Manganese-oxide-coated alumina: a promising sorbent for defluoridation of water

In this study, adsorption potential of a new sorbent manganese-oxide-coated alumina (MOCA) was investigated for defluoridation of drinking water using batch and continuous mode experiments. The effects of different parameters such as pH, initial fluoride concentration and co-existing ions (usually present in groundwater sample) were studied to understand the adsorption behavior of the sorbent under various conditions. Optimum removal of fluoride ions occurred in a pH range of 4-7. Results of the present study indicate that fluoride adsorption rate and adsorption capacity of MOCA are far superior to that of activated alumina (AA), which was used as the base material for MOCA preparation. The MOCA can be effectively regenerated using 2.5% NaOH as eluent. The Langmuir equilibrium model was found to be suitable for describing the fluoride sorption on AA and MOCA. The maximum fluoride uptake capacity for MOCA and AA was found to be 2.85 and 1.08 mg g(-1), respectively. The kinetic results showed that the fluoride sorption to MOCA followed pseudo--second-order kinetics with a correlation coefficient greater than 0.98. The fluoride sorption capacity at breakthrough point for both the adsorbents was greatly influenced by bed depth. A bed depth service time (BDST) approach was adopted to describe the continuous flow system. The batch and column studies demonstrated the superiority of MOCA over AA in removing fluoride from the drinking water system.     

Removal of fluoride from semiconductor wastewater by electrocoagulation-flotation

This work employs an anodic surfactant, sodium dodecyl sulfate (SDS), to improve the flotation performance of the electrocoagulation-flotation (ECF) process to treated fluoride containing semiconductor wastewater following calcium precipitation. The dissolved fluoride ions and CaF(2) particles in the wastewater after calcium precipitation were effectively removed in the ECF process simultaneously. The dosage of SDS required for ECF was much less than those for dispersed air flotation (DiAF) or dissolved air flotation (DAF) processes because the CaF(2) particles can be collected by hydro-fluoro-aluminum flocs in ECF. Thus, SDS only served as a frother to make the bubbles tiny and stable in the ECF defluoridation process. The interference of co-existing anions can be overcome by increasing the dosage of calcium ions and SDS. The optimum initial acidity for ECF is close to the initial fluoride concentration after calcium precipitation; the amount of SS removed dropped rapidly if the initial acidity exceeded the optimal value because the surface charge of the hydro-fluoro-aluminum particles increased. The initial acidity of the wastewater after calcium precipitation can be modified by changing the [Ca(OH)(2)]/[Ca(2+)](T) ratio and the appropriate ratio is approximately given by the acid dissociation constant of hydrofluoric acid and the initial pH of the wastewater before calcium precipitation.     

Treatment of high fluoride concentration water by MgAl-CO3 layered double hydroxides: kinetic and equilibrium studies

MgAl-CO(3) layered double hydroxides (LDHs) have been employed to treat high fluoride concentration solution. The influences of solution pH, initial fluoride concentration and other anions in the solution were investigated by a series of batch experiments. A marked decrease in the amount of adsorbed fluoride by LDHs is observed with increasing pH. The extent of fluoride removal in the presence of other anions decreases in the order HCO(3)(-)>Cl(-)>H(2)PO(4)(-)>SO(4)(2-). The equilibrium isotherm for fluoride uptake corresponds closely to the Langmuir-Freundlich (L-F) model. The maximum capacity of LDHs for fluoride ions and the Gibbs free energy (DeltaG(0)) for the defluoridation process were calculated to be 319.8+/-5.7mg/g and -9.0+/-0.66kJ/mol, respectively. The negative value of DeltaG(0) indicates the spontaneous nature of the treatment process. Four kinetic models have been evaluated in order to attempt to fit the experimental data, namely the pseudo-first order, the pseudo-second order, the modified multiplex and the double exponential models. It was found that the modified multiplex model, involving a rapid first order step and a slow second order step most closely described the kinetics. The activation energies for the two steps are 37.2+/-5.26 and 72.6+/-4.52kJ/mol, respectively, suggesting that the rapid step is controlled by diffusion processes, whilst the second step is controlled by the reaction of fluoride with the LDHs.     

