Removal of arsenic from groundwater by granular titanium dioxide adsorbent

A novel granular titanium dioxide (TiO2) was evaluated for the removal of arsenic from groundwater. Laboratory experiments were carried out to investigate the adsorption capacity of the adsorbent and the effect of anions on arsenic removal. Batch experimental results showed that more arsenate [As(V)] was adsorbed on TiO2 than arsenite [As(III)] in US groundwater at pH 7.0. The adsorption capacities for As(V) and As(III) were 41.4 and 32.4 mgg(-1) TiO2, respectively. However, the adsorbent had a similar adsorption capacity for As(V) and As(III) (approximately 40 mgg(-1)) when simulated Bangladesh groundwater was used. Silica (20 mgl(-1)) and phosphate (5.8 mgl(-1)) had no obvious effect on the removal of As(V) and As(III) by TiO2 at neutral pH. Point-of-entry (POE) filters containing 3 l of the granular adsorbent were tested for the removal of arsenic from groundwater in central New Jersey, USA. Groundwater was continuously passed through the filters at an empty bed contact time (EBCT) of 3 min. Approximately 45,000 bed volumes of groundwater containing an average of 39 microgl(-1) of As(V) was treated by the POE filter before the effluent arsenic concentration increased to 10 microgl(-1). The total treated water volumes per weight of adsorbent were about 60,000 l per 1 kg of adsorbent. The field filtration results demonstrated that the granular TiO2 adsorbent was very effective for the removal of arsenic in groundwater.     

Arsenic uptake and speciation and the effects of phosphate nutrition in hydroponically grown kikuyu grass (Pennisetum clandestinum Hochst)

Background

This work focuses on the accumulation and mobility properties of arsenic (As) and the effects of phosphate (P) on its movement in Pennisetum clandestinum Hochst (kikuyu grass), grown hydroponically under increasing arsenate (As(V)) concentrations. The uptake of both ions and the relative kinetics show that phosphate is an efficient competitive inhibitor of As(V) uptake. The P/As uptake rate ratios in roots indicate that P is taken up preferentially by P/As transporters. An arsenite (As(III)) efflux from roots was also found, but this decreased when the arsenate concentration in the solution exceeded 5???M.

Methods

Increases in both arsenite and arsenate concentrations in roots were observed when the arsenate concentration in the solution was increased, and the highest accumulation of As(III) in roots was found when plants were grown at 5???M As(V). The low ratios of As accumulated in shoots compared to roots suggest limited mobility of the metalloid within Kikuyu plants.

Results

The results indicate that arsenic resistance in kikuyu grass in conditions of moderate exposure is mainly dependent on the following factors: 1) phosphate nutrition: P is an efficient competitive inhibitor of As(V) uptake because of the higher selectivity of membrane transporters with respect to phosphate rather than arsenate; and 2) a detoxification mechanism including a reduction in both arsenate and arsenite root efflux.

Conclusions

The As tolerance strategy of Kikuyu limits arsenate uptake and As translocation from roots to shoots; therefore, this plant cannot be considered a viable candidate for use in the phytoextraction of arsenic from contaminated soils or water.     

Arsenic species in ecosystems affected by arsenic-rich spring water near an abandoned mine in Korea

The objectives of this study were to quantitatively estimate the distribution of arsenic with its speciation and to identify potential pathways for transformation of arsenic species from samples of water, sediments, and plants in the ecosystem affected by the Cheongog Spring, where As(V) concentration reached levels up to 0.270 mg L⁻¹. After flowing about 100 m downstream, the arsenic level showed a marked reduction to 0.044 mg L⁻¹ (about 84% removal) without noticeable changes in major water chemistry. The field study and laboratory hydroponic experiments with the dominant emergent plants along the creek (water dropwort and thunbergian smartweed) indicated that arsenic distribution, reduction, and speciation appear to be controlled by, (i) sorption onto stream sediments in exchangeable fractions, (ii) bioaccumulation by and possible release from emergent plants, and (iii) transformation of As(V) to As(III) and organic species through biological activities.     

