Preparation and evaluation of a novel Fe-Mn binary oxide adsorbent for effective arsenite removal

Arsenite (As(III)) is more toxic and more difficult to remove from water than arsenate (As(V)). As there is no simple treatment for the efficient removal of As(III), an oxidation step is always necessary to achieve higher removal. However, this leads to a complicated operation and is not cost-effective. To overcome these disadvantage, a novel Fe-Mn binary oxide material which combined the oxidation property of manganese dioxide and the high adsorption features to As(V) of iron oxides, were developed from low cost materials using a simultaneous oxidation and coprecipitation method. The adsorbent was characterized by BET surface areas measurement, powder XRD, SEM, and XPS. The results showed that prepared Fe-Mn binary oxide with a high surface area (265 m2 g(-1)) was amorphous. Iron and manganese existed mainly in the oxidation state +III and IV, respectively. Laboratory experiments were carried out to investigate adsorption kinetics, adsorption capacity of the adsorbent and the effect of solution pH values on arsenic removal. Batch experimental results showed that the adsorbent could completely oxidize As(III) to As(V) and was effective for both As(V) and As(III) removal, particularly the As(III). The maximal adsorption capacities of As(V) and As(III) were 0.93 mmol g(-1) and 1.77 mmol g(-1), respectively. The results compare favorably with those obtained using other adsorbent. The effects of anions such as SO4(2-), PO4(3-), SiO3(2-), CO3(2-) and humic acid (HA), which possibly exist in natural water, on As(III) removal were also investigated. The results indicated that phosphate was the greatest competitor with arsenic for adsorptive sites on the adsorbent. The presence of sulfate and HA had no significant effect on arsenic removal. The high uptake capability of the Fe-Mn binary oxide makes it potentially attractive adsorbent for the removal of As(III) from aqueous solution.     

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.     

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.     

Effects of water chemistry on arsenic removal from drinking water by electrocoagulation

Exposure to arsenic through drinking water poses a threat to human health. Electrocoagulation is a water treatment technology that involves electrolytic oxidation of anode materials and in-situ generation of coagulant. The electrochemical generation of coagulant is an alternative to using chemical coagulants, and the process can also oxidize As(III) to As(V). Batch electrocoagulation experiments were performed in the laboratory using iron electrodes. The experiments quantified the effects of pH, initial arsenic concentration and oxidation state, and concentrations of dissolved phosphate, silica and sulfate on the rate and extent of arsenic removal. The iron generated during electrocoagulation precipitated as lepidocrocite (γ-FeOOH), except when dissolved silica was present, and arsenic was removed by adsorption to the lepidocrocite. Arsenic removal was slower at higher pH. When solutions initially contained As(III), a portion of the As(III) was oxidized to As(V) during electrocoagulation. As(V) removal was faster than As(III) removal. The presence of 1 and 4 mg/L phosphate inhibited arsenic removal, while the presence of 5 and 20 mg/L silica or 10 and 50 mg/L sulfate had no significant effect on arsenic removal. For most conditions examined in this study, over 99.9% arsenic removal efficiency was achieved. Electrocoagulation was also highly effective at removing arsenic from drinking water in field trials conducted in a village in Eastern India. By using operation times long enough to produce sufficient iron oxide for removal of both phosphate and arsenate, the performance of the systems in field trials was not inhibited by high phosphate concentrations.     

Kinetic and thermodynamic aspects of adsorption of arsenic onto granular ferric hydroxide (GFH)

Relatively limited information is available regarding the impacts of temperature on the adsorption kinetics and equilibrium capacities of granular ferric hydroxide (GFH) for arsenic (V) and arsenic (III) in an aqueous solution. In general, very little information is available on the kinetics and thermodynamic aspects of adsorption of arsenic compounds onto other iron oxide-based adsorbents as well. In order to gain an understanding of the adsorption process kinetics, a detailed study was conducted in a controlled batch system. The effects of temperature and pH on the adsorption rates of arsenic (V) and arsenic (III) were investigated. Reaction rate constants were calculated at pH levels of 6.5 and 7.5. Rate data are best described by a pseudo first-order kinetic model at each temperature and pH condition studied. At lower pH values, arsenic (V) exhibits greater removal rates than arsenic (III). An increase in temperature increases the overall adsorption reaction rate constant values for both arsenic (V) and arsenic (III). An examination of thermodynamic parameters shows that the adsorption of arsenic (V) as well as arsenic (III) by GFH is an endothermic process and is spontaneous at the specific temperatures investigated.     

