Iron and aluminium oxides containing industrial wastes as adsorbents of heavy metals: Application possibilities and limitations.

Industrial wastes with a high iron or aluminium oxide content are produced in huge quantities as by-products of water treatment (water treatment residuals), bauxite processing (red mud) and hard and brown coal burning in power plants (fly ash). Although they vary in their composition, the wastes have one thing in common--a high content of amorphous iron and/or aluminium oxides with a large specific surface area, whereby this group of wastes shows very good adsorbability towards heavy metals, arsenates, selenates, etc. But their physical form makes their utilisation quite difficult, since it is not easy to separate the spent sorbent from the solution and high bed hydraulic resistances occur in dynamic regime processes. Nevertheless, because of the potential benefits of utilising the wastes in industrial effluent treatment, this issue attracts much attention today. This study describes in detail the waste generation processes, the chemical structure of the wastes, their physicochemical properties, and the mechanisms of fixing heavy metals and semimetals on the surface of iron and aluminium oxides. Typical compositions of wastes generated in selected industrial plants are given. A detailed survey of the literature on the adsorption applications of the wastes, including methods of their thermal and chemical activation, as well as regeneration of the spent sorbents, is presented. The existing and potential ways of modifying the physical form of the discussed group of wastes, making it possible to overcome the basic limitation on their practical use, are discussed.

Multifunctional Composite Materials Based on Anion Exchangers Modified with Copper Compounds-A Review of Their Synthesis Methods, Characteristics and Applications.

As copper and its compounds are of fundamental importance for the development of innovative materials, the synthesis of composites intended for water purification was undertaken in which submicron copper containing particles were dispersed within the matrix of a strongly basic anion exchanger, with a macroporous and gel-like structure. Due to their trimethylammonium functional groups, the host materials alone exhibited an affinity to anionic water contaminants and antimicrobial properties. The introduction of such particles as CuO, Cu2O, metallic Cu, CuO/FeO(OH), Cu4O3, Cu(OH)2, Cu4(OH)6SO4, Cu2(OH)3Cl increased these properties and demonstrated new properties. The composites were obtained unconventionally, in ambient conditions, using eco-friendly reagents. Alternative synthesis methods were compared and optimized, as a result of which a new group of hybrid ion exchangers was created (HIXs) containing 3.5-12.5 wt% of Cu. As the arrangement of the inorganic phase in the resin matrix was atypical, i.e., close to the surface of the beads, the obtained HIXs exhibited excellent kinetic properties in the process of oxidation and adsorption of As(III), as well as catalytic properties for the synthesis of triazoles via click reaction, and also antimicrobial properties in relation to Gram-positive Enterococcus faecalis and Gram-negative Pseudomonas aeruginosa and Escherichia coli, preventing biofilm formation. Using thermogravimetry, the effect of the inorganic phase on decomposition of the polymeric phase was evaluated for the first time and comprehensively, confirming the relationship and finding numerous regularities. It was also found that, depending on the oxidation state (CuO, Cu2O, Cu), copper-containing particles affected the textural properties of the polymeric phase endowing a tighter structure, limiting the porosity and reducing the affinity for water.

Biocidal activity of multifunctional cuprite-doped anion exchanger - Influence of bacteria type and medium composition.

The study presents unconventional, bifunctional, heterogeneous antimicrobial agents - Cu2O-loaded anion exchangers. The synergetic effect of a cuprous oxide deposit and polymeric support with trimethyl ammonium groups was studied against the reference strains of Enterococcus faecalis ATCC 29212 and Pseudomonas aeruginosa ATCC 27853. Biological testing (minimum bactericidal concentration, MBC), time- and dose-dependent bactericidal effect (under different conditions - medium composition and static/dynamic culture) demonstrated promising antimicrobial activity and confirmed its multimode character. The standard values of MBC, for all studied hybrid polymers and bacteria, were similar (64-128 mg/mL). However, depending on the medium conditions, due to the copper release into the bulk solution, bacteria were actively killed even at much lower doses of the hybrid polymer (25 mg/mL) and low Cu(II) concentrations in solution (0.01 mg/L). Simultaneously, confocal microscopic studies confirmed the effective inhibition of bacterial adhesion and biofilm formation on their surface. The studies conducted under different conditions showed also the influence of the structure and physical properties of studied materials on the biocidal efficacy and an antimicrobial action mechanism was proposed that could be significantly affected by electrostatic interactions and copper release to the solution. Although the antibacterial activity was also dependent on various strategies of bacterial cell resistance to heavy metals present in the aqueous medium, the studied hybrid polymers are versatile and efficient biocidal agents against bacteria of both types, Gram-positive and Gram-negative. Therefore, they can be a convenient alternative for point-of-use water disinfection systems providing water quality in medical devices such as dental units, spa equipment, and aesthetic devices used in the cosmetic sector.

