Comparing polyaluminum chloride and ferric chloride for antimony removal

Antimony has been one of the contaminants required to be regulated, however, only limited information has been collected to date regarding antimony removal by polyaluminium chloride (PACl) and ferric chloride (FC). Accordingly, the possible use of coagulation by PACl or FC for antimony removal was investigated. Jar tests were used to determine the effects of solution pH, coagulant dosage, and pre-chlorination on the removal of various antimony species. Although high-efficiency antimony removal by aluminum coagulation has been expected because antimony is similar to arsenic in that both antimony and arsenic are a kind of metalloid in group V of the periodic chart, this study indicated: (1) removal density (arsenic or antimony removed per mg coagulant) for antimony by PACl was about one forty-fifth as low as observed for As(V); (2) although the removal of both Sb(III) and Sb(V) by coagulation with FC was much higher than that of PACl, a high coagulant dose of 10.5mg of FeL(-1) at optimal pH of 5.0 was still not sufficient to meet the standard antimony level of 2 microg as SbL(-1) for drinking water when around 6 microg as SbL(-1) were initially present. Consequently, investigation of a more appropriate treatment process is necessary to develop economical Sb reduction; (3) although previous studies concluded that As(V) is more effectively removed than As(III), this study showed that the removal of Sb(III) by coagulation with FC was much more pronounced than that of Sb(V); (4) oxidation of Sb(III) with chlorine decreased the ability of FC to remove antimony. Accordingly, natural water containing Sb(III) under anoxic condition should be coagulated without pre-oxidation.     

Simultaneous speciation of inorganic selenium and antimony in water samples by electrothermal vaporization inductively coupled plasma mass spectrometry following selective cloud point extraction

A new method was developed for the simultaneous speciation of inorganic selenium and antimony in water by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) following selective cloud point extraction (CPE). The method is based on the fact that Se(IV) and Sb(III) could form complexes with diethyldithiocarbamate (DDTC) at pH 6.00, and the complexes were quantitatively extracted into the non-ionic surfactant-rich phase of octylphenoxypolyethoxyethanol (Triton X-114), whereas the Se(VI) and Sb(V) remained as free species in aqueous solutions. Sb(III) and Se(IV) in concentrate were determined by ETV-ICP-MS after proper disposal. The total Se and total Sb were determined by the same protocol after Se(VI) and Sb(V) were reduced by l-cysteine, and Se(VI) and Sb(V) concentrations were obtained by respectively subtracting Se(IV) and Sb(III) from the total Se and the total Sb. Under the optimized conditions, the limits of detection (LODs) were 0.05 microg L(-1) for Se(IV) and 0.03 microg L(-1) for Sb(III), the relative standard deviations (RSDs) were 3.5% for Se(IV) and 4.2% for Sb(III) (C=1.00 microg L(-1), n=5). The proposed method was applied to the speciation of inorganic selenium and antimony in different water samples with satisfactory results.     

Sb(III) oxidation by iodate in seawater: a cautionary tale

Knowledge of antimony redox kinetics is crucial in understanding the impact and fate of antimony in the environment. The oxidation of Sb(III) with iodate was measured in 0.5 mol L(-1) NaCl solutions as a function of pH at environmentally significant concentrations of antimony and iodate. The oxidation of Sb(III) with iodate is pH dependent: no measurable oxidation is observed below pH 9. The undissociated Sb(OH)3 does not react with iodate and the formation of significant amounts of Sb(OH)4- is needed for the reaction to take place. It is thus unlikely that iodate oxidizes Sb(III) in seawater. Our results support that the observed presence of the thermodynamically unstable Sb(III) in oxic waters can be due to the kinetic stabilization of the trivalent state vis-à-vis some common abiotic oxidants at natural pH values. However, caution must be exercised because the presence of iodate in seawater favours fast oxidation of Sb(III) if water samples are acidified, as is the case in many analytical procedures.     

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.     