氯盐对再生混凝土硫酸盐侵蚀的抑制作用研究

将再生骨料取代率为50%的混凝土试块自然浸泡在单一Na₂SO₄溶液、MgSO₄溶液和NaCl-Na₂SO₄复合溶液、NaCl-MgSO₄复合溶液中,其中复合溶液中的氯盐质量分数分别为0%,2%,5%和10%。在整个试验周期内,每隔30 d测量不同溶液中再生混凝土试块的表观形貌、超声声速和质量变化率,得出了氯盐对Na₂SO₄溶液和MgSO₄溶液侵蚀再生混凝土的抑制规律。最后结合试验结果,详细分析了氯盐抑制不同硫酸盐溶液侵蚀再生骨料混凝土相关性能差异的机理。研究结果表明:氯盐对再生混凝土的硫酸钠侵蚀有明显抑制作用,氯盐质量分数为5%时抑制效果最明显,但是氯盐质量分数继续增大,抑制效果没有明显的提高; 氯盐对硫酸镁溶液侵蚀再生混凝土的抑制效果较弱,甚至在氯化钠质量分数为2%时,再生混凝土试块表观侵蚀程度比未掺加氯化钠的还严重; 氯离子对硫酸根离子侵蚀有抑制作用,但是对镁离子的侵蚀无明显抑制作用; 所得结论为再生骨料混凝土在实际工程中的耐久性应用提供了借鉴。     

Damage on lining concrete in highway tunnels under combined sulfate and chloride attack

The combined effect from sulfate and chloride is one of the important reasons to cause the damage of lining concrete in highway tunnels. To investigate the effect of chloride ions on the corrosion of lining concretes under sulfate attack, ultrasonic detecting, compression test and X-ray Diffraction (XRD) were performed on the concretes to obtain the ultrasonic velocity, corrosion thickness, compression strength and corrosion products. The ultrasonic results, compression strength and XRD patterns confirmed that the existence of chloride certainly depressed the corrosion damage on the lining concretes under sulfate attack, and the depressing effect increased with the content of chloride in the composite solution. The corrosion damage on the concretes experienced three stages independent of the composition of corrosive solution: initial slower enhancement on the strength, stabilization period and linear degradation period. The existence of chloride mainly affected the final degradation stage and obviously decreased the corrosion thickness.     

氯盐和硫酸盐侵蚀下水泥净浆中钢筋锈蚀过程

针对氯盐和硫酸盐耦合作用下钢筋混凝土的腐蚀问题,设计制作了含水泥净浆保护层的水泥净浆-钢筋试件,测试了试件在氯盐和硫酸盐腐蚀溶液中的电化学阻抗谱(EIS),并分析了溶液类型、水灰比及水泥净浆保护层厚度对试件电化学参数及钢筋锈蚀程度的影响.结果表明:同单一氯盐溶液中的试件相比,在硫酸盐-氯盐复合溶液腐蚀前期,试件内钢筋表面电荷转移电阻较大,腐蚀电流密度较小,此时硫酸盐减缓了水泥净浆内钢筋的锈蚀进程;在硫酸盐-氯盐复合溶液腐蚀后期,试件内钢筋表面电荷转移电阻显著减小,腐蚀电流密度明显增加,此时硫酸盐加速了水泥净浆中钢筋的锈蚀进程.此外,试件中水泥净浆水灰比越大,钢筋锈蚀程度也越大,当水泥净浆保护层厚度增加时,钢筋锈蚀程度降低.     

Electrochemical removal of fluoride from water by PAOA-modified carbon felt electrodes in a continuous flow reactor

A novel poly(aniline-co-o-aminophenol) (PAOA) modified carbon felt electrode reactor was designed and investigated for fluoride removal from aqueous solutions. This reactor design is innovative because it operates under a wider pH range because of coating with a copolymer PAOA ion exchange film. In addition, contaminant mass transfer from bulk solution to the electrode surface is enhanced by the porous carbon felt as an electron-conducting carrier material compared to other reactors. The electrically controlled anion exchange mechanism was investigated by X-ray photoelectron spectroscopy and cyclic voltammetry. The applicability of the reactor in the field was tested through a series of continuous flow experiments. When the flow rate and initial fluoride concentration were increased, the breakthrough curve became sharper, which lead to a decrease in the breakthrough time and the defluoridation capacity of the reactor. The terminal potential values largely influenced fluoride removal by the reactor and the optimal defluoridation efficiency was observed at around 1.2 V. The breakthrough capacities were all >10 mg/g over a wide pH range (pH 5-9) with an initial fluoride concentration of 10 mg/L. Consecutive treatment-regeneration studies over a week (once each day) revealed that the PAOA-modified carbon felt electrode could be effectively regenerated for reuse. The PAOA-modified carbon felt electrode reactor is a promising system that could be made commercially available for fluoride removal from aqueous solutions in field applications.     