Photocatalytically-assisted oxidative adsorption of As(III) using sustainable multifunctional composite material - Cu2O doped anion exchanger.

The purpose of the presented study was to explore the photocatalytic activity of Cu2O-supported anion exchangers and to explain the mechanism of their action in water purification processes. The functionality of this type of material was studied in the process of As(III) removal from water. As a result of the reactivity of cuprous oxide and functional groups of the polymer, the obtained composite exhibited complex activity towards arsenic(III) species. The adsorption studies were conducted under various conditions: dark, UV-VIS irradiation, VIS irradiation, under aerobic and anoxic conditions. The results from chemical analyses were supported by instrumental analyses - X-ray photoelectron spectroscopy, and FTIR and Raman spectroscopy. These studies showed that the mechanism of As(III) oxidative adsorption is based on the coupling of several reaction pathways: 1) photocatalytic oxidation involving Cu2O as a photocatalyst, and photogenerated holes and ROS as oxidative agents, 2) chemical oxidation on the surface of CuO (being a result of the ageing process) with a re-oxidation of the produced Cu2O to CuO by ROS and oxygen present in water, and 3) photochemical oxidation of As(III) in solution under UV light irradiation and subsequent adsorption of arsenates in the functional groups of the polymer.

Weakly Hydrated Anion Exchangers Doped with Cu2O and Cu0 Particles-Thermogravimetric Studies.

Hybrid ion exchangers (HIXs) containing fine Cu2O and Cu0 particles were subjected to thermal analysis in order to determine their hygroscopic water content (with regard to their anomalously low porosity) and to determine the effect of the oxidation state of the copper atom in the deposit on the thermal properties of composite materials. Commercially available anion exchangers, Amberlite IRA 900Cl (macroreticular, M) and Amberlite IRA 402OH (gel-like, G), were used as supporting materials. M/Cu2O, G/Cu2O, M/Cu and G/Cu, containing 4.3-8.4 wt% Cu, were subjected to thermal analysis under respectively air and N2. TG/DTG curves revealed that dry M/Cu and G/Cu contained as little as 7.2% and 4.3% hygroscopic water, while M/Cu2O and G/Cu2O contained respectively 10.6% and 9.4% (Cu0 was a stronger water repellent than Cu2O). The oxidation state of the copper atom in the deposit was found to affect the amount of the forming char, and also Cu0 was found to contribute to the formation of more char than in the pyrolysis of the pure resin (the anion exchanger with no copper deposit). Under air the two kinds of particles transformed into CuO, while under N2 metallic copper and char (from the resin phase) made up the solid residue. This means that in the pyrolysis of the HIXs the inorganic phase participated in char formation and it also transformed itself (undergoing reduction when possible). The above findings provide a basis for in-depth research aimed at the innovative use of copper-containing HIXs and at obtaining usable composite materials with a designed (organic-inorganic) composition.

Copper Rich Composite Materials Based on Carboxylic Cation Exchangers and Their Thermal Transformation.

The effect of a cupric deposit (Cu2+, CuO) on the thermal decomposition of carboxylic cation exchangers (CCEs) is not known, and such studies may have practical significance. CCEs have a very high ion exchange capacity, so an exceptionally large amount of CuO (which is a catalyst) can be precipitated inside them. Two CCEs, macroreticular (Amberlite IRC50) and gel-like (Amberlite IRC86), served as a polymeric support to obtain copper-rich hybrid ion exchangers. Composites with CuO particles inside a polyacrylic matrix (up to 35.0 wt% Cu) were obtained. Thermal analyses under air and under N2 were performed for CCEs in the H+ and Cu2+ form with and without a CuO deposit. The results of sixteen experiments are discussed based on the TG/DTG curves and XRD patterns of the solid residues. Under air, the cupric deposit shifted the particular transformations and the ultimate polymeric matter decomposition (combustion) toward lower temperatures (even about 100-150 °C). Under N2, the reduction of the cupric deposit to metallic copper took place. Unique composite materials enriched in carbonaceous matter were obtained, as the products of polymeric matrix decomposition (free radicals and hydrogen) created an additional amount of carbon char due to the utilization of a certain amount of hydrogen to reduce Cu (II) to Cu0.

Adsorptive-Oxidative Removal of Sulfides from Water by MnO2-Loaded Carboxylic Cation Exchangers.