Natural attenuation processes applying to antimony: A study in the abandoned antimony mine in Goesdorf, Luxembourg

The processes leading to the attenuation of the antimony concentration in the water draining from the abandoned antimony mine in Goesdorf, Luxembourg, have been studied. Antimony has been mined in Goesdorf since Roman times from a stibnite-rich mesothermal vein system hosted in metasedimentary schist. The draining waters have pH values between 7 and 8 because the mineralization itself contains calcite and dolomite. This study combines the identification of minerals in the supergene zone with the application of bulk techniques (e.g., measurement of antimony in the waters of the adit and the creek draining the mine, sediment sequential extractions) over a period of five years. Antimony concentrations in the water that leaves the supergene zone are controlled by the dissolution of stibnite and the subsequent formation of Sb(III) oxides and sulphates. The relative proportions of the main secondary minerals can be qualitatively estimated as follows: 70% valentinite, 15% senarmontite and 12% sulphates (coquandite, klebelsbergite and peretaite). Further antimony attenuation along the adit and the creek that drain the mine waters is due partly to dilution, through mixing with waters that have not been in contact with the ore, and partly to sorption onto amorphous iron and manganese oxides present in the colluvial sediments.     

Adsorption of As(V) and As(III) by nanocrystalline titanium dioxide

This study evaluated the effectiveness of nanocrystalline titanium dioxide (TiO(2)) in removing arsenate [As(V)] and arsenite [As(III)] and in photocatalytic oxidation of As(III). Batch adsorption and oxidation experiments were conducted with TiO(2) suspensions prepared in a 0.04 M NaCl solution and in a challenge water containing the competing anions phosphate, silicate, and carbonate. The removal of As(V) and As(III) reached equilibrium within 4h and the adsorption kinetics were described by a pseudo-second-order equation. The TiO(2) was effective for As(V) removal at pH<8 and showed a maximum removal for As(III) at pH of about 7.5 in the challenge water. The adsorption capacity of the TiO(2) for As(V) and As(III) was much higher than fumed TiO(2) (Degussa P25) and granular ferric oxide. More than 0.5 mmol/g of As(V) and As(III) was adsorbed by the TiO(2) at an equilibrium arsenic concentration of 0.6mM. The presence of the competing anions had a moderate effect on the adsorption capacities of the TiO(2) for As(III) and As(V) in a neutral pH range. In the presence of sunlight and dissolved oxygen, As(III) (26.7 microM or 2mg/L) was completely converted to As(V) in a 0.2g/L TiO(2) suspension through photocatalytic oxidation within 25 min. The nanocrystalline TiO(2) is an effective adsorbent for As(V) and As(III) and an efficient photocatalyst.     

Antimony leaching from polyethylene terephthalate (PET) plastic used for bottled drinking water

Antimony is a regulated contaminant that poses both acute and chronic health effects in drinking water. Previous reports suggest that polyethylene terephthalate (PET) plastics used for water bottles in Europe and Canada leach antimony, but no studies on bottled water in the United States have previously been conducted. Nine commercially available bottled waters in the southwestern US (Arizona) were purchased and tested for antimony concentrations as well as for potential antimony release by the plastics that compose the bottles. The southwestern US was chosen for the study because of its high consumption of bottled water and elevated temperatures, which could increase antimony leaching from PET plastics. Antimony concentrations in the bottled waters ranged from 0.095 to 0.521 ppb, well below the US Environmental Protection Agency (USEPA) maximum contaminant level (MCL) of 6 ppb. The average concentration was 0.195+/-0.116 ppb at the beginning of the study and 0.226+/-0.160 ppb 3 months later, with no statistical differences; samples were stored at 22 degrees C. However, storage at higher temperatures had a significant effect on the time-dependent release of antimony. The rate of antimony (Sb) release could be fit by a power function model (Sb(t)=Sb 0 x[Time, h]k; k=8.7 x 10(-6)x[Temperature ( degrees C)](2.55); Sb 0 is the initial antimony concentration). For exposure temperatures of 60, 65, 70, 75, 80, and 85 degrees C, the exposure durations necessary to exceed the 6 ppb MCL are 176, 38, 12, 4.7, 2.3, and 1.3 days, respectively. Summertime temperatures inside of cars, garages, and enclosed storage areas can exceed 65 degrees C in Arizona, and thus could promote antimony leaching from PET bottled waters. Microwave digestion revealed that the PET plastic used by one brand contained 213+/-35 mgSb/kg plastic; leaching of all the antimony from this plastic into 0.5L of water in a bottle could result in an antimony concentration of 376 ppb. Clearly, only a small fraction of the antimony in PET plastic bottles is released into the water. Still, the use of alternative types of plastics that do not leach antimony should be considered, especially for climates where exposure to extreme conditions can promote antimony release from PET plastics.     