High yield combustion synthesis of nanomagnesia and its application for fluoride removal

We describe a novel combustion synthesis for the preparation of Nanomagnesia (NM) and its application in water purification. The synthesis is based on the self-propagated combustion of the magnesium nitrate trapped in cellulose fibers. Various characterization studies confirmed that NM formed is crystalline with high phase purity, and the particle size varied in the range of 3-7 nm. The fluoride scavenging potential of this material was tested as a function of pH, contact time and adsorbent dose. The result showed that fluoride adsorption by NM is highly favorable and the capacity does not vary in the pH range usually encountered in groundwater. The effects of various co-existing ions usually found in drinking water, on fluoride removal were also investigated. Phosphate was the greatest competitor for fluoride followed by bicarbonate. The presence of other ions studied did not affect the fluoride adsorption capacity of NM significantly. The adsorption kinetics followed pseudo-second-order equation and the equilibrium data are well predicted by Frendlich equation. Our experimental evidence shows that fluoride removal happened through isomorphic substitution of fluoride in brucite. A batch household defluoridation unit was developed using precipitation-sedimentation-filtration techniques, addressing the problems of high fluoride concentration as well as the problem of alkaline pH of the magnesia treated water. The method of synthesis reported here is advantageous from the perspectives of small size of the nanoparticle, cost-effective recovery of the material and improvement in the fluoride adsorption capacity.     

基于SO42-吸附与反应的硬化水泥基材料中Cl-传输与固化机制

通过自行设计的离子空间传输试验装置,分析研究了硫酸盐和氯盐的空间传输性能,并通过测试硫酸盐和氯盐共存时产物的组成和形貌,分析硫酸根离子对氯离子固化行为的影响。结果表明,在SO42-与Cl-共存的情况下,Cl-在不同时间和空间传输量较纯溶液时均有减小,说明SO42-会阻碍Cl-的传输;SO42-与Cl-均可与水泥基材料的水化产物发生反应,其中SO42-反应生成AFt,Cl-反应生成Friedel盐,当两者共存时,Friedel盐生成量减少,说明SO42-会减弱Cl-的固化能力,从而减弱混凝土结构中氯盐的腐蚀破坏程度。     

Efficient arsenic(V) removal from water by ligand exchange fibrous adsorbent

This study is an efficient arsenic(V) removal from contaminated waters used as drinking water in adsorption process by zirconium(IV) loaded ligand exchange fibrous adsorbent. The bifunctional fibers contained both phosphonate and sulfonate groups. The bifunctional fiber was synthesised by graft polymerization of chloromethylstyrene onto polyethylene coated polypropylene fiber by means of electron irradiation graft polymerization technique and then desired phosphonate and sulfonate groups were introduced by Arbusov reaction followed by phosphorylation and sulfonation. Arsenic(V) adsorption was clarified in column methods with continuous flow operation in order to assess the arsenic(V) removal capacity in various conditions. The adsorption efficiency was evaluated in several parameters such as competing ions (chloride and sulfate), feed solution acidity, feed flow rate, feed concentration and kinetic performances at high feed flow rate of trace concentration arsenic(V). Arsenic(V) adsorption was not greatly changed when feed solutions pH at 3.0-7.0 and high breakthrough capacity was observed in strong acidic area below pH 2.2. Increasing the flow rate brings a decrease both breakthrough capacity and total adsorption. Trace level of arsenic(V) (0.015 mM) in presence of competing ions was also removed at high flow rate (750 h⁻¹) with high removal efficiency. Therefore, the adsorbent is highly selective to arsenic(V) even in the presence of high concentration competing ions. The adsorbent is reversible and reusable in many cycles without any deterioration in its original performances. Therefore, Zr(IV) loaded ligand exchange adsorbent is to be an effective means to treat arsenic(V) contaminated water efficiently and able to safeguard the human health.     

