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Environ Chem Lett DOI 10.

1007/s10311-010-0303-1

ORIGINAL PAPER

Removal of arsenic from aqueous solution by two types of nano TiO2 crystals
L. Ma S. X. Tu

Received: 19 June 2010 / Accepted: 20 October 2010 Springer-Verlag 2010

Abstract Titanium dioxide (TiO2) is a promising sorbent for As removal. There are two main and physico-chemically distinct polymorphs of TiO2 in nature, namely anatase and rutile. Since the difference of arsenic removal by the two polymorphs of TiO2 is now well known, study on the arsenic removal efciency and the underlying mechanism is of great signicance in developing new remediation strategies for As-polluted waters. Here batch experiments were carried out in combination with instrumental analysis of X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS) to investigate the effects, inuential factors and mechanisms of As removal from aqueous solution by two types of nano TiO2 crystals. The adsorption behavior of anatase and rutile for As(V) and As(III) are well described by Freundlich equations. Anatase had higher As removal efciency and adsorption capacity than rutile. Solution pH had no inuence on the As adsorption of anatase TiO2, whereas the As removal by rutile TiO2 was increased by 718% with pH from 4 to 10. Presence of accompanying anions such as phosphate, silicate, nitrate and sulfate, decreased the As(V) and As(III) removal by both crystals, with phosphate being the most effective. However, removal of As by rutile TiO2 was greatly enhanced in the presence of divalent cations i.e. Ca2? and Mg2?. Shading

of light decreased the removal of As(V) and As(III) of anatase by 15.5% and 17.5%, respectively, while a slight increase of As removal was observed in the case of Rutile TiO2. FT-IR characterization of As(V) or As(III)-treated nano TiO2 crystals indicated that both Ti-O and As-O groups participated in As adsorption. Both FT-IR and XPS analysis demonstrated that As(III) was photooxidated into As(V) when adsorbed by anatase under the light condition. Thus, the effect of crystal types and light condition on As removal should be taken into consideration when nano TiO2 is applied for As removal from water. Keywords Anatase Rutile Sorption Photocatalytic activity Titanium dioxide

Introduction Recently, arsenic (As) contamination of groundwater has been reported in more than ten provinces and municipalities of China. Chronic health effects associated with arsenic ingestion are endemic in Shanxi (Wang et al. 2004), Xinjiang (Wang 1984), Inner Mongolia (Smedley et al. 2003), and in Taiwan (Lin et al. 2004) where As concentrations in the groundwater used for drinking exceed the new China national maximum level of 10 lg L-1. Arsenic is also ingested with agricultural products from farms that use As-contaminated groundwater for irrigation or raising farm animals. Similar situations exist in India, Bengal, Australia, South America, and Japan where millions of people suffer deleterious health effects from drinking As-contaminated water (Alaerts and Khouri 2001; Mandal and Suzuki 2002; Ohno et al. 2007). The search for safe and effective ways to remove As from drinking water requires an ongoing international effort.

Electronic supplementary material The online version of this article (doi:10.1007/s10311-010-0303-1) contains supplementary material, which is available to authorized users.
L. Ma S. X. Tu (&) Department of Environmental Sciences and Engineering, Huazhong Agricultural University, 430070 Wuhan, China e-mail: stu@mail.hzau.edu.cn