Evaluation of a novel hybrid inorganic/organic polymer type material in the arsenic removal process from drinking water

The objective of this paper is the evaluation of a hybrid inorganic/organic polymer type material based on hydrated ferric oxide (HFO), in the adsorption process of arsenic oxyanions from contaminated waters used as drinking water. The study includes rapid small-scale column tests conducted in continuous flow operation in order to assess the arsenic removal capacity in various conditions. Thus it was evaluated the influence of some competing ions like silicate and phosphate on As(V) adsorption and the influence of feed water pH in the removal process of As(V) and As(III) species. Based on the As/pH variation in time at different feed water pH (5, 7 and 9), a possible sorption mechanism that fits the experimental data was suggested. The regeneration and re-use of the hybrid adsorbent was studied in the presence and in the absence of the contaminant ions. The novel hybrid material is very selective towards arsenic oxyanions even though the presence of silica and phosphate reduces the adsorption capacity.     

Anchorage of iron hydro(oxide) nanoparticles onto activated carbon to remove As(V) from water

The adsorption of arsenic (V) by granular iron hydro(oxides) has been proven to be a reliable technique. However, due to the low mechanical properties of this material, it is difficult to apply it in full scale water treatment. Hence, the aim of this research is to develop a methodology to anchor iron hydro(oxide) nanoparticles onto activated carbon, in which the iron hydro(oxide) nanoparticles will give the activated carbon an elevated active surface area for arsenic adsorption and also help avoid the blockage of the activated carbon pores. Three activated carbons were modified by employing the thermal hydrolysis of iron as the anchorage procedure. The effects of hydrolysis temperature (60-120 °C), hydrolysis time (4-16 h), and FeCl₃ concentration (0.4-3 mol Fe/L) were studied by the surface response methodology. The iron content of the modified samples ranged from 0.73 to 5.27%, with the higher end of the range pertaining to the carbons with high oxygen content. The materials containing smaller iron hydro(oxide) particles exhibited an enhanced arsenic adsorption capacity. The best adsorbent material reported an arsenic adsorption capacity of 4.56 mg As/g at 1.5 ppm As at equilibrium and pH 7.     

Adsorption and desorption of arsenic on an oxisol and its constituents

The present work investigates the adsorption and mobility (desorption) of As(III) and As(V) on an oxisol, and its main mineral constituents, as part of a broader project aimed at selecting a soil liner to be used in tailings dams at a sulfidic gold ore plant. Emphasis was given to a quantitative comparison of As mobility-here assessed by the amount of As leached from the loaded samples-under different experimental conditions. From among the soil constituents, goethite was the most efficient adsorbent with regard to arsenic adsorption, 12.4 mg x g(-1) for As(V) and 7.5 mg x g(-1) for As(III), respectively. Gibbsite also presented a relevant adsorption capacity (4.6 mg x g(-1) for As(V) and 3.3 mg x g(-1) for As(III)); adsorption on kaolinite was negligible (<0.23 mg x g(-1) for As(V) and As(III)). Desorption of the arsenic was shown to vary largely with the arsenic oxidation state, the adsorbents and the leaching solutions. While only 1-2% max. of As(V) was released from the loaded samples, leaching the A(III) reached 32%, the highest values corresponding to the solutions containing sulfate ions. Oxisol and goethite were superior to gibbsite with respect to As immobilization. Adsorption and mobility were also discussed with the help of electrophoretic mobility and isoelectric points (IEP) determined prior and following arsenic adsorption on goethite and gibbsite. The results indicated that As(V) is mainly adsorbed as an inner sphere complex. As(III) may be adsorbed as an inner or an outer neutral complex.     

