Adsorption and heterogeneous oxidation of As(III) on ferrihydrite

Redox transformation of arsenic strongly influences its fate and transport in the environment. It is of interest to investigate heterogeneous oxidation of As(III) on the surface of major metal oxide in sediments. Whether As(III) can be oxidized on ferrihydrite and the role ferrihydrite plays as catalyst or oxidant are inconsistent in previous researches. In this work, oxidation of As(III) on ferrihydrite was studied by analysis of dissolved and adsorbed As(III) and As(V) quantitatively and qualitatively. X-ray absorption near edge spectroscopy (XANES) and pH_pznpc (point of zero net proton charge) of ferrihydrite with adsorbed As(III) showed clear evidence for partial oxidation on ferrihydrite. Oxidation of As(III) occurred when it was brought to contact with ferrihydrite at high Fe/As molar ratio (i.e. 50, 200). The concentration of As(V) in solid phase increased gradually while adsorbed As(III) concentration dropped. Fe(II) was not detectable during the oxidation of As(III). These results showed that ferrihydrite had the catalytic effect on oxidation of As(III). Only a fraction of As(III) was oxidized even when the system was exposed to air. The effects of ferrihydrite aging, media pH, coexistence of ions on As(III) oxidation were also investigated. The results suggest that catalytic oxidation of As(III) on ferrihydrite may play a role in geochemical cycling of arsenic in environment.     

Removal of arsenic from water: Effect of calcium ions on As(III) removal in the KMnO4–Fe(II) process

A novel KMnO₄–Fe(II) process was developed in this study for As(III) removal. The optimum As(III) removal was achieved at a permanganate dosage of 18.6 μM. At the optimum dosage of permanganate, the KMnO₄–Fe(II) process was much more efficient than the KMnO₄–Fe(III) process for As(III) removal by 15–38% at pH 5–9. The great difference in As(III) removal in these two processes was not ascribed to the uptake of arsenic by the MnO₂ formed in situ but to the different properties of conventional Fe(III) and the Fe(III) formed in situ. It was found that the presence of Ca²⁺ had limited effects on As(III) removal under acidic conditions but resulted in a significant increase in As(III) removal under neutral and alkaline conditions in the KMnO₄–Fe(II) process. Moreover, the effects of Ca²⁺ on As(III) removal in the KMnO₄–Fe(II) process were greater at lower permanganate dosage when Fe(II) was not completely oxidized by permanganate. This study revealed that the improvement of As(III) removal at pH 7–9 in the KMnO₄–Fe(II) process by Ca²⁺ was associated with three reasons: (1) the specific adsorption of Ca²⁺ increased the surface charge; (2) the formation of amorphous calcium carbonate and calcite precipitate that could co-precipitate arsenate; (3) the introduction of calcium resulted in more precipitated ferrous hydroxide or ferric hydroxide. On the other hand, the enhancement of arsenic removal by Ca²⁺ under acidic conditions was ascribed to the increase of Fe retained in the precipitate. FTIR tests demonstrated that As(III) was removed as arsenate by forming monodentate complex with Fe(III) formed in situ in the KMnO₄–Fe(II) process when KMnO₄ was applied at 18.6 μM. The strength of the “non-surface complexed” As–O bonds of the precipitated arsenate species was enhanced by the presence of Ca²⁺ and the complexation reactions of arsenate with Fe(III) formed in situ in the presence or absence of Ca²⁺ were proposed.     

Exceptional arsenic (III,V) removal performance of highly porous,nanostructured ZrO2 spheres for fixed bed reactors and the full-scale system modeling

