Optimization of capacity and kinetics for a novel bio-based arsenic sorbent, TiO2-impregnated chitosan bead

The optimization of TiO₂-impregnated chitosan beads (TICB) as an arsenic adsorbent is investigated to maximize the capacity and kinetics of arsenic removal. It has been previously reported that TICB can 1) remove arsenite, 2) remove arsenate, and 3) oxidize arsenite to arsenate in the presence of UV light and oxygen. Herein, it is reported that adsorption capacity for TICB is controlled by solution pH and TiO₂ loading within the bead and enhanced with exposure to UV light. Solution pH is found to be a critical parameter, whereby arsenate is effectively removed below pH 7.25 and arsenite is effectively removed below pH 9.2. A model to predict TICB capacity, based on TiO₂ loading and solution pH, is presented for arsenite, arsenate, and total arsenic in the presence of UV light. The rate of removal is increased with reductions in bead size and with exposure to UV light. Phosphate is found to be a direct competitor with arsenate for adsorption sites on TICB, but other relevant common background groundwater ions do not compete with arsenate for adsorption sites. TICB can be regenerated with weak NaOH and maintain full adsorption capacity for at least three adsorption/desorption cycles.     

Adsorption of arsenite and arsenate on amorphous iron hydroxide

Adsorption isotherms in solutions with ionic strengths of 0.01 at 25°C were measured over the arsenite and arsenate concentration range 10⁻⁷−10⁻³ M and the pH range 4–10. At low concentrations, these isotherms obeyed equations of the Langmuir type. At higher concentrations the adsorption isotherms were linear, indicating the existence of more than one type of surface site on the amorphous iron hydroxide adsorbent. Removal of arsenite and arsenate by amorphous iron hydroxide throughout the concentration range were determined as a function of pH. By careful selection of the relative concentration of arsenic and amorphous iron hydroxide and pH, removals on the order of 92% can be achieved.     

Removal of arsenite and arsenate ions from aqueous solution by basic yttrium carbonate

A new method has been developed to remove arsenite and arsenate ions from aquatic systems by using basic yttrium carbonate (BYC). Various parameters such as pH, anion concentration and reaction time were studied to establish optimum conditions. The removal by adsorption of arsenite and arsenate ions was found to be > 99% depending on initial concentration in the pH range of 9.8–10.5 and 7.5–9.0, respectively. The arsenate was also removed by precipitation at pH lower than 6.5 due to dissolution of BYC. The kinetic study shows that the adsorption follows the first order reaction. The adsorption isotherms of these anions were also studied at different temperatures. The equilibrium data fit well in the Langmuir model of adsorption. The Langmuir constants were calculated at different temperatures and the adsorption capacity for both anions increases with temperature. Anions such as Cl⁻, Br⁻, I⁻, NO⁻₃ and SO²⁻₄ have no interference in the removal process. The mechanism of the removal by adsorption was interpreted in terms of the surface charge and ligand orientation of BYC. The method was applied on synthetic wastewaters. Arsenite was oxidized to arsenate by 3% hydrogen peroxide. The yttrium was regenerated as basic yttrium carbonate.     

The role of Mn2+-rich hydrous manganese oxide in the accumulation of arsenic in lake sediments

Arsenic is present at high concentrations in the upper layer of Lake Biwa sediments and shows a depth profile similar to that of Mn. Adsorption experiments of As onto synthetic hydrous Mn oxide (HMO) in the presence of Mn²⁺ and the speciation of Mn in the sediment cores, suggest that the accumulation of As at the sediment surface results from post-depositional migration of arsenite in the sediment pore water followed by oxidation to arsenate at the sediment surface and adsorption onto Mn²⁺-rich HMO.     

The role of Mn-rich hydrous manganese oxide in the accumulation of arsenic in lake sediments

Arsenic is present at high concentrations in the upper layer of Lake Biwa sediments and shows a depth profile similar to that of Mn. Adsorption experiments of As onto synthetic hydrous Mn oxide (HMO) in the presence of Mn²⁺ and the speciation of Mn in the sediment cores, suggest that the accumulation of As at the sediment surface results from post-depositional migration of arsenite in the sediment pore water followed by oxidation to arsenate at the sediment surface and adsorption onto Mn²⁺-rich HMO.     