Application of biological processes for the removal of arsenic from groundwaters

Bacteria are widespread, abundant, geochemically reactive components of aquatic environments. In particular, iron-oxidizing bacteria, are involved in the oxidation and subsequent precipitation of ferrous ions. Due to this property, they have been applied in drinking water treatment processes, in order to accelerate the removal of ferrous iron from groundwaters. Iron also exerts a strong influence on arsenic concentrations in groundwater sources, while iron oxides are efficient adsorbents in arsenic removal processes. In the present study, the removal of arsenic (III and V), during biological iron oxidation has been investigated. The results showed that both inorganic forms of arsenic could be efficiently treated, for the concentration range of interest in drinking water (50-200microg/L). In addition, the oxidation of trivalent arsenic was found to be catalyzed by bacteria, leading to enhanced overall arsenic removal, because arsenic in the form of arsenites cannot be efficiently sorbed onto iron oxides. This method comprises a cost competitive technology, which can find application in treatment of groundwaters with elevated concentrations of iron and arsenic.     

Polymer composite adsorbents using particles of molecularly imprinted polymers or aluminium oxide nanoparticles for treatment of arsenic contaminated waters

Removal of As(V) by adsorption from water solutions was studied using three different synthetic adsorbents. The adsorbents, (a) aluminium nanoparticles (Alu-NPs, <50 nm) incorporated in amine rich cryogels (Alu-cryo), (b) molecular imprinted polymers (<38 μm) in polyacrylamide cryogels (MIP-cryo) and (c) thiol functionalised cryogels (SH-cryo) were evaluated regarding material characteristics and arsenic removal in batch test and continuous mode. Results revealed that a composite design with particles incorporated in cryogels was a successful means for applying small particles (nano- and micro- scale) in water solutions with maintained adsorption capacity and kinetics. Low capacity was obtained from SH-cryo and this adsorbent was hence excluded from the study. The adsorption capacities for the composites were 20.3 ± 0.8 mg/g adsorbent (Alu-cryo) and 7.9 ± 0.7 mg/g adsorbent (MIP-cryo) respectively. From SEM images it was seen that particles were homogeneously distributed in Alu-cryo and heterogeneously distributed in MIP-cryo. The particle incorporation increased the mechanical stability and the polymer backbones of pure polyacrylamide (MIP-cryo) were of better stability than the amine containing polymer backbone (Alu-cryo). Both composites worked well in the studied pH range of pH 2-8. Adsorption tested in real wastewater spiked with arsenic showed that co-ions (nitrate, sulphate and phosphate) affected arsenic removal for Alu-cryo more than for MIP-cryo. Both composites still adsorbed well in the presence of counter-ions (copper and zinc) present at low concentrations (μg/l). The unchanged and selective adsorption in realistic water observed for MIP-cryo was concluded to be due to a successful imprinting, here controlled using a non-imprinted polymer (NIP). A development of MIP-cryo is needed, considering its low adsorption capacity.     

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.     

A study on arsenic adsorption on polymetallic sea nodule in aqueous medium

A detailed study on As(III) and As(V) adsorption on polymetallic sea nodule in aqueous medium has been reported. Elemental composition of sea nodule comprises primarily, iron, manganese and silicon with trace quantities of aluminium, copper, cobalt and nickel. As(V) adsorption on sea nodule is dependent on pH while As(III) is insensitive to it. Adsorption data broadly follow Langmuir isotherm. Kinetic data follow a pseudo-second-order model for both As(III) and As(V). Arsenic loading on sea nodule is dependent on initial arsenic concentration. Optimum As(III) loading is 0.74 mg/g at 0.34 mg/L and for As(V) it is 0.74 mg/g at 0.78mg/L. As(III) adsorption is broadly independent of ionic environment. Except for PO(4)(3-), As(III) adsorption is not influenced by anions but cations influence it significantly. As(V) adsorption, on the other hand, is influenced by anions and not by cations. Experimental evidence indicates an inner sphere complex for As(III) and partial inner and partial outer sphere complex for As(V). Both As(III) and As(V) adsorptions are marked with very little desorption in the pH range of 2-10. Sea nodule can speciate As(III) and As(V) in groundwater at or above pH 6. Sea nodule was successfully tested as an adsorbent for the removal of arsenic from six contaminated groundwater samples of West Bengal, India, containing arsenic in the range 0.04-0.18mg/L.     