Highly porous, nanostructured zirconium oxide spheres were fabricated from ZrO₂ nanoparticles with the assistance of agar powder to form spheres with size at millimeter level followed with a heat treatment at 450 °C to remove agar network, which provided a simple, low-cost, and safe process for the synthesis of ZrO₂ spheres. These ZrO₂ spheres had a dual-pore structure, in which interconnected macropores were beneficial for liquid transport and the mesopores could largely increase their surface area (about 98 m²/g) for effective contact with arsenic species in water. These ZrO₂ spheres demonstrated an even better arsenic removal performance on both As(III) and As(V) than ZrO₂ nanoparticles, and could be readily applied to commonly used fixed-bed adsorption reactors in the industry. A short bed adsorbent test was conducted to validate the calculated external mass transport coefficient and the pore diffusion coefficient. The performance of full-scale fixed bed systems with these ZrO₂ spheres as the adsorber was estimated by the validated pore surface diffusion modeling. With the empty bed contact time (EBCT) at 10 min and the initial arsenic concentration at 30 ppb, the number of bed volumes that could be treated by these dry ZrO₂ spheres reached ∼255,000 BVs and ∼271,000 BVs for As(III) and As(V), respectively, until the maximum contaminant level of 10 ppb was reached. These ZrO₂ spheres are non-toxic, highly stable, and resistant to acid and alkali, have a high arsenic adsorption capacity, and could be easily adapted for various arsenic removal apparatus. Thus, these ZrO₂ spheres may have a promising potential for their application in water treatment practice.     

As(III) removal by hybrid reactive membrane process combined with ozonation

The removal of arsenite (As(III)) was investigated using a combined ozonation-reactive ceramic membrane incorporated with iron oxide nanoparticles (IONs). A disk-type γ-Al₂O₃ ultrafiltration membrane (CM) was covered with IONs using an annealing method. The reactive ceramic membrane (RM) was then characterized using SEM, zeta potential measurements, and pure water permeability tests. The results showed that IONs were well attached on the RM surface. In addition, doped IONs had no significant effects on the pure water permeability and the isoelectric point (IEP) of RM. Laboratory-scale experiments were subsequently conducted to investigate the impact of combined RM and ozonation processes on As(III) rejection. The experimental results revealed that As(III) rejection rate of RM with an ozonation process (92%) significantly enhanced compared with that of CM (63%). The influence of operating parameters (i.e., pH, NOM, co-existing ions and temperature) revealed that an increase of pH, a decrease of temperature and presence of NOM led to a higher As(III) rejection, whereas the presence of co-existing ions in the feed water significantly reduced the As(III) rejection; divalent counter-ions were the greatest inhibitors for As(III) rejection. Finally, a comparison of As(III) rejection in synthetic water and real groundwater confirmed the importance of real conditions in the hybrid reactive membrane process with continuous ozonation.     

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.     

As(V) removal using carbonized yeast cells containing silver nanoparticles

The present study involves the development of adsorbent containing silver nanoparticles for arsenate removal using silver reducing property of a novel yeast strain Saccharomyces cerevisiae BU-MBT-CY1 isolated from coconut cell sap. Biological reduction of silver by the isolate was deduced at various time intervals. The yeast cells after biological silver reduction were harvested and subjected to carbonization at 400 °C for 1 h and its properties were analyzed using Fourier Transform Infra-Red spectroscopy, X-ray diffraction, scanning electron microscope attached with energy dispersive spectroscopy and transmission electron microscope. The average size of the silver nanoparticles present on the surface of the carbonized silver containing yeast cells (CSY) was 19 ± 9 nm. The carbonized control yeast cells (CCY) did not contain any particles on its surface. As(V) adsorption efficiency of CCY and CSY was deduced in batch mode by varying parameters like contact time, initial concentration, and pH. Desorption studies were also carried out by varying the pH. The experimental data were fitted onto Langmuir and D-R Isotherms and Lagergren and pseudo second order kinetic models. The CSY was more efficient in arsenate removal when compared to CCY.     

Effect of moderate pre-oxidation on the removal of Microcystis aeruginosa by KMnO4-Fe(II) process: significance of the in-situ formed Fe(III)