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Arsenic can be removed from water by physical, chemical, or biological separation processes. Physical methods include enhanced coagulation (Song et al. 2006), adsorption (Tuutijarvi et al. 2009), reverse-osmosis (Walker et al. 2008), membrane separation (Ferella et al. 2007), and electro-adsorption (Basha et al. 2008). Chemical methods include anion exchange (Anirudhan and Unnithan 2007), pre-oxidation (Balarama Krishna et al. 2001), and oxidative adsorption (Bang et al. 2005a; Kanel et al. 2005). Biological methods include either bioremediation (Katsoyiannis and Zouboulis 2004) or phytoremediation (Ma et al. 2001; Tu et al. 2004). Many adsorbents have been used to remove As from water including iron oxide (Pierce and Moore 1982), iron rock (Zhang et al. 2004), ferrous manganese ore (Chakravarty et al. 2002), zero-valent iron (Zeng 2003), activated carbon (Lorenzen et al. 1995), activated alumina (Hao et al. 2009), etc. More recently, nano-sized particles of materials such as titanium dioxide (TiO2), zero-valent iron, cupric oxide and maghemite have emerged as promising new adsorbents for As removal from waters (Pena et al. 2005; Kanel et al. 2005; Martinson and Reddy 2009; Tuutijarvi et al. 2009). It is well known that TiO2 is a good adsorbent of As, with anatase and rutile being the two main and physico-chemically distinct polymorphs of TiO2 in nature. Anatase has much greater photocatalytic activity than rutile while it is thermodynamically less stable (Fujishima and Honda 1972). Studies have shown differences between nano-sized TiO2 polymorphs in the photocatalytic degradation of organic pollutants (Watanabe et al. 2003) and those in the photochemical reaction of inorganic compounds (Kim et al. 2003). We hypothesized that differences would also exist in the efcacy of nano-particles of TiO2 polymorphs to adsorb As from water. Also, the factors such as accompanying ions, pH, temperature, and light intensity would inuence As removal. Thus, the objectives of this study were (1) to compare the As removal efcacy and As adsorption capacity by nano anatase and rutile; (2) to understand the effect of accompanying ions, pH, and temperature as well as light condition on the As removal; and (3) to illustrate the mechanisms of As removal by the two nano crystals of TiO2.

more acidic on rutile than on anatase (Pena et al. 2005). The particle sizes of anatase and rutile crystals were 15 and 25 nm, respectively (Table S1; Fig. S2). The BET-determined surface area for anatase and rutile were 68.0 and 50.0 m2 g-1, respectively (Table S1). The X-ray diffraction patterns of anatase and rutile in the Joint Committee for Powder Diffraction Studies database (JCPDF card 00-021-1272 and 00-004-0551, respectively) show different diagnostic peaks (Fig. S3). Standard stock solution of As(V) containing 1,000 mg As L-1 (CB/T601-2002) was purchased from Sinopharm Chemical Reagent Co., Ltd, and standard stock solution of As(III) was prepared in 18 MX puried water using analytical reagent As2O3. Test solutions containing different concentrations of As (V) and As (III) were made by diluting these stock solutions. Batch experiments The efcacy of As removal by anatase and rutile was studied using increasing concentrations of As(V) or As(III) in aqueous solution. Studies on the efcacy of As removal, light intensity, and pH were done using a sorbent concentration of 8 g L-1 for both anatase and rutile. Except for the batch adsorption isotherms and the efcacy of As removal, a solution of 200 lg L-1 As(V) or As(III) was used in all cases due to \200 lg L-1 of As concentration in most of natural As-contaminated groundwater. Each batch treatment was replicated three times in all studies. All batch adsorption studies were done at pH 7.0 except for the experiment to determine pH effects on As. In all cases, the pH of the initial As solution was adjusted using 0.1 mol L-1 HCl or 0.1 mol L-1 NaOH. The 50-ml sorbent/solution suspensions used for all studies were prepared in 250-ml Erlenmeyer asks, shaken for 1 h at 180 oscillations per minute at 25C, and centrifuged at 18,300 g acceleration for 5 min. The samples of the supernatant were withdrawn for As analysis. The concentrations of As(V) and As(III) in the supernatant were determined using Atomic Fluorescence Spectrometer (AFS) using a Beijing Jitian, Model 8220 AF spectrometer. Mixed reagent of 10% thiourea and 10% ascorbic acid was used for pre-reduction of arsenate, and hydrochloric acid (5%) was used for hydride generation. The standard reference solution (1,000 mg L-1) from Sinopharm (CB/T601-2002) was analyzed as part of the quality assurance and quality control protocol. Reagent blanks and internal standards were used where appropriate to ensure accuracy and precision in the AFS analysis for As. The experiment for comparing the efcacy of As removal by anatase and rutile and As adsorption isotherms were obtained by adding 50 mL of 0.1, 0.2, 0.5, 1, 2, 4, 6,