Health risk associated with dietary co-exposure to high levels of antimony and arsenic in the world's largest antimony mine area

Like arsenic (As), antimony (Sb) is known to be a genotoxic element in vitro and in vivo. Sb is now recognized as a global contaminant and has aroused the global concerns recently. However, knowledge is scarce concerning the transfer of Sb from the environment to humans and the related hazards to human health. In this pilot study, the health risk and main pathway of long-term human exposure to Sb and As for residents around Chinese Xikuangshan (XKS) Sb mine, the world's largest Sb mine, were evaluated by dietary exposure and hair accumulations survey. The concentrations and species of Sb and As in food samples (n = 209) from three main categories and six subcategories, and in hair samples (n = 89) were determined. Residents in the vicinity of XKS had an estimated dietary intake of Sb (554 μg/day) which was 1.5 times higher than the tolerable daily intake (TDI) (Sb, 360 μg/day), whereas their dietary intake of inorganic As (107 μg/day) was slightly lower than the provisional tolerable weekly intake (PTWI) of 15 μg/kg BW/week (equal to 129 μg As/day). Hair Sb and As concentrations (Sb, 15.7 mg/kg, DW; As, 3.99 mg/kg, DW) in XKS residents are both above the normal/toxic level. Rice, vegetables (especially leafy vegetable), drinking water, and meat/poultry were the dominant dietary intake sources of Sb for the residents. In contrast, rice was the uniquely dominant dietary intake source of As. Antimonate (Sb(V)) was the dominant Sb species in vegetables, drinking water and residents' hairs. This study highlighted the difference of exposure characteristics between Sb and As. The preliminary results suggested that dietary exposures to Sb, rather than As, was the dominant health risk to local residents. Nevertheless, the adverse effects of As levels on the health of residents still can not be ignored since the elevated As concentrations in human hair have reached the critical level for health risks. In addition, this pilot study did not consider the possible Sb and As combined effects.     

Polyaluminum chloride with high Al30 content as removal agent for arsenic-contaminated well water

Polyaluminum chloride (PACl) is a well-established coagulant in water treatment with high removal efficiency for arsenic. A high content of Al₃₀ nanoclusters in PACl improves the removal efficiency over broader dosage and pH range. In this study we tested PACl with 75% Al₃₀ nanoclusters (PACl_Al30) for the treatment of arsenic-contaminated well water by laboratory batch experiments and field application in the geothermal area of Chalkidiki, Greece, and in the Pannonian Basin, Romania. The treatment efficiency was studied as a function of dosage and the nanoclusters’ protonation degree. Acid-base titration revealed increasing deprotonation of PACl_Al30 from pH 4.7 to the point of zero charge at pH 6.7. The most efficient removal of As(III) and As(V) coincided with optimal aggregation of the Al nanoclusters at pH 7-8, a common pH range for groundwater. The application of PACl_Al30 with an Al_tot concentration of 1-5 mM in laboratory batch experiments successfully lowered dissolved As(V) concentrations from 20 to 230 μg/L to less than 5 μg/L. Field tests confirmed laboratory results, and showed that the WHO threshold value of 10 μg/L was only slightly exceeded (10.8 μg/L) at initial concentrations as high as 2300 μg/L As(V). However, As(III) removal was less efficient (<40%), therefore oxidation will be crucial before coagulation with PACl_Al30. The presence of silica in the well water improved As(III) removal by typically 10%. This study revealed that the Al₃₀ nanoclusters are most efficient for the removal of As(V) from water resources at near-neutral pH.     

Enhanced coagulation for high alkalinity and micro-polluted water: the third way through coagulant optimization

Conventional coagulation is not an effective treatment option to remove natural organic matter (NOM) in water with high alkalinity/pH. For this type of water, enhanced coagulation is currently proposed as one of the available treatment options and is implemented by acidifying the raw water and applying increased doses of hydrolyzing coagulants. Both of these methods have some disadvantages such as increasing the corrosive tendency of water and increasing cost of treatment. In this paper, an improved version of enhanced coagulation through coagulant optimization to treat this kind of water is demonstrated. A novel coagulant, a composite polyaluminum chloride (HPAC), was developed with both the advantages of polyaluminum chloride (PACl) and the additive coagulant aids: PACl contains significant amounts of highly charged and stable polynuclear aluminum hydrolysis products, which is less affected by the pH of the raw water than traditional coagulants (alum and ferric salts); the additives can enhance both the charge neutralization and bridging abilities of PACl. HPAC exhibited 30% more efficiency than alum and ferric salts in dissolved organic carbon (DOC) removal and was very effective in turbidity removal. This result was confirmed by pilot-scale testing, where particles and organic matter were removed synergistically with HPAC as coagulant by sequential water treatment steps including pre-ozonation, coagulation, flotation and sand filtration.     