Arsenic removal from water employing heterogeneous photocatalysis with TiO2 immobilized in PET bottles

Arsenic oxidation (As(III) to As(V)) and As(V) removal from water were assessed by using TiO₂ immobilized in PET (polyethylene terephthalate) bottles in the presence of natural sunlight and iron salts. The effect of many parameters was sequentially studied: TiO₂ concentration of the coating solution, Fe(II) concentration, pH, solar irradiation time; dissolved organic carbon concentration. The final conditions (TiO₂ concentration of the coating solution: 10%; Fe(II): 7.0 mg l⁻¹; solar exposure time: 120 min) were applied to natural water samples spiked with 500 μg l⁻¹ As(III) in order to verify the influence of natural water matrix. After treatment, As(III) and total As concentrations were lower than the limit of quantitation (2 μg l⁻¹) of the voltammetric method used, showing a removal over 99%, and giving evidence that As(III) was effectively oxidized to As(V). The results obtained demonstrated that TiO₂ can be easily immobilized on a PET surface in order to perform As(III) oxidation in water and that this TiO₂ immobilization, combined with coprecipitation of arsenic on Fe(III) hydroxides(oxides) could be an efficient way for inorganic arsenic removal from groundwaters.     

High-level arsenite removal from groundwater by zero-valent iron

The objectives of this study were to conduct batch and column studies to (i) assess the effectiveness of zero-valent iron for arsenic remediation in groundwater, (ii) determine removal mechanisms of arsenic, and (iii) evaluate implications of these processes with regard to the stability of arsenic and long-term remedial performance of the permeable reactive barrier (PRB) technology. A high concentration arsenic solution (50 mg l(-1)) was prepared by using sodium arsenite (arsenic (III)) to simulate groundwater at a heavily contaminated Superfund site in the USA. Batch studies indicate that the removal of arsenic is a two-step reaction with fast initial disappearance of arsenite followed by a slow subsequent removal process. Flow-through columns were conducted at a flow rate of 17 ml h(-1) under reducing conditions for 6.6 mo. Kinetic analysis suggested that arsenic removal behaves as a zero-order reaction at high arsenic concentrations. Arsenic removal rate constants decreased with time and arsenic breakthrough was observed in the column study. Arsenic removal capacity of zero-valent iron was determined to be approximately 7.5 mg As/g Fe. Carbonate green rust was identified from the analysis of surface precipitates; arsenite uptake by green rust may be a major mechanism responsible for arsenic remediation by zero-valent iron. Analysis of HCl-extractable arsenic from iron samples indicated that approximately 28% of arsenic was in the form of arsenate suggesting that a surface oxidation process was involved in the arsenic removal with zero-valent iron.     

Removal of arsenic from water by electrocoagulation

In the present study electrocoagulation (EC) has been evaluated as a treatment technology for arsenite [As(III)] and arsenate [As(V)] removal from water. Laboratory scale experiments were conducted with three electrode materials namely, iron, aluminum and titanium to assess their efficiency. Arsenic removal obtained was highest with iron electrodes. EC was able to bring down aqueous phase arsenic concentration to less than 10 microgl(-1) with iron electrodes. Current density was varied from 0.65 to 1.53 mAcm(-2) and it was observed that higher current density achieved rapid arsenic removal. Experimental results at different current densities indicated that arsenic removal was normalized with respect to total charge passed and therefore charge density has been used to compare the results. Effect of pH on arsenic removal was not significant in the pH range 6-8. Comparative evaluation of As(III) and As(V) removal by chemical coagulation (with ferric chloride) and electrocoagulation has been done. The comparison revealed that EC has better removal efficiency for As(III), whereas As(V) removal by both processes was nearly same. The removal mechanism of As(III) by EC seems to be oxidation of As(III) to As(V) and subsequent removal by adsorption/complexation with metal hydroxides generated in the process.     

Investigation of arsenic removal in batch wise water treatments by means of sequential hydride generation flow injection analysis

Arsenic water pollution is a big issue worldwide. Determination of inorganic arsenic in each oxidation state is important because As(III) is much more toxic than As(V). An automated arsenic measurement system was developed based on complete vaporization of As by a sequential procedure and collection/preconcentration of the vaporized AsH(3), which was subsequently measured by a flow analysis. The automated sensitive method was applied to monitoring As(III) and As(V) concentrations in contaminated water standing overnight. Behaviors of arsenics were investigated in different conditions, and unique time dependence profiles were obtained. For example, in the standing of anaerobic water samples, the As(III) concentration immediately began decreasing whereas dead time was observed in the removal of As(V). In normal groundwater conditions, most arsenic was removed from the water simply by standing overnight. To obtain more effective removal, the addition of oxidants and use of steel wools were investigated. Simple batch wise treatments of arsenic contaminated water were demonstrated, and detail of the transitional changes in As(III) and As(V) were investigated.     

