Surface complexation modeling of the removal of arsenic from ion-exchange waste brines with ferric chloride

Brine disposal is a serious challenge of arsenic (V) removal from drinking water using ion-exchange (IX). Although arsenic removal with ferric chloride (FeCl(3)) from drinking waters is well documented, the application of FeCl(3) to remove arsenic (V) from brines has not been thoroughly investigated. In contrast to drinking water, IX brines contain high ionic strength, high alkalinity, and high arsenic concentrations; these factors are known to influence arsenic removal by FeCl(3). Surface complexation modeling and experimental coagulation tests were performed to investigate the influence of ionic strength, pH, Fe/As molar ratios, and alkalinity on the removal of arsenic from IX brines. The model prediction was in good agreement with the experimental data. Optimum pH range was found to be between 4.5 and 6.5. The arsenic removal efficiency slightly improved with higher ionic strength. The Fe/As ratios needed to treat brines were significantly lower than those used to treat drinking waters. For arsenic (V) concentrations typical in IX brines, Fe/As molar ratios varying from 1.3 to 1.7 were needed. Sludge solid concentrations varying from 2 to 18 mg L(-1) were found. The results of this research have direct application to the treatment of residual wastes brines containing arsenic.     

A method for preparing ferric activated carbon composites adsorbents to remove arsenic from drinking water

Iron oxide/activated carbon (FeO/AC) composite adsorbent material, which was used to modify the coal-based activated carbon (AC) 12 x 40, was prepared by the special ferric oxide microcrystal in this study. This composite can be used as the adsorbent to remove arsenic from drinking water, and Langmuir isotherm adsorption equation well describes the experimental adsorption isotherms. Then, the arsenic desorption can subsequently be separated from the medium by using a 1% aqueous NaOH solution. The apparent characters and physical chemistry performances of FeO/AC composite were investigated by X-ray diffraction (XRD), nitrogen adsorption, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). Batch and column adsorption experiments were carried out to investigate and compare the arsenic removal capability of the prepared FeO/AC composite material and virgin activated carbon. It can be concluded that: (1) the main phase present in this composite are magnetite (Fe(3)O(4)), maghemite (gamma-Fe(2)O(3)), hematite (alpha-Fe(2)O(3)) and goethite (alpha-FeO(OH)); (2) the presence of iron oxides did not significantly affect the surface area or the pore structure of the activated carbon; (3) the comparisons between the adsorption isotherms of arsenic from aqueous solution onto the composite and virgin activated carbon showed that the FeO/AC composite behave an excellent capacity of adsorption arsenic than the virgin activated carbon; (4) column adsorption experiments with FeO/AC composite adsorbent showed that the arsenic could be removed to below 0.01 mg/L within 1250 mL empty bed volume when influent concentration was 0.5mg/L.     

Removal of heavy metal ions by iron oxide coated sewage sludge

The municipal sewage sludge was modified with iron oxide employed in metal ions removal. The surface modification method was proposed and the effect of parameters in the preparation was studied. The iron oxide coated sludge had higher surface area, pore volume and iron content, compared to uncoated sludge. The suitable conditions for removal of Cu(II), Cd(II), Ni(II) and Pb(II) ions from solutions were investigated using batch method. The suitable pH value in the extraction was 7 for adsorption of Cd(II) and Ni(II), 6 for Cu(II) and 5 for Pb(II) ions. The presence of NaNO(3), Ca(NO(3))(2) and Na(2)SO(4) in metal solution in the concentration of 0.01 M and 0.50 M could reduce the removal efficiency. The adsorption isotherms for the adsorption of the metal ions were defined by Langmuir relation. The maximum adsorption capacity of the iron oxide coated sludge for Cu(II), Cd(II), Ni(II) and Pb(II) was 17.3, 14.7, 7.8 and 42.4 mg g(-1), respectively. The adsorption kinetics for every metal ions followed pseudo-second order model. The metal removal from wastewater by iron oxide coated sludge was also demonstrated.     

Synthesis and characterization of a mesoporous hydrous zirconium oxide used for arsenic removal from drinking water

Powder (20-50 μm) mesoporous hydrous zirconium oxide was prepared from a zirconium salt granular precursor. The effect of some process parameters on product morphology, porous structure and adsorption performance has been studied. The use of hydrous zirconium oxide for selective arsenic removal from drinking water is discussed.     

