Mesoporous (organo) silica decorated with magnetic nanoparticles as ...

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Mesoporous (organo) silica decorated with magnetic nanoparticles as a reusable nanoadsorbent for arsenic removal from water samples a

b

Mohammad Hasanzadeh , Farzad Farajbakhsh , Nasrin Shadjou

cd

a

& Abolghasem Jouyban

a

Drug Applied Research Center and Faculty of Pharmacy, Tabriz University of Medical Sciences, Tabriz 51664, Iran b

Liver and Gastrointestinal Diseases Research Center, Tabriz University of Medical Sciences, Tabriz 51664, Iran c

Department of Chemistry, Faculty of Chemistry, Urmia University, Urmia, Iran

d

Department of Nanochemistry, Nano Technology Center, Urmia University, Urmia, Iran Accepted author version posted online: 16 Jun 2014.Published online: 11 Jul 2014.

To cite this article: Mohammad Hasanzadeh, Farzad Farajbakhsh, Nasrin Shadjou & Abolghasem Jouyban (2015) Mesoporous (organo) silica decorated with magnetic nanoparticles as a reusable nanoadsorbent for arsenic removal from water samples, Environmental Technology, 36:1, 36-44, DOI: 10.1080/09593330.2014.934744 To link to this article: http://dx.doi.org/10.1080/09593330.2014.934744

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Environmental Technology, 2015 Vol. 36, No. 1, 36–44, http://dx.doi.org/10.1080/09593330.2014.934744

Mesoporous (organo) silica decorated with magnetic nanoparticles as a reusable nanoadsorbent for arsenic removal from water samples Mohammad Hasanzadeha∗ , Farzad Farajbakhshb , Nasrin Shadjouc,d and Abolghasem Jouybana a Drug Applied Research Center and Faculty of Pharmacy, Tabriz University of Medical Sciences, Tabriz 51664, Iran; b Liver and Gastrointestinal Diseases Research Center, Tabriz University of Medical Sciences, Tabriz 51664, Iran; c Department of Chemistry, Faculty of Chemistry, Urmia University, Urmia, Iran; d Department of Nanochemistry, Nano Technology Center, Urmia University, Urmia, Iran

Downloaded by [Hacettepe University] at 02:42 20 November 2014

(Received 26 March 2014; final version received 10 June 2014 ) Over the last decade, numerous removal methods using solid-supported magnetic nanocomposites have been employed in order to remove arsenic from aqueous solution. In this report, removal of arsenic from aqueous solution by an organo silica, namely, magnetic mobile crystalline material-41 (MCM-41) functionalized by chlorosulphonic acid (MMCM-41-SO3 H), was investigated using atomic absorption spectroscopy. The synthesized magnetic mesoporous materials have satisfactory As (V) adsorption capacity. Linearity for arsenic was observed in the concentration range of 5–100 ppb. In addition, the coefficient of determination (R2 ) was more than 0.999 and the limit of detection (LOD) was 0.061 ppb. Considering these results, MMCM-41-SO3 H has a great potential for the removal of As (V) contaminants and potentially for the application in large-scale wastewater treatment plants. Keywords: magnetic nanoparticles; mesoporous; arsenic removal; atomic absorption spectroscopy; adsorbent

Introduction Water polluted by toxic materials remains as an important environmental issue, and there has recently been a growing interest in the research of materials capable of removing toxic materials from contaminated water. Arsenic is one of these materials that has a severe impact on the public health and the economy. During the past two decades, arsenic poisoning via groundwater has become a worldwide problem.[1,2] Elevated levels of arsenic in groundwater not only cause significant problems in the provision of safe drinking water,[3] but lately have also raised concern regarding food safety.[4,5] Long-term exposure to arsenic has been associated with cancer (skin, lungs, urinary tract, kidneys and liver) and also with various non-cancerous diseases.[6] Therefore, the World Health Organization (WHO) has reduced arsenic permissible levels in drinking water from 50 to 10 μgL−1 and most of the industrialized countries also take 10 μgL−1 as a statutory limit. Different technologies to remove arsenic from water are based on co-precipitation,[7] adsorption, i.e. activated alumina,[8] iron-coated sand,[9] ion exchange resin,[10] natural iron ores,[11] carbonaceous adsorbents,[12–14] low-cost mineral materials [15] and biosorbents,[15,16] and membrane-based methods, i.e. reverse osmosis [17] and nanofiltration.[18] Among these methods, adsorption offers many advantages including simple and stable operation, easy handling of waste, absence of added reagents, ∗ Corresponding

author: Email: [email protected]

