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.     

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).     

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

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

Adsorption 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 As(V) from wastewaters by chemically modified fungal biomass

Biosorption has been demonstrated to be a useful alternative to conventional treatment systems for the removal of toxic metals from dilute aqueous solution. The objective of this paper was to examine the main aspects of a possible strategy for the removal of arsenates, employing P. chrysogenum biomass. The pretreatment of biomass with common surfactants (as hexadecyl-trimethylammonium bromide and dodecylamine) and a cationic polyelectrolyte was found to improve the biosorption efficiency. The initial biomass showed a relative low affinity for metallic anions, whereas with the application of modified samples a significant uptake of arsenic was observed. Sorption data were well described by typical Langmuir and Freundlich adsorption isotherms. Promising results were obtained in laboratory experiments and effective As(V) removals were observed.     

Removal of As(III) and As(V) by Tin(II) compounds

The retention capacity for arsenic species of new nanomaterials based on tin(II) inorganic oxides or hybrid (inorganic and organic) materials was studied. The synthesis of a polymer-metal complex was performed with poly(acrylic acid) and tin(II) chloride. Poly(AA)-Sn(II) with 10 and 20 wt% of tin and a structure with a mol ratio tin:carboxylate group of 1:1, were characterized. These compounds with 10 and 20 wt% of tin content were used to compare the arsenic removal capability through the liquid-phase polymer-based retention, (LPR), technique. Also, tin oxide was prepared by adding alkaline solution to tin(II) chloride salt. The intermediate tin compound was studied by UV-Vis spectroscopy at different pH values and quantified by potentiometric titration. The solid structure is characterized by Fourier transformed infrared spectroscopy, X-ray diffraction, and specific area BET (N₂). Removal of arsenite and arsenate species from solution by hydrolysated tin was carried out by LPR technique with ultrafiltration membranes and a fixed-bed column unsupported or supported on SiO₂. In all these cases, a washing method at constant pH was applied. The arsenic retention ability depended on the class of tin compounds prepared, with a higher efficiency for arsenic being observed at basic pH for soluble complex poly(AA)-Sn(II) than that for tin hydroxide or hydrolysate of Sn⁺².     

Preparation and evaluation of iron–chitosan composites for removal of As(III) and As(V) from arsenic contaminated real life groundwater

A study on the removal of arsenic from real life groundwater using iron–chitosan composites is presented. Removal of arsenic(III) and arsenic(V) was studied through adsorption at pH 7.0 under equilibrium and dynamic conditions. The equilibrium data were fitted to Langmuir adsorption models and the various model parameters were evaluated. The monolayer adsorption capacity from the Langmuir model for iron chitosan flakes (ICF) (22.47 ± 0.56 mg/g for As(V) and 16.15 ± 0.32 mg/g for As(III)) was found to be considerably higher than that obtained for iron chitosan granules (ICB) (2.24 ± 0.04 mg/g for As(V); 2.32 ± 0.05 mg/g for As(III)). Anions including sulfate, phosphate and silicate at the levels present in groundwater did not cause serious interference in the adsorption behavior of arsenate/arsenite. The column regeneration studies were carried out for two sorption–desorption cycles for both As(III) and As(V) using ICF and ICB as sorbents. One hundred and forty-seven bed volumes of As(III) and 112 bed volumes of As(V) spiked groundwater were treated in column experiments using ICB, reducing arsenic concentration from 500 to <10 μg/l. The eluent used for the regeneration of the spent sorbent was 0.1 M NaOH. The adsorbent was also successfully applied for the removal of total inorganic arsenic down to <10 μg/l from real life arsenic contaminated groundwater samples.     

Removal of arsenic(III) from aqueous solutions using fresh and immobilized plant biomass

The ability of Garcinia cambogia, an indigenous plant found in many parts of India, to remove trivalent arsenic from solution was assessed. Batch experiments were carried out to characterize the As(III) removal capability of fresh and immobilized biomass of G. cambogia. It was found that the kinetic property and uptake capacity of fresh biomass were significantly enhanced by the immobilization procedure. The uptake of As(III) by fresh and immobilized biomass was not greatly affected by solution pH with optimal biosorption occurring at around pH 6--8. The presence of common ions such as Ca and Mg at concentrations up to 100mg/l had no effect on As(III) removal. However, the presence of Fe(III) at 100mg/l caused a noticeable drop in the extent of As(III) removal but the effect was minimal when Fe(III) was present at 10mg/l. The adsorption isotherms quantitatively predicted the extent of As(III) removal in groundwater samples collected from an arsenic-contaminated site in India. Immobilized biomass loaded with As(III) was amenable to efficient regeneration with NaOH solution. Column studies showed that immobilized biomass could be reused over five cycles of loading and elution. The excellent As(III) sequestering capability of fresh and immobilized G. cambogia biomass could lead to the development of a viable and cost-effective technology for arsenic removal in groundwater.     