Laboratory based approaches for arsenic remediation from contaminated water: recent developments

Arsenic contamination in water has posed severe health problems around the world. In spite of the availability of some conventional techniques for arsenic removal from contaminated water, development of new laboratory based techniques along with enhancement and cost reduction of conventional techniques are essential for the benefit of common people. This paper provides an overview of the arsenic issue in water such as modes of contamination of ground water as well as surface water by arsenic, its metabolism and health impacts, factors influencing arsenic poisoning, fundamentals of arsenic poisoning mechanism and world scenario of arsenic poisoning. It discusses and compares the conventional laboratory based techniques, like precipitation with alum, iron, Fe/Mn, lime softening, reverse osmosis, electro dialysis, ion exchanges, adsorption on activated alumina/carbon, etc., for arsenic removal from contaminated water. It also discusses the best available techniques and mentions the cost comparison among these techniques too. Recent developments in the research on the laboratory based arsenic removal techniques, like improvement of conventional techniques and advances in removal technology along with its scopes and limitations have also been reviewed.     

Phosphorus removal from aqueous solution using iron coated natural and engineered sorbents

New filtration materials covered with metallic oxides are good adsorbents for both cation and anion forms of pollutants. Sfax is one of the most important industrial towns in Tunisia. Its phosphate manufacture in particular is causing considerable amounts of water pollution. Therefore, there is a need to find out a new way of getting rid of this excessive phosphate from water. This work is aimed to examining the potential of three sorbent materials (synthetic iron oxide coated sand (SCS), naturally iron oxide coated sand (NCS) and iron oxide coated crushed brick (CB)) for removing phosphate ions from aqueous solutions. According to our literature survey CB was not used as adsorbent previously. Phosphate ions are used here as species model for the elimination of other similar pollutants (arsenates, antimonates). Optical microscope and scanning electron microscope (SEM) analyses were used to investigate the surface properties and morphology of the coated sorbents. Infra-red spectroscopy and X-ray diffraction techniques were also used to characterize the sorbent structures. Results showed that iron coated crushed brick possess more micro pores and a higher surface area owing to its clay nature. The comparative sorption of PO4(3-) from aqueous solutions by SCS, CB and NCS was investigated by batch experiments. The estimated optimum pH of phosphate ion retention for the considered sorbents was 5. The equilibrium data were analysed using the Langmuir and Freundlich isotherms. The sorption capacities of PO(4)3- at pH 5 were 1.5 mg/g for SCS, 1.8 mg/g for CB and 0.88 mg/g for NCS. The effect of temperature on sorption phenomenon was also investigated. The results indicated that adsorption is an endothermic process for phosphate ions removal. This study demonstrates that all the considered sorbents can be used as an alternative emerging technology for water treatment without any side effect or treatment process alteration.     

Adsorption characteristics of As(III) from aqueous solution on iron oxide coated cement (IOCC)

Contamination of potable groundwater with arsenic is a serious health hazard, which calls for proper treatment before its use as drinking water. The objective of the present study is to assess the effectiveness of iron oxide coated cement (IOCC) for As(III) adsorption from aqueous solution. Batch studies were conducted to study As(III) adsorption onto IOCC at ambient temperature as a function of adsorbent dose, pH, contact time, initial arsenic concentration and temperature. Kinetics reveal that the uptake of As(III) ion is very rapid and most of fixation occurs within the first 20 min of contact. The pseudo-second order rate equation successfully described the adsorption kinetics. Langmuir, Freundlich, Redlich-Peterson (R-P), and Dubinin-Radushkevich (D-R) models were used to describe the adsorption isotherms at different initial As(III) concentrations and at 30 g l(-1) fixed adsorbent dose. The maximum adsorption capacity of IOCC for As(III) determined from the Langmuir isotherm was 0.69 mg g(-1). The mean free energy of adsorption (E) calculated from the D-R isotherm was found to be 2.86 kJ mol(-1) which suggests physisorption. Thermodynamic parameters indicate an exothermic nature of adsorption and a spontaneous and favourable process. The results suggest that IOCC can be suitably used for As(III) removal from aqueous solutions.     