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.     

Environmental geochemistry of antimony in Chinese coals

Environmental geochemistry of antimony (Sb) has gained much attention recently because of its potential toxicity. We have reviewed the distribution, modes of occurrence, geological processes and environmental effects of Sb in Chinese coals. Data of Sb in 1058 coal samples from China were compiled and the average Sb content in Chinese coals is estimated to be 2.27 microg/g. Average Sb content in coals from provinces, cities and autonomous regions may be divided into three groups. Group 1 has a low average Sb content of lower than 1 microg/g, Group 2 has a medium average Sb content of 1-3 microg/g, and Group 3 has a high average Sb content of >3 microg/g. Coals from Guizhou and Inner Mongolia are extremely enriched in Sb. The abundance of Sb in coals differs among coal-forming periods and coal ranks. Antimony occurs in several modes in coals. It may substitute for iron or sulfur in discrete pyrite grains or occurs as tiny dispersed sulfide particles in organic matter. During coal combustion Sb is partly released to the atmosphere and partly partitioned into solid residues. Antimony in the environment brings about definite harm to human health.     

Photochemical oxidation of As(III) by vacuum-UV lamp irradiation

In this study, vacuum-UV (VUV) lamp irradiation emitting both 185 and 254 nm lights has been investigated as a new oxidation method for As(III). Laboratory scale experiments were conducted with a batch reactor and a commercial VUV lamp. Under the experimental conditions of this study, the employed VUV lamp showed a higher performance for As(III) oxidation compared to other photochemical oxidation methods (UV-C/H(2)O(2), UV-A/Fe(III)/H(2)O(2), and UV-A/TiO2). The VUV lamp oxidized 100 microM As(III) almost completely in 10 min, and the reaction occurred mainly due to OH radicals which were produced by photo-splitting of water (H(2)O+hv (lambda=185 nm)-->OH.+H.). There was a little possibility that photo-generated H(2)O(2) acted as a minor oxidant of As(III) at alkaline pHs. The effects of Fe(III), H(2)O(2), and humic acid (HA) on the As(III) oxidation by VUV lamp irradiation were investigated. While Fe(III) and H(2)O(2) increased the As(III) oxidation efficiency, HA did not cause a significant effect. The employed VUV lamp was effective for oxidizing As(III) not only in a Milli-Q water but also in a real natural water, without significant decrease in the oxidation efficiency. Since the formed As(V) should be removed from water, activated alumina (AA) was added as an adsorbent during the As(III) oxidation by VUV lamp irradiation. The combined use of VUV lamp irradiation and AA was much more effective for the removal of total arsenic (As(tot)=As(III)+As(V)) than the single use of AA. The As(tot) removal seemed to occur as a result of the pre-oxidation of As(III) and the subsequent adsorption of As(V) on AA. Alternatively, the combination of VUV lamp irradiation and coagulation/precipitation with FeCl(3) was also an effective removal strategy for As(tot). This study shows that vacuum-UV (VUV) lamp irradiation emitting both 185 and 254 nm lights is a powerful and environmentally friendly method for As(III) oxidation which does not require additional oxidants or catalysts. The As(III) oxidation by VUV lamp irradiation was tested not only in a batch reactor but also in a flow-through quartz reactor. The As(III) oxidation rate became much faster in the latter reactor.     

混凝法去除水体中邻苯二甲酸二甲酯

研究采用强化混凝法去除水体中特征性有机污染物邻苯二甲酸酯类化合物(PAEs).以邻苯二甲酸二甲酯(DMP)为目标物,阳离子混凝剂聚二甲基二烯丙基氯化铵(PDMDAAC)与聚丙烯酰胺(CPAM)为混凝剂,对含DMP的水体进行强化混凝处理,混凝处理后水体中DMP的残余浓度采用高效液相色谱法(HPLC)测定.研究内容还包括混...     

