Coprecipitation of arsenate with iron(III) in aqueous sulfate media: effect of time, lime as base and co-ions on arsenic retention

The removal and immobilization of arsenic from industrial mineral-processing effluents typically involves lime neutralization and coprecipitation of arsenate with ferric iron. Despite the wide practice and environmental importance of this technique, no laboratory study has focused on the roles of lime as base and third ions like Ca2+, Ni2+ and SO(2)4(-) on the kinetics of arsenic retention by the coprecipitates. In this work, coprecipitation was performed at 22 degrees C by fast (10 min) neutralization of industrially relevant concentrated arsenate-iron(III) (Fe/As=2, 4) acidic sulfate solutions to different pHs (4, 6, 8) in batch reactors, and the concentration of arsenic was monitored up to 1 year. The tests showed that maximum removal of arsenic was achieved upon neutralization to the target pH. Arsenic was found to be released back into solution from the precipitates upon continuing mild agitation at constant pH. Near-equilibrium was attained at different times depending on the applied pH: 10 days at pH 4, 6 months at pH 6 and 9 months at pH 8. An aging treatment at pH 4 significantly enhanced arsenic retention (arsenic release was reduced by at least 50%) after the system was finally stabilized at pH 8. The retention of arsenic at pH 8 was multifold improved (by a factor x 25) when lime was used instead of NaOH. Similarly, the retention of arsenic was enhanced by the presence of calcium and nickel ions in the starting solution. Finally, evidence of Ca(II)-Fe(III)-As(V) association was found, but not sulfate incorporation at pH 8.     

Arsenic (V) removal from aqueous system using adsorbent developed from a high iron-containing fly ash

A novel adsorbent for arsenic (V) removal from wastewater was developed through simple chemical processes using a special iron-abundant fly ash. In the synthesis process, the inherent iron in the fly ash was rearranged and loaded on the surface of the fly ash by dissolution and precipitation processes. The adsorbent (HIOFAA) was characterized by XRD, FT-IR, SEM, LPS and BET surface area. The results showed that porous amorphous FeOOH was loaded on the surface of HIOFAA successfully. The BET surface area of HIOFAA was 22 times of those of the original fly ash, and furthermore, the mean particle size of HIOFAA increased 3 times compared to the raw fly ash, thus effectively accelerated the solid/liquid separation after the adsorptive treatment. The adsorption isotherm data could be well described by Langmuir isotherm model, and the adsorption capacity for arsenic removal was 19.46 mg g^− 1. Accordingly, it is believed that the adsorbent developed in this study is effective for arsenic polluted wastewater treatment.     

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.     

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.     

Removal of arsenic(III) from aqueous solutions using fresh and immobilized plant biomass

The ability of Garcinia cambogia, an indigenous plant found in many parts of India, to remove trivalent arsenic from solution was assessed. Batch experiments were carried out to characterize the As(III) removal capability of fresh and immobilized biomass of G. cambogia. It was found that the kinetic property and uptake capacity of fresh biomass were significantly enhanced by the immobilization procedure. The uptake of As(III) by fresh and immobilized biomass was not greatly affected by solution pH with optimal biosorption occurring at around pH 6--8. The presence of common ions such as Ca and Mg at concentrations up to 100mg/l had no effect on As(III) removal. However, the presence of Fe(III) at 100mg/l caused a noticeable drop in the extent of As(III) removal but the effect was minimal when Fe(III) was present at 10mg/l. The adsorption isotherms quantitatively predicted the extent of As(III) removal in groundwater samples collected from an arsenic-contaminated site in India. Immobilized biomass loaded with As(III) was amenable to efficient regeneration with NaOH solution. Column studies showed that immobilized biomass could be reused over five cycles of loading and elution. The excellent As(III) sequestering capability of fresh and immobilized G. cambogia biomass could lead to the development of a viable and cost-effective technology for arsenic removal in groundwater.     