Materials and methods Materials Nano-sized rutile (VK-T25H) and anatase (VK-TA18H) were obtained from Aldrich (Lot: 718467), U.S.A. The pHzpc values for anatase and rutile powders were 6.42 and 2.72, respectively (see supporting information, Table S1 and Fig. S1), indicating that the titanyl group, Ti-OH, was

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10, 20, 30, 40 mg L-1 of As(V) solution, and 0.1, 0.2, 0.5, 1, 2, 4, 6, 10, 15, 20, 30 mg L-1 of As(III) solution to sorbent at 0.400 g of anatase or rutile nano-particles. Effects of As removal was determined by dark, simulated natural sunlight (using 10 W uorescent lamp), and UV (using 10 W SW-CJ-1D UV lamp). To determine pH effects on As adsorption, 50 ml of 200 lg As L-1 solutions was adjusted to pH 4, 5, 6, 7, 8, 9, and 10 and then mixed with anatase or rutile nano-particles. To study the effect of different types and concentrations of accompanying ions on As adsorption, anatase or rutile nano-particles were added to 50 mL of 40 mmol L-1 of NaCl solution containing 200 lg L-1 of As. The following anions or cations were added based on Pena et al.(2005) and Bang et al. (2005b): Ca2? (as CaCl2), Mg2? (as MgCl2), SiO32- (as Na2SiO3), NO3- (as NaNO3), SO42-(as Na2SO4), H2PO4- (as Na3PO4) at 0, 5, 10, 50, 100, 1,000 lmol L-1, respectively. X-ray diffraction (XRD) analysis was made to characterize the different nano-crystalline of TiO2 by using D8 Advance X-ray power diffractometer (Bruker, Germany) equipped with Cu Ka radiation at a scanning speed of 2/ min from 20 to 60, voltage of 40 kV, and applied potential current 40 mv. The surface area of the TiO2 particles was analyzed by Brunauer-Emmett-Teller (BET) method, N2 gas adsorption at 77 K using a Quantachrome Autosorb-1 automatic surface and pore size distribution analyzer (Malvern Instruments, England). The pHzpc analysis of the TiO2 was recorded using a 90 plus Particle Size Analyzer Brookhaven Zeta-Plus system (the U.S. Brookhaven Instruments Corporation). The FT-IR spectra of pure TiO2 and As-adsorbed TiO2 were recorded in KBr media using a AVATAR 330 FT-IR Thermo Nicolet (German Blue Man Company). The As-adsorbed crystals were acquired by reaction with As 100 mg L-1 solution with pH of 7.0 at 25C for 1 h. Ten milligrams of the dried samples were dispersed in 200 mg of spectroscopic grade KBr to record the spectra. Forty scans were collected on each sample at a resolution of 4 cm-1.The oxidation state of As on the surface of TiO2 nano-particles was determined by MULTILAB 2000 X-ray photoelectron spectroscopy (XPS) (Thermo Fisher thermoelectric). The As-adsorbed crystals were acquired after reaction with As 100 mg L-1 solution with pH of 7.0 at 25C for 1 h. The XPS pattern showed a double-anode Al of 300 w and passage energy of 25 eV. All data were the average of three replications. SigmaPlot 10.0 and Origin7.0 drawings were used to edit and draw the gures. The tables were made by MS ofce 2003. Freundlich models were computed using least square regression. Regression analysis was carried out using the SAS 8.1 software.