Arsenic removal from aqueous solutions by adsorption on magnetite nanoparticles

Magnetite nanoparticles were used to treat arsenic‐contaminated water. Because of their large surface area, these particles have an affinity for heavy metals by adsorbing them from a liquid phase. The results of the study showed that the maximum arsenic adsorption occurred at pH 2, with a value of approximately 3.70 mg/g for both As(III) and As(V) when the initial concentration of both arsenic species was maintained at 2 mg/L. The study showed that, apart from pH, the removal of arsenic from contaminated water also depends on the contact time, the initial concentration of arsenic, the phosphate concentration in the water and the adsorbent concentration. The results suggest that arsenic adsorption involved the formation of weak arsenic–iron oxide complexes at the magnetite surface. At a fixed adsorbent (magnetite nanoparticles) concentration of 0.4 g/L, percent arsenic removal decreased with increasing phosphate concentration. Magnetite nanoparticles removed <50% of arsenic from water containing >6 mg/L phosphate. In this case, an optimum design for achieving high arsenic removal by magnetite nanoparticles may be required.     

Removal of arsenic from water: Effect of calcium ions on As(III) removal in the KMnO4–Fe(II) process

A novel KMnO₄–Fe(II) process was developed in this study for As(III) removal. The optimum As(III) removal was achieved at a permanganate dosage of 18.6 μM. At the optimum dosage of permanganate, the KMnO₄–Fe(II) process was much more efficient than the KMnO₄–Fe(III) process for As(III) removal by 15–38% at pH 5–9. The great difference in As(III) removal in these two processes was not ascribed to the uptake of arsenic by the MnO₂ formed in situ but to the different properties of conventional Fe(III) and the Fe(III) formed in situ. It was found that the presence of Ca²⁺ had limited effects on As(III) removal under acidic conditions but resulted in a significant increase in As(III) removal under neutral and alkaline conditions in the KMnO₄–Fe(II) process. Moreover, the effects of Ca²⁺ on As(III) removal in the KMnO₄–Fe(II) process were greater at lower permanganate dosage when Fe(II) was not completely oxidized by permanganate. This study revealed that the improvement of As(III) removal at pH 7–9 in the KMnO₄–Fe(II) process by Ca²⁺ was associated with three reasons: (1) the specific adsorption of Ca²⁺ increased the surface charge; (2) the formation of amorphous calcium carbonate and calcite precipitate that could co-precipitate arsenate; (3) the introduction of calcium resulted in more precipitated ferrous hydroxide or ferric hydroxide. On the other hand, the enhancement of arsenic removal by Ca²⁺ under acidic conditions was ascribed to the increase of Fe retained in the precipitate. FTIR tests demonstrated that As(III) was removed as arsenate by forming monodentate complex with Fe(III) formed in situ in the KMnO₄–Fe(II) process when KMnO₄ was applied at 18.6 μM. The strength of the “non-surface complexed” As–O bonds of the precipitated arsenate species was enhanced by the presence of Ca²⁺ and the complexation reactions of arsenate with Fe(III) formed in situ in the presence or absence of Ca²⁺ were proposed.     

Adsorption of arsenite and arsenate within activated alumina grains: equilibrium and kinetics

Equilibrium and kinetic adsorption of tri-valent (arsenite) and penta-valent (arsenate) arsenic to activated alumina is elucidated. The properties of activated alumina, including porosity, specific surface area, and skeleton density were first measured. A batch reactor with temperature control was employed to determine both adsorption capacity and adsorption kinetics for arsenite and arsenate to activated-alumina grains. The Freundlich and Langmuir isotherm equations were then used to describe the partitioning behavior for the system at different pH. A pore diffusion model, coupled with the observed Freundlich or Langmuir isotherm equations, was used to interpret an observed experimental adsorption kinetic curve for arsenite at one specific condition. The model was found to fit with the experimental data fairly well, and pore diffusion coefficients can be extracted. The model, incorporated with the interpreted pore diffusion coefficient, was then employed to predict the experimental data for arsenite and arsenate at various conditions, including different initial arsenic concentrations, grain sizes of activated alumina, and system pHs. The model predictions were found to describe the experimental data fairly well, even though the tested conditions substantially differed from one another. The agreement among the models and experimental data indicated that the adsorption and diffusion of arsenate and arsenite can be simulated by the proposed model.     