Rapid column-mode removal of arsenate from water by crosslinked poly(allylamine) resin

Performances of crosslinked poly(allylamine) resin (PAA) as arsenate (As(V)) adsorbent were studied using a column packed with PAA in hydrochloride form. PAA has a high amino group content of 14.6 mmol/g in free amine form and a high chloride content of 10.2 mmol/g in hydrochloride form. Its wet volumes in water were 4.5 and 3.1 mL/g in hydrochloride and free amine forms, respectively, indicating its high hydrophilicity. Breakthrough capacities for As(V) were evaluated changing conditions of adsorption operations: pH of feeds from 2.2 to 7.0, concentration of As(V) in feeds from 0.020 to 2.0 mM, and feed flow rate from 250 to 4000 h⁻¹ in space velocity. Breakthrough capacities increased from 2.6 to 3.4 mmol/g with a decrease in pH from 7.0 and 2.2, and also from 0.81 to 2.8 mmol/g with an increase in As(V) concentration from 0.020 to 2.0 mM. When feed flow rate increased from 250 to 4000 h⁻¹, breakthrough capacities changed form 3.5 to 0.81 mmol/g. Because of non-Hofmeister anion selectivity behavior of PAA, the interference of chloride and nitrate was minor. Although PAA slightly preferred As(V) to sulfate, the latter more markedly interfered with uptake of As(V) than chloride and nitrate. Competitive uptake of As(V) and phosphate revealed that PAA slightly preferred phosphate to As(V). The adsorbed As(V) was quantitatively eluted with 2 M HCl and PAA was simultaneously regenerated into hydrochloride form. All results were obtained using the same column without change of the packed PAA and any deterioration in column performances for 4 months.     

Fe(III) homogeneous photocatalysis for the removal of 1,2-dichlorobenzene in aqueous solution by means UV lamp and solar light

Chlorinated hydrocarbons are widely used in chemical industries as solvents and intermediates for pesticides and dyes manufacture. Their presence was documented in rivers, groundwaters and seawaters.

In this work, the oxidation of 1,2-dichlorobenzene in aqueous solutions by means of Fe(III) homogeneous photocatalysis under UV lamp and sunlight irradiations is studied. The results show that the best working conditions are found for pH=3.0 and initial [Fe(III)] concentration equal to 1.0×10⁻⁴ mol L⁻¹ although the investigated system can be utilized even at pH close to 4.0 but with slower abatement kinetics.

Some dicholoroderivatives, such as 2,3-dichlorophenol, 3,4-dichlorophenol and 2-chlorophenol, are identified as oxidation intermediates. The values of the kinetic constant for the photochemical reoxidation of Fe(II) to Fe(III) are evaluated by a mathematical model in the range 1.58–3.78 L mol⁻¹ s⁻¹ and 0.69–0.78 L mol⁻¹ s⁻¹ for the systems irradiated by UV lamp and sunlight, respectively.     

Removal of benzoic acid in aqueous solution by Fe(III) homogeneous photocatalysis

The behaviour of the system Fe(III)/Air/UV-benzoic acid is investigated in the pH range 2.0-5.5 and Fe(III) concentration up to 60 microM. The oxidation process develops through the establishment of an iron cycle in which HO radicals are produced by Fe(OH)2+ photolysis and the resulting Fe(II) photo-oxidized to Fe(III) by dissolved oxygen. A kinetic model is developed and used to simulate the behaviour of the system.     

Fast and highly efficient removal of dyes under alkaline conditions using magnetic chitosan-Fe(III) hydrogel

The dyeing effluent of high alkalinity, which could not be treated efficiently by traditional wastewater technologies, highlighted the need to explore a technically feasible, highly efficient and cost effective method. Thus, a fast and highly efficient method for the removal of dyes under alkaline conditions using magnetic chitosan-Fe(III) hydrogel was proposed. Firstly, chitosan-Fe(III) hydrogel was prepared by a chelation procedure with cheap and environmentally friendly chitosan and iron salts. We characterized the sorption and desorption of C. I. Acid Red 73, a common type of anionic dye, on magnetic chitosan-Fe(III) hydrogel, to understand its availability for alkaline dyeing wastewater. Sorption of dye to chitosan-Fe(III) hydrogel was fast (adsorption could reach equilibrium in less than 10 min) in a wide pH range, and agreed well to the Langmuir-Freundlich adsorption model with a high maximum adsorption capacity of 294.5 mg/g under pH = 12. Meanwhile, 1 mol/L NaOH was used to desorb the dye efficiently (desorption efficiency 94.4%) and 0.1 mol/L HCl was applied to regenerate the chitosan-Fe(III) hydrogel. The results showed that the chitosan-Fe(III) hydrogel could retain its high efficiency after the desorption and regeneration. The common coexisting ions almost had no negative effect on the dye adsorption of chitosan-Fe(III) and the removals of a variety of anionic dyes suggest that the magnetic chitosan-Fe(III) hydrogel could efficiently adsorb both the acid and reactive dyes under alkaline condition. Overall, the results reported herein indicated that magnetic chtisoan-Fe(III) with high adsorption efficiency and strong magnetic property is very attractive and implies a potential of practical application for alkaline dyeing effluent treatment.     

