TiO2-photocatalyzed As(II) oxidation in aqueous suspensions: reaction kinetics and effects of adsorption

Oxidation of arsenite, As(III), to arsenate, As(V), is required for the efficient removal of arsenic by many water treatment technologies. The photocatalyzed oxidation of As(III) on titanium dioxide, TiO2, offers an environmentally benign method for this unit operation. In this study, we explore the efficacy and mechanism of TiO2-photocatalyzed As(III) oxidation at circumneutral pH and over a range of As(III) concentrations approaching those typically encountered in water treatment systems. We focus on the effect of As adsorption on observed rates of photooxidation. Adsorption (in the dark) of both As(III) and As(V) on Degussa P25 TiO2 was examined at pH 6.3 over a range in dissolved arsenic concentrations, [As]diss, of 0.10-89 microM and 0.2 or 0.05 g L(-1) TiO2 for As(III) and As(V), respectively. Adsorption isotherms generally followed the Langmuir-Hinshelwood model with As(III) exhibiting an adsorption maxima of 32 micromol g(-1). As(V) adsorption did not reach a plateau under the experimental conditions examined; the maximum adsorbed concentration observed was 130 micromol g(-1). The extent of As(III) and As(V) adsorption observed at the beginning and end of the kinetic studies was consistent with that observed in the adsorption isotherms. Kinetic studies were performed in batch systems at pH 6.3 with 0.8-42 microM As(III) and 0.05 g L(-1) TiO2; complete oxidation of As(III) was observed within 10-60 min of irradiation at 365 nm. The observed effect of As(III) concentration on reaction kinetics was consistent with surface saturation at higher concentrations. Addition of phosphate at 0.5-10 microM had little effect on either As(III) sorption or its photooxidation rate but did inhibit adsorption of the product As(V). The selective use of hydroxyl radical quenchers and superoxide dismutase demonstrated that superoxide, O2-, plays a major role in the oxidation of As(III) to As(V).     

Photocatalytic oxidation of arsenic(III): evidence of hydroxyl radicals

Arsenic contamination has been found in the groundwater of several countries. Photocatalysis can rapidly oxidize arsenite (As(III)) to less labile and less toxic arsenate (As(V)), which then can be removed by adsorption onto photocatalyst surfaces. This study investigates the photocatalytic oxidation of As(III) to As(V) as a function of As(III) concentration, pH, catalyst loading, light intensity, dissolved oxygen concentration, type of TiO2 surfaces, and ferric ions to understand the kinetics and the mechanism of As(III) oxidation in the UV/TiO2 system. Photocatalytic oxidation of As(III) to As(V) takes place in minutes and follows zero-order kinetics. Benzoic acid (BA) was used as a hydroxyl radical (.OH) scavenger to provide evidence for the .OH as the main oxidant for oxidation of As(III). The .OH radical was independently generated by nitrate photolysis, and kinetics of As(III) oxidation by the .OH radical was determined. Formation of salicylic acid (SA) from the oxidation of BA by .OH also demonstrates the involvement of .OH in the mechanism of As(III) oxidation. The effect of Fe(III) on As(III) oxidation at different pH values with and without TiO2 under UV light was examined. The results suggest that .OH is the dominant oxidant for As(III) oxidation. Two commercially available TiO2 suspensions, Degussa P25 and Hombikat UV100, were tested for the removal of arsenic through oxidation of As(III) to As(V) followed by adsorption of As(V) onto TiO2 surfaces. Results showed that complete removal of arsenic below the World Health Organization drinking water limit of 10 microg/L could be achieved.     

Electrically regenerated ion exchange for removal and recovery of Cr(VI) from wastewater

Ion exchange is widely used for removal and recovery of Cr(VI) from wastewater. Generally, the exhausted ion exchanger is regenerated using chemicals. Although chemical regeneration is efficient, contaminants are introduced, leading to difficulty for the subsequent recovery of Cr(VI). To overcome such a problem, a new regeneration method, namely electrical regeneration, which is carried out on the principle of electrodialysis, is presented in this paper. Experimental results showed that the weak-base resin used could be effectively regenerated electrically. About 93% capacity of the resin was restored under a constant current of 0.25 A over a period of 24 h. The pure chromic acid was recovered in the anode chamber with a concentration of 5.03 g Cr(VI)/L. It was found that the weak-base resin regenerated electrically could remove Cr(VI) from wastewater as effectively as that regenerated chemically. The Cr(VI) concentration was reduced from initial 50 mg/L to lower than the detectable limit, 0.01 mg/L, after treatment.     

