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.     

Study of arsenic(V) adsorption on bone char from aqueous solution

Arsenic is a toxic element and may be found in natural waters as well as in industrial waters. Leaching of arsenic from industrial wastewater into groundwater may cause significant contamination, which requires proper treatment before its use as drinking water. The present study described the removal of As(V) on bone char in batch studies conducted as a function of pH, dosage of adsorbent, and contact time. Kinetics revealed that uptake of As(V) ion by bone char was very rapid in the first 30min and equilibrium time was independent of initial As(V) concentration. And the adsorption process followed a first-order kinetics equation. The arsenic removal was strongly dependent on pH and dosage of adsorbent. Fourier transform infrared spectra of bone char before and after As(V) adsorption demonstrated that Ca-OH functional group plays an important role for As(V) ions removal, and the mechanisms of the removal of As(V) on bone char was complex mechanism where both co-precipitation and ion exchange. The results suggested that bone char can be used effectively for the removal of As(V) ion from aqueous solution.     

Effect of Mn substitution on the oxidation/adsorption abilities of iron(III) oxyhydroxides

In this study, divalent manganese ions [Mn(II)] were substituted a part of divalent iron ions [Fe(II)] present in Fe oxyhydroxides to prepare novel composites (Mn@Feox). The composites were prepared by (1) simultaneous hydrolysis of Fe(II) and Mn(II), and (2) rapid oxidation with H₂O₂. The resulting Mn@Feox prepared with different molar ratios of Fe and Mn was characterized and evaluated for their abilities to adsorb arsenic species [As(III) and As(V)] in aqueous solution. X-ray diffraction and field emission transmission electron microscope analyses revealed Mn@Feox has a δ-(Fe_1?x, Mn_x)OOH-like structure with their mineralogical properties resembling those of feroxyhyte (δ-FeOOH). The increase in Mn substitution in Mn@Feox enhanced the oxidative ability to oxidize As(III) to As(V), but it decreased the adsorption capacity for both arsenic species. The optimal Mn/Fe molar ratio that could endow oxidation and magnetic capabilities to the composite without significantly compromising As adsorption capability was determined to be 0.1 (0.1Mn@Feox). The adsorption of As(III) on 0.1Mn@Feox was weakly influenced by pH change while As(V) adsorption showed high dependence on pH, achieving nearly complete removal at pH?<?5.7 but gradual decrease at pH?>?5.7. The adsorption kinetics and isotherms of As(III) and As(V) showed good conformity to pseudo-second-order kinetics model and Freundlich model, respectively.     

A combined treatment approach using Fenton's reagent and zero valent iron for the removal of arsenic from drinking water

Studies on the development of an arsenic remediation approach using Fenton's reagent (H2O2 and Fe(II)) followed by passage through zero valent iron is reported. The efficiency of the process was investigated under various operating conditions. Potable municipal water and ground water samples spiked with arsenic(III) and (V) were used in the investigations. The arsenic content was determined by ICP-QMS. A HPLC-ICPMS procedure was used for the speciation and determination of both As(III) and (V) in the processed samples, to study the effectiveness of the oxidation step and the subsequent removal of the arsenic.The optimisation studies indicate that addition of 100 microl of H2O2 and 100 mg of Fe(II) (as ferrous ammonium sulphate) per litre of water for initial treatment followed by passing through zero valent iron, after a reaction time of 10 min, is capable of removing arsenic to lower than the US Environmental Protection Agency (EPA) guideline value of 10 microg/l, from a starting concentration of 2 mg/l of As(III). Using these suggested amounts, several experiments were carried out at different concentrations of As(III). Residual hydrogen peroxide in the processed samples can be eliminated by subsequent chlorination, making the water, thus, processed, suitable for drinking purposes. This approach is simple and cost effective for use at community levels.     