Preparation and evaluation of iron–chitosan composites for removal of As(III) and As(V) from arsenic contaminated real life groundwater

A study on the removal of arsenic from real life groundwater using iron–chitosan composites is presented. Removal of arsenic(III) and arsenic(V) was studied through adsorption at pH 7.0 under equilibrium and dynamic conditions. The equilibrium data were fitted to Langmuir adsorption models and the various model parameters were evaluated. The monolayer adsorption capacity from the Langmuir model for iron chitosan flakes (ICF) (22.47 ± 0.56 mg/g for As(V) and 16.15 ± 0.32 mg/g for As(III)) was found to be considerably higher than that obtained for iron chitosan granules (ICB) (2.24 ± 0.04 mg/g for As(V); 2.32 ± 0.05 mg/g for As(III)). Anions including sulfate, phosphate and silicate at the levels present in groundwater did not cause serious interference in the adsorption behavior of arsenate/arsenite. The column regeneration studies were carried out for two sorption–desorption cycles for both As(III) and As(V) using ICF and ICB as sorbents. One hundred and forty-seven bed volumes of As(III) and 112 bed volumes of As(V) spiked groundwater were treated in column experiments using ICB, reducing arsenic concentration from 500 to <10 μg/l. The eluent used for the regeneration of the spent sorbent was 0.1 M NaOH. The adsorbent was also successfully applied for the removal of total inorganic arsenic down to <10 μg/l from real life arsenic contaminated groundwater samples.     

Oxidation and removal of arsenic (III) from aerated groundwater by filtration through sand and zero-valent iron

Removing arsenic from contaminated groundwater in Bangladesh is challenging due to high concentrations of As(III), phosphate and silicate. Application of zero-valent iron as a promising removal method was investigated in detail with synthetic groundwater containing 500 microg/L As(III), 2-3mg/L P, 20mg/L Si, 8.2mM HCO3-, 2.5mM Ca2+, 1.6mM Mg2+ and pH 7.0. In a series of experiments, 1L was repeatedly passed through a mixture of 1.5 g iron filings and 3-4 g quartz sand in a vertical glass column (10mm diameter), allowing the water to re-aerate between each filtration. At a flow rate of 1L/h, up to 8 mg/L dissolved Fe(II) was released. During the subsequent oxidation of Fe(II) by dissolved oxygen, As(III) was partially oxidized and As(V) sorbed on the forming hydrous ferric oxides (HFO). HFO was retained in the next filtration step and was removed by shaking of the sand-iron mixture with water. Rapid phosphate removal provided optimal conditions for the sorption of As(V). Four filtrations lead to almost complete As(III) oxidation and removal of As(tot) to below 50 microg/L. In a prototype treatment with a succession of four filters, each containing 1.5 g iron and 60 g sand, 36 L could be treated to below 50 microg/L in one continuous filtration, without an added oxidant.     

Equilibrium dialysis and ultrafiltration investigations of perchlorate removal from aqueous solution using poly(diallyldimethylammonium) chloride

Use of perchlorate salts in military activities and the aerospace industry is widespread. These salts are highly water-soluble and are, to a large extent, kinetically inert as aqueous species. As a groundwater contaminant, perchlorate is now being detected in an increasing number of locations and is believed to interfere with the uptake of iodide by the thyroid, which can result in decreased hormone production. The United States Environmental Protection Agency (US EPA) has established a reference dose for perchlorate of 0.0007 mg/kg/day, which translates to a drinking water equivalent level of 24.5 ppb. This study investigated the application of polyelectrolyte-enhanced ultrafiltration (PEUF) for the selective removal of perchlorate from aqueous solution through equilibrium dialysis and ultrafiltration experiments. Using poly(diallyldimethylammonium) chloride, the effectiveness and efficiency of PEUF in the removal of perchlorate from other aqueous solution components was investigated by testing parameters such as polyelectrolyte concentration, pH, and ionic strength. Removal of perchlorate from synthetic groundwater initially containing 10.3 ppm perchlorate and also containing chloride, sulfate, and carbonate was also examined. Perchlorate separations of greater than 95% were achieved, even in the presence of 10-fold excesses of competing ions.     