Rose biomass as a potential biosorbent to remove chromium,mercury and zinc from contaminated waters

Rose flowers are used for the extraction of essential oil or rose water. The vast majority of the leftover biomass is generally wasted. The aim of the present study was to analyse the rose flower biomass as a potential biosorbent for metals chromium(III), mercury(II) and zinc(II), to remove them from industrial effluents. A number of variables were analysed, including untreated, acid-treated and base-treated biomass, biomass dosage, metal ion concentration, contact time, and pH. Increase in biomass dosage and metal ion concentration increased biosorption. The pH proved to be a very important factor and all the metals showed high adsorption at slightly acidic to moderately basic pH 6–10. They showed very low uptake at low pH. Contact time had little effect on the adsorption capacity of zinc, but was very crucial in the case of mercury. Base treatment favoured adsorption of mercury and zinc. The adsorption of Cr³⁺, Hg²⁺ and Zn²⁺ on rose biomass can be explained by Langmuir and Freundlich isotherms equally well, and the adsorption process followed pseudo second order kinetics. The study suggests that the rose flower biomass can be used in the removal of these metals from contaminated waters employing optimum conditions indicated by the present work.     

A comparative study of As(III) and As(V) in aqueous solutions and adsorbed on iron oxy-hydroxides by Raman spectroscopy

The sorption of the arsenite (AsO₃³⁻) and the arsenate (AsO₄³⁻) ions and their conjugate acids onto iron oxides is one of main processes controlling the distribution of arsenic in the environment. The present work intends to provide a large vibrational spectroscopic database for comparison of As(III) and As(V) speciation in aqueous solutions and at the iron oxide - solution interface. With this purpose, ferrihydrite, feroxyhyte, goethite and hematite were firstly synthesized, characterized in detail and used for adsorption experiments. Raman spectra were recorded from As(III) and As(V) aqueous solutions at various pH conditions selected in order to highlight arsenic speciation. Raman Scattering and Diffuse Reflectance Infrared Fourier Transform (DRIFT) studies were carried out to examine the respective As-bonding mechanisms. The collected data were curve-fitted and discussed according to molecular symmetry concepts. X-ray Absorption Near Edge Spectroscopy (XANES) was applied to confirm the oxidation state of the sorbed species. The comprehensive spectroscopic investigation contributes to a better understanding of arsenic complexation by iron oxides.     

Enhanced arsenic removal using mixed metal oxide impregnated chitosan beads

Mixed metal oxide impregnated chitosan beads (MICB) containing nanocrystalline Al₂O₃ and nanocrystalline TiO₂ were successfully developed. This adsorbent exploits the high capacity of Al₂O₃ for arsenate and the photocatalytic activity of TiO₂ to oxidize arsenite to arsenate, resulting in a removal capacity higher than that of either metal oxide alone. The composition of the beads was optimized for maximum arsenite removal in the presence of UV light. The mechanism of removal was investigated and a mode of action was proposed wherein TiO₂ oxidizes arsenite to arsenate which is then removed from solution by Al₂O₃. Pseudo-second order kinetics were used to validate the proposed mechanism. MICB is a more efficient and effective adsorbent for arsenic than TiO₂-impregnated chitosan beads (TICB), previously reported on, yet maintains a desirable life cycle, free of complex synthesis processes, toxic materials, and energy inputs.     

Magnetic binary oxide particles (MBOP): a promising adsorbent for removal of As (III) in water

Magnetic binary oxide particles (MBOP) synthesized using chitosan template has been investigated for uptake capacity of arsenic (III). Batch experiments were performed to determine the rate of adsorption and equilibrium isotherm and also effect of various rate limiting factors including adsorbent dose, pH, optimum contact time, initial adsorbate concentration and influence of presence cations and anions. It was observed that uptake of arsenic (III) was independent of pH of the solution. Maximum adsorption of arsenic (III) was ∼99% at pH 7.0 with dose of adsorbent 1 g/L and initial As (III) concentration of 1.0 mg/L at optimal contact time of 14 h. The adsorption equilibrium data fitted well to Langmuir and Freundlich isotherm. The maximum adsorption capacity of adsorbent was 16.94 mg/g. With increase in concentration of Ca²⁺, Mg²⁺ from 50 mg/L to 600 mg/L, adsorption of As (III) was significantly reduced while for Fe³⁺ the adsorption of arsenic (III) was increased with increase in concentration. Temperature study was carried out at 293 K, 303 K and 313 K reveals that the adsorption process is exothermic nature. A distinct advantage of this adsorbent is that adsorbent can readily be isolated from sample solutions by application of an external magnetic field. Saturation magnetization is a key factor for successful magnetic separation was observed to be 18.78 emu/g which is sufficient for separation by conventional magnate.     