生物除锰滤池对砷(Ⅲ)的去除效果研究

砷是对人体有毒害作用的典型元素,且在水源水中普遍存在.为此人工配制了含As（Ⅲ）为0.05～0.25 mg/L、Mn2＋为0.5～3.0 mg/L的原水,并通过已培养成熟的生物除锰滤池进行过滤,分别考察了滤速为3、5、7 m/h时滤池对As（Ⅲ）及Mn2＋的去除效果.结果表明,在开始阶段由于受原水中As（Ⅲ）的影响,滤池的除锰能力有所下降,出水As（Ⅲ）也不能达标;经过15 d左右的运行培养后,滤池表现出了良好的除锰和除砷能力,出水As（Ⅲ）、Mn2＋浓度分别为0.02mg/L和0.05 mg/L左右.经过对不同取样口的水样进行检测,发现滤池的除砷能力集中在厚度为0～800 mm的滤层.     

Removal of arsenic(V) from spent ion exchange brine using a new class of starch-bridged magnetite nanoparticles

Ion exchange (IX) is considered by US EPA as one of the best available technologies for removing arsenic from drinking water. However, typical IX processes will generate large volumes of arsenic-laden regenerant brine that requires costly further handling and disposal. This study aimed to develop an engineered strategy to minimize the production and arsenic leachability of the process waste residual. We prepared and tested a new class of starch-bridged magnetite nanoparticles for removal of arsenate from spent IX brine. A low-cost, “green” starch at 0.049% (w/w) was used as a stabilizer to prevent the nanoparticles from agglomerating and as a bridging agent allowing the nanoparticles to flocculate and precipitate while maintaining their high arsenic sorption capacity. When applied to a simulated spent IX brine containing 300 mg/L As and 6% (w/w) NaCl, nearly 100% removal of arsenic was achieved within 1 h using the starch-bridged nanoparticles at an Fe-to-As molar ratio of 7.6, compared to only 20% removal when bare magnetite particles were used. Increasing NaCl in the brine from 0 to 10% (w/w) had little effect on the arsenic sorption capacity. Maximum uptake was observed within a pH range of 4-6. The Langmuir capacity coefficient was determined to be 248 mg/g at pH 5.0. The final treatment sludge was able to pass the TCLP (Toxicity Characteristic Leaching Procedure) based leachability of 5 mg/L as As.     

Removal of antimony(V) and antimony(III) from drinking water by coagulation-flocculation-sedimentation (CFS)

Antimony occurs widely in the environment as a result of natural processes and human activity. Although antimony is similar to arsenic in chemical properties and toxicity, and a pollutant of priority interest to the USEPA and the EU, its environmental behaviors, control techniques, and even solution chemistry, are yet barely touched. In this study, antimony removal from drinking water with coagulation-flocculation-sedimentation (CFS) is comprehensively investigated with respect to the dependence of both Sb(III) and Sb(V) removal on the initial contaminant-loading level, coagulant type and dosage, pH and interfering ions. The optimum pH for Sb(V) removal with ferric chloride (FC) was observed at pH 4.5-5.5, and continuously reduced with further pH increase. Over a broad pH range from 4.0 to 10.0, effective Sb(III) removal with FC was obtained. Contrary to the effective Sb removal with FC, the degree of both Sb(III) and Sb(V) removal with aluminum sulfate (AS) was very low, indicating the impracticability of AS application for antimony removal. The presence of phosphate and humic acid (HA) markedly impeded Sb(V) removal, while exhibited insignificant effect on Sb(III) removal. The effects of coagulant type, Sb species and pH are more pronounced than the effects of coagulant dose and initial pollutant concentration. After preliminarily excluding the possibility of precipitation and the predominance of coprecipitation, the adsorption mechanism is used to rationalize and simulate Sb/FC coagulation with good result by incorporating diffuse-layer model (DLM).     

Modeling As(V) removal by a iron oxide impregnated activated carbon using the surface complexation approach

The objective of this research was to model As(V) removal onto a iron oxide impregnated activated carbon (FeAC) using the surface complexation model (SCM) approach. As(V) removal by FeAC was due to the impregnated Fe oxide, not the base carbon material and was a strong function of pH. The two-monoprotic site-triple layer model adequately described As(V) removal using 2 fitting parameters compared with the 3 parameters needed for the diprotic site model. This, along with a better representation of the recognized As(V) removal mechanism (ligand exchange with -OH) as well as the acid-base behavior makes the two-monoprotic approach the better model for As(V) removal by the impregnated iron oxide although the diprotic model was able to describe the pH dependent removal of As(V). Both models were also able to predict As(V) removal at different adsorbent/adsorbate ratios using K(As) determined from a single FeAC adsorption experiment. Thus, fewer adsorption experiments are required in order to model As(V) removal in equilibrium and column systems. The results described in this work will be used as a foundation in developing a dynamic model to predict As(V) adsorption in a fixed-bed adsorber.     

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.     