Removal of quinol from aqueous solution by adsorption onto Fe(III)/Cr(III) hydroxide and application to real effluent treatment

The adsorption capacity of ‘waste’ Fe(III)/Cr(III) hydroxide for removal of quinol at varying agitation time, quinol concentration, adsorbent dose, pH and temperature was investigated by batch method. The Langmuir isotherm was found to represent the equilibrium sorption data well and the adsorption capacity was found to be 24.4 mg g^?1 and 28.2 mg g^?1 for untreated and pre‐treated adsorbent, respectively. Adsorption followed second‐order kinetics. Adsorption was maximum and uniform in the pH range 4.0–10.0 and 6.0–10.0 for untreated and pre‐treated adsorbent, respectively. The adsorption was endothermic in nature. Application of the adsorbent to the treatment of real effluent was demonstrated.     

The removal of hexacyanoferrate(II) and (III) ions in dilute aqueous solution by activated carbon

The removal of iron cyano-complex ions [hexacyanoferrate(II) and (III) ions] in a dilute aqueous solution by activated carbon was investigated. The maximum adsorption of iron cyano-complex ions on activated carbon occurred at pH around 3. The hexacyanoferrate(III) ion was more adsorbable than the hexacyanoferrate(II) ion. Activated carbon promoted the oxidation of hexacyanoferrate(II) ion to (III) ion with dissolved oxygen in an acidic solution and the reduction of hexacyanoferrate(III) ion to (II) ion in an alkaline solution. The iron cyano-complex ion adsorbed on activated carbon could be eluted with higher concentrated acidic and alkaline solutions. The degree of elution decreased with an increase in potassium hydroxide concentration, since parts of the iron cyano-complexes on activated carbon were decomposed to form the iron hydroxide and the hexacyanoferrate(II) ion with an alkaline solution. The behavior of iron cyano-complexes in the presence of activated carbon, in the lower pH range (pH < 1) and at higher temperatures (80°C), was discussed.     

Phragmites australis: a novel biosorbent for the removal of heavy metals from aqueous solution

Reed (Phragmites australis), a commonly used macrophyte in the wetlands constructed for water purification, was investigated as a new biosorbent for the removal of Cu(2+), Cd(2+), Ni(2+), Pb(2+) and Zn(2+) from aqueous solution. The metal adsorption capacity of reed biomass was improved significantly by water-wash, base- and acid-treatment. The maximum sorption of NaOH-pretreated reed biomass was observed near neutral pH for Cu(2+), Cd(2+), Ni(2+) and Zn(2+), while that for Pb(2+) was from an acidic range of pH 4.0 or higher. The maximum metal adsorption capacity on a molar basis assumed by Langmuir model was in the order of Cu(2+)>Ni(2+)>Cd(2+)>Zn(2+)>Pb(2+). Reed biosorbent showed a very high adsorption affinity value, which helps predict its high ability to adsorb heavy metals at low concentration. Desorption of heavy metals and regeneration of the biosorbent was attained simultaneously by acid elution. Even after three cycles of adsorption-elution, the adsorption capacity was regained completely and the desorption efficiency of metal was maintained at around 90%.     

Selective removal of gallium (III) from aqueous solutions containing zinc or aluminum using sodium di-(n-octyl) phosphinate

Gallium was removed selectively from aqueous solutions containing zinc or aluminum using sodium di-(n-octyl) phosphinate as a ligand (NaL). At low pH or low mole ratios, the gallium was removed by complexation with the ligand as GaL(3(S)), while the zinc or the aluminum remained in the solution. Nearly complete separation of gallium was obtained. By increasing the amount of ligand or by increasing the pH, the zinc or aluminum remaining in the solution was then removed as a solid complex: ZnL(2(S)) or AlL(3(S)), respectively. At a pH between 1.5 and 2 and a mole ratio ligand to total metals of 0.75 for zinc solutions and 1.0 for aluminum solutions, more than 98% of the gallium was selectively removed with a high molar selectivity, alpha(Ga/Zn) and alpha(Ga/Al), respectively. Over 95% of gallium was recovered from the solid GaL(3(S)) complex by treatment of the complex with a 3M NaOH solution and diethyl ether. The gallium was concentrated in the aqueous solution to 4 times its initial concentration and the ligand was extracted into the ether phase. After evaporation of the ether, 95% of the ligand was regenerated in its sodium form as a solid.     