The effect of nanocrystalline magnetite size on arsenic removal

Higher environmental standards have made the removal of arsenic from water an important problem for environmental engineering. Iron oxide is a particularly interesting sorbent to consider for this application. Its magnetic properties allow relatively routine dispersal and recovery of the adsorbent into and from groundwater or industrial processing facilities; in addition, iron oxide has strong and specific interactions with both As(III) and As(V). Finally, this material can be produced with nanoscale dimensions, which enhance both its capacity and removal. The objective of this study is to evaluate the potential arsenic adsorption by nanoscale iron oxides, specifically magnetite (Fe₃O₄) nanoparticles. We focus on the effect of Fe₃O₄ particle size on the adsorption and desorption behavior of As(III) and As(V). The results show that the nanoparticle size has a dramatic effect on the adsorption and desorption of arsenic. As particle size is decreased from 300 to 12 nm the adsorption capacities for both As(III) and As(V) increase nearly 200 times. Interestingly, such an increase is more than expected from simple considerations of surface area and suggests that nanoscale iron oxide materials sorb arsenic through different means than bulk systems. The desorption process, however, exhibits some hysteresis with the effect becoming more pronounced with small nanoparticles. This hysteresis most likely results from a higher arsenic affinity for Fe₃O₄ nanoparticles. This work suggests that Fe₃O₄ nanocrystals and magnetic separations offer a promising method for arsenic removal.     

Intracellular Nanoparticle Coating Stability Determines Nanoparticle Diagnostics Efficacy and Cell Functionality

Iron oxide nanoparticles (NPs) are frequently employed in biomedical research as magnetic resonance (MR) contrast agents where high intracellular levels are required to clearly depict signal alterations. To date, the toxicity and applicability of these particles have not been completely unraveled. Here, we show that endosomal localization of different iron oxide particles results in their degradation and in reduced MR contrast, the rate of which is governed mainly by the stability of the coating. The release of ferric iron generates reactive species, which greatly affect cell functionality. Lipid‐coated NPs display the highest stability and furthermore exhibit intracellular clustering, which significantly enhances their MR properties and intracellular persistence. These findings are of considerable importance because, depending on the nature of the coating, particles can be rapidly degraded, thus completely annihilating their MR contrast to levels not detectable when compared to controls and greatly impeding cell functionality, thereby hindering their application in functional in vivo studies.     

Removal of arsenic from water by zero-valent iron

Batch and column experiments were conducted to investigate the effect of dissolved oxygen (DO) and pH on arsenic removal with zero-valent iron [Fe(0)]. Arsenic removal was dramatically affected by the DO content and the pH of the solution. Under oxic conditions, arsenate [As(V)] removal by Fe(0) filings was faster than arsenite [As(III)]. Greater than 99.8% of the As(V) was removed whereas 82.6% of the As(III) was removed at pH 6 after 9h of mixing. When the solution was purged with nitrogen gas to remove DO, less than 10% of the As(III) and As(V) was removed. High DO content and low solution pH also increased the rate of iron corrosion. The removal of arsenic by Fe(0) was attributed to adsorption by iron hydroxides generated from the oxic corrosion of Fe(0). The column results indicated that a filtration system consisting of an iron column and a sand filter could be used for treatment of arsenic in drinking water.     

The management of arsenic wastes: problems and prospects

Arsenic has found widespread use in agriculture and industry to control a variety of insect and fungicidal pests. Most of these uses have been discontinued, but residues from such activities, together with the ongoing generation of arsenic wastes from the smelting of various ores, have left a legacy of a large number of arsenic-contaminated sites. The treatment and/or removal of arsenic is hindered by the fact that arsenic has a variety of valence states. Arsenic is most effectively removed or stabilized when it is present in the pentavalent arsenate form. For the removal of arsenic from wastewater, coagulation, normally using iron, is the preferred option. The solidification/stabilization of arsenic is not such a clear-cut process. Factors such as the waste's interaction with the additives (e.g. iron or lime), as well as any effect on the cement matrix, all impact on the efficacy of the fixation. Currently, differentiation between available solidification/stabilization processes is speculative, partly due to the large number of differing leaching tests that have been utilized. Differences in the leaching fluid, liquid-to-solid ratio, and agitation time and method all impact significantly on the arsenic leachate concentrations.This paper reviews options available for dealing with arsenic wastes, both solid and aqueous through an investigation of the methods available for the removal of arsenic from wastewater as well as possible solidification/stabilization options for a variety of waste streams.     

Treatment of 1,10-phenanthroline laboratory wastewater using the solar photo-Fenton process

The red Fe(2+)-phenanthroline complex is the basis of a classical spectrophotometric method for determination of iron. Due to the toxicity of this complexing agent, direct disposal of the wastewaters generated in analytical laboratories is not environmentally safe. This work evaluates the use of the solar photo-Fenton process for the treatment of laboratory wastewaters containing phenanthroline. Firstly, the degradation of phenanthroline in water was evaluated at two concentration levels (0.1 and 0.01%, w/v) and the efficiencies of degradation using ferrioxalate (FeOx) and ferric nitrate were compared. The 0.01% w/v solution presented much higher mineralization, achieving 82% after 30min of solar irradiation with both iron sources. The solar photo-Fenton treatment of laboratory wastewater containing, in addition to phenanthroline, other organic compounds such as herbicides and 4-chlorophenol, equivalent to 4,500mgL(-1) total organic carbon (TOC) resulted in total degradation of phenanthroline and 25% TOC removal after 150min, in the presence of either FeOx or ferric nitrate. A ratio of 1:10 dilution of the residue increased mineralization in the presence of ferrioxalate, achieving 38% TOC removal after 120min, while use of ferric nitrate resulted in only 6% mineralization over the same period.     