生物固锰除锰机理与生物除铁除锰技术

在pH中性条件下生物接触滤层中Mn^2 的氧化是生物氧化，滤层中以除锰菌为核心的生物群系的平衡与稳定是除锰活性的基础。生物滤层不但可以同时氧化去除Fe^2 、Mn^2 ，而且对进入滤层前已氧化成Fe^3 的微细颗粒也有良好的截留作用。以此生物固锰除锰机制为基础开发了弱曝气、一级过滤的生物除铁除锰简缩流程，确定了相应的设计与运行参数并指导了沈阳市开发区生物除铁除锰水厂的设计与运行。投产一年多来出水水质良好，总铁为痕量，锰＜0．0.05mg/L。     

高锰酸盐预氧化去除太湖原水中稳定性铁、锰

太湖B支流河水属于低浊、高藻、高铁锰、高色度和高耗氧量水质，其中铁、锰主要以溶解态和胶体态（铁、锰化合物胶体）存在。胶体态铁、锰被有机物膜包裹，和溶解态铁、锰形成了高稳定性铁、锰，采用常规给水工艺处理时难于去除。为此，开展了高锰酸盐（PPC）预氧化去除该原水中稳定性铁、锰的研究。结果表明，高锰酸盐对稳定性铁、锰的去除效果好，但受预氧化时间、pH值、水中本底成分的影响较大。在预氧化时间为30min、原水锰含量〈0．67mg／L时，对锰的去除率接近100％；在预氧化时间为60min、原水铁含量〈0．5mg／L时，对铁的去除率约为100％。当原水为酸性和碱性时，预氧化对铁、锰的去除率较高，在中性条件下去除率则相对较低。     

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.     

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.     

Fabrication of polymer-supported nanosized hydrous manganese dioxide (HMO) for enhanced lead removal from waters

In the current study, a new hybrid adsorbent HMO-001 was fabricated by impregnating nanosized hydrous manganese dioxide (HMO) onto a porous polystyrene cation exchanger resin (D-001) for enhanced lead removal from aqueous media. D-001 was selected as a support material mainly because of the potential Donnan membrane effect exerted by the immobilized negatively charged sulfonic acid groups bound to the polymeric matrix, which would result in preconcentration and permeation enhancement of lead ions prior to their effective sequestration by the impregnated HMO. HMO-001 was characterized by scanning electron micrograph (SEM), transmission electron micrograph (TEM), and X-ray diffraction (XRD). Lead adsorption onto HMO-001 was dependent upon solution pH due to the ion-exchange nature, and it can be represented by the Freundlich isotherm model and pseudo-first order kinetic model well. The maximum capacity of HMO-001 toward lead ion was about 395 mg/g. As compared to D-001, HMO-001 exhibited highly selective lead retention from waters in the presence of competing Ca²⁺, Mg²⁺, and Na⁺ at much greater levels than the target toxic metal. Fixed-bed column adsorption of a simulated water indicated that lead retention on HMO-001 resulted in a conspicuous decrease of this toxic metal from 1 mg/L to below 0.01 mg/L (the drinking water standard recommended by WHO). The exhausted adsorbent particles are amenable to efficient regeneration by the binary NaAc-HAc solution for repeated use without any significant capacity loss. All the results validated the feasibility of HMO-001 for highly effective removal of lead from contaminated waters.     

生物除铁除锰在地下水处理厂的应用

黑龙江省兰西镇地下水处理厂采用生物除铁除锰技术取得了满意的铁、锰去除效果。尽管原水含铁量为10～14mg/L、含锰量为0．65～1．1mg/L，出厂水水质仍然优于国家饮用水标准，总铁＜0．05～0．1mg/L，总锰＜0．05mg/L，彻底解决了兰西镇居民的生产和生活用水问题。     

Mn(II)、Cr(III)在黄土上共存吸附特性研究

重金属是土体污染中最重要的污染物质之一,土中的重金属污染往往是复合污染的形式。通过一系列室内试验,研究了锰铬重金属共存时在黄土上的吸附特性。在Mn(II)、Cr(III)重金属复合体系中,Mn(II)在黄土上的吸附明显受到抑制,吸附量减小14.6%~46.5%,而Cr(III)在黄土上的吸附基本不受Mn(II)的影响。Mn(II)的吸附能较好地符合Langmuir模型,受Cr(III)的抑制而不能很好地符合Fredunlich、D-R模型,Cr(III)的吸附仍能较好地符合Fredunlich、D-R模型。在pH=5~7酸性条件下Cr(III)促进了Mn(II)在黄土上的吸附,Mn(II)对Cr(III)的吸附稍有抑制;在碱性条件下,Cr(III)基本不受影响能完全被去除,而Mn(II)的吸附受到很大的抑制作用。重金属本身的物理属性比如水解常数大小以及黄土中的矿物成分都对Mn(II)、Cr(III)在黄土上吸附特性发挥了重要作用。