Organo-modified sericite in the remediation of an aquatic environment contaminated with As(III) or As(V)

The aim of this investigation was to obtain the hybrid material precursor to the naturally and abundantly available sericite, a mica-based clay; the materials were further employed in the remediation of arsenic from aqueous solutions. The study was intended to provide a cost-effective and environmentally benign treatment technology. The hybrid organo-modified sericite was obtained using hexadecyltrimethylammonium bromide (HDTMA) and alkyldimethylbenzylammonium chloride (AMBA) organic surfactants by introducing regulated doses of HDTMA or AMBA. The materials were characterized using infrared and X-ray diffraction analytical data, whereas the surface morphology was discussed by taking its SEM images. These materials were employed to assess the pre-concentration and speciation of As(III) and As(V) from aqueous solutions. The batch reactor data showed that increasing the sorptive concentration (from 1.0 to 15.0 mg/L) and pH (i.e., pH 2.0 to 10.0) caused the percent uptake of As(III) and As(V) to decrease significantly. The kinetic data showed that a sharp initial uptake of arsenic reached its equilibrium state within about 50 min of contact time, and the sorption kinetics followed a pseudo-second-order rate law both for As(III) and As(V) sorption. A 1,000 times increase in the background electrolyte concentration, i.e., NaNO₃, caused a significant decrease in As(III) removal, whereas As(V) was almost unaffected, which inferred that As(III) was adsorbed, mainly by the van der Waals or even by the electrostatic attraction, whereas As(V) was adsorbed chemically and formed “inner-sphere” complexes at the solid/solution interface. The equilibrium state modeling studies indicated that the sorption data fitted well the Freundlich and Langmuir adsorption isotherms. Henceforth, the removal capacity was calculated under these equilibrium conditions. It was noted that organo-modified sericite possessed a significantly higher removal capacity compared to its virgin sericite. Between these two organo-modified sericite, the HDTMA-modified sericite possessed a higher removal capacity compared to the AMBA-modified sericite.     

Simultaneous reduction of Cr(VI) and oxidation of As(III) by Bacillus firmus TE7 isolated from tannery effluent

Hexavalent chromium [Cr(VI)] and arsenite [As(III)] are the most toxic forms of chromium and arsenic respectively, and reduction of Cr(VI) to Cr(III) and oxidation of As(III) to As(V) has great environmental implications as they affect toxicity and mobility of these toxic species. Bacillus firmus strain TE7, resistant to chromium and arsenic was isolated from tannery effluent. The strain exhibited ability to reduce Cr(VI) and oxidize As(III). It reduced 100 mg L^?1 Cr(VI) within 60 h in nutrient broth and oxidized 150 mg L^?1 As(III) within 10 h in minimal medium. It also completely reduced 15 mg L^?1 Cr(VI) and oxidized 50 mg L^?1 of As(III) simultaneously in minimal medium. To the best of our knowledge, this is the first bacterial strain showing simultaneous reduction of Cr(VI) and oxidation of As(III) and is a potential candidate for bioremediation of environments contaminated with these toxic metal species.     

Magnetite/mesocellular carbon foam as a magnetically recoverable fenton catalyst for removal of phenol and arsenic

A magnetite-loaded mesocellular carbonaceous material, Fe₃O₄/MSU-F-C, exhibited superior activity as both a Fenton catalyst and an adsorbent for removal of phenol and arsenic, and strong magnetic property rendering it separable by simply applying magnetic field. In the presence of hydrogen peroxide, the catalytic process by Fe₃O₄/MSU-F-C completely oxidized phenol and As(III) under the conditions where commercial iron oxides showed negligible effects. Notably, the decomposition of H₂O₂ by Fe₃O₄/MSU-F-C was not faster than those by commercial iron oxides, indicating that hydroxyl radical produced via the catalytic process by Fe₃O₄/MSU-F-C was used more efficiently for the oxidation of target contaminants compared to the other iron oxides. The homogeneous Fenton reaction by the dissolved iron species eluted from Fe₃O₄/MSU-F-C was insignificant. At relatively high doses of Fe₃O₄/MSU-F-C, total concentration of arsenic decreased to a significant extent due to the adsorption of arsenic on the catalyst surface. The removal of arsenic by adsorption was found to proceed via preoxidation of As(III) into As(V) and the subsequent adsorption of As(V) onto the catalyst.     