© 2014 Taylor & Francis

compact facilities and generally lowers operation cost. [19,20] Adsorption is a fundamental process involving the enrichment of guest species at the interface of a certain adsorbent.[21–23] Such a process provides one of the most efficient ways to dramatically reduce the release of pollutants.[24,25] Therefore, adsorption-based processes lead to one of the most efficient routes for the removal of As. The fundamental and great challenge is developing highly efficient adsorbents. One of the important requirements for a good adsorbent is a large interface.[19] Traditionally, functionalized silica-based mesoporous materials are widely adopted as adsorbents.[19] While keeping high porosity, silica-based mesoporous materials with more sophisticated functions, such as magnetic property, are highly demanded in adsorption and separation processes.[19] Silica-based mesoporous materials with magnetic centres were recently developed. They possess high magnetization, high surface area, large pore volume and uniform mesopore, showing a fast removal of heavy metals with high efficiency. Magnetic silica-based mesoporous materials possess intrinsic high specific surface areas, regular and tunable pore sizes, large pore volumes, as well as stable and interconnected frameworks with active pore surfaces for modification or functionalization. The integration of functionalized mesoporous silica with magnetic nanoparticles to form porous magnetic nanocomposite is undoubtedly of great interest for practical applications. This type of

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magnetic nanocomposites has the advantages of both mesoporous silica and magnetic nanoparticles. Also magnetic separation by an appropriate magnetic field provides a convenient and low-cost method for the separation of these magnetic adsorbents in a multiphase suspension without using extra organic solvents and additional filteration steps or tedious work-up.[26,27] Such features meet the requirements as excellent adsorbents, not only providing huge interface and large space capable of accommodating capacious guest species, e.g. As (V), but also enabling the possibility of specific binding, enrichment and separation. The present work reports the synthesis of MMCM-41SO3 H and its applications for the removal of As (V) from aquatic systems.

Experimental Reagent and apparatus Silica (SiO2 ), hexadecyltrimethylammonium bromide (CTAB), As (V) standard solutions and sodium borohydride [NaBH4 ], diethyl amino borane [(Et)2 NBH2 ], tributyl amine borane [BNH(But)3 ] and hydrochloric acid were purchased from Merck Co. (Germany). Cholorosulphonic acid and ammonium hydroxide were from Scharlau and Sigma, respectively. All reagents were used in their analytical grade without further purification. Atomic absorption spectrometry (AAS) was used for adsorption experiments of standard solution of As (V). Working standards were prepared from the dilution of the stock solution every day. All aqueous solutions were prepared by de-ionized water at room temperature. Fourier transform infrared (FT–IR) spectra were recorded on a Shimadzu model FT–IR prestige 21 spectrophotometer using KBr discs. Powder X-ray diffraction (XRD) measurements were performed using a Philips diffractometer manufactured by X’pert with monochromatized CuKα radiation. The pore structure of the prepared adsorbent was verified by the nitrogen sorption isotherm ([5.0.0.3] Belsorp, BEL Japan, Inc.). Transmission electron microscope (TEM, Hitachi Ltd, Tokyo, Japan) was recorded on a Philips CM-10 instrument on an accelerating voltage of 100 kV. The hydride-generation (HG)-AAS (CTA-3000, Chemtech Limited Co., UK) was used for the determination of As (V) generated by the thermal decomposition of As (V) hydride. A well-developed procedure was followed for the determination of As where hydride was generated in 20% HCl in the presence of 4% NaBH4 stabilized by 0.4% NaOH at 193.7 nm.

Preparation of MMCM-41-SO3 H In this work, MCM-41 and magnetic MCM-41 grafted by chlorosulphonic acid (MMCM-41–SO3 H) were synthesized according to the previously reported method.[28] Briefly naked Fe3 O4 nanoparticles were prepared from a