A laboratory study for the treatment of arsenic, iron, and manganese bearing ground water using Fe(3+) impregnated activated carbon: effects of shaking time, pH and temperature

This paper deals with the experimental investigation related to removal of arsenic from a simulated contaminated ground water by the adsorption onto Fe(3+) impregnated granular activated carbon (GAC-Fe) in presence of Fe(2+), Fe(3+), and Mn(2+). Similar study has also been done with granular activated carbon (GAC) for comparison. The effects of shaking time, pH, and temperature on the percentage removal of As(T), As(III), As(V), Fe(2+), Fe(3+), and Mn have been discussed. The shaking time for optimum removal of arsenic species has been noted as 8h for GAC-Fe and 12h for GAC, respectively. As(T) removal was less affected by the change in pH within the pH range of 2-11. Maximum removal of As(V) and As(III) was observed in the pH range of 5-7 and 9-11, respectively, for both the adsorbents. Under the experimental conditions at 30 degrees C, the optimum removal of As(T), As(III), As(V), Fe, and Mn are 95.5%, 93%, 98%, 100%, and 41%, respectively, when GAC-Fe is used. For GAC these values are 56%, 41%, 71%, 99%, and 98%. The adsorbent dose (AD) and its particle size (PS) for both GAC and GAC-Fe were 30 g/l and 125-150 mum, respectively. The initial arsenic concentration in the synthetic water sample was 200 ppb.     

Treatment of concentrated arsenic(V) solutions by micellar enhanced ultrafiltration with high molecular weight cut-off membrane

In this work arsenic removal by micellar enhanced ultrafiltration (MEUF) was investigated using cetylpyridinium chloride (CPC) and a cross-flow polyethersulphone (PES) membrane apparatus. The effects of some operating factors on permeate flux, arsenic and CPC rejections were investigated and, in particular, transmembrane pressure, pH, CPC concentration, As concentration and ionic strength. The novel aim of this work is evaluating the possible advantages of using large molecular weight cut-off membrane (100 kDa) and reduced surfactant concentrations (1-3 mM) for treating high fluxes of concentrated arsenic-bearing solutions (6-10 ppm). The experimental results reported in this paper show that PES membrane apparatus with high molecular weight cut-off allowed to treat large fluxes of concentrated arsenic-bearing solutions (6-10 ppm) even by using low surfactant concentration (1-3mM). In particular arsenic removal ranged from 93-98% to 70-74% depending on initial As concentration (6 and 10 ppm, respectively). In addition surfactant leakage in the permeate was always below CMC due to presieving of concentration polarisation layer. The favourable combination of high MWCO membranes and low surfactant concentration can benefit to overall process economics for the lower membrane area requirement (due to greater flux) and the reduced surfactant consumption.     

Arsenic removal by adsorption on iron(III) phosphate

Under natural conditions, arsenic is often associated with iron oxides and iron(III) oxidative capacity towards As(III) is well known. In this study, As(III) and As(V) removal was performed using synthesised iron(III) phosphate, either amorphous or crystalline. This solid can combine (i) As(III) oxidation by iron(III) and (ii) phosphate substitution by As(V) due to their similar properties. Results showed that adsorption capacities were higher towards As(III), leading to Fe2+ and HAsO4(2-) leaching. Solid dissolution and phosphate/arsenate exchange led to the presence of Fe3+ and PO4(3-) in solution, therefore various precipitates involving As(V) can be produced: with Fe2+ as Fe3(AsO4)2.8H2O(s) and with Fe3+ as FeAsO4.2H2O(s). Such formations have been assessed by thermodynamic calculations. This sorbent can be a potential candidate for industrial waste treatment, although the high release of phosphate and iron will exclude its application in drinking water plants.     

Removal of As(V) and As(III) by reclaimed iron-oxide coated sands

This paper aims at the feasibility of arsenate and arsenite removal by reclaimed iron-oxide coated sands (IOCS). Batch experiments were performed to examine the adsorption isotherm and removal performance of arsenic systems by using the IOCS. The results show that the pH(zpc) of IOCS was about 7.0 +/- 0.4, favoring the adsorption of As(V) of anion form onto the IOCS surface. As the adsorbent dosage and initial arsenic concentration were fixed, both the As(V) and As(III) removals decrease with increasing initial solution pH. Under the same initial solution pH and adsorbent dosage, the removal efficiencies of total arsenic (As(V) and As(III)) were in the order as follows: As(V)>As(V)+As(III)>As(III). Moreover, adsorption isotherms of As(V) and As(III) fit the Langmuir model satisfactorily for the four different initial pH conditions as well as for the studied range of initial arsenic concentrations. It is concluded that the reclaimed IOCS can be considered as a feasible and economical adsorbent for arsenic removal.     