Stabilization of arsenic-bearing solid residuals in polymeric matrices

This research investigates the use of polymeric matrices to encapsulate solid sorbents used to remove arsenic from drinking water. Arsenic-containing granular ferric oxy/hydroxide and ferric hydroxide amended alumina residuals were encapsulated in a polymeric matrix using a novel aqueous-based manufacturing process. The polymer was a blend of poly(styrene butadiene) and an epoxy resin. The polymeric waste forms produced were capable of containing more than 60 wt% of sorbent (dry basis), while keeping good mechanical properties. Arsenic leaching from encapsulated and unencapsulated residuals was evaluated using the standard toxicity characteristic leaching procedure (TCLP) and the California Waste Extraction Test (CA-WET). The results show that waste forms of the polymer-encapsulated residuals crushed for testing retain good leaching resistance when evaluated with the more aggressive CA-WET test, yielding leachate arsenic concentrations below the toxicity characteristic (TC) standard of 5mg/L. When residuals were preprocessed and encapsulated in a polymer form that avoided the size reduction required by leaching protocols, arsenic leached up to 700 times less than that from the unencapsulated residuals. Comparison of the waste form developed here with conventional cement matrices containing the same residuals show that the polymeric matrices were capable of encapsulating appreciably more material and leached arsenic at concentration levels that were more than an order of magnitude lower than cement.     

Color removal of distillery wastewater by ozonation in the absence and presence of immobilized iron oxide catalyst

Ozone is a strong oxidant, which can oxidize both biodegradable and non-biodegradable organics. The main objective of this study was to use iron oxide as a heterogeneous catalyst to enhance the ozone oxidation process. The wastewater used in this study was distillery wastewater, which was diluted 20 times before use. The diluted distillery wastewater was fed continuously in a downflow direction in an ozonation column. The iron oxide catalyst was coated on 10.3mm diameter alumina balls (5.5 m2/g specific surface area) by using Fe(NO3)3 as a precursor. The prepared catalyst was in the form of ferric oxide, and its loading was 0.07%. From the experimental results of both with and without the iron oxide catalyst, an increase in hydraulic retention time resulted in an increase in the treatment efficiencies of both chemical oxygen demand (COD) and color reduction, since the residence time of ozone increased. When the ozone mass flow rate increased, both COD and color reduction increased, resulting from an increase in the hydroxyl radical available in the system. The ozonation system with the iron oxide catalyst gave the highest efficiency in both COD and color removals because the hydroxyl free radical generated from the catalyst is more reactive than the ozone molecule itself.     

Arsenic removal by electrocoagulation using combined Al-Fe electrode system and characterization of products

Combination of electrodes, such as aluminum and iron in a single electrochemical cell provide an alternative method for removal of arsenic from water by electrocoagulation. The removal process has been studied with a wide range of arsenic concentration (1–1000 ppm) at different pH (4–10). Analysis of the electrochemically generated by-products by XRD, XPS, SEM/EDAX, FT-IR, and Mössbauer Spectroscopy revealed the expected crystalline iron oxides (magnetite (Fe₃O₄), lepidocrocite (FeO(OH)), iron oxide (FeO)) and aluminum oxides (bayerite (Al(OH)₃), diaspore (AlO(OH)), mansfieldite (AlAsO₄·2(H₂O)), as well as some interaction between the two phases. The amorphous or very fine particular phase was also found in the floc. The substitution of Fe³⁺ ions by Al³⁺ ions in the solid surface has been observed, indicating an alternative removal mechanism of arsenic in these metal hydroxides and oxyhydroxides by providing larger surface area for arsenic adsorption via retarding the crystalline formation of iron oxides.     