Diel cycles of arsenic speciation due to photooxidation in acid mine drainage from the Iberian Pyrite Belt (Sw Spain)

Twenty four hours diel cycles of arsenic speciation in Acid Mine Drainage (AMD) due to photooxidation have been reported for the first time. AMD samples were taken during 48 h (31st March and 1st April, 2005) at 6 h intervals from the effluent of a massive abandoned polymetallic sulphide mine of the Iberian Pyrite Belt (Sw Spain). Samples were preserved in situ using cationic exchange prior to analysis by coupled high performance liquid chromatography, hydride generation and atomic fluorescence spectrometry (HPLC-HG-AFS) for arsenic speciation. The results indicated the presence of inorganic arsenic species with daily means of 262mugl(-1) for As(V) and 107 microg l(-1) for As(III). No marked diel trend was observed for As(V). However, a marked diel trend was observed for As(III) in the two studied days, with maximum concentrations during nighttime (141-143 microg l(-1)) and minimum concentrations at daytime (72-77 microg l(-1)). This difference in concentration during daytime and nighttime is ca. 100%. A similar diel cycle was observed for iron. An explanation for the arsenic diel cycles observed is the light induced photooxidation of As(III) and the elimination of As(V) due to its adsorption onto Fe precipitates during the daytime. Furthermore, the diel changes in arsenic speciation emphasize the importance of designing suitable sampling strategies in AMD systems.     

Removal of arsenic(III,V) by a granular Mn-oxide-doped Al oxide adsorbent: surface characterization and performance

In order to remove arsenic (As) from contaminated water, granular Mn-oxide-doped Al oxide (GMAO) was fabricated using the compression method with the addition of organic binder. The analysis results of XRD, SEM, and BET indicated that GMAO was microporous with a large specific surface area of 54.26 m^2/g, and it was formed through the aggregation of massive Al/Mn oxide nanoparticles with an amorphous pattern. EDX, mapping, FTIR, and XPS results showed the uniform distribution of Al/Mn elements and numerous hydroxyl groups on the adsorbent surface. Compression tests indicated a satisfactory mechanical strength of GMAO. Batch adsorption results showed that As(V) adsorption achieved equilibrium faster than As(III), whereas the maximum adsorption capacity of As(III) estimated from the Langmuir isotherm at 25 °C (48.52 mg/g) was greater than that of As(V) (37.94 mg/g). The As removal efficiency could be maintained in a wide pH range of 3~8. The presence of phosphate posed a significant adverse effect on As adsorption due to the competition mechanisms. In contrast, Ca²⁺ and Mg²⁺ could favor As adsorption via cation-bridge involvement. A regeneration method was developed by using sodium hydroxide solution for As elution from saturated adsorbents, which permitted GMAO to keep over 75% of its As adsorption capacity even after five adsorption–regeneration cycles. Column experiments showed that the breakthrough volumes for the treatment of As(III)-spiked and As(V)-spiked water (As concentration = 100 μg/L) were 2224 and 1952, respectively. Overall, GMAO is a potential adsorbent for effectively removing As from As-contaminated groundwater in filter application.

     

Interactions of arsenic and phenanthrene on their uptake and antioxidative response in Pteris vittata L

The interactions of arsenic and phenanthrene on plant uptake and antioxidative response of Pteris vitatta L. were studied hydroponically. The combination of arsenic and phenanthrene decreased arsenic contents in fronds by 30-51%, whereas increased arsenic concentrations 1.2-1.6 times in roots, demonstrating the suppression of arsenic translocation compared to the corresponding treatment without phenanthrene. Under the co-exposure, As(III) concentrations in fronds deceased by 12-73%, and at higher arsenic exposure level (≥10 mg/L), As(V) in fronds and As(III) in roots increased compared to the single arsenic treatment. Arsenic exposure elevated phenanthrene concentrations in root by 39-164%. The co-existence of arsenic and phenanthrene had little impact on plant arsenic accumulation, although synergistic effect on antioxidants was observed, suggesting the special physiological process of P. vitatta in the co-exposure and application potential of P. vitatta in phytoremediation of arsenic and PAHs co-contamination.     