Efficient removal of heavy metal ions with biopolymer template synthesized mesoporous titania beads of hundreds of micrometers size

We demonstrated that mesoporous titania beads of uniform size (about 450 μm) and high surface area could be synthesized via an alginate biopolymer template method. These mesoporous titania beads could efficiently remove Cr(VI), Cd(II), Cr(III), Cu(II), and Co(II) ions from simulated wastewater with a facile subsequent solid-liquid separation because of their large sizes. We chose Cr(VI) removal as the case study and found that each gram of these titania beads could remove 6.7 mg of Cr(VI) from simulated wastewater containing 8.0 mg·L(-1) of Cr(VI) at pH = 2.0. The Cr(VI) removal process was found to obey the Langmuir adsorption model and its kinetics followed pseudo-second-order rate equation. The Cr(VI) removal mechanism of titania beads might be attributed to the electrostatic adsorption of Cr(VI) ions in the form of negatively charged HCrO(4)(-) by positively charged TiO(2) beads, accompanying partial reduction of Cr(VI) to Cr(III) by the reductive surface hydroxyl groups on the titania beads. The used titania beads could be recovered with 0.1 mol·L(-1) of NaOH solution. This study provides a promising micro/nanostructured adsorbent with easy solid-liquid separation property for heavy metal ions removal.     

Adsorption mechanism of arsenic on nanocrystalline titanium dioxide

Arsenate [As(V)] and arsenite [As(III)] interactions at the solid-water interface of nanocrystalline TiO2 were investigated using electrophoretic mobility (EM) measurements, Fourier transform infrared (FTIR) spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy, and surface complexation modeling. The adsorption of As(V) and As(III) decreased the point of zero charge of TiO2 from 5.8 to 5.2, suggesting the formation of negatively charged inner-sphere surface complexes for both arsenic species. The EXAFS analyses indicate that both As(V) and As(III) form bidentate binuclear surface complexes as evidenced by an average Ti-As(V) bond distance of 3.30 A and Ti-As(III) bond distance of 3.35 A. The FTIR bands caused by vibrations of the adsorbed arsenic species remained at the same energy levels at different pH values. Consequently, the surface complexes on TiO2 maintained the same nonprotonated speciation at pH values from 5 to 10, and the dominant surface species were (TiO)2AsO2- and (TiO)2AsO- for As(V) and As(III), respectively. The surface configurations constrained with the spectroscopic results were formulated in the diffuse layer model to describe the adsorption behavior of As in the pH range between 4 and 12. The study suggests that TiO2 is an effective adsorbent for As removal due to its high surface area and the presence of high affinity surface hydroxyl groups.     

混凝-光催化联用技术处理制浆中段废水的研究——TiO2-SiO2光催化剂的制备

以钛酸丁酯、正硅酸乙酯、无水乙醇等为原料,采用Sol-Gel法制备TiO2-SiO2光催化剂,通过单因素实验得到最佳制备工艺条件为:n(钛酸丁酯)∶n(正硅酸乙酯)为2.33∶1,煅烧温度为600℃,煅烧时间为3 h,反应溶液pH值为3。当进水CODCr为379.5 mg/L,TiO2-SiO2光催化剂的投加量为0.5 g/L,紫外光照时间为3 h时,出水CODCr为67.8 mg/L。TiO2-SiO2光催化剂颗粒大小为100～500 nm,具有较高的催化活性和稳定性,可以多次重复使用。对比实验表明,TiO2-SiO2处理制浆中段废水的效率比TiO2高。     

阳离子淀粉絮凝剂制备及脱色性能研究

以马铃薯淀粉为原料,3～氯-2-羟丙基三甲基氯化铵为醚化剂,干法工艺制备了季铵型阳离子淀粉絮凝剂(DS=0.099),以荧光黄E-8G染料溶液模拟印染废水,研究了染料浓度、絮凝剂用量、脱色时间和废水pH对脱色率和吸附量的影响.结果表明:阳离子淀粉絮凝剂对碱性印染废水有较好的脱色能力;在废水pH为12.5,染料浓度113.5 mg/L,絮凝剂用量120 mg/L,脱色时间2 h条件下,脱色率达63.2%,吸附量为0.612 mg/mg;絮凝剂对酸性染料分子的吸附符合Langmuir单分子层吸附理论.     