Results and discussion As removal and adsorption capacity of two TiO2 crystals Anatase removed more As than rutile when adding 0.400 g of the minerals in 50 ml solution spiked with 030 mg L-1 of As(V) or As(III) for 1 h (Fig. 1). The octahedra of rutile are slightly ortho-rhombic, while those of anatase are distorted ortho-rhombic-type (Fujishima et al. 2000). In addition, each octahedron is connected to 10 surrounding octahedrons for anatase and 8 for rutile. These crystal structural differences would inuence the activity of chemical reactions and might also contribute to greater ability of anatase to remove As. The As adsorption isotherm curves for anatase and rutile varied with the TiO2 crystals and As species and were well t n 2 by the Freundlich equation (Qe = KfC1/ e ) (R = 0.950.99) (Thirunavukkarasu et al. 2003) (Fig. 1; Table 1). Values of n and Kf in Freundlich models reect the reaction speed and adsorption capacity (Thirunavukkarasu
25

As adsorption capacity (mg g )

-1

As(V) As(III)
20

Anatase Rutile

15

10

0 0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14 16
-1

As concentration in equilibrium solution (mg L )


Fig. 1 Arsenic adsorption isotherms of nano-sized particles of anatase and rutile. The reaction conditions included adding 0.400 g of the crystals in 50 ml of As(V) or As(III) solutions at pH 7.0, 25C and simulated sunlight (10 W uorescent lamp) for 1 h. Each value is the mean of 3 measurements

Table 1 Parameters (n and Kf) and coefcients of determination (R2) of Freundlich model (Qe = KfC1/n e ) for As adsorption isotherms of two types of nano TiO2 crystals (n = 11) Crystals Anatase Rutile As species As(V) As(III) As(V) As(III) n 2.972 1.100 1.139 1.010 Kf 15.417 2.236 0.682 0.369 R2 0.9606** 0.9532** 0.9928** 0.9537**

** Signicant at P B 0.01, respectively

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et al. 2003). Values n and Kf in Table 1 shows that anatase exhibited a greater arsenic adsorption capacity than rutile. And in addition, Table 1 shows that n and Kf values of As(V) adsorption by anatase were up to 2.7-fold and 6.9fold those of As(III) adsorption; and n and Kf values of As(V) adsorption by rutile were 1.1-fold and 1.8-fold those of As(III) adsorption, respectively. This suggested that As (V) adsorption by both anatase and rutile was not only greater but also faster than As(III) adsorption under the experimental conditions. These results were consistent with the result by Bang et al. (2005b) who reported that adsorption of As(V) and As (III) by TiO2 reached equilibrium after a reaction time of 63 and 240 min, respectively, indicating that the removal of As(V) was faster than As(III). In our experiment, for instances, calculation showed that anatase had greater adsorption capacity for both As(V) and As(III) under the same experimental conditions, with maximum adsorption capacity of anatase being about 23.70 and 6.25 mg g-1 for As(V) and As(III), respectively, and maximum adsorption capacity of rutile being about 13.20 and 4.66 mg g-1 for As(V) and As(III), respectively. Effect of pH and temperature on As removal Experimental conditions of adding 0.400 g of minerals in 50 ml solution containing 200 lg L-1 of As were used in following studies due to the concentrations of As in most of natural contaminated groundwater were less than 200 lg L-1. Increasing solution pH had no effect on As(V) or As(III) removal by anatase, but improved As removal by rutile (Fig. 2). For example, when solution pH was increased from 4 to 10, the removal of As(V) and As(III) by rutile

was enhanced from 66 to 84% and 83 to 90%, respectively (Fig. 2). The surface charge of TiO2 varies with the pH solution (Ragai and Selim 1987), which is showed as follows: O Ti H pH [ pHPZC ! O Ti OH pH \pHPZC