Adsorption/desorption of arsenite and arsenate on chitosan and nanochitosan

Equilibrium sorption studies of anionic species of arsenite, As(III) ions and arsenate As(V) ions onto two biosorbents, namely, chitosan and nanochitosan, have been investigated and compared. The results and trends in the sorption behavior are novel, and we have observed during the sorption process of the As(III) and As(V) on chitosan, a slow process of desorption occurred after an initial maximum adsorption capacity was achieved, before reaching a final but lower equilibrium adsorption capacity. The same desorption trend, however, is not observed on nanochitosan. The gradual desorption of As(III) and As(V) in the equilibrium sorption on chitosan is attributed to the different fractions of the dissociated forms of arsenic on the adsorbent surface and in solution and the extent of protonation of chitosan with the changing of solution pH during sorption. The change of solution pH during the sorption of arsenite ions on chitosan was also influenced by the interaction between the buffering effect of the arsenite species in the aqueous medium and the physical properties of chitosan. The final equilibrium adsorption capacity of chitosan for As(III) and As(V) was found to be around 500 and 8000 μg/g, respectively, whereas the capacities on nanochitosan are 6100 and 13,000 μg/g, respectively.

     

Iron oxide-loaded slag for arsenic removal from aqueous system

An effective adsorbent for arsenic removal from aqueous system was synthesized by loading iron(III) oxide on municipal solid waste incinerator melted slag. The loading was accomplished via chemical processes and thermal coating technique. The key point of the technique was the simultaneous generation of amorphous FeOOH sol and silica sol in-situ and eventually led to the formation of Fe-Si surface complexes which combined the iron oxide with the melted slag tightly. The surface morphology of the iron oxide-loaded slag was examined and the loading mechanisms were discussed in detail. The adsorbent was effective for both arsenate and arsenite removal and its removal capabilities for As(V) and As(III) were 2.5 and 3 times of those of FeOOH, respectively. Both affinity adsorption and chemical reactions contributed to arsenic removal. The effects of solution pH, contact time, arsenic concentration and adsorbent dosage on arsenic removal were examined and the optimum removal conditions were established. Furthermore, leaching of hazardous elements such as Cr(VI), As, Se, Cd and Pb from the adsorbent at a pH range of 2.5-12.5 was below the regulation values. Accordingly, it is believed that the iron oxide-loaded slag developed in this study is environmentally acceptable and industrially applicable for wastewater treatment.     

Zerovalent iron encapsulated chitosan nanospheres - a novel adsorbent for the removal of total inorganic arsenic from aqueous systems

Evaluation of Chitosan zerovalent Iron Nanoparticle (CIN) towards arsenic removal is presented. Addition of chitosan enhances the stability of Fe(0) nano particle. Prepared adsorbent was characterized by FT-IR, SEM EDX, BET and XRD. It was found that, with an initial dose rate of 0.5 g L⁻¹, concentrations of As (III) and As (V) were reduced from 2 mg L⁻¹ to <5 μg L⁻¹ in less than 180 min and the adsorbent was found to be applicable in wide range of pH. Langmuir monolayer adsorption capacity was found to be 94 ± 1.5 mg g⁻¹ and 119 ± 2.6 mg g⁻¹ at pH 7 for As (III) and As (V) respectively. Major anions including sulfate, phosphate and silicate did not cause significant interference in the adsorption behavior of both arsenite and arsenate. The adsorbent was successfully recycled five times and applied to the removal of total inorganic arsenic from real life groundwater samples.     