Efficient removal of Cr(VI) from aqueous solution with Fe@Fe2O3 core-shell nanowires

The batch removal of Cr(VI) from simulated wastewater with Fe@Fe2O3 core-shell nanowires (FCSNs) was investigated in this study. Itwas found that each gram of the FCSNs could remove 7.78 mg of Cr(VI) from simulated wastewater containing 8.0 mg L(-1) of Cr(VI) with an initial pH of 6.5 at room temperature. The Freundlich adsorption isotherm was applicable to describe the removal processes. Kinetics of the Cr(VI) removal was found to follow pseudo-second-order rate equation. Furthermore, the as-prepared and Cr(VI)-adsorbed FCSNs were carefully examined by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopic analysis (XPS). The characterization results suggested that the adsorbed Cr(VI) was partially reduced to Cr(lll) in Cr2O3/Cr(OH)3 on the FCSNs. The possible mechanism of removal of Cr(VI) on FCSNs was proposed, which involved the dominant Cr(VI) adsorption, followed by the partial reduction of Cr(VI) to Cr(III) (chromium(III) oxyhydroides) on the surface of FCSNs. These Fe@Fe2O3 core-shell nanowires with high specific surface area and strong magnetic property are very attractive for the removal of Cr(VI) from wastewater.     

Photocatalytic oxidation of arsenite in TiO2 suspension: kinetics and mechanisms

Arsenite [As(III)] and arsenate [As(V)] are highly toxic aquatic contaminants. Since arsenite is more mobile in natural waters and less efficiently removed in adsorption/coagulation processes than arsenate, the oxidation of arsenite to arsenate is desirable in water treatment. We performed the photocatalytic oxidation of arsenite in aqueous TiO2 suspension and investigated the effects of pH, dissolved oxygen, humic acid (HA), and ferric ions on the kinetics and mechanisms of arsenite oxidation. Arsenite oxidation in UV-illuminated TiO2 suspension was highly efficient in the presence of dissolved oxygen. Homogeneous photooxidation of arsenite in the absence of TiO2 was negligibly slow. Since the addition of excess tert-butyl alcohol (OH radical scavenger) did not reduce the rate of arsenite oxidation, the OH radicals should not be responsible for As(III) oxidation. The addition of HA increased both arsenite oxidation and H2O2 production at pH 3 under illumination, which could be ascribed to the enhanced superoxide generation through sensitization. We propose that the superoxide is the main oxidant of arsenite in the TiO2/UV process. The addition of ferric ions also significantly enhanced the arsenite photooxidation. In this case, the addition of tert-butyl alcohol reduced the arsenite oxidation rate, which implied thatthe OH radical-mediated oxidation path was operative in the presence of ferric ions. Since both Fe3+ and HA that were often found with the arsenic in groundwater were beneficial to the photocatalytic oxidation of arsenite, the TiO2/UV process could be a viable pretreatment method. This can be as simple as exposing the arsenic-polluted water in a TiO2-coated trough to sunlight.     

Chromium(III) removal in tannery waste waters using Chinese Reed ( Miscanthus Sinensis), a fast growing plant

Dried Chinese Reed (Miscanthus sinensis) was investigated as adsorbent for the removal of Cr(III) from tannery wastewater. Batch mode adsorption studies were conducted using aqueous solutions of Cr(III). Parameters studied include Cr(III) concentration, agitation time, adsorbent dose and pH. Adsorption followed pseudo-second order kinetic model. Equilibrium adsorption data obeyed both Langmuir and Freundlich isotherms. Langmuir adsorption capacity was found to be 1.85 mg/g. Effects of pH on adsorption and desorption show that both ion exchange and chemisorption are involved in the adsorption process.     