氯盐、硫酸盐作用下高性能混凝土损伤研究

通过 3 5 %NaCl溶液 ,5 %Na2 S0 4 溶液以及 3 5 %NaCl+5 %Na2 SO4 复合溶液的浸泡腐蚀试验 ,研究了C30、C5 0两种强度等级 ,三种大掺量矿物掺合料混凝土在腐蚀溶液中的自由氯离子扩散规律 ,以及基于相对动弹性模量变化的损伤规律。结果表明 :复合腐蚀下 ,C30的自由氯离子含量是C5 0的 2倍左右 ;氯离子扩散系数为C5 0的 1 7～ 1 95倍 ;混凝土相对动弹性模量先上升后下降。矿物掺合料提高了混凝土抗氯离子渗透和抗硫酸盐损伤能力 ,硫酸盐降低了混凝土抗氯离子腐蚀能力 ,氯盐减缓了硫酸盐对混凝土的损伤速度。     

碳硫硅钙石的化学定量分析

基于混凝土中含硫水化产物化学特性的差异,采用氯化钡和氯化钙溶液处理水泥水化浆体样品,将碳硫硅钙石（TSA）与其他含硫水化产物进行分离,进而测得TSA含量.结果表明：采用该方法测定的硫酸钠硫化钙单硫型水化硫铝酸钙（AFm）石膏钙矾石（AFt）TSA混合物中的TSA含量,平均准确率可达92%以上;用该法定量测试了浸泡于硫酸盐溶液中水泥净浆试件的TSA含量,其含量顺序为硫酸镁＞硫酸铝＞硫酸钠.由此可见,用该化学定量法定量碳硫硅钙石可行而且可靠.     

Role of anions on heavy metal sorption of a cellulose modified with poly(glycidyl methacrylate) and polyethyleneimine.

The influence of anions on the equilibrium and kinetic uptake of heavy metals from an aqueous solution by a novel nitrogen-type chelating adsorbent was evaluated. Equilibrium experiments revealed that stoichiometric amounts of metals and anions are adsorbed by the resin. Kinetic studies showed that during the initial stage of adsorption, the anions are adsorbed by the adsorbent prior to the metal ions. This occurred almost simultaneously with an increase in solution pH. At equilibrium, the pH returned towards its initial value. The concentration of anion also fluctuated during the entire equilibration process. Following these observations, mechanisms governing the role of anions on enhancing capacity and rate of metal uptake of this type of chelating adsorbent type were established.     

电极工作面积和孔隙液pH值对钢筋脱钝临界氯离子浓度的影响

基于模拟混凝土孔隙液中的钢筋脱钝试验,揭示了钢筋电极的工作面积和模拟混凝土孔隙液的pH值对钢筋脱钝过程中开路电位、极化电阻和腐蚀电流密度的影响规律,确定了不同钢筋电极工作面积和pH值条件下钢筋脱钝的临界氯离子浓度,分别建立了钢筋电极工作面积和模拟混凝土孔隙液pH值与钢筋脱钝临界氯离子浓度之间的定量关系.结果 表明:随着钢筋电极工作面积的增大,钢筋脱钝的临界氯离子浓度降低;随着模拟混凝土孔隙液pH值的增加,以自由氯离子浓度[Cl-]表征的临界氯离子浓度增加,而以[Cl-]/[OH-]表征的临界氯离子浓度降低;与开路电位和极化电阻相比,钢筋脱钝过程中腐蚀电流密度的突变点更加明显.     

Chloride induced reinforcement corrosion in lightweight aggregate high-strength fly ash concrete

Reinforced lightweight aggregate high-strength concrete slabs that incorporated fly ash were exposed to 2% chloride solution for over 15 months. Chloride ion ingress, corrosion potentials, corrosion current density and electrical resistivity were determined. These slabs were compared with slabs from normal weight concrete of medium and high-strength. The results indicated that lightweight high-strength concrete slabs with fly ash in the concrete mixture showed the least amount of chloride concentration. Values of corrosion current density were very low and values of electrical resistivity were very high and indicative of extremely low corrosion current. The dense matrix of the lightweight high-strength concrete is believed to restrict continuous pores that may carry chloride ions. The effect of fly ash in lowering the chloride diffusivity further contributed to reduce harmful chloride ions. In addition, the porous sintered fly ash aggregates are believed to have acted as buffer reservoirs for the chloride laden solution and thus prevented the chloride ions from reaching the steel surface.     