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 arsenic contaminated water in a laboratory scale up-flow bio-column reactor

The present paper describes the observations on the treatment of arsenic contaminated synthetic industrial effluent in a bio-column reactor. Ralstonia eutropha MTCC 2487 has been immobilized on the granular activated carbon (GAC) bed in the column reactor. The synthetic water sample containing As(T) (As(III):As(V)=1:1), Fe, Mn, Cu and Zn at the initial concentrations of 25, 10, 2, 5, 10 ppm, respectively, was used. Concentrations of all the elements have been found to be reduced below their permissible limits in the treated water. The significant effect of empty bed contact time (EBCT) and bed height on the arsenic removal was observed in the initial stage. However, after some time of operation (approximately 3-4 days) no such effect was observed. Removal of As(III) and As(V) was almost similar after approximately 2 days of operation. However, at the initial stage As(V) removal was slightly more than that of As(III). In absence of washing, after approximately 4-5 days of operation, the bio-column reactor was observed to act as a GAC column reactor based on physico-chemical adsorption. Like arsenic, the percent removals of Fe, Mn, Cu and Zn also attained minimum after approximately 1 day and increased significantly to the optimum value within 3-4 days of operation. Dissolved oxygen (DO) has been found to decrease along with the increasing bed height from the bottom. The pH of the solution in the reactor has increased slightly and oxidation-reduction potential (ORP) has decreased with the time of operation.     

Mechanism of arsenate coprecipitation at the solid/liquid interface of ferrihydrite: A perspective review

Arsenate (As(V)) is a toxic element in acid mine drainage and has to be removed during the neutralization process. Coprecipitation with ferrihydrite is the main mechanism for As(V) removal from acid mine drainage. To improve treatment efficiency, a quantitative understanding of the coprecipitation mechanism is required. Coprecipitation can incorporate more As(V) into ferrihydrite than adsorption. The results of XRD (X-ray Diffraction) and XANES (X-ray Adsorption Near Edge Structure) analysis confirmed that the formation of poorly crystalline ferric arsenate increased when the initial As/Fe molar ratio increased in the coprecipitation with ferrihydrite. EXAFS (Extended X-ray Adsorption Fine Structure) analysis at the iron K-edge showed that the proportion of octahedral structures in ferrihydrite increased when the initial As/Fe molar ratio increased. Moreover, EXAFS analysis at the arsenic K-edge, assuming three kinds of surface complexes for the AsFe bond, revealed that the coordination number for AsFe with an atomic distance of 2.85 × 10⁻¹⁰ m increased and that for As-Fe with an atomic distance of 3.24 × 10⁻¹⁰ m decreased as the initial As/Fe molar ratio increased. Thus, for more efficient wastewater treatment, active control of coprecipitation phenomena according to mechanistic details is essential.     

Removal of arsenic from water streams: an overview of available techniques

Arsenic poisoning has become one of the major environmental worries worldwide, as millions of people, which have been exposed to high arsenic concentrations (through contaminated drinking water), developed severe health problems. The high toxicity of this element made necessary the enforcement of stringent maximum allowable limits in drinking water. So, the development of novel techniques for its removal from aqueous streams is a very important issue. This paper offers an overview of geochemistry, distribution, sources, toxicity, regulations and applications of selected techniques for arsenic removal. The contribution briefly summarizes adsorption processes and mechanism of arsenic species removal from water streams by means of iron oxide/oxyhydroxide based materials. Sorption capacities of various sorbents (e.g. akaganeite, goethite, hydrous ferric oxide, iron oxide coated sand, Fe(III) loaded resin, granular ferric hydroxide, Ce(IV) doped iron oxide, natural iron ores, iron oxide coated cement, magnetically modified zeolite, Fe-hydroxide coated alumina) have been compared.     

Speciation of dissolved inorganic arsenic by diffusive gradients in thin films: selective binding of AsIII by 3-mercaptopropyl-functionalized silica gel