Effective adsorbent for arsenic removal: core/shell structural nano zero-valent iron/manganese oxide

Recently, nano zero-valent iron (nZVI) has emerged as an effective adsorbent for the removal of arsenic from aqueous solutions. However, its use in various applications has suffered from reactivity loss resulting in a decreased efficiency. Thus, the aim of this study was to develop an effective arsenic adsorbent as a core/shell structural nZVI/manganese oxide (or nZVI/Mn oxide) to minimize the reactivity loss of the nZVI. As the major result, the arsenic adsorption capacities of the nZVI/Mn oxide for As(V) and As(III) were approximately two and three times higher than that of the nZVI, respectively. In addition, the As(V) removal efficiency of the nZVI/Mn oxide was maintained through 4 cycles of regeneration whereas that of the nZVI was decreased significantly. The enhanced reactivity and reusability of the nZVI/Mn oxide can be successfully explained by the synergistic interaction of the nZVI core and manganese oxide shell, in which the manganese oxides participate in oxidation reactions with corroded Fe²⁺ and subsequently retard the release of aqueous iron providing additional surface sites for arsenic adsorption. In summary, this study reports the successful fabrication of a core/shell nZVI/Mn oxide as an effective adsorbent for the removal of arsenic from aqueous solutions.     

Arsenic contamination of soils and agricultural plants through irrigation water in Nepal

This study monitored the influence of arsenic-contaminated irrigation water on alkaline soils and arsenic uptake in agricultural plants at field level. The arsenic concentrations in irrigation water ranges from <0.005 to 1.014 mg L(-1) where the arsenic concentrations in the soils were measured from 6.1 to 16.7 mg As kg(-1). The arsenic content in different parts of plants are found in the order of roots>shoots>leaves>edible parts. The mean arsenic content of edible plant material (dry weight) were found in the order of onion leaves (0.55 mg As kg(-1))>onion bulb (0.45 mg As kg(-1))>cauliflower (0.33 mg As kg(-1))>rice (0.18 mg As kg(-1))>brinjal (0.09 mg As kg(-1))>potato (<0.01 mg As kg(-1)).     

Influence of organic matter on arsenic removal by continuous flow electrocoagulation treatment of weakly mineralized waters

The aim of this study is to evaluate and understand the electrocoagulation/flocculation (ECF) process to remove arsenic from both model and natural waters with low mineral content and to compare its performances to the coagulation/flocculation (CF) process already optimized. Experiments were thus conducted with iron electrodes in the same specific treatment conditions (4≤current density (mAcm(-2))≤33) to study the influence of organic matter on arsenic removal in conditions avoiding the oxidation step usually required to improve As(III) removal. The process performance was evaluated by combining quantification of arsenic residual concentrations and speciation and dissolved organic carbon residual concentrations with zeta potential and turbidity measurements. When compared to CF, ECF presented several disadvantages: (i) lower As(V) removal yield because of the ferrous iron dissolved from the anode and the subsequent negative zeta potential of the colloidal suspension, (ii) higher residual DOC concentrations because of the fractionation of high molecular weight compounds during the treatment leading to compounds less prone to coagulate and (iii) higher residual turbidities because of the charge neutralization mechanisms involved. However, during this process, As(III) was oxidized to As(V) improving considerably its removal whatever the matrix conditions. ECF thus allowed to improve As(III) removal without applying an oxidation step that could potentially lead to the formation of toxic oxidation by-products.     

Arsenic(III) and iron(II) co-oxidation by oxygen and hydrogen peroxide: Divergent reactions in the presence of organic ligands

Iron-catalyzed oxidation of As(III) to As(V) can be highly effective for toxic arsenic removal via Fenton reaction and Fe(II) oxygenation. However, the contribution of ubiquitous organic ligands is poorly understood, despite its significant role in redox chemistry of arsenic in natural and engineered systems. In this work, selected naturally occurring organic ligands and synthetic ligands in co-oxidation of Fe(II) and As(III) were examined as a function of pH, Fe(II), H₂O₂, and radical scavengers (methanol and 2-propanol) concentration. As(III) was not measurably oxidised in the presence of excess ethylenediaminetetraacetic acid (EDTA) (i.e. Fe(II):EDTA < 1:1), contrasting with the rapid oxidation of Fe(II) by O₂ and H₂O₂ at neutral pH under the same conditions. However, partial oxidation of As(III) was observed at a 2:1 ratio of Fe(II):EDTA. Rapid Fe(II) oxidation in the presence of organic ligands did not necessarily result in the coupled As(III) oxidation. Organic ligands act as both iron speciation regulators and radicals scavengers. Further quenching experiments suggested both hydroxyl radicals and high-valent Fe species contributed to As(III) oxidation. The present findings are significant for the better understanding of aquatic redox chemistry of iron and arsenic in the environment and for optimization of iron-catalyzed arsenic remediation technology.