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solution with molar composition of 3.2 FeCl3 :1.6 FeCl2 :1 CTAB NH4 OH/H2 O (39: 2300) at room temperature. Typically, 2 g of iron (III) chloride (FeCl3 . 6H2 O) and 0.8 g of iron (II) chloride (FeCl2 . 4H2 O) were dissolved in 10 mL of distilled water under N2 atmosphere. The resulting solution was added dropwise to a 100 mL solution of 1.0 M NH4 OH solution containing 0.4 g of CTAB to construct a colloidal suspension of iron oxide magnetic nanoparticles. The magnetic MCM-41 was prepared by adding 20 mL of the magnetic colloid to 1 mL solution with the molar composition of NH4 OH/CTAB/H2 O (292: 1: 2773) under vigorous mixing and sonication. Then sodium silicate (0.016 mL) was added, and the mixture was allowed to react at room temperature for 24 h under well-mixed conditions. The magnetic MCM-41 [MMCM-41] was filtered and washed with alcoholic ammonium nitrate. The surfactant template was then removed from the synthesized material by calcination at 450◦ C for 4 h to give the [MMCM-41]. To Fe2 O3 -MCM-41 (1 g), chlorosulphonic acid (1 g, 9 mmol) in 0.005 mL of dichloromethane was added dropwise at room temperature within 30 min. After completion of the addition, the mixture was mechanically stirred for another 30 min until HCl was removed from reaction vessel. The mixture was then filtered and washed with CH2 Cl2 to give MMCM-41-SO3 H as brown powder. The amount of sulphonic acid groups of MMCM-41-SO3 H which were determined by acid–base titration was found to be (0.56 g SO3 H). Scheme 1 shows the synthesis mechanism of MMCM-41-SO3 H. Characterization of MMCM-41 and MMCM-41-SO3 H The prepared magnetic adsorbent was characterized by FT– IR, XRD and nitrogen physico-sorption measurements. The FT–IR spectra of MMCM-41 before and after functionalization are shown in Figure S1 (see supplementary data). In FT–IR spectra, the band from 400 to 650 cm−1 is assigned to the stretching vibrations of the (Fe–O) bond in Fe2 O3 , and the band at about 1100 cm−1 belongs to the stretching of the (Si–O) bond. It should be mentioned that the C–N stretching vibration in the region of 1030–1230 cm−1 overlap with the broad absorption band of the silanol group and the Si–O–Si vibrations. The XRD analysis of MMCM-41-SO3 H was performed from 2.0◦ (2θ ) to 10.0◦ (2θ ). The XRD patterns of the MMCM-41-SO3 H are presented in Figure S2 (see supplementary data). The sample of MMCM-41-SO3 H showed relatively well-defined XRD patterns, with one major peak along with two small peaks identical to those of MCM41 materials. Also, MMCM-41-SO3 H showed some lowintensity diffraction peaks that were indexed to cubic Fe2 O3 . The XRD peaks of MMCM-41-SO3 H were indexed to (2 0 0), (3 1 1), (4 0 0), (4 2 2), (5 1 1) and (4 4 0) planes of a cubic unit cell of magnetite, appearing at 26.1◦ 36.07◦ , 50.00◦ , 69.22◦ , 76.11◦ , and 75.20◦ , respectively. Similar results were obtained by Chen et al.[29]

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M. Hasanzadeh et al.


Scheme 1.

Synthesis process of MMCM-41-SO3 H.

Table 1. Surface area, average pore size and pore volume of MMCM-41 and MMCM-41-SO3 H.

Adsorbent MMCM-41 MMCM-41-SO3 H

Surface area (m2 g−1 )

Average pore size a (nm)

Pore volume b (cm3 g−1 )

1213 1024

5.26 4.89

1.59 1.25

a Pore size is calculated by the method described by Brunauer-

Emmett-Teller. Pore volume determined from nitrogen physisorption isotherm.

b

The specific surface area and pore volume obtained by the N2 adsorption isotherms and calculated by the Brunauer–Emmett–Teller (BET) method [30] are reported in Table 1. Figure S3 (see supplementary data) shows the TEM images of MMCM-41-SO3 H in which all the materials possess hollow structures. They provide a large active surface area for the adsorption of As (V). Generally, these characterization results by FT–IR, XRD and TEM can be

found in supplementary data. Similar results were obtained by Chen et al.[29]

Optimization of analytical conditions Effect of HCl and NaBH4 concentrations on hydride generation The majority of the proposed hydride-generation methods for arsenic determination make use of arsine, which is generated from As (V), after a pre-reduction step of arsenate to arsenite. In batch methods, arsine can be directly generated from arsenate, with slower reaction rate than that from arsenite.[31] The effect of the As oxidation state on the measured signal can be decreased by using higher NaBH4 and HCl concentrations, longer reaction times and integrated measurements.[32–36] The concentration of HCl and NaBH4 solutions was studied for direct arsine generation from As (V), employing the manifold presented in Figure 1, using 70 ppb As (V) solutions. The effect of HCl concentration on the absorbance of As (V) was studied in the range of 5–60%v/v HCl, using a medium concentration

Figure 1. (A) Effect of HCl concentration on the absorbance 70 ppb As (V); [NaBH4 ] = 4% WV. (B) Effect of NaBH4 concentration on the absorbance 70 ppb As (V); Concentration of HCl is 10% V/V.