This study developed a novel KMnO₄-Fe(II) process to remove the cells of Microcystis aeruginosa, and the mechanisms involved in have been investigated. At KMnO₄ doses of 0-10.0 μM, the KMnO₄-Fe(II) process showed 23.4-53.3% higher efficiency than the KMnO₄-Fe(III) process did. This was first attributed to the moderate pre-oxidation of M. aeruginosa by KMnO₄, achieved by dosing Fe(II) after a period of pre-oxidation, to cease the further release of intracellular organic matter (IOM) and the degradation of dissolved organic matter (DOM). The extensive exposure of M. aeruginosa to KMnO₄ in KMnO₄-Fe(III) process led to high levels and insufficient molecular weight of DOM, inhibiting the subsequent Fe(III) coagulation. Additionally, Fe(II) contributed to lower levels of the in-situ formed MnO₂, the reduction product of KMnO₄ which adversely affected algae removal by Fe(III) coagulation. However, the in-situ formed Fe(III), which was derived from the oxidation of Fe(II) by KMnO₄, in-situ MnO₂, and dissolved oxygen, dominated the remarkably high efficiency of KMnO₄-Fe(II) process with respect to the removal of M. aeruginosa. On one hand, in-situ formed Fe(III) had more reactive surface area than pre-formed Fe(III). On the other hand, the continuous introduction of fresh Fe(III) coagulant showed higher efficiency than one-off dosage of coagulant to destabilize M. aeruginosa cells and to increase the flocs size. Moreover, the MnO₂ precipitated on algae cell surfaces and contributed to the formation of in-situ formed Fe(III), which may act as bridges to enhance the removal of M. aeruginosa.     

Removal of arsenic (III) and arsenic (V) from aqueous medium using chitosan-coated biosorbent

A biosorbent was prepared by coating ceramic alumina with the natural biopolymer, chitosan, using a dip-coating process. Removal of arsenic (III) (As(III)) and arsenic (V) (As(V)) was studied through adsorption on the biosorbent at pH 4.0 under equilibrium and dynamic conditions. The equilibrium adsorption data were fitted to Langmuir, Freundlich, and Redlich-Peterson adsorption models, and the model parameters were evaluated. All three models represented the experimental data well. The monolayer adsorption capacity of the sorbent, as obtained from the Langmuir isotherm, is 56.50 and 96.46 mg/g of chitosan for As(III) and As(V), respectively. The difference in adsorption capacity for As(III) and As(V) was explained on the basis of speciation of arsenic at pH 4.0. Column adsorption results indicated that no arsenic was found in the effluent solution up to about 40 and 120 bed volumes of As(III) and As(V), respectively. Sodium hydroxide solution (0.1M) was found to be capable of regenerating the column bed.     

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.     

Photoinitiated oxidation of geosmin and 2-methylisoborneol by irradiation with 254 nm and 185 nm UV light

The degradation of geosmin and 2-methylisoborneol (2-MIB) by UV irradiation at different wavelengths was investigated under varying boundary conditions. The results showed that conventional UV radiation (254 nm) is ineffective in removing these compounds from water. In contrast to the usual UV radiation UV/VUV radiation (254 + 185 nm) was more effective in the removal of the taste and odour compounds. The degradation could be described by a simple pseudo first-order rate law with rate constants of about 1.2 × 10⁻³ m² J⁻¹ for geosmin and 2-MIB in ultrapure water. In natural water used for drinking water abstraction the rate constants decreased to 2.7 × 10⁻⁴ m² J⁻¹ for geosmin and 2.5 × 10⁻⁴ m² J⁻¹ for 2-MIB due to the presence of NOM. Additionally, the formation of the by-product nitrite was studied. In the UV/VUV irradiation process up to 0.6 mg L⁻¹ nitrite was formed during the complete photoinitiated oxidation of the odour compounds. However, the addition of low ozone doses could prevent the formation of nitrite in the UV/VUV irradiation experiments.     

Mechanism of phenol photodegradation in the presence of pure and modified-TiO(2): A review

In recent years, the application of heterogeneous photocatalytic water purification processes has gained wide attention due to its effectiveness in degrading and mineralizing the recalcitrant organic compounds as well as the possibility of utilizing the solar UV and visible-light spectrum. By far, titania has played a much larger role in this scenario compared to other semiconductor photocatalysts due to its costly effectiveness, inert nature and photostability. A substantial amount of research has focused on the enhancement of TiO₂ photocatalysis by modification with metal, non-metal and ion doping.This paper aims to review and summarize the recent works on the titanium dioxide (TiO₂) photocatalytic oxidation of phenol and discusses various mechanisms of phenol photodegradation (indicating the intermediates products) and formation of OH radicals. Phenol degradation pathway in both systems, TiO₂/UV and doped-TiO₂/Vis, are described.     

