regenerated at least five runs.The adsorption process can be described by the pseudo-second-order kinetic model and Langmuir monolayer adsorption.The adsorption mechanisms consisted of electrostatic interaction,oxidation and inner sphere surface complexation.     

Modified activated carbon with interconnected fibrils of iron-oxyhydroxides using Mn2 + as morphology regulator, for a superior arsenic removal from water

The arsenic removal efficiency of iron-modified activated carbons depends greatly on the number of available iron oxide surface sites, which are given by the surface area of the anchored particles. In this sense, aiming the generation of an adsorbent with superior arsenic adsorption capacity, we developed a protocol to anchor interconnected fibrils of iron oxyhydroxides, using Mn^2 + as a morphology regulator. The protocol was based on a microwave-assisted hydrothermal method, using bituminous based activated carbon and both Fe^2 + and Mn^2 + ions in the hydrolysis solution. The elemental analysis of modified carbons revealed that Mn does not anchor to the carbon. However, when Mn is included in the hydrolysis solution, the iron content in the activated carbon increased up to 3.5?wt%, without considerable decreasing the adsorbent surface area. Under specific hydrothermal conditions, the Mn^2 + promoted the formation of iron oxide nanoparticles shaped as interconnected fibrils. This material showed a superior arsenic adsorption capacity in comparison to similar iron modified activated carbons (5?mg As/g carbon, at 2?mg As/L), attributed to the increase in quantity and availability of active sites located on the novel interconnected fibrils of iron oxyhydroxides nanostructures.     

Review on heterogeneous oxidation and adsorption for arsenic removal from drinking water

The long term exposure of arsenic via drinking water has resulted in wide occurrence of arsenisim globally, and the oxidation of the non-ionic arsenite (As(III)) to negatively-charged arsenate (As(V)) is of crucial importance for the promising removal of arsenic. The chemical oxidants of ozone, chlorine, chlorine dioxide, and potassium permanganate may achieve this goal; however, their application in developing countries is sometimes restricted by the complicate operation and high cost. This review paper focuses on the heterogeneous oxidation of As(III) by solid oxidants such as manganese oxide, and the adsorption of As(V) accordingly. Manganese oxide may be prepared by both chemical and biological methods to achieve good oxidation performance towards As(III). Additionally, manganese oxide may be combined with other metal oxides, e.g., iron oxide, to improve the adsorption capability towards As(V). Furthermore, manganese oxide may be coated onto porous materials of metal organic frameworks to develop novel adsorbents for arsenic removal. To achieve the application in engineering works, the adsorbents granulation may be achieved by drying and calcination, agglomeration, and the active components may also be in situ coated onto the porous materials to maintain the oxidation and adsorption activities as much as possible. The novel adsorbents with heterogeneous oxidation and adsorption capability may be carefully designed for the removal of arsenic in household purifiers, community-level decentralized small systems, and the large-scale drinking water treatment plants (DWTPs). This review provides insight into the fundamental studies on novel adsorbents, the development of innovative technologies, and the demonstration engineering works involved in the heterogeneous oxidation and adsorption, and may be practically valuable for the arsenic pollution control globally.     

Effect of precipitation pH and coexisting magnesium ion on phosphate adsorption onto hydrous zirconium oxide

To understand the effect of precipitation pH and coexisting Mg~(2+) on phosphate adsorption onto zirconium oxide(ZrO_2), ZrO_2 particles precipitated at pH 5.3, 7.1 and 10.5, i.e., ZrO_2(5.3), ZrO_2(7.1)and ZrO_2(10.5), respectively were prepared and characterized, then their adsorption performance and mechanism in the absence and presence of Mg~(2+) were comparatively investigated in this study. The results showed that the Elovich, pseudo-second-order and Langmuir isotherm models correlated with the experimental data well. The adsorption mechanism involved the complexation between phosphate and zirconium. Coexisting Mg~(2+) slightly inhibited the adsorption of phosphate on ZrO_2(5.3), including the adsorption capacity and rate, but coexisting Mg~(2+) greatly increased the adsorption capacity and rate for ZrO_2(7.1)and ZrO_2(10.5). The enhanced adsorption of phosphate on ZrO_2(7.1) and ZrO_2(10.5) in the presence of Mg~(2+) was mainly due to the formation of Mg~(2+)-HPO_4~(2-) ion pair(MgHPO_4~0) in the solution and then the adsorption of MgHPO_4~0 on the adsorbent surface, forming the phosphatebridged ternary complex Zr(OPO_3H)Mg. In the absence of Mg~(2+) , the maximum phosphate adsorption capacity at pH 7 calculated from the Langmuir isotherm model decreased in the order of ZrO 2(7.1)(67.3 mg/g) ZrO_2(5.3)(53.6 mg/g) ≈ ZrO_2(10.5)(53.1 mg/g), but it followed the order of Zr O2(7.1)(97.0 mg/g) ZrO_2(10.5)(79.7 mg/g) ZrO_2(5.3)(51.3 mg/g) in the presence of Mg~(2+) . The results of this work suggest that ZrO_2(7.1) is more suitable for use as an adsorbent for the effective removal of phosphate from municipal wastewater than ZrO_2(5.3) and ZrO_2(10.5),because Mg~(2+) is generally present in this wastewater.