Removal of arsenate from water by adsorbents: a comparative case study.

Laboratory and field filtration experiments were conducted to study the effectiveness of As(V) removal for five types of adsorbent media. The media included activated alumina (AA), modified activated alumina (MAA), granular ferric hydroxide (GFH), granular ferric oxide (GFO), and granular titanium dioxide (TiO2). In laboratory batch and column experiments, the synthetic challenge water was used to evaluate the effectiveness for five adsorbents. The results of the batch experiments showed that the As(V) adsorption decreased as follows at pH 6.5: TiO2 > GFO > GFH > MAA > AA. At pH 8.5, however, As(V) removal decreased in the following order: GFO = TiO2 > GFH > MAA > AA. In column experiments, at pH 6.5, the adsorbed As(V) for adsorbents followed the order: TiO2 > GFO > GFH, whereas at pH 8.5 the order became: GFO = TiO2 > GFH when the challenge water containing 50 µg/L of As(V) was used. Field filtration experiments were carried out in parallel at a wellhead in New Jersey. Before the effluent arsenic concentration increased to 10 µg/L, approximately 58,000 and 41,500 bed volumes of groundwater containing an average of 47 µg/L of As(V) were treated by the filter system packed with GFO and TiO2, respectively. The As(V) adsorption decreased in the following sequence: GFO > TiO2 > GFH > MAA > AA. Filtration results demonstrated that GFO and TiO2 adsorbents could be used as media in small community filtration systems for As(V) removal.

Challenges of arsenic removal from municipal wastewater by coagulation with ferric chloride and alum.

Discharge of treated municipal wastewater containing arsenic (As) may cause adverse effects on the environment and drinking water sources. Arsenic concentrations were measured throughout the treatment systems at two municipal wastewater plants in New Jersey, USA. The efficiency of As removal by ferric chloride and alum coagulants were evaluated. Besides, the effects of suspended solids in the mixed liquor, pH, and orthophosphate (PO43-) on As removal were investigated. The total recoverable As (TAs) concentrations in the influent and effluent of Plant A were in the ranges of 2.00-3.00 and 1.50-2.30 µg/L, respectively. The results indicated that <30% of the As was removed by the conventional biological wastewater treatment processes. The influent and effluent TAs concentrations at Plant B was below 1.00 µg/L. The bench-scale coagulation results demonstrated for the first time that the coagulation treatment could not effectively remove As from the municipal wastewater to <2.00 µg/L. Very high doses of the coagulants (8 and 40 mg/L of Fe(III) or Al(III)) were required to reduce the TAs from 2.84 and 8.61 µg/L in the primary clarifier effluent and arsenate-spiked effluent samples to <2.00 µg/L, respectively, which could be attributed to the high concentrations of PO43- and dissolved organic matters (DOM) in the wastewater. The protein DOM in wastewater may negatively impact removal efficiencies more than the DOM in natural water, which mainly consists of humic substances. Furthermore, an artificial neural network was constructed to determine the relative importance of different parameters for As removal. Under the experimental conditions, the importance followed the order: coagulant dose>dissolved PO43- > initial As concentration > pH. The findings of this study will help develop effective treatment processes to remove As from municipal wastewater.

Modeling, rate-limiting step investigation, and enhancement of the direct bio-regeneration of perchlorate laden anion-exchange resin.

Anion-exchange with high perchlorate affinity resins is one of the most promising technologies for removing low levels of perchlorate. However, the traditional brine desorption technique is difficult and costly for regeneration of this type of resin. Previously, a direct bio-regeneration method by contacting the spent high perchlorate affinity resin with the perchlorate-reducing bacteria was proved feasible. This research is a further study of that method. Firstly, a direct bio-regeneration process model, based on the physicochemical and biological fundamentals, was developed and calibrated with experimental data. Thereafter, the rate-limiting step in regeneration of the high perchlorate affinity resin was investigated. Methods to enhance the regeneration efficiency were developed. The results indicated that the calibrated model well described the regeneration process. It thus might provide useful insights into the regeneration system. The results also demonstrated that the perchlorate desorption from the loaded resin could be the rate-limiting step. Addition of proper amount of counter anions such as chloride and sulfate improved the regeneration efficiency because these anions could promote both the extent and rate of perchlorate desorption from the loaded resin. These findings aided us in achieving good and efficient regeneration of high perchlorate affinity resins like the A-530E and SR-7 resins. The findings also suggested that the application of bacteria that could efficiently reduce perchlorate in highly saline solution would make the method more promising for the regeneration of high perchlorate affinity resins.

Feasibility and kinetics study on the direct bio-regeneration of perchlorate laden anion-exchange resin.

Anion exchange is one of the most promising treatment technologies for the removal of low levels of perchlorate. The spent anion-exchange resins, however, need to be disposed of or regenerated because they contain high contents of perchlorate. This study investigated the feasibility and kinetics of a direct bio-regeneration method. The method accomplished resin regeneration and biological perchlorate destruction concurrently, by directly contacting the spent resin with the perchlorate-reducing bacteria (PRB). The results indicated that the method was effective in regeneration of perchlorate and nitrate loaded resin and the resin could be repeatedly regenerated with the method. The regenerated resin was effective, stable, and durable in the filtration treatment of perchlorate in well water from the Saddle River area, NJ. Moreover, the method was also effective in regeneration of the spent A-530E resin, which had high perchlorate affinity and was yet very difficult for regeneration with the conventional brine desorption technique. Besides, the results further suggested that the perchlorate and nitrate desorption from the loaded resin coupling with their subsequent biological reduction could be the direct bio-regeneration mechanism. No biofilm was formed on the regenerated resin surface according to a scanning electron microscopy (SEM) analysis.