Hybrid ion exchangers (HIX) containing manganese(IV) oxide (MnO2) based on macroporous and gel-type carboxylic cation exchangers as supporting materials were obtained. The hybrid materials were characterized using scanning electron microscopy with energy dispersive spectrometry (SEM/EDS), Fourier transform infrared spectroscopy (FTIR), X-ray powder diffraction (XRD) and nitrogen adsorption isotherms at 77 K and mercury porosimetry. HIX with introduced MnO2 (20.0-32.8 wt% Mn) were tested for removal of dissolved sulfides from anoxic aqueous solutions with 100-500 mg S2-/dm3 concentrations. The process proceeded effortlessly at pH 10-13 despite unfavorable electrostatic interactions of the reactants. The highest exhibited sorption capacity was 144.3 ± 7.1 mg S2-/g. Approximately 65% of dissolved sulfides were oxidized to S2O32- ions and repelled from HIX structure. On average, 13% of sulfide removal products were adsorbed by the MnO2 surface. The impact of MnO2 load and the ionic form of HIX functional groups on removal of sulfides and resulting products was examined. The mechanism of the process is suggested.

Size-Controlled Transformation of Cu2O into Zero Valent Copper within the Matrix of Anion Exchangers via Green Chemical Reduction.

Composite materials containing zero valent copper (ZVC) dispersed in the matrix of two commercially available strongly basic anion exchangers with a macroreticular (Amberlite IRA 900Cl) and gel-like (Amberlite IRA 402OH) structure were obtained. Cu0 particles appeared in the resin phase as the product of the reduction of the precursor, i.e., copper oxide(I) particles previously deposited in the two supporting materials. As a result of a one-step transformation of preformed Cu2O particles as templates conducted using green reductant ascorbic acid and under mild conditions, macroporous and gel-type hybrid products containing ZVC were obtained with a total copper content of 7.7 and 5.3 wt%, respectively. X-ray diffraction and FTIR spectroscopy confirmed the successful transformation of the starting oxide particles into a metallic deposit. A scanning electron microscopy study showed that the morphology of the deposit is mainly influenced by the type of matrix exchanger. In turn, the drying steps were crucial to its porosity and mechanical resistance. Because both the shape and size of copper particles and the internal structure of the supporting solid materials can have a decisive impact on the potential applications of the obtained materials, the results presented here reveal a great possibility for the design and synthesis of functional nanocrystalline solids.

Cu(II)-Fe(III) oxide doped anion exchangers - Multifunctional composites for arsenite removal from water via As(III) adsorption and oxidation.

The aim of the present study was to investigate As(III) oxidation and adsorption on the surface of hybrid anion exchangers containing Cu(II)-Fe(III) binary oxide deposited in their porous structure with the same Cu:Fe ratio of 1:2 but with different amounts and distribution of inorganic deposit within polymeric beads. The equilibrium studies confirmed high adsorption capacity of the best hybrid polymer: 94.4 mg As/g. Moreover, the adsorption was effective over a wide pH range, selective in the presence of interfering ions, and the material was effectively regenerated. The performance of the hybrid polymer was also confirmed in the column process which enabled both As(III) and As(V) concentrations to be lowered from 500 µg/L to below 10.0 µg/L in a solution with a composition similar to natural groundwater. The breakthrough point of the bed was reached after the solution amounting to 1833 bed volumes passed through the column. Desorbed As speciation, FTIR and XPS studies showed that As(III) was mainly adsorbed on the surface of Cu-Fe oxides followed by its oxidation to As(V). In the oxidation reaction metal oxides acted as catalysts and adsorbents, while the oxidant was probably oxygen dissolved in solution.

Evaluation of hybrid anion exchanger containing cupric oxide for As(III) removal from water.

The aim of this study was investigate of arsenite adsorption on a hybrid polymer based on a polystyrene/divinylbenzene macroporous anion exchanger containing cupric oxide deposited within its porous structure. The study included batch kinetic and equilibrium experiments, and investigation of influence of the pH, regeneration of spent adsorbent and the column process on arsenic(III) adsorption. The experimental data were evaluated using kinetic, isotherm and fixed-bed column models. The adsorption capacity calculated from the Langmuir model was 6.61 mg As(III) g-1. The adsorption rate was controlled by both chemisorption of arsenic on the adsorbent surface and external diffusion, and at a higher initial As(III) concentration also by intraparticle diffusion. The spent adsorbent was easily regenerated with 1.0 M NaOH solution. Based on batch adsorption studies and X-ray photoelectron spectroscopic analyses a mechanism of As(III) adsorption was proposed. Arsenite removal proceeded in two stages: oxidation to arsenate on the CuO surface, followed by an ion exchange reaction. The studied hybrid polymer also showed very good adsorption characteristics under the dynamic regime. The S-shape of breakthrough curves and insignificant influence of bed height, initial concentration and flow rate on the adsorption capacity confirmed its applicability in water treatment.