Removal of humic substances (HS) from water by electro-microfiltration (EMF)

Humic substances (HS) represent the common agents contributing to flux decline during membrane filtration of natural water. In order to minimize the fouling during microfiltration (MF) of HS, modifying the operation of MF presents a promising alternative. A laboratory-scale electro-microfiltration (EMF) module was used to separate Aldrich HS from water by applying a voltage across the membrane. The presence of an electric field significantly reduced the flux decline. A flux comparable to that of ion-free water was attained when the voltage was near the critical electric field strength (Ecritical), i.e., the electrical field gradient that balances the advective and electrophoretic velocities of solute. At an applied voltage of 100 V (approximately 110 V/cm), it was able to reduce UV absorbance at 254 nm (UV254), total organic carbon (TOC) and trihalomethane formation potential (THMFP) by over 50% in the permeate. Results from 1H nuclear magnetic resonance (1H NMR) analysis suggest that the aromatic and functionalized aliphatic fractions decreased significantly in the permeate. The charged HS have large molecule weight compared with those passing through membrane. Results clearly indicate that a combination of electric force with MF can increase HS rejection and decrease flux decline. Electrophoretic attraction was the major mechanism for the improvement of flux and rejection over time.     

Oxidation of 2,4-dichlorophenol and 3,4-dichlorophenol by means of Fe(III)-homogeneous photocatalysis and algal toxicity assessment of the treated solutions

Chlorophenols are used worldwide as broad-spectrum biocides and fungicides. They have half-life times in water from 0.6 to 550 h and in sediments up to 1700 h and, due to their numerous origins, they can be found in wastewaters, groundwaters or soils. Moreover, chlorophenols are not readily biodegradable.Recently, classic Advanced Oxidation Processes (AOP) have been proposed for their abatement in an aqueous solution. This paper investigates the oxidation of 2,4-dichlorophenol and 3,4-dichlorophenol, at starting concentrations of 6.1 · 10⁻⁵ mol L⁻¹, in aqueous solutions through Fe(III)/O₂ homogeneous photocatalysis under UV light (303 ÷ 366 nm). The Fe(III)/O₂ homogeneous photocatalysis is less expensive than using H₂O₂ due to the capability of Fe(III) to produce OH radicals, if irradiated with an UVA radiation, and of oxygen to re-oxidize ferrous ions to ferric ones when dissolved in solution. The results show that the best working conditions, for both compounds, are found for pH = 3.0 and initial Fe(III) concentration equal to 1.5·10⁻⁴ mol L⁻¹ although the investigated oxidizing system can be used even at pH close to 4.0 but with slower abatement kinetics. Toxicity assessment on algae indicates that treated solutions of 2,4-dichlorophenol are less toxic on algae Pseudokirchneriella subcapitata if compared to not treated solutions whereas in the case of 3,4-dichlorophenol only the samples collected during the runs at 20 and 60 min are capable of inhibiting the growth of the adopted organism.The values of the kinetic constant for the photochemical re-oxidation of iron (II) to iron (III) and for HO attack to intermediates are evaluated by a mathematical model for pH range of 2.0-3.0 and initial Fe(III) concentrations range of 1.5 · 10⁻⁵-5.2 · 10⁻⁴ mol L⁻¹.     

Impact of UV/H(2)O(2) advanced oxidation treatment on molecular weight distribution of NOM and biostability of water

The presence of natural organic matter (NOM) poses several challenges to the commercial practice of UV/H₂O₂ process for micropollutant removal. During the commercial application of UV/H₂O₂ advanced oxidation treatment, NOM is broken down into smaller species potentially affecting biostability by increasing Assimilable Organic Carbon (AOC) and Biodegradable Organic Carbon (BDOC) of water. This work investigated the potential impact of UV/H₂O₂ treatment on the molecular weight distribution of NOM and biostability of different water sources. A recently developed flow cytometric method for enumeration of bacteria was utilized to assess biological stability of the treated water at various stages through measurement of AOC. BDOC was also assessed for comparison and to better study the biostability of water. Both AOC and BDOC increased by about 3-4 times over the course of treatment, indicating the reduction of biological stability. Initial TOC and the source of NOM were found to be influencing the biostability profile of the treated water. Using high performance size exclusion chromatography, a wide range of organic molecule weights were found responsible for AOC increase; however, low molecular weight organics seemed to contribute more. Positive and meaningful correlations were observed between BDOC and AOC of different waters that underwent different treatments.     