A diffusive gradients in thin films (DGT) technique for selectively measuring As(III) utilizes commercially available 3-mercaptopropyl-functionalized silica gel. Deployment of the new technique alongside the Metsorb-DGT for total inorganic arsenic allows the calculation of As(III) directly and As(V) by difference. Uptake of As(III) by mercapto-silica was quantitative and elution with a mixture of 1 mol L(-1) HNO(3) and 0.01 mol L(-1) KIO(3) gave a recovery of 85.6 ± 1.7%. DGT validation experiments showed linear accumulation of As(III) over time (R(2) > 0.998). Accumulation was unaffected by varying ionic strength (0.0001-0.75 mol L(-1) NaNO(3)) and pH (3.5-8.5). Deployment of mercapto-silica DGT and Metsorb DGT in seawater spiked with As(III) and As(V) demonstrated the ability of the combined approach to accurately quantify both species in the presence of potential competing ions. Ferrihydrite DGT, which has been previously reported for the measurement of total inorganic arsenic, was evaluated in seawater and shown to underestimate both As(III) and As(V) at longer deployment times (72 h). Reproducibility of the new mercapto-silica DGT technique was good (relative standard deviations < 9%), and the average method detection limit was sufficiently low to allow quantification of ultratrace concentrations of As(III) (0.03 μg L(-1); 72 h deployment).     

Effects of adsorbent dose, its particle size and initial arsenic concentration on the removal of arsenic, iron and manganese from simulated ground water by Fe3+ impregnated activated carbon

This paper presents the observations of the study on arsenic removal from a contaminated ground water (simulated) by adsorption onto Fe³⁺ impregnated granular activated carbon (GAC-Fe). Fe²⁺, Fe³⁺ and Mn²⁺ have also been considered along with arsenic species in the water sample. Similar study has also been done with untreated granular activated carbon (GAC) for comparison. The effects of adsorbent dose, particle size of adsorbent and initial arsenic concentration on the removal of As(T), As(III), As(V), Fe²⁺, Fe³⁺ and Mn²⁺ have been discussed. Under the experimental conditions, the optimum adsorbent doses for GAC-Fe and GAC have been found to be 8 g/l and 24 g/l, respectively with an agitation time of 15 h. Particle size of the adsorbents (both GAC and GAC-Fe) has shown negligible effect on the removal of arsenic and Fe species. However, for Mn removal the effect of adsorbent particle size is comparatively more. Percentage removal of As(T), As(V) and As(III) increase with the decrease in initial arsenic concentration (As₀). However, the increase in percentage removal of all the arsenic species with decrease in As₀ are less for higher value of As₀ (3000–500 ppb) than those of the lower value of As₀ (500–10 ppb). The % removal of As(T), As(III), As(V), Fe, and Mn were 95%, 92.4%, 97.6%, 99% and 41.2%, respectively when 8 g/l GAC-Fe was used at the As₀ value of 200 ppb. However, for GAC these values were 55.5%, 44%, 71%, 98% and 97%. The pH and temperature of the study were 7 ± 0.1 and 30 ± 1 °C, respectively.     

Enhancement of electrokinetic remediation of arsenic spiked soil by chemical reagents

An enhanced electrokinetic remediation process for removal of arsenic, presented as As(V) form, from spiked soil has been investigated with groundwater (GW) and chemical reagents of cetylpyridinium chloride (CPC, a cationic surfactant), ethylenediaminetetraacetic acid (EDTA) and citric acid (CA) under potential gradient of 2.0-3.3V/cm for 5 days treatment. The removal efficiency of As(V) in EK-EDTA system was better than that in other two EK systems. As potential gradient increased from 2.0V/cm to 3.0V/cm, the removal efficiency of As(V) was increased from 35.4% to 44.8% in EK-EDTA system. It showed that the arsenic removal could be enhanced by selecting suitable chemical reagent and increasing potential gradient. The intensive of electroosmotic flow towards the cathode caused a significant retardation of electromigration of arsenic towards the anode. The quantity of As(V) collected in anode reservoir was 1.4-2.5 times greater than that in cathode reservoir for all EK systems. It implied that As(V) removal was directly related to the electromigration rather than electroosmosis mechanism in EK systems. A further investigation need to be conducted to achieve higher removal efficiency of As(V).     