纳米TiO2富集分离原子吸收法测定食品中的锌

以火焰原子吸收为检测手段,研究纳米TiO2 对金属Zn 的吸附性能,考察吸附和洗脱的主要影响因素。结果表明,在pH9～11 范围内,TiO2 对金属Zn 具有良好的吸附性,0.5mol/L 的硝酸即可将TiO2 吸附的Zn 洗脱95%,且吸附速度快。在优化的实验条件下,静态吸附量为15.9mg/g,本法的检出限(3σ)为20.15ng/L,相对标准偏差(RSD)为3.5%(n=10,C=10μg/ml) ,富集倍数为75 倍,加标回收率在92.5%～105.0% 之间。本法对实际食品样品的测定结果令人满意。     

向日葵盘低酯化果胶对重金属离子Pb2+的吸附性能研究

重金属污染由于缺乏有效的治理方法而对公众健康有严重威胁,为了开发吸附重金属离子的生物新材料,本文以向日葵盘为原料提取天然的低酯化果胶LAHP,并研究LAHP对水溶液中Pb2+的吸附性能、优化LAHP吸附Pb2+的条件。采用草酸溶液80 oC提取、乙醇沉淀的方法获得LAHP,产率为14.68%±0.76%。质量分析显示LAHP符合国家质量标准对食品添加剂果胶的要求,结构分析说明LAHP主要由半乳糖醛酸（GalA,86.34%）组成,甲酯化度为23.93%±1.57%,分子量为257 kDa,是天然的低酯化果胶。LAHP对Pb2+的吸附能力受果胶用量、溶液pH、吸附温度和干扰离子等因素的影响,优化确定了LAHP吸附Pb2+的最佳条件:果胶添加量为30 mg/L（Pb2+浓度为11.0 mg/L）、溶液的pH=8.0、处理温度30 ℃。LAHP对Pb2+的最大吸附量为44.57±2.50 mg/g,二价金属离子会在一定程度上影响LAHP对Pb2+的吸附能力。因此,从向日葵盘中提取的低酯果胶是一种良好的天然重金属吸附剂,具有广阔的应用前景。     

Zinc adsorption effects on arsenite oxidation kinetics at the birnessite-water interface

Arsenite is more toxic and mobile than As(V) in soil and sediment environments, and thus it is advantageous to explore factors that enhance oxidation of As(III) to As(V). Previous studies showed that manganese oxides, such as birnessite (delta-MnO2), directly oxidized As(III). However, these studies did not explore the role that cation adsorption has on As(III) oxidation. Accordingly, the effects of adsorbed and nonadsorbed Zn on arsenite (As(III)) oxidation kinetics at the birnessite-water interface were investigated using batch adsorption experiments (0.1 g L(-1); pH 4.5 and 6.0; I= 0.01 M NaCl). Divalent Zn adsorption on synthetic delta-MnO2 in the absence of As(II) increased with increasing pH and caused positive shifts in electrophoretic mobility values at pH 4-6, indirectly suggesting inner-sphere Zn adsorption mechanisms. Arsenite was readily oxidized on birnessite in the absence of Zn. The initial As(III) oxidation rate constant decreased with increasing pH from 4.5 to 6.0 and initial As(III) concentrations from 100 to 300 microM. Similar pH and initial As(III) concentration effects were observed in systems when Zn was present (i.e., presorbed Zn prior to As(III) addition and simultaneously added Zn-As(III) systems), but As(III) oxidation reactions were suppressed compared to the respective control systems. The suppression was more pronounced when Zn was presorbed on the delta-MnO2 surfaces as opposed to added simultaneously with As(III). This study provides further understanding of As(III) oxidation reactions on manganese oxide surfaces under environmentally applicable conditions where metals compete for reactive sites.     