Kinetics and mechanisms of DMSO (dimethylsulfoxide) degradation by UV/H(2)O(2) process

The objective of this study was to elucidate the degradation pathways of dimethylsulfoxide (DMSO) during its mineralization caused by UV/H(2)O(2) treatment. In order to accomplish this, we measured the concentration time-profiles of DMSO and its degradation intermediates during the UV/H(2)O(2) treatment. In addition, we proposed a kinetic model that could account for the degradation pathways of DMSO during its UV/H(2)O(2) treatment. The results show that the degradation of DMSO by the UV/H(2)O(2) treatment can be classified into two major pathways, and this is supported by both the analysis of the intermediates and total organic carbon (TOC) measurements. Firstly, DMSO was degraded into sulfate (SO(4)(2-)) through the formation of methansulfinate (CH(3)SO(2)(-)) and methansulfonate (CH(3)SO(3)(-)) as sulfur-containing intermediates. One of the two carbon constituents of DMSO was highly resistant to mineralization, due to the formation of methansulfonate, which reacted very slowly with (.-)OH k = 0.8 x 10(7) M(-1)s(-1)). Secondly, the other carbon constituent of DMSO was relatively easily mineralized through the formation of formaldehyde (HCHO) and formate (HCO(2)(-)) as non-sulfur-containing intermediates. The kinetic model proposed in this study for the degradation of DMSO by (.-)OH in the UV/H(2)O(2) process was able to successfully predict the patterns of concentration time-profiles of all components during the UV/H(2)O(2) treatment of DMSO.     

Removal of quinol from aqueous solution by adsorption onto Fe(III)/Cr(III) hydroxide and application to real effluent treatment

The adsorption capacity of ‘waste’ Fe(III)/Cr(III) hydroxide for removal of quinol at varying agitation time, quinol concentration, adsorbent dose, pH and temperature was investigated by batch method. The Langmuir isotherm was found to represent the equilibrium sorption data well and the adsorption capacity was found to be 24.4 mg g^?1 and 28.2 mg g^?1 for untreated and pre‐treated adsorbent, respectively. Adsorption followed second‐order kinetics. Adsorption was maximum and uniform in the pH range 4.0–10.0 and 6.0–10.0 for untreated and pre‐treated adsorbent, respectively. The adsorption was endothermic in nature. Application of the adsorbent to the treatment of real effluent was demonstrated.     

NOx monitoring of a simultaneous nitrifying-denitrifying (SND) activated sludge plant at different oxidation reduction potentials

Simultaneous nitrification-denitrification (SND) allows biological nitrogen removal in a single reactor without separation of the two processes in time or space but requires adapted control strategies (anoxic/aerobic conditions). In this study, the formation of gaseous nitric oxide (NO(G)) and nitrogen dioxide (NO(2G)) was monitored for SND in relation to the oxidation-reduction potential (ORP) and nitrogen removal in a lab batch reactor and a pilot membrane bio-reactor (MBR). In addition hospital wastewater (COD/N(tot)>6:1) was treated on site for 1 year. The highest total nitrogen removal rates of max 90% were reached at 220-240mV ORP (given as E(h)) with corresponding maximal NO(G) emissions rates of 0.9microgg(-1)VSSh(-1). The maximal emission rates of NO(2G) (0.2microgg(-1)VSSh(-1)) were reached at the same ORP level and the NO(2G) emissions correlated to the nitrite accumulation in the activated sludge up to 5mgl(-1)NO(2L)-N. It was shown that this correlation was due to biological production and not due to pH-dependent chemical conversion. Therefore, NO(2G) can be used as additional control loop for ORP-controlled SND systems to avoid the inhibition of denitrification and high nitrite concentrations in the plant effluent.     