Ion chromatographic analysis of corrosion inhibitors in concrete

A method employing ion chromatography for identifying and quantifying ions present in the aqueous phase of concrete after surface treatment with corrosion inhibitors is reported in this paper. With this technique, a broad range of ions including ethanolamine, nitrite and monofluorophosphate, present in the inhibitors tested, could be identified in solution. When ethanolamine and nitrite were applied to the surface of concrete, they were readily detected in samples into which they had penetrated. In the case of monofluorophosphate-treated concrete, only the hydrolysis products, fluoride and phosphate were detected and not the monofluorophosphate ion itself. Furthermore, concentrations of other important ions, such as chloride, were also quantifiable by this technique. One of the main advantages of ion chromatography for this type of application is its ability to analyse a wide range of ions in a given sample.     

混凝土应力腐蚀研究现状

为了更好表达建筑结构耐久性的真实情况,了解、掌握应力作用’下混凝土的耐久性问题,介绍了混凝土结构在氯离子、硫酸盐、碳化等因素影响下的腐蚀效应,对混凝土应力腐蚀的研究现状进行了评述。     

The investigation of the efficiency of coagulants based on titanium when purifying water

We have studied the efficiency of the coagulation effects of titanyl sulfate and titanium chloride compared with aluminum sulfate on model water at pH 5.5–10 and alkalinity 0.5–5 mmol/dm³. It was found that titanium coagulants are expedient to be used for treating water with low alkalinity within the interval 9 < pH < 7, i.e., in conditions whereby aluminum sulfate does not work. At the same time in the pH region optimal for aluminum sulfate and average values of water alkalinity (turbidity, color, temperature 18–20°C) this reagent ensures the same degree of purification at consumptions on average by 20 and 30% lower compared with respectively titanyl sulfate and titanium chloride.     

Defluoridation of water via electrically controlled anion exchange by polyaniline modified electrode reactor

A polyaniline (PANI) modified electrode reactor was designed for fluoride removal from aqueous solutions. The innovative concept behind the reactor design is that the uptake and elute of fluoride could be well controlled by modulating the potential of the PANI film. The maximum fluoride removal capacity of PANI is more than 20 mg/g at a positive voltage based on the electrically controlled anion-exchange mechanism. The results of batch tests showed that terminal potential values had a major impact on fluoride removal by this PANI, with optimal removal occurring at 1.5 V. The fluoride removal capacity (q_e) increased rapidly within 5 min and reached equilibrium within 10 min, which indicated a rapid removal velocity of fluoride by PANI under this condition. The applicability of defluoridation using the PANI reactor to treat fluoride-contaminated tap water was also tested through flow cell breakthrough studies. At initial fluoride concentrations of 5 mg/L and 10 mg/L, the breakthrough capacities were 20.08 mg/g and 19.24 mg/g, respectively. Moreover, during the first half of the period before the breakthrough point, the fluoride concentration of the treated solution was below the WHO’s recommended levels (1.5 mg/L). The results of the five consecutive treatment-regeneration studies also showed that the PANI films could be reused. Taken together, these results implied that the electrically controlled anion exchange by the PANI-modified electrode reactor may be an effective technique for the removal of fluoride from water.     

Electrochemical denitrificaton of simulated ground water

Electrochemical denitrification of ground water was studied with an objective to maximize nitrate transformation to nitrogen gas. Aluminum, graphite, iron and titanium were selected as electrode materials. While aluminum, iron and titanium electrodes showed 70-97% nitrate reduction, with graphite electrode the removal was only 8%. Nitrate was transformed to ammonia with iron and aluminum electrodes but with titanium electrodes nitrogen was apparently the major end product. Iron electrodes exhibited the maximum reducing condition (ORP=-463mV) and titanium showed the minimum (ORP=-206mV). Nitrate reduction with titanium electrodes was retarded in the presence of chloride ions possibly due to formation of hypochlorite ions. The first-order nitrate transformation rate constant with respect to time decreased with decrease in current density. However, when the rate constant was expressed with respect to charge passed (Coulomb/l) it was nearly same under different experimental conditions (current density and pH). The study indicates that the process might be suitable for denitrification of drinking water.