Effect of interferences on the breakthrough of arsenic: rapid small scale column tests

The influences of three important interferences (silica, phosphate, and vanadate) and the effect of different pH levels and initial arsenate concentrations on the breakthrough of arsenic in adsorptive media columns were examined by using the Rapid Small Scale Column Test with a 3⁵⁻² fractional factorial design. Three commercially available adsorbents used for arsenic removal (E33, GFH and Metsorb) were tested. Results indicated that GFH was more susceptible to water quality changes than Metsorb and E33 under conditions tested. GFH also adsorbed more anions than the other two media. The pH was the factor that had the most impact on the performance of the columns, followed by arsenic concentration and silica concentration. Lowering pH from 8.3 to 7.0 resulted in an increase of the mean bed volume treated until 10 μg/L arsenic breakthrough by 40, 12 and 18 thousands BV treated by GFH, E33 and Metsorb columns, respectively. However, at high silica concentration, lowering pH did not increase the performance of the media. GFH and Metsorb were more sensitive to changes in arsenic concentration at low pH than at high pH. Although vanadium and phosphate were previously reported to reduce arsenic adsorption in batch tests, in column mode with the presence of competitors, their effect was insignificant compared to that of pH, arsenic or silica under the conditions used in this study.     

Removal of As(III) and As(V) by Tin(II) compounds

The retention capacity for arsenic species of new nanomaterials based on tin(II) inorganic oxides or hybrid (inorganic and organic) materials was studied. The synthesis of a polymer-metal complex was performed with poly(acrylic acid) and tin(II) chloride. Poly(AA)-Sn(II) with 10 and 20 wt% of tin and a structure with a mol ratio tin:carboxylate group of 1:1, were characterized. These compounds with 10 and 20 wt% of tin content were used to compare the arsenic removal capability through the liquid-phase polymer-based retention, (LPR), technique. Also, tin oxide was prepared by adding alkaline solution to tin(II) chloride salt. The intermediate tin compound was studied by UV-Vis spectroscopy at different pH values and quantified by potentiometric titration. The solid structure is characterized by Fourier transformed infrared spectroscopy, X-ray diffraction, and specific area BET (N₂). Removal of arsenite and arsenate species from solution by hydrolysated tin was carried out by LPR technique with ultrafiltration membranes and a fixed-bed column unsupported or supported on SiO₂. In all these cases, a washing method at constant pH was applied. The arsenic retention ability depended on the class of tin compounds prepared, with a higher efficiency for arsenic being observed at basic pH for soluble complex poly(AA)-Sn(II) than that for tin hydroxide or hydrolysate of Sn⁺².     

Effects of hardness and alkalinity on the removal of arsenic(V) from humic acid-deficient and humic acid-rich groundwater by zero-valent iron

The effects of hardness (Ca²⁺) and alkalinity (HCO₃⁻) on arsenic(V) removal from humic acid (HA)-deficient and HA-rich groundwater by zero-valent iron (Fe⁰) were investigated using batch experiments. Arsenic, in general, is removed from groundwater possibly by adsorption and co-precipitation with the iron corrosion products. However, in the co-presence of HCO₃⁻ and Ca²⁺, the removal rate of arsenic increased with increasing concentrations of either Ca²⁺ or HCO₃⁻. It was observed that the removal of arsenic was significantly enhanced by the formation of CaCO₃ as a nucleation seed for the growth of large iron (hydr)oxide particles. In the co-existence of Ca²⁺, HCO₃⁻ and HA, the presence of HA diminished the positive role of Ca²⁺ due to the formation of Fe-humate complexes in solution and delaying of the formation of CaCO₃. As a result, the formation of the large iron (hydr)oxide particles was inhibited in the earlier stage which, in turn, affected the removal of arsenic. However, after the formation of CaCO₃ and the subsequent growth of such particles, the presence of large iron (hydr)oxide particles resulted in the rapid removing of arsenic and Fe-humate by adsorption and/or co-precipitation.     

Arsenic removal by iron-modified activated carbon

Iron-impregnated activated carbons have been found to be very effective in arsenic removal. Oxyanionic arsenic species such as arsenate and arsenite adsorb at the iron oxyhydroxide surface by forming complexes with the surface sites. Our goal has been to load as much iron within the carbon pores as possible while also rendering as much of the iron to be available for sorbing arsenic. Surface oxidation of carbon by HNO3/H2SO4 or by HNO3/KMnO4 increased the amount of iron that could be loaded to 7.6-8.0%; arsenic stayed below 10 ppb until 12,000 bed volumes during rapid small-scale tests (RSSCTs) using Rutland, MA groundwater (40-60 ppb arsenic, and pH of 7.6-8.0). Boehm titrations showed that surface oxidation greatly increased the concentration of carboxylic and phenolic surface groups. Iron impregnation by precipitation or iron salt evaporation was also evaluated. Iron content was increased to 9-17% with internal iron-loading, and to 33.6% with both internal and external iron loading. These iron-tailored carbons reached 25,000-34,000 bed volumes to 10 ppb arsenic breakthrough during RSSCTs. With the 33.6% iron loading, some iron peeled off.     