Kinetics and mechanistic aspects of As(III) oxidation by aqueous chlorine, chloramines, and ozone: relevance to drinking water treatment

Kinetics and mechanisms of As(III) oxidation by free available chlorine (FAC-the sum of HOCl and OCl-), ozone (O3), and monochloramine (NH2Cl) were investigated in buffered reagent solutions. Each reaction was found to be first order in oxidant and in As(III), with 1:1 stoichiometry. FAC-As(III) and O3-As(III) reactions were extremely fast, with pH-dependent, apparent second-order rate constants, k'app, of 2.6 (+/- 0.1) x 10(5) M(-1) s(-1) and 1.5 (+/- 0.1) x 10(6) M(-1) s(-1) at pH 7, whereas the NH2Cl-As(III) reaction was relatively slow (k'app = 4.3 (+/- 1.7) x 10(-1) M(-1) s(-1) at pH 7). Experiments conducted in real water samples spiked with 50 microg/L As(III) (6.7 x 10(-7) M) showed that a 0.1 mg/L Cl2 (1.4 x 10-6 M) dose as FAC was sufficient to achieve depletion of As(III) to <1 microg/L As(III) within 10 s of oxidant addition to waters containing negligible NH3 concentrations and DOC concentrations <2 mg-C/L. Even in a water containing 1 mg-N/L (7.1 x 10(-5) M) as NH3, >75% As(III) oxidation could be achieved within 10 s of dosing 1-2 mg/L Cl2 (1.4-2.8 x 10(-5) M) as FAC. As(III) residuals remaining in NH3-containing waters 10 s after dosing FAC were slowly oxidized (t1/2 > or = 4 h) in the presence of NH2Cl formed by the FAC-NH3 reaction. Ozonation was sufficient to yield >99% depletion of 50 microg/L As(III) within 10 s of dosing 0.25 mg/L O3 (5.2 x 10(-6) M) to real waters containing <2 mg-C/L of DOC, while 0.8 mg/L O3 (1.7 x 10(-5) M) was sufficientfor a water containing 5.4 mg-C/L of DOC. NH3 had negligible effect on the efficiency of As(III) oxidation by O3, due to the slow kinetics of the O3-NH3 reaction at circumneutral pH. Time-resolved measurements of As(III) loss during chlorination and ozonation of real waters were accurately modeled using the rate constants determined in this investigation.     

Removal of arsenic from Laminaria japonica Aresch juice using As(III)-imprinted chitosan resin

An As(III)-imprinted chitosan resin (As-ICR) was successfully prepared to selectively remove arsenic from Laminaria japonica Aresch (LJA) juice. Batch adsorption experiments and column adsorption experiments were performed to evaluate the adsorption conditions, selectivity, and reusability. The results showed that the minimum total arsenic concentration of the juice was 4.16 mg/L at pH 6.0, 40 °C, with equilibrium time 4 h. The selectivity of As-ICR for arsenic was much higher than that of non-imprinted chitosan resin. As-ICR could be reused for 10 times with only about 13% regeneration loss. FTIR spectra demonstrated that the adsorption of As-ICR for arsenic occurred on amino and hydroxyl groups. Total arsenic concentration of the juice decreased significantly, while the other metal ions decreased except Zn²⁺ insignificantly. This suggests that As-ICR is a very promising sorbent for selective removal of arsenic from the juice.     

Visible light-induced degradation of carbon tetrachloride on dye-sensitized TiO2

This study investigated an application of TiO2 photocatalyst sensitized with tris(4,4'-dicarboxy-2,2'-bipyridyl)ruthenium-(II) complex to CCl4 degradation under visible light irradiation. By injecting electrons from the photoexcited sensitizer to the conduction band, the sensitized TiO2 degraded CCl4 under the irradiation of lambda > 420 nm. The quantum yield of CCl4 dechlorination was about 10(-3). The dechlorination rate of CCl4 was reduced in the presence of dissolved O2 due to its competition for conduction band electrons. The photolysis rate was dependent on pH due to the strong pH dependence of the sensitizer adsorption on TiO2 surface with a maximum degradation rate achieved at pH approximately 3. A two-site Langmurian model successfully described the adsorption of the sensitizer on TiO2 particles. The monolayer coverage was achieved at the added sensitizer concentration of 10 microM at [TiO2] = 0.5 g/L. However, the photolysis rate of CCl4 showed a maximum at a sensitizer surface coverage of 0.3 monolayer. Since the photoinduced electron injection gradually depleted active sensitizer molecules on TiO2, sacrificial electron donors to regenerate the sensitizer were sought. 2-Propanol as an electron donor was efficient in the present RuIIL3/TiO2/CCl4 system, which showed no sign of deceleration in the dechlorination rate up to 6 h of irradiation.     