The formula shows that net positive charge occur at pH \ pHpzc, whereas net negative charge exists at pH [ pHzpc. Since pHzpc values of anatase and rutile are 6.42 and 2.72, respectively, it is understood that under solution pH of 410, the rutile particle surface would be more negatively charged than anatase. In addition, the predominant As (V) species are H2AsO4- and HAsO42- in the pH range of 2.211.5, and As (III) exists in H3AsO3 at pH \ 9.2 and in H2AsO3- at pH [ 9.2. Therefore, the adsorption of As (V) and As (III) at pH [ pHpzc was by surface complexation, rather than by electrostatic interactions (Kosmulski 2002). Increase of As(III) adsorption in alkaline solution suggested that the simple electrostatic factors cannot control the adsorption of As(III) onto TiO2 particles. In alkaline solution, the release of proton from AsOH3 ) H AsOOH As(OH)3 2 ; pK1 9:23 (Dutta et al. 2004) may remove the hydroxyl ion from the coordinating layer of the TiO2 surface TiIV OH 2 ) IV H Ti OH; pKs 4:58 (Spanos et al. 1995). This process created sites with positive charge at the surface of TiO2 to adsorb negative As(III) anions at alkaline pH. The adsorption of arsenic acid is through the formation of surface complexation reaction: Ti OH H3 AsO4 Ti Hn AsO4 H2 O 2 nH , where n = 0, 1, 2. The reaction indicated that As(V) adsorption increases with decreasing proton concentration or increasing pH (Pena et al. 2005). The pH dependence of As adsorption by rutile corresponded with ndings in other studies that showed As (III) removal by non-specic TiO2 polymorphs increased from 84 to 95% as pH value increased from 4.6 to 8.5 (Bang et al. 2005b) and that As (V) and As (III) et al. 2010; Jegadeesan adsorption was less affected (Pirila et al. 2010). Effect of accompanying ions on As removal
3n1

100

As removed from solution (%)

95 90 85 80 75 70
As(V) As(III)
Anatase Rutile

65 4 5 6 7 8 9 10 4 5 6 7 8 9 10

Solution pH
Fig. 2 Effect of solution pH on As removal after 1-h equilibration of 0.400 g of nano-sized particles of TiO2 polymorphs anatase and rutile with 50 ml of 200 lg L-1 As(V) or As(III) solutions at 25C under simulated sunlight (10 W uorescent lamp). Each value is the mean of 3 measurements

The addition of 4 anions (SiO32-, NO3-, SO42-, H2PO4) had a pronounced effect on removal of As(V) and As(III) by both polymorphs compared to the 2 cations (Ca2?, Mg2?) (Fig. 3). The order for decreasing As removal was H2PO4- [ SiO32- [ NO3- [ SO42- for anatase at the 1,000 lmol L-1 of accompanying ions. For example, compared with the control (no accompanying ions), As(V) removal by anatase was reduced by 17, 10.8, 5.5, and 3.4% by the addition of the four anions, respectively. Similarly,

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100 95 90

As removed from solution (%)

H2 PO4 -

85 80 75 80 75 70 65 60 55 0

SiO3 2NO3 SO4 2Ca2+ Mg2+

As(V), Anatase

As(III), Anatase

As(III), Rutile As(V) Rutile As(V), Rutile

200

400

600

800 1000 0

200

400

600

800 1000
-1

Concentration of accompanying ions (mol L )

Fig. 3 The effect of species and concentrations of accompanying ions in solution on As removal by 0.400 g nano-sized particles of TiO2 polymorphs anatase and rutile from 50 ml of 200 lg L-1 As(V) or As(III) solutions at pH 7.0 and 25C under simulated sunlight (10 W uorescent lamp) for 1 h. Each value is the mean of 3 measurements