Adsorption and removal of arsenic(V) from drinking water by aluminum-loaded Shirasu-zeolite

The demand for effective and inexpensive adsorbents is to increase in response to the widespread recognition of the deleterious health effects of arsenic exposure through drinking water. A novel adsorbent, aluminum-loaded Shirasu-zeolite P1 (Al-SZP1), was prepared and employed for the adsorption and removal of arsenic(V) (As(V)) ion from aqueous system. The process of adsorption follows first-order kinetics and the adsorption behavior is fitted with a Freundlich isotherm. The adsorption of As(V) is slightly dependent on the initial pH over a wide range (3-10). Al-SZP1 was found with a high As(V) adsorption ability, equivalent to that of activated alumina, and seems to be especially suitable for removal of As(V) in low concentration. The addition of arsenite, chloride, nitrate, sulfate, chromate, and acetate ions hardly affected the As(V) adsorption, whereas the coexisting phosphate greatly interfered with the adsorption. The adsorption mechanism is supposed as a ligand-exchange process between As(V) ions and the hydroxide groups present on the surface of Al-SZP1. The adsorbed As(V) ions were desorbed effectively by a 40 mM NaOH solution. Continuous operation was demonstrated in a column packed with Al-SZP1. The feasibility of this technique to practical utilization was also assessed by adsorption/desorption multiple cycles with in situ desorption/regeneration operation.     

三维层级花状活性氧化铝纳米材料的制备及其除砷性能研究

以硝酸铝和尿素为原料, 通过简单的水热和高温煅烧法自组装形成三维层级花状活性氧化铝。这种结构既保留了氧化铝丰富的纳米级别活性位点, 同时具有微米级的三维尺寸, 在柱吸附除砷实验中起到骨架支撑作用, 而其较大的比表面积可以确保水中的砷酸根离子与吸附位点充分接触, 从而有效吸附水中砷酸根离子, 相较商用活性氧化铝具有更好的除砷性能, 且不会对水体产生二次污染。对制备的活性氧化铝材料的除砷动力学进行了分析, 明确了吸附动力学准一级和准二级模型的应用条件和范围。通过对该材料吸附砷酸根前后Zeta电位的变化的研究和离子强度实验进一步验证发现, γ-Al₂O₃对As(V)的吸附机理遵循内球配位模型, 而对As(III)的吸附机理遵循外球配位模型。     

Studies on the removal of arsenic (III) from water by a novel hybrid material

The present work provides a method for removal of the arsenic (III) from water. An ion-exchanger hybrid material zirconium (IV) oxide-ethanolamine (ZrO-EA) is synthesized and characterized which is subsequently used for the removal of selective arsenic (III) from water containing 10,50,100 mg/L of arsenic (III) solution. The probable practical application for arsenic removal from water by this material has also been studied. The various parameters affecting the removal process like initial concentration of As (III), adsorbent dose, contact time, temperature, ionic strength, and pH are investigated. From the data of results, it is indicated that, the adsorbent dose of 0.7 mg/L, contact time 50 min after which the adsorption process comes to equilibrium, temperature (25 ± 2), solution pH (5-7), which are the optimum conditions for adsorption. The typical adsorption isotherms are calculated to know the suitability of the process. The column studies showed 98% recovery of arsenic from water especially at low concentration of arsenic in water samples.     

Assessing arsenic leachability from pulverized cement concrete produced from arsenic-laden solid CalSiCo-sludge

Synthetically prepared arsenic-laden CalSiCo-sludge was converted to pulverized cement concrete (PCC) using solidification/stabilization technology with cement. Batch leaching experiments were conducted to estimate the leaching of As(III) and As(V) from the CalSiCo-sludge as well as from the PCC. The leaching of As(III) and As(V) was found to be the function of time, pH and concentration of anions such as Cl(-), NO(3)(-), and SO(4)(2-) present in the extraction fluid. It is observed that from the CalSiCo-sludge the leaching of As(III) is >0.05mg/l (which is above the permissible limit for arsenic in drinking water) at any pH. But in case of As(V) the leaching is >0.05mg/l only at pH>8 and at pH<4. It is noted that maximum leaching occurs when the extraction liquid contains Cl(-). In contrary, NO(3)(-) and SO(4)(2-) have negligible effect on arsenic leaching from the CalSiCo-sludge. Extraction tests were carried out to determine the maximum leachable concentration under the chosen conditions of leaching medium and leaching time. Leaching of As(III) and As(V) from exhausted arsenic-laden CalSiCo-sludge and from PCC was carried out in both tap water and rain water. It was noticed that tap water has no effect in leaching of arsenic from CalSiCo-sludge but rain water causes significant amount of leaching, which is mostly due to pH effect. However, in all cases the leaching of As(III) was more than that of As(V). When compared with CalSiCo-sludge PCC showed negligible leaching of arsenic. It was noticed further that the variation of 28 days compressive strength was within 15% of the original strength after replacing 35% cement with exhausted CalSiCo-sludge.