纳米二氧化钛薄膜光催化处理造纸废水的研究

采用微波辅助低温法制备锐钛矿结构的二氧化钛薄膜。通过X射线衍射(XRD)、扫描电子显微镜(SEM)和接触角测定分析技术对其物相、显微结构和亲水性进行了表征;在波长为254nm的紫外灯照射下,对TiO2薄膜光催化降解造纸废水前后COD值变化作了研究,探讨了不同光催化条件、造纸废水初始COD浓度、pH值及水温变化对COD去除率的影响。结果表明:与传统溶胶凝胶法制备的薄膜相比,微波辅助低温制备的薄膜光催化效果更佳。当废水初始COD值在500～1000mg/L之间、pH为4.0、水温为35℃、紫外灯照射8.0h时,光催化效果最佳,COD去除率为81.3%。     

壳聚糖基杂化气凝胶对活性染料的吸附性能

为有效去除印染废水中的活性染料,以壳聚糖高分子为骨架材料,甲壳素微晶作为偶联剂,多巴胺作为交联剂,原位生成的纳米二氧化钛为掺杂剂,通过溶液共混和冷冻干燥技术制备了壳聚糖/微晶/聚多巴胺/二氧化钛(CS/WSK/PDA/TiO2)杂化气凝胶,并用于吸附活性红紫X-2R、活性红KE-3B和活性黄M-3BE.借助全反射红外光...     

Arsenic-bicarbonate interaction on goethite particles

The As(V) and As(III) interaction with HCO3 has been studied for goethite systems using a pH and As concentration range that is relevant for field situations. Our study shows that dissolved bicarbonate may act as a competitor for both As(V) and As(III). In our closed systems, the largest effect of bicarbonate occurs at the lowest experimental pH values (pH approximately 6.5), which is related to the pH dependency of the carbonate adsorption process. The experimental data have been modeled with the charge distribution (CD) model. The CD model was separately parametrized for goethite with "single ion" adsorption data of HCO3, As(III), and As(V). The competitive effect of HCO3 on the As(III) and As(V) release could be predicted well. Application of the model shows that the natural As loading of aquifer materials (approximately < 0.01-0.1 micromol/m2 or < 1-5 mg/kg) is at least about > 1-2 orders of magnitude smaller than the As loading based on the competition of As-HCO3 alone. It indicates that another, very prominent competitor, like phosphate and natural organic matter, will strongly contribute to the control of As in natural systems.     

Long-term effects of titanium dioxide nanoparticles on nitrogen and phosphorus removal from wastewater and bacterial community shift in activated sludge

The expanding use of titanium dioxide nanoparticles (TiO(2) NPs) in a wide range of fields raises concerns about their potential environmental impacts. However, investigations of the potential effects of TiO(2) NPs on biological nitrogen and phosphorus removal and bacterial community in activated sludge are sparse. This study evaluated the influences of TiO(2) NPs on biological nutrient removal in the anaerobic-low dissolved oxygen (0.15-0.50 mg/L) sequencing batch reactor. It was found that 1 and 50 mg/L TiO(2) NPs had no acute effects on wastewater nitrogen and phosphorus removal after short-term exposure (1 day). However, 50 mg/L TiO(2) NPs (higher than its environmentally relevant concentration) was observed to significantly decrease total nitrogen (TN) removal efficiency from 80.3% to 24.4% after long-term exposure (70 days), whereas biological phosphorus removal was unaffected. Denaturing gradient gel electrophoresis profiles showed that 50 mg/L TiO(2) NPs obviously reduced the diversity of microbial community in activated sludge, and fluorescence in situ hybridization analysis indicated that the abundance of nitrifying bacteria, especially ammonia-oxidizing bacteria, was highly decreased after long-term exposure to 50 mg/L TiO(2) NPs, which was the main reason for the serious deterioration of ammonia oxidation. Further study revealed that 50 mg/L TiO(2) NPs inhibited the activities of ammonia monooxygenase and nitrite oxidoreductase after long-term exposure, but had no significant impacts on the activities of exopolyphosphatase and polyphosphate kinase, and the transformations of intracellular polyhydroxyalkanoates and glycogen, which were consistent with the observed influences of TiO(2) NPs on biological nitrogen and phosphorus removal.