Removal of antimony(V) and antimony(III) from drinking water by coagulation-flocculation-sedimentation (CFS)

Antimony occurs widely in the environment as a result of natural processes and human activity. Although antimony is similar to arsenic in chemical properties and toxicity, and a pollutant of priority interest to the USEPA and the EU, its environmental behaviors, control techniques, and even solution chemistry, are yet barely touched. In this study, antimony removal from drinking water with coagulation-flocculation-sedimentation (CFS) is comprehensively investigated with respect to the dependence of both Sb(III) and Sb(V) removal on the initial contaminant-loading level, coagulant type and dosage, pH and interfering ions. The optimum pH for Sb(V) removal with ferric chloride (FC) was observed at pH 4.5-5.5, and continuously reduced with further pH increase. Over a broad pH range from 4.0 to 10.0, effective Sb(III) removal with FC was obtained. Contrary to the effective Sb removal with FC, the degree of both Sb(III) and Sb(V) removal with aluminum sulfate (AS) was very low, indicating the impracticability of AS application for antimony removal. The presence of phosphate and humic acid (HA) markedly impeded Sb(V) removal, while exhibited insignificant effect on Sb(III) removal. The effects of coagulant type, Sb species and pH are more pronounced than the effects of coagulant dose and initial pollutant concentration. After preliminarily excluding the possibility of precipitation and the predominance of coprecipitation, the adsorption mechanism is used to rationalize and simulate Sb/FC coagulation with good result by incorporating diffuse-layer model (DLM).     

Removal of Ga(III) from aqueous solution by adsorption on activated bentonite using a factorial design

The purpose of the work is to study the adsorption of gallium(III) on bentonite from aqueous solutions. The important parameters, which affect the adsorption, such as pH of solution, mass of bentonite and temperature have been investigated. The results of parameters study showed that when pH and mass of bentonite increase there was a significant increase of Ga(III) at 20 degrees C and the optimum conditions were as follows: pH of solution (2.50), mass of bentonite (3.50 g) and temperature (20 degrees C). An experimental test carried out using a factorial design 2(3) indicated that pH and mass of bentonite have a positive effect, whereas temperature has negative effect. The interaction effect between pH and mass of bentonite was an important significant factor for gallium adsorption.     

As(III) removal by hydrous titanium dioxide prepared from one-step hydrolysis of aqueous TiCl4 solution

Hydrous titanium dioxide (TiO₂·xH₂O) nanoparticles were synthesized by a low-cost one-step hydrolysis process with aqueous TiCl₄ solution. These TiO₂·xH₂O nanoparticles ranged from 3 to 8 nm and formed aggregates with a highly porous structure, resulting in a large surface area and easy removal capability from aqueous environment after the treatment. Their effectiveness on the removal of As(III) (arsenite) from water was investigated in both laboratory and natural water samples. The adsorption capacity on As(III) of these TiO₂·xH₂O nanoparticles reached over 83 mg/g at near neutral pH environment, and over 96 mg/g at pH 9.0. Testing with a As(III) contaminated natural lake water sample confirmed the effectiveness of these TiO₂·xH₂O nanoparticles in removing As(III) from natural water. The high adsorption capacity of the TiO₂·xH₂O nanoparticles is related to the high surface area, large pore volume, and the presence of high affinity surface hydroxyl groups.     

The simultaneous removal of calcium and chloride ions from calcium chloride solution using magnesium-aluminum oxide

We investigated the removal of Ca(2+) and Cl(-) from CaCl(2) solution at 20-60 degrees C, using magnesium-aluminum oxide, Mg(0.80)Al(0.20)O(1.10), prepared by the thermal decomposition of a hydrotalcite-like compound, Mg(0.80)Al(0.20)(OH)(2)(CO(3))(0.10).0.78 H(2)O. The degree of Ca(2+) and Cl(-) removal from the solution increased with increasing initial CaCl(2) concentration, temperature, and quantity of Mg(0.80)Al(0.20)O(1.10) added. When Mg(0.80)Al(0.20)O(1.10) was added to 0.25 M CaCl(2) solution in a Mg(0.80)Al(0.20)O(1.10)/CaCl(2) molar ratio of 20, the degree of Ca(2+) and Cl(-) removal from the solution at 60 degrees C after 0.5 h was 93.0% and 98.2%, respectively. These results reveal that Mg(0.80)Al(0.20)O(1.10) has the capacity to remove Ca(2+) and Cl(-) simultaneously from aqueous solution.