The removal of hexacyanoferrate(II) and (III) ions in dilute aqueous solution by activated carbon

The removal of iron cyano-complex ions [hexacyanoferrate(II) and (III) ions] in a dilute aqueous solution by activated carbon was investigated. The maximum adsorption of iron cyano-complex ions on activated carbon occurred at pH around 3. The hexacyanoferrate(III) ion was more adsorbable than the hexacyanoferrate(II) ion. Activated carbon promoted the oxidation of hexacyanoferrate(II) ion to (III) ion with dissolved oxygen in an acidic solution and the reduction of hexacyanoferrate(III) ion to (II) ion in an alkaline solution. The iron cyano-complex ion adsorbed on activated carbon could be eluted with higher concentrated acidic and alkaline solutions. The degree of elution decreased with an increase in potassium hydroxide concentration, since parts of the iron cyano-complexes on activated carbon were decomposed to form the iron hydroxide and the hexacyanoferrate(II) ion with an alkaline solution. The behavior of iron cyano-complexes in the presence of activated carbon, in the lower pH range (pH < 1) and at higher temperatures (80°C), was discussed.     

Laboratory investigation of aluminum solubility and solid-phase properties following alum treatment of lake waters

Water samples from two southern California lakes adversely affected by internal nutrient loading were treated with a 20 mg/L dose of Al3+ in laboratory studies to examine Al solubility and solid-phase speciation over time. Alum [Al2(SO4)3 . 18 H2O] applications to water samples from Big Bear Lake and Lake Elsinore resulted in a rapid initial decrease in pH and alkalinity followed by a gradual recovery in pH over several weeks. Dissolved Al concentrations increased following treatment, reaching a maximum of 2.54 mg/L after 17 days in Lake Elsinore water and 0.91 mg/L after 48 days in Big Bear Lake water; concentrations in both waters then decreased to <0.25 mg/L after 150 days. The solid phase was periodically collected and analyzed using X-ray diffraction (XRD), differential scanning calorimetry-thermogravimetric analysis (DSC-TGA), scanning electron microscopy (SEM), and surface area analyses to investigate the nature of the reaction products and crystallinity development over time. Poorly ordered, X-ray amorphous solid phases transformed over time to relatively well-ordered gibbsite, with strong diffraction peaks at 4.8 and 4.3 A. XRD also indicated the formation of a second (possibly aluminosilicate) crystalline phase after 150 days in Lake Elsinore water. Surface areas also decreased over time as crystals reordered to form gibbsite/microcrystalline gibbsite species. DSC-TGA results suggested that the initially formed amorphous Al(OH)3 underwent transformation to >45% gibbsite. These results were supported by geochemical modeling using Visual MINTEQ, with Al solubility putatively controlled by amorphous Al(OH)3 shortly after treatment and approaching that of microcrystalline gibbsite after about 150 days. These findings indicate that Al(OH)3 formed after alum treatment undergoes significant chemical and mineralogical changes that may alter its effectiveness as a reactive barrier to phosphorus release from lake sediments.     

Removal of arsenic from water: Effects of competing anions on As(III) removal in KMnO4–Fe(II) process

Effects of sulfate, phosphate, silicate and humic acid (HA) on the removal of As(III) in the KMnO₄–Fe(II) process were investigated in the pH range of 4–9 with permanganate and ferrous sulfate applied at selected dosage. Sulfate decreased the removal of arsenic by 6.5–36.0% at pH 6–9 and the decrease in adsorption did not increase with increasing concentration of sulfate from 50 to 100 mg/L. In the presence of 1 mg/L phosphate, arsenic removal decreased gradually as pH increased from 4 to 6, and a sharp drop occurred at pH 7–9. The presence of 10 mg/L silicate had negligible effect on arsenic removal at pH 4–5 whereas decreased the arsenic removal at pH 6–9 and the decrease was more significant at higher pH. The presence of HA dramatically decreased the arsenic removal over the pH range of 6–9 and HA of higher concentration resulted in greater drop in arsenic removal. The effects of the competing anions on arsenic removal in the KMnO₄–Fe(II) process were highly dependent on pH and the degree of these four anions influencing As(III) removal decreased in the following order, phosphate > humic acid > silicate > sulfate. Sulfate differed from the other three anions because sulfate decreased the removal of arsenic mainly by competitive adsorption while phosphate, silicate and HA decreased the removal of As(III) by competitive adsorption and sequestering the formation of ferric hydroxide derived from Fe(II).