Kinetics of biological perchlorate reduction and pH effect.

Batch experiments were conducted to investigate the kinetics of perchlorate reduction by heterotrophic and mixed perchlorate-reducing bacteria. Substrate-utilizing and cellular maintenance models were employed to fit the experimental data for microbial perchlorate reduction. The half saturation constant, K(s), obtained in this study was below 0.1mg/L, which indicated that perchlorate-reducing bacteria are effective at utilizing low concentrations of perchlorate. The effect of pH on the kinetics of microbial perchlorate reduction was also studied. Perchlorate reduction occurred throughout the pH range from 5.0 to 9.0. Nevertheless, the rates of perchlorate removal by a unit mass of bacteria were significantly different at various pHs with a maximum rate at pH 7.0. The variation of q(max) with pH was described well with a Gaussian peak equation. This equation is expected to be applicable for practical purposes when pH effects need to be considered.

Determination of configuration of arsenite-glutathione complexes using ECSTM.

Inorganic arsenicals such as arsenite [As(III)] and arsenate [As(V)] are known human carcinogens. The interactions of As(III) with sulfhydryl groups of peptides and proteins are very important mechanisms for the toxicity and metabolism of arsenic in mammals. The present study was designed to explore the application of electrochemical scanning tunneling microscopy (ECSTM) for determining the configuration of complexes formed between As(III) and glutathione (GSH) in solution. The configurations of GSH and As(III)-GSH complexes were imaged on the Au(111) surface in a 0.1M NaClO(4) solution. High-resolution STM images revealed that the As(III) and GSH formed a As(GS)(3) complex. The orientation and packing arrangement of the molecular adlayers were also seen clearly from the images and molecular models constructed using the Chemical Window and Hyperchem software package. The configuration of GSH in As(GS)(3) was found to be different from single GSH. UV-vis spectra indicated the emergence of an absorption shoulder in the range 250-280 nm for the aged As(III)-GSH solution, compared to the spectra of single As(III) and GSH solutions. MS spectra showed the presence of a new peak for the aged As(III)-GSH solution at m/z 992 corresponding to the As(GS)(3) complex. The results obtained by the last two methods verify the compound imaged by using STM is As(GS)(3). Studying the interactions of As(III) and peptides and knowing the structure details of the complexes are a significant step toward a better understanding of the interactions between As(III) and proteins and the mechanism of arsenic toxicology. ECSTM will be especially valuable for the determination of competitive interactions of GSH and proteins with arsenic.

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.

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.

Rapid Ti(III) reduction of perchlorate in the presence of beta-alanine: kinetics, pH effect, complex formation, and beta-alanine effect.

Ti(III) reduction of perchlorate might be a useful method for the treatment of highly perchlorate-contaminated water. Though the reaction rate was usually low, we observed that beta-alanine (HOOCCH(2)CH(2)NH(2)) could significantly promote the reaction. A complete (>99.9%) perchlorate removal was obtained in a solution containing [ClO(4)(-)]=1.0mM, [Ti(III)]=40 mM, and [beta-alanine]=120 mM after 2.5h of reaction under 50 degrees C. The effects of both pH and complex formation on the reaction were then studied. The results showed that without beta-alanine the optimal pH was 2.3. When pH increased from 1.6 to 2.3, the reduction rate increased remarkably. In the pH range >2.3, however, the reduction was significantly inhibited, attributed to the formation of Ti(III) precipitate. The presence of beta-alanine at a molar ratio of [beta-alanine]:[Ti(III)]=3:1 significantly increased the reduction rate of perchlorate even at near neutral pH. This is because beta-alanine formed complexes with Ti(III), which greatly improved the total soluble [Ti(III)] in the pH range between 3.5 and 6. The findings may lead to the development of rapid treatment methods for intermittent and small stream of highly perchlorate-contaminated water, which are resulted from the manufacturing, storage, handling, use and/or disposal of large quantities of perchlorate salts.

Perchlorate adsorption and desorption on activated carbon and anion exchange resin.

The mechanisms of perchlorate adsorption on activated carbon (AC) and anion exchange resin (SR-7 resin) were investigated using Raman, FTIR, and zeta potential analyses. Batch adsorption and desorption results demonstrated that the adsorption of perchlorate by AC and SR-7 resin was reversible. The reversibility of perchlorate adsorption by the resin was also proved by column regeneration test. Solution pH significantly affected perchlorate adsorption and the zeta potential of AC, while it did not influence perchlorate adsorption and the zeta potential of resin. Zeta potential measurements showed that perchlorate was adsorbed on the negatively charged AC surface. Raman spectra indicated the adsorption resulted in an obvious position shift of the perchlorate peak, suggesting that perchlorate was associated with functional groups on AC at neutral pH through interactions stronger than electrostatic interaction. The adsorbed perchlorate on the resin exhibited a Raman peak at similar position as the aqueous perchlorate, indicating that perchlorate was adsorbed on the resin through electrostatic attraction between the anion and positively charged surface sites.