Perspectives of low cost arsenic remediation of drinking water in Pakistan and other countries

Arsenic concentrations above acceptable standards for drinking water have been detected in many countries and this should therefore is a global issue. The presence of arsenic in subsurface aquifers and drinking water systems is a potentially serious human health hazard. The current population growth in Pakistan and other developing countries will have direct bearing on the water sector for meeting the domestic, industrial and agricultural needs. Pakistan is about to exhaust its available water resources and is on the verge of becoming a water deficit country. Water pollution is a serious menace in Pakistan, as almost 70% of its surface waters as well as its groundwater reserves have contaminated by biological, organic and inorganic pollutants. In some areas of Pakistan, a number of shallow aquifers and tube wells are contaminated with arsenic at levels which are above the recommended USEPA arsenic level of 10 ppb (10 μg L⁻¹). Adverse health effects including human mortality from drinking water are well documented and can be attributed to arsenic contamination. The present paper reviews appropriate and low cost methods for the elimination of arsenic from drinking waters. It is recommended that a combination of low cost chemical treatment like ion exchange, filtration and adsorption along with bioremediation may be useful option for arsenic removal from drinking water.     

Treatment of groundwater polluted by arsenic compounds by zero valent iron

Batch experiments were carried out to study the kinetics and efficiency of inorganic arsenic removal by zero valent iron (ZVI) powder, and as well as the effects of pH, anions, and humic material (HM) on this process. Moreover, column experiment was conducted for 31 days to treat arsenate solution of 500 microg As/L using waste iron chippings as filling. Batch experiments showed that both arsenate and arsenite compounds could be removed efficiently from simulated groundwater by ZVI under aerobic and relative anaerobic conditions. Aerobic condition was favorable to arsenic removal especially for arsenate, while arsenite could be removed more rapidly than arsenate in relative anaerobic condition. Oxidation of arsenite to arsenate by iron species in aerobic environment was observed, which is thought to be an important pathway of arsenite removal. In an unsealed system, the removal efficiency of both arsenate and arsenite decreased at higher pH value. In a sealed system, acidic and alkaline condition seemed to be favorable for arsenate and arsenite removal, respectively. Phosphate and low concentration sulfate caused a decrease in arsenate removal, while high concentration sulfate as well as nitrate caused slight increase in arsenate removal. Presence of HM in solution slightly inhibited arsenic removal. Arsenic removal efficiency in column study was influenced by flow rate and work period of the column. More than 98% of arsenate could be removed stably with a hydraulic resident time of 2 h at last, and the effluent meet the drinking water standard.     

The role of functionalised multiwalled carbon nanotubes based supercapacitor for arsenic removal and desalination of sea water

In order to investigate the simultaneous adsorption property of functionalised multiwalled carbon nanotubes (MWNTs) for sodium and arsenic, a new type of carbon fabric supported functionalised MWNTs (f-MWNTs) based supercapacitor was developed. In addition, this setup was tested for desalination of sea water. MWNTs were synthesised by chemical vapour deposition technique and purified, followed by functionalisation. MWNTs were characterised by different techniques. Performance of supercapacitor-based water filter was analysed for the adsorption of high concentration of arsenic (trivalent and pentavalent) and sodium as well as for desalination of sea water by using cyclic voltametry and inductively coupled plasma-optical emission spectroscopy techniques. Adsorption isotherms and kinetic characteristics were studied for the simultaneous removal of sodium and arsenic. High desalination (removal of sodium and magnesium) efficiency of sea water and cyclic repeatability for simultaneous removal of arsenic (arsenate and arsenite) and sodium have been demonstrated in this study. Easy handling and flexibility of this new type of electrodes-based setup provides a platform for the development of portable water filter.     

Removal of arsenic from water using Fe-exchanged natural zeolite

An elevated arsenic (As) content in groundwater imposes a great threat to people worldwide. Thus, developing new and cost-effective methods to remove As from groundwater and drinking water becomes a priority. Using iron/aluminum hydroxide to remove As from water is a proven technology. However, separation of As-bearing fine particles from treated water presented a challenge. An alternative method was to use coarse-grained sorbents to increase the flow rate and throughput. In this research, a natural zeolite (clinoptilolite) was exchanged with iron(III) to enhance its As removal. Batch test results showed a Fe(III) sorption capacity of 144 mmol/kg on the zeolite. The As sorption on the Fe-exchanged zeolite (Fe-eZ) could reach up to 100mg/kg. Columns packed with Fe-eZ were tested for As removal from water collected from acid mine drainage (AMD) and groundwater containing high natural organic matter and high As(III). With an initial concentration of 147 μg/L in the AMD water, a complete As removal was achieved up to 40 pore volumes. However, the Fe-eZ was not effective to remove As from Chia-Nan Plain groundwater due to its high initial As concentration (511 μg/L), high amounts of natural organic matter, as well as its low oxidation-reduction potential, under which the As was in reduced As(III) form.