0.2 mmol L-1, but no decrease of As(III) removal by CuO was found in the same conditions (Martinson and Reddy 2009). However, adding high concentrations of PO43dramatically decreased As (III) and As(V) adsorption by ferric hydroxide (Meng et al. 2002; Bang et al. 2002). Addition of Ca2? and Mg2? at 1,000 lmol L-1 increased As(V) removal by 9.2, 5.13% and As(III) removal by 9.35 and 7.21% for rutile, respectively (Fig. 3). Je0 ze0 quel and Chu (2005) also reported that the addition of Ca2? and Mg2? promoted As(V) adsorption on nano-sized TiO2 due to formation of CaH(AsO4) and CaH2(AsO4)? through a co-precipitation mechanism. As (V) adsorbed on top of a TiO2-calcium layer, leading to an enhancement of As (V) adsorption (Chusuei et al. 1999). In contrast, additional As (V) in the form of HAsO42- was adsorbed electrostatically with Ca2? acting as a bridge to initially adsorbed As (V) which is a bidentate surface complex (Ronson and McQuillan 2002). It is reasonable to assume that these hypotheses regarding the cooperative effect of calcium on As (V) adsorption could be extrapolated to magnesium. Zhang et al. (2008) demonstrated that Ca2?, Mg2?, and other divalent cations increased As removal by manganese ore, quartz sand, and red mud. Effect of light on As adsorption by two TiO2 and its mechanism Under the conditions of simulated sunlight or ultraviolet light, anatase completely removed As (V) and As (III), while the dark condition reduced the removal by 15.5 and 17.5%, respectively (Fig. 4). This suggested that UV and sunlight would improve As removal by anatase. For rutile, however, the dark condition slightly increased As (V) and As (III) removal by 1.5 and 5.7%, respectively (Fig. 4). Fujishima and Honda (1972) suggested that anatase lattices, containing more defects and dislocations than rutile, cause more oxygen vacancies to capture electrons. Higher photocatalytic activity might be the important reason for

As(III) removal by anatase was decreased by 15.2, 7.75, 5.08, and 3.97%, respectively. Generally similar effects of the four anions on As removal were obtained in the case of rutile (Fig. 3). The obvious inhibition of As removal with H2PO4addition was mainly due to the similar chemical property of As(V) and PO43-, resulting in competitive adsorption (Je0 ze0 quel and Chu 2006). Gupta and Ghosh (2009) found no signicant effects on As(III) removal by a nano-sized synthetic bimetal iron(III)-titanium(IV) oxide when phosphate was added but reduction from 83.0 to 23.4% in As(V) removal was observed with a PO43- to As mole ratio of 1.6. Removal of As (V) by CuO was decreased by more than 10% when phosphate concentration was greater than
Fig. 4 Effect of light conditions on As(V) and As (III) removal after 1-h equilibration of 0.400 g nano-sized particles of TiO2 polymorphs anatase and rutile with 50 ml of a 200 lg L-1 As(V) or As (III) solution at pH 7.0 and 25C. Each value is the mean of 3 measurements

100

As(V)

As removed from solution (%)

Rutile Anatase

As(III)