不同混凝剂强化除藻、除浊的研究

采用聚合氯化铝(PAC)、聚合氯化铝铁(PAFC)、聚合硫酸铁(PFS)、聚合硫酸铝(PAS)和硫酸铝(AS)五种混凝剂对某含藻湖水进行强化混凝除藻、除浊试验研究,考察了混凝剂种类及投量、原水pH、沉降时间等因素对强化混凝效果的影响。结果表明,五种混凝剂的综合除藻、除浊性能排序为:PACPAFCPFSPASAS;在原水pH值为5~9的范围内,含铁混凝剂PFS和PAFC对pH的适应性较强,且在pH值为5~7的弱酸性条件下,PFS的除藻、除浊性能最优,当其投量为4 mg/L时,除藻率近80%,除浊率可达80%以上;而在pH值为7~9的弱碱性条件下,PAC则表现出更好的除藻、除浊效果,当其投量为4 mg/L时,除藻率和除浊率可分别达到83%和90%;AS对pH的适应性最差,其除藻、除浊效果最差;另外,五种混凝剂的除藻率、除浊率均随沉降时间的延长而增大,最佳沉降时间为20 min。     

Removal of As(III) and As(V) from water using a natural Fe and Mn enriched sample

The arsenic removal capacity of a natural oxide sample consisting basically of Mn-minerals (birnessite, cryptomelane, todorokite), and Fe-oxides (goethite, hematite), collected in the Iron Quadrangle mineral province in Minas Gerais, Brazil, has been investigated. As-spiked tap water and an As-rich mining effluent with As-concentrations from 100 μg L⁻¹ to 100 mg L⁻¹ were used for the experiments. Sorbent fractions of different particle sizes (<38 μm to 0.5 mm), including spherical material (diameter 2 mm), have been used. Batch and column experiments (pH values of 3.0, 5.5, and 8.5 for batch, and about pH 7.0 for column) demonstrated the high adsorption capacity of the material, with the sorption of As(III) being higher than that of As(V). At pH 3.0, the maximum uptake for As(V) and for As(III)-treated materials were 8.5 and 14.7 mg g⁻¹, respectively. The Mn-minerals promoted the oxidation of As(III) to As(V), for both sorbed and dissolved As-species. Column experiments with the cFeMn-c sample for an initial As-concentration of 100 μg L⁻¹ demonstrated a very efficient elimination of As(III), since the drinking water limit of 10 μg L⁻¹ was exceeded only after 7400 BV total throughput. The As-release from the loaded samples was below the limit established by the toxicity characteristic leaching procedure, thus making the spent material suitable for discharge in landfill deposits.     

吸附法处理锑污染水的研究进展

介绍了水解性金属混凝剂、无机矿物、活性炭和有机吸附剂对水溶液中锑的吸附性能,通过比较,指出了活性炭和有机吸附剂具有很好的吸附去除和回收水溶液中锑的应用前景,而无机矿物则更适用于控制环境中锑的行为。     

Role of Fe(II), phosphate, silicate, sulfate, and carbonate in arsenic uptake by coprecipitation in synthetic and natural groundwater

Competitive effects of phosphate, silicate, sulfate, and carbonate on As(III) and As(V) removal at pH approximately 7.2 have been investigated to test the feasibility of Fe(II)(aq) and hydroxylapatite crystals as inexpensive and potentially efficient agents for remediation of contaminated well-water, using Bangladesh as a type study. Arsenic(III) removal approximately 50-55% is achieved, when Fe(II)(aq) oxidizes to Fe(III) and precipitates as Fe(OH)3 at 25 degrees C and 3h reaction time, in the presence of all the oxyanion. Similar results were obtained for well-water samples from two sites in Bangladesh. Heating at 95 degrees C for 24h results in 70% As(III) uptake due to precipitation of magnesian calcite. A two-step process, Fe(II) oxidation and Fe(OH)3 precipitation at 25 degrees C for 2h, followed by magnesian calcite precipitation at 95 degrees C for 3h, yields approximately 65% arsenic removal while reducing the expensive heating period. In the absence of silicate, up to 70% As(III) uptake occurs at 25 degrees C. In all cases, As(III) was oxidized to As(V) in solution by dissolved oxygen and the reaction rate was probably promoted by intermediates formed during Fe(II) oxidation. Iron-catalyzed oxidation of As(III) by oxygen and hydrogen peroxide is pH-dependent with formation of oxidants in the Fenton reaction. Buffering pH at near-neutral values by dissolved carbonate and hydroxylapatite seeds is important for faster Fe(II) oxidation kinetics ensuring rapid coprecipitation of As as As(V) in the ferric phases.     