Arsenic remobilization in water treatment adsorbents under reducing conditions: Part I. Incubation study

The redox transformation and mobility of arsenic in spent adsorbents under reducing conditions were studied using an incubation test with mixed reducing bacteria, high-performance liquid chromatography-atomic fluorescence spectrometry for speciation of soluble arsenic (As), and thermodynamic calculations. The spent adsorptive media, including granular ferric hydroxide, granular ferric oxide, titanium dioxide, activated alumina and modified activated alumina, were collected from pilot-scale filters that were tested for removal of arsenate [As(V)] from groundwater in New Jersey, USA. During 65 days of incubation of the spent adsorbents with nutrient media in closed containers, the electron activity, pe, was reduced from about 1.7 to -7. Meanwhile, reduction of Fe(III) to Fe(II), As(V) to arsenite [As(III)], and sulfate to sulfide occurred. Less than 4% total As was released from iron-based media in the pe range between -3 and -7 due to reduction of As(V) to As(III) and reductive dissolution of ferric (hydr)oxides. Up to 38% As was released from the TiO2 adsorbent, which occurred at extremely low redox potential (i.e., pe<-6). The findings of this study will improve our ability to predict arsenic mobility when As-containing spent media are disposed of in landfills and the environment.     

Magnetic zeolites: a new adsorbent for removal of metallic contaminants from water

In this work the adsorption features of Na Y zeolite with the magnetic properties of iron oxides have been combined in a composite to produce a magnetic adsorbent. These magnetic composites can be used as an adsorbent for metallic contaminants in water and subsequently removed from the medium by a simple magnetic process. The zeolites:iron oxide magnetic composites, were prepared by using Na Y with weight ratio of 3:1 and were characterized by powder X-ray diffraction (XRD), magnetization measurements, chemical analyses, N(2) adsorption isotherms and M?ssbauer spectroscopy. Nitrogen adsorption isotherms showed that the surface area decreased from 505 m(2)g(-1) for the pure Na Y to 353 m(2)g(-1) for the Na Y:Fe oxide 3:1 composite. The adsorption isotherms of metal ions Cr(3+), Cu(2+) and Zn(2+) from aqueous solution onto the composites also showed that the presence of iron oxide does not affect the adsorption capacity.     

Magnetic powder MnO-Fe2O3 composite--a novel material for the removal of azo-dye from water

Fine powder adsorbents or catalysts often show better adsorptive or catalytic properties, but they encounter the difficulties of separation and recovery in application. In this study, four inexpensive magnetic powder MnO-Fe2O3 composites used as adsorbent-catalyst materials were prepared and characterized. These materials could be recovered efficiently by a magnetic separation method. Their adsorptive properties for the removal of an azo-dye, acid red B (ARB), from water and the regeneration of adsorbents containing ARB by catalytic combustion was studied. These powder adsorbents showed excellent adsorption towards ARB under acidic conditions. A very fast adsorption rate was observed and could be well described by a pseudo-second-order kinetics model. The adsorption capacity increased with increasing Fe content and surface area of the adsorbent, and the highest adsorption capacity of 105.3 mg/g was obtained at pH 3.5. The adsorption was not affected by the presence of Cl-, but was significantly affected by SO4(2-). The adsorbent containing ARB can be regenerated by catalytic combustion of adsorbed ARB at 400 degrees C in air. Laboratory experiments demonstrated that this material is reusable.     

Advanced phosphorus removal from membrane filtrates by adsorption on activated aluminium oxide and granulated ferric hydroxide

The advanced phosphorus (P) removal by adsorption was studied for its suitability as a post-treatment step for membrane bioreactor (MBR) effluents low in P concentration and particle content. Two commercial adsorbents, granulated ferric hydroxide (GFH) and activated aluminium oxide (AA), were studied in batch tests and lab-scale filter tests for P adsorption in MBR filtrates. GFH showed a higher maximum capacity for phosphate and a higher affinity at low P concentrations compared to AA. Competition by inorganic ions was negligible for both adsorbents at the original pH (8.2). When equilibrium P concentrations exceeded 2 mg L(-1) in the spiked MBR filtrates, a precipitation of calcium phosphates occurred additionally to adsorption. During column studies the effluent criteria of 50 microgL(-1) P was reached after a throughput of 8000 bed volumes for GFH and 4000 for AA. Dissolved organic carbon appears to be the strongest competitor for adsorption sites. A partial regeneration and reloading of both adsorbents could be achieved by the use of sodium hydroxide.     