Removal of arsenic(V) from spent ion exchange brine using a new class of starch-bridged magnetite nanoparticles

Ion exchange (IX) is considered by US EPA as one of the best available technologies for removing arsenic from drinking water. However, typical IX processes will generate large volumes of arsenic-laden regenerant brine that requires costly further handling and disposal. This study aimed to develop an engineered strategy to minimize the production and arsenic leachability of the process waste residual. We prepared and tested a new class of starch-bridged magnetite nanoparticles for removal of arsenate from spent IX brine. A low-cost, “green” starch at 0.049% (w/w) was used as a stabilizer to prevent the nanoparticles from agglomerating and as a bridging agent allowing the nanoparticles to flocculate and precipitate while maintaining their high arsenic sorption capacity. When applied to a simulated spent IX brine containing 300 mg/L As and 6% (w/w) NaCl, nearly 100% removal of arsenic was achieved within 1 h using the starch-bridged nanoparticles at an Fe-to-As molar ratio of 7.6, compared to only 20% removal when bare magnetite particles were used. Increasing NaCl in the brine from 0 to 10% (w/w) had little effect on the arsenic sorption capacity. Maximum uptake was observed within a pH range of 4-6. The Langmuir capacity coefficient was determined to be 248 mg/g at pH 5.0. The final treatment sludge was able to pass the TCLP (Toxicity Characteristic Leaching Procedure) based leachability of 5 mg/L as As.     

Adsorptive separation of arsenate and arsenite anions from aqueous medium by using orange waste

Cellulose and orange waste were chemically modified by means of phosphorylation. The chemically modified gels were further loaded with iron(III) in order to create a suitable chelating environment for arsenate and arsenite removal. The loading capacity for iron(III) on the gel prepared from orange waste (POW) was 1.21 mmol g⁻¹ compared with 0.96 mmol g⁻¹ for the gel prepared from cellulose (PC). Removal tests of arsenic with the iron(III)-loaded gel were carried out batchwise and by using a column. Arsenite removal was favored under alkaline condition for both PC and POW gels, however, the POW gel showed some removal capability even at neutral pH. On contrary, arsenate removal took place under acidic conditions at pH=2–3 and 2–6 for the PC and POW gels, respectively. Since iron(III) loading is higher on the POW gel than on the PC gel greater arsenic removal has been achieved by the POW gel compared with the PC gel. It can be concluded that the POW gel can be used for the removal and recovery of both arsenite and arsenate from arsenic contaminated wastewater.     

Arsenic in coastal waters of South Australia

Surface seawater samples from South Australian coastal locations were analysed for dissolved inorganic arsenic [As(III) + As(V)], arsenite [As(III)] and particulate arsenic.Dissolved inorganic arsenic concentrations ranged from 1.10 to 1.61 μg As l^?1 (average 1.3 ± 0.1 μg As l^?1) with 1.2–4.3% (average 2.7%) present as arsenite. Particulate arsenic concentrations were below the limit of detection (0.0006 μg As l^?1) at most sampling stations.     

Photodegradation of roxarsone in poultry litter leachates

Arsenic compounds have been used extensively in agriculture in the US for applications ranging from cotton herbicides to animal feed supplements. Roxarsone (3-nitro-4-hydroxyphenylarsonic acid), in particular, is used widely in poultry production to control coccidial intestinal parasites. It is excreted unchanged in the manure and introduced into the environment when litter is applied to farmland as fertilizer. Although the toxicity of roxarsone is less than that of inorganic arsenic, roxarsone can degrade, biotically and abiotically, to produce more toxic inorganic forms of arsenic, such as arsenite and arsenate. Experiments were conducted on aqueous litter leachates to test the stability of roxarsone under different conditions. Laboratory experiments have shown that arsenite can be cleaved photolytically from the roxarsone moiety at pH 4-8 and that the degradation rate increases with increasing pH. Furthermore, the rate of photodegradation increases with nitrate and natural organic matter concentration, reactants that are commonly found in poultry-litter-water leachates. Additional photochemical reactions rapidly oxidize the cleaved arsenite to arsenate. The formation of arsenate is not entirely undesirable, because it is less mobile in soil systems and less toxic than arsenite. A possible mechanism for the degradation of roxarsone in poultry litter leachates is proposed. The results suggest that poultry litter storage and field application practices could affect the degradation of roxarsone and subsequent mobilization of inorganic arsenic species.