Individual and combined effects of water quality and empty bed contact time on As(V) removal by a fixed-bed iron oxide adsorber: Implication for silicate precoating

The individual and combined effects of changes in water quality (i.e. pH, initial concentrations of arsenate (As(V)) and competing ions) and empty bed contact time (EBCT) on As(V) removal performance of a fixed-bed adsorber (FBA) packed with a nanostructured goethite-based granular porous adsorbent were systematically studied under environmentally relevant conditions. Rapid small scale column tests (RSSCTs) were extensively conducted at different EBCTs with synthetic waters in which pH and the concentrations of competing ions (phosphate, silicate, and vanadate) were controlled. In the absence of the competing ions, the effects of initial As(V) concentration, pH, and EBCT on As(V) breakthrough curves were successfully predicted by the homogeneous surface diffusion model (HSDM) with adsorption isotherms predicted by the extended triple layer model (ETLM). The interference effects of silicate and phosphate on As(V) removal were strongly influenced by pH, their concentrations, and EBCT. In the presence of silicate (≤21 mg/L as Si), a longer EBCT surprisingly resulted in worse As(V) removal performance. We suggest this is because silicate, which normally exists at much higher concentration and moves more quickly through the bed than As(V), occupies or blocks adsorption sites on the media and interferes with later As(V) adsorption. Here, an alternative operating scheme of a FBA for As(V) removal is proposed to mitigate the silicate preloading. Silicate showed a strong competing effect to As(V) under the tested conditions. However, as the phosphate concentration increased, its interference effect dominated that of silicate. High phosphate concentration (>100 μg/L as P), as experienced in some regions, resulted in immediate As(V) breakthrough. In contrast to the observation in the presence of silicate, longer EBCT resulted in improved As(V) removal performance in the presence of phosphate. Vanadate was found to compete with As(V) as strongly as phosphate. This study reveals the competitive interactions of As(V) with the competing ions in actual adsorptive treatment systems and the dependence of optimal operation scheme and EBCT on water quality in seeking improved As(V) removal in a FBA.     

Comparative study of arsenic removal by iron using electrocoagulation and chemical coagulation

This research studied As(III) and As(V) removal during electrocoagulation (EC) in comparison with FeCl₃ chemical coagulation (CC). The study also attempted to verify chlorine production and the reported oxidation of As(III) during EC. Results showed that As(V) removal during batch EC was erratic at pH 6.5 and the removal was higher-than-expected based on the generation of ferrous iron (Fe²⁺) during EC. As(V) removal by batch EC was equal to or better than CC at pH 7.5 and 8.5, however soluble Fe²⁺ was observed in the 0.2-μm membrane filtrate at pH 7.5 (10-45%), and is a cause for concern. Continuous steady-state operation of the EC unit confirmed the deleterious presence of soluble Fe²⁺ in the treated water. The higher-than-expected As(V) removals during batch mode were presumed due to As(V) adsorption onto the iron rod oxyhydroxides surfaces prior to the attainment of steady-state operation. As(V) removal increased with decreasing pH during both CC and EC, however EC at pH 6.5 was anomalous because of erratic Fe²⁺ oxidation. The best adsorption capacity was observed with CC at pH 6.5, while lower but similar adsorption capacities were observed at pH 7.5 and 8.5 with CC and EC. A comparison of As(III) adsorption showed better removals during EC compared with CC possibly due to a temporary pH increase during EC. In contrast to literature reports, As(III) oxidation was not observed during EC, and As(III) adsorption onto iron hydroxides during EC was only 5-30% that of As(V) adsorption. Also in contrast to literature, significant Cl₂ was not generated during EC, in fact, the rods actually produced a significant chlorine demand due to reduced iron oxides on the rod. Although Cl₂ generation and As(III) oxidation are possible using a graphite anode, a combination of graphite and iron rods in the same EC unit did not produce As(III) oxidation. However, a two-stage process (graphite anode followed by iron anode in separate chambers) was effective in As(III) oxidation and removal. The competing ions, silica and phosphate interfered with As(V) adsorption during both CC and EC. However, the degree of interference depends on the concentration and presence of other competing ions. In particular, the presence of silica lowered the effect of phosphate with increasing pH due to silica’s own significant effect at high pHs.