Vanadium removal by metal (hydr)oxide adsorbents

Vanadium is listed on the United States Environment Protection Agency (USEPA) candidate contaminant list # 2 (CCL2), and regulatory guidelines for vanadium exist in some US states. The USEPA requires treatability studies before making regulatory decisions on CCL2 contaminants. Previous studies have examined vanadium adsorption onto some metal hydroxides but not onto commercially available adsorbents. This paper briefly summarizes known vanadium occurrence in North American groundwater and assesses vanadium removal by three commercially available metal oxide adsorbents with different mineralogies. GTO (Dow) is TiO2 based and E-33 (Seven Trents) and GFH (US Filter) are iron based. Preliminary vanadate adsorption kinetics onto GFH, E-33 and GTO has been studied and the homogenous surface diffusion model (HSDM) is used to describe the adsorption kinetics data. The effects of pH, vanadium concentration, and volume/mass ratio are assessed. Vanadium adsorption decreases with increasing pH, with maximum adsorption capacities achieved in at pH 3-4. Results indicate that all adsorbents remove vanadium; GFH has the highest adsorption capacity, followed by GTO and E-33. Data are best fit with the Langmuir model rather than Freundlich isotherms. Both the sorption maxima (Xm) and binding energy constant (b) follow the trend GFH>GTO>E-33. Naturally occurring vanadium is also removed from Arizona ground water in rapid small-scale column tests (RSSCTs). Metal oxide adsorption technologies currently used for arsenic removal may also remove vanadium but not always with the same effectiveness.     

Removal of estrone and 17beta-estradiol from water by adsorption

Endocrine disrupting chemicals (EDCs) are the focus of current environment concern, as they can cause adverse health effects in an intact organism, or its progeny, subsequent to endocrine function. The paper reports on the removal of estrone (E1) and 17beta-estradiol (E2) from water through the use of various adsorbents including granular activated carbon (GAC), chitin, chitosan, ion exchange resin and a carbonaceous adsorbent prepared from industrial waste. The results show that the kinetics of adsorption were adsorbent and compound-dependent, with equilibration being reached within 2 h for a waste-derived carbonaceous adsorbent to 71 h for an ion-exchange resin for E1, and within 7 h for the waste-derived carbonaceous adsorbent to 125 h for GAC for E2. Of all the adsorbents tested, the carbonaceous adsorbent showed the highest adsorption capacity, with a maximum adsorption constant of 87500 ml/g for E1 and 116000 ml/g for E2. The GAC also had a very high adsorption capacity for the two compounds, with a maximum adsorption constant of 9290 ml/g for E1 and 12200 ml/g for E2. The effects of some fundamental environmental parameters including adsorbent concentration, pH, salinity and the presence of humic acid and surfactant on adsorption were studied. The results show that adsorption capacity of activated carbon was decreased with an increase in adsorbent concentration and by the presence of surfactant and humic acid. The results have demonstrated excellent performance of a waste derived adsorbent in removing E1 and E2 from water, and indicated the potential of converting certain solid waste into useful adsorbents for pollution-control purposes.     

Adsorption of arsenic from a Nova Scotia groundwater onto water treatment residual solids

Water treatment residual solids were examined in batch adsorption and column adsorption experiments using a groundwater from Halifax Regional Municipality that had an average arsenic concentration of 43 μg/L (±4.2 μg/L) and a pH of 8.1. The residual solids studied in this paper were from five water treatment plants, four surface water treatment plants that utilized either alum, ferric, or lime in their treatment systems, and one iron removal plant. In batch adsorption experiments, iron-based residual solids and lime-based residual solids pre-formed similarly to GFH, a commercially-available adsorbent, while alum-based residual solids performed poorly. Langmuir isotherm modeling showed that ferric residuals had the highest adsorptive capacity for arsenic (Q_max = 2230 mg/kg and 42,910 mg/kg), followed by GFH (Q_max = 640 mg/kg), lime (Q_max = 160 mg/kg) and alum (Q_max = <1 mg/kg and 3 mg/kg). Similarly, the maximum arsenic removal was >93% for the ferric and lime residuals and GFH, while the maximum arsenic removal was <49% for the alum residuals under the same conditions. In a column adsorption experiment, ferric residual solids achieved arsenic removal of >26,000 bed volumes before breakthrough past 10 μg As/L, whereas the effluent arsenic concentration from the GFH column was under the method detection limit at 28,000 bed volumes. Overall, ferric and lime water treatment residuals were promising adsorbents for arsenic adsorption from the groundwater, and alum water treatment residuals did not achieve high levels of arsenic adsorption.