Alginate beads containing water treatment residuals for arsenic removal from water-formation and adsorption studies.

Water treatment residuals (WTRs) produced in large quantities during deironing and demanganization of infiltration water, due to high content of iron and manganese oxides, exhibit excellent sorptive properties toward arsenate and arsenite. Nonetheless, since they consist of microparticles, their practical use as an adsorbent is limited by difficulties with separation from treated solutions. The aim of this study was entrapment of chemically pretreated WTR into calcium alginate polymer and examination of sorptive properties of the obtained composite sorbent toward As(III) and As(V). Different products were formed varying in WTR content as well as in density of alginate matrix. In order to determine the key parameters of the adsorption process, both equilibrium and kinetic studies were conducted. The best properties were exhibited by a sorbent containing 5 % residuals, formed in alginate solution with a concentration of 1 %. In slightly acidic conditions (pH 4.5), its maximum sorption capacity was 3.4 and 2.9 mg g-1 for As(III) and As(V), respectively. At neutral pH, the adsorption effectiveness decreased to 3.3 mg As g-1 for arsenites and to 0.7 mg As g-1 for arsenates. The presence of carboxylic groups in polymer chains impeded in neutral conditions the diffusion of anions into sorbent beads; therefore, the main rate-limiting step of the adsorption, mainly in the case of arsenates, was intraparticle diffusion. The optimal condition for simultaneous removal of arsenates and arsenites from water by means of the obtained composite sorbent is slightly acidic pH, ensuring similar adsorption effectiveness for both arsenic species.

Synthesis and characterization of hybrid materials containing iron oxide for removal of sulfides from water.

Hybrid materials containing iron oxides based on macroporous and gel-type sulfonic and carboxylic cation exchangers as supporting materials were obtained. Multiple factors, including the kind of functional groups, ion exchange capacity, and polymer matrix type (chemical constitution and porous structure), affected the amount of iron oxides introduced into their matrix (7.8-35.2% Fe). Products containing the highest iron content were obtained using carboxylic cation exchangers, with their inorganic deposit being mostly a mixture of iron(III) oxides, including maghemite. Obtained hybrid polymers were used for removal of sulfides from anoxic aqueous solutions (50-200mgS(2-)/dm(3)). The research showed that the form (Na(+) or H(+)) of ionic groups of hybrid materials had a crucial impact on the sulfide removal process. Due to high iron oxide content (35% Fe), advantageous chemical constitution and porous structure, the highest removal efficiency (60mgS(2-)/g) was exhibited by a hybrid polymer obtained using a macroporous carboxylic cation exchanger as the host material. The process of sulfide removal was very complex and proceeded with heterogeneous oxidation, iron(III) oxide reductive dissolution and formation of sulfide oxidation and precipitation products such as iron(II) sulfides, thiosulfates and polysulfides.

Oxidation of As(III) in aqueous solutions by means of macroporous redox copolymers with N-chlorosulfonamide pendant groups.

The possibility of oxidizing As(III) to As(V) in aqueous solutions by means of heterogeneous oxidants, i.e. synthetic macromolecular redox compounds, was studied. The materials contain N-chlorosulfonamide functional groups in the sodium form: [P]-SO(2)NClNa (R/ClNa, 2.1 mmol/g) or in the hydrogen form: [P]-SO(2)NClH (R/ClH, 2.4 mmol/g), attached to a cross-linked macroporous poly(styrene-divinylbenzene) matrix. They were obtained through the transformation of Amberlyst 15 (Rohm and Haas) commercial cation exchanger's sulfonic functional groups. The experiments were conducted in the H(2)O and 0.01 M NaOH environment (R/ClNa) and in the H(2)O and 0.01 M H(2)SO(4) environment (R/ClH), using the batch process and the column process and NaAsO(2) solutions (93-375 mg As(III)/dm(3)). The experiments showed that the two copolymers' capacity to oxidize As(III) is high and depends on the process conditions. In the column process experiments, conducted using NaAsO(2) solutions with a concentration of ∼ 93 mg As(III)/dm(3) at a flow rate of 4 BV/h (R/ClH) and 6 BV/h (R/ClNa), a breakthrough (defined as the exceedance of 0.05 mg As(III)/dm(3) in the effluent) would occur after the solutions amounting to about 400 bed volumes had been passed through the column.