80

60

40

20

Ultraviolet Natural light

Dark

Ultraviolet Natural light

Dark

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anatase to adsorb greater amount of As than rutile under light. FT-IR spectra of pure crystal of anatase showed the characteristic peaks at the bands of 829.06 and 1,632.33 cm-1 which attributed to Ti-O bond extending and cOH or dOH bond bending, respectively (curve a in Fig. S5A and B). Under light (curve b in Fig. S5A) and dark (the curve c in Fig. S5A) conditions, As(V)-adsorbed anatase crystal showed bands at 1,462.43 and 1,470.60 cm-1 by H2AsO4- ion stretching, the bands at 1,000.68 and 1,000.68 cm-1 by As-O-Ti stretching, the bands at 1,131.44 and 1,127.36 cm-1 by the stretching of As-O bond in AsO43- group, and the bands at 1,262.63 and 1,282.63 cm-1 by As-O and H2AsO4- group, respectively. For the spectra by As(III)-adsorbed anatase crystal, the bands at 1,094.67 and 1,281.21 cm-1 were due to As-O/ AsO33- stretching and As-O/HAsO42- stretching, respectively (Fig.S5B). The characteristic peaks for the FT-IR spectra of pure crystal of rutile were 778.94 and 1,635.62 cm-1 (curve a in Fig. S5C and D). Under light (curve b in Fig. S5C) and dark (curve c in Fig. S5C) conditions, As(V)-adsorbed rutile showed the bands at 1,121.11 and 1,125.20 cm-1, probably because of As-O and AsO43- stretching, the bands showed at 1,000.44 and 1,000.48 cm-1 by As-O-Ti stretching. In As(III)-adsorbed rutile crystals, FT-IR spectra analysis indicated that the stretching of As-O and AsO33- produced bands at 1,017.03 and 1,025.20 cm-1 (Fig. S5D). The FT-IR analysis clearly indicated the formation of AsO-AsO43- and As-O-H2AsO4- groups in As(V)-adsorbed anatase crystals, and the appearance of As-O-AsO43- in As(V)-adsorbed rutile crystals under light or dark conditions. In the case of As(III)-adsorbed anatase crystals, however, the only As-O-AsO33- was found under dark condition, while simultaneous formation of As-O-AsO33and As-O-HAsO42- occurred under light conditions, but AsO-AsO33- was found in As(III)-adsorbed rutile under light or dark conditions. The above suggested that light conditions had no effect on the FT-IR spectra of As-adsorbed rutile crystals, further indicating a possible photooxidation of As(III) into As(V) on the anatase crystals (Fig. S5). Further high-resolution analysis on the XPS spectra (Fig. S6) at As3d peak of anatase TiO2 nano-particles indicated that the binding energies (BE) of 45.1 eV for As3d by As(V)-adsorbed anatase crystals under light and dark conditions corresponded to the characteristic peak position of AsO43- or H2AsO4-. The BEs of 44.4 and 45.1 eV for As3d by As(III)-adsorbed anatase crystals under light condition were in close agreement with those of AsO33-, HAsO42-, so was the BE of 44.1 eV under dark condition with that of AsO33- (Wagner et al. 1979). Therefore, we assumed a transformation of As(III) into

As(V) under light condition, which was consistent with the results by Roberts et al. (1975) and Bang et al. (2005c) who reported possible oxidization of As(III) into As(V) in the solution under light conditions (Fig. S6A). There was no photooxidation in the case of rutile crystals. The BEs for As3p by As(V)-adsorbed rutile crystals under light and dark conditions were 144.3 and 144.0 eV, respectively, which corresponded to the characteristic BE of TiO2-As2O5 system, while the BEs for As(III) under light and dark conditions were 143.7 and 143.6 eV, respectively, which are typical BEs of As2O3 based on the reports by Borgmann et al. (1993) (Fig. S6B).

Conclusions Both anatase and rutile adsorbent were very effective for As removal from water, of which anatase had a higher adsorption capacity across a wide range of As concentrations, water pH, and water temperature. Increasing solution pH increased As removal by rutile TiO2. The optimum temperature for As removal by two TiO2 crystals was around 25C. The As adsorption of accompanying anions, such as H2PO4- decreased, but cations, like Ca2? and Mg2?, increased. Sunlight and UV facilitated the removal of As (V) and As (III) by anatase TiO2, but slightly reduced the As removal by rutile TiO2. FT-IR analysis of As-adsorbed TiO2 indicated that the adsorption As(V) and As(III) on the two crystals of TiO2 through As-O-Ti and As-O bonds. Both XPS and FT-IR analysis suggested that As(III) be directly adsorbed by anatase TiO2 in dark condition, but both As(V) and As(III) be adsorbed due to photooxidation of As(III) under light condition.
Acknowledgments This research was supported by the National High Tech Developmental Project (863 project) of China (2007AA06Z332), and the Professional Developmental Project of Chinese Ministry of Agriculture (200803034). The authors acknowledge Zhang L and Qian X for their assistance in chemical and instrumental analysis. We thank Professor Cao Xinde from Shanghai Jiaotong University and Professor Naraine Persaud from Virginia Tech. for valued comments and proofreading for this manuscript.

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