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surface with the aqueous sample solution. In order to study the effect of type of reducing agent on determination of As, NaBH4 , (Et)2 NBH2 and BNH(But)3 were tested. Finally, NaBH4 was selected as a better reducing agent (Figure 2).


Effect of ultrasonic and shaking time The effects of ultrasonic and shaking times on the removal of As (V) by MMCM-41-SO3 H as adsorbent are shown in Figures 3(a) and 3(b). It is observed that with an increase in sonication time up to 60 min, there is an increase in As (V) removal. A similar trend is observed at different shaking times, where the As (V) removal remains almost constant after 120 min of shaking. Figure 2. Effect of the reducing agent type on the determination of 70 ppb of As (V) in the absence of an adsorbent. Concentration of HCl is 10% V/V.

of 4% NaBH4 solution. As shown in Figure 1(a), the signal related to As (V) increases rapidly up to 20% and decreased for higher concentrations. The effect of NaBH4 concentration on the absorbance was studied in the range of 0.2–4% NaBH4 , using the optimized concentration of HCl (20%). The results are presented in Figure 1(b). As it is shown in Figure 2(b), the absorbance of As (V) increases with an increase in NaBH4 concentration up to 4% and levels off for higher NaBH4 concentrations. Thus, 20% HCl and 4% W/V NaBH4 can be used for selective As (V) determination. This observation shows that at the above conditions (20% HCl and 4% W/V NaBH4 ) the arsine generation from As (V) is completed, and they can be adopted for arsenic determination. Selection of reducing agent Selection of a reducing agent plays a key role in HGAAS. The reducing agent helps in the pre-reduction step for arsenic discrimination and in this way increases the contact

Effect of pH Arsenic acid is a triprotic acid and dissociates according to reactions (1)–(3) [36]: + H3 AsO4 + H2 O ⇔ H2 AsO− 4 + H3 O

pKa1 = 2.19, (1)

2− + H2 AsO− 4 + H2 O ⇔ HAsO4 + H3 O

pKa2 = 6.94, (2)

3− + HAsO2− 4 + H2 O ⇔ AsO4 + H3 O

pKa3 = 11.50. (3)

Based on reactions (1) and (2), within the pH range of 2 and 7 the H2 AsO− 4 ion was dominated and divalent and 3− trivalent anionic species of arsenate (HAsO2− 4 and AsO4 ) increase with an increase in the pH value above 7 and 12, respectively. In other words, the dominant species of As (V) in the pH range of 2.19, 2.19–6.94, 6.94–11.5 and >11.5 2− 3− are H3 AsO4 , H2 AsO− 4 , HAsO4 and AsO4 , respectively. As shown in Figure 4, the less the negative charges on the analyte at lower pH values, the more As (V) adsorption occurs on the MMCM-41-SO3 H particles.

Figure 3. Effect of ultrasonic time (A) and shaking time (B) on the sorption of As(V) by MMCM-41-SO3 H (initial concentration of As(V): 70 ppb; amount of MMCM-41-SO3 H: 5 mg/mL).


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Figure 4. Effect of pH on the sorption of As (V) by MMCM-41-SO3 H (initial concentration of As (V): 70 ppb; contact time: 120 min).

Figure 6. Effect of adsorbent volume on the sorbtion of As (V) by MMCM-41-SO3 H (A). (Initial concentration of As (V): 70 ppb; amount of MMCM-41-SO3 H: 5 mg mL−1 ).

of absorbance is 2 mL. This phenomenon can be attributed to the fact that with an increase in the adsorbent dose of 2 mL, more adsorbent surface is available for the solute to be adsorbed. But after the saturation of pores with As (V), the available surface was decreased. Scheme 2 shows this behaviour. The application of porous magnetic nanoparticles as adsorbents was investigated by using MMCM-41-SO3 H for the adsorption of As (V) from aqueous solution. At first, 40 mg of MMCM-41-SO3 H was added to 70 ppb of As (V) solution and rigorously shaken; the colour of the solution Figure 5. Effect of contact time on the sorption of As(V) by MMCM-41-SO3 H (initial concentration of As(V): 70 ppb; amount of MMCM-41-SO3 H: 5 mg/mL).

Effect of contact time The effect of contact time on the removal of As (V) by MMCM-41-SO3 H is shown in Figure 5. It is observed that As (V) absorbance was rapidly increased during the initial contact time, and then reaches the steady state after 120 min. Based on this result, the optimum contact time of 120 min can be adopted for arsenic determination. Results and discussion At first, the effect of adsorbent dose was tested for the optimization of mesoporous amount of MMCM-41-SO3 H for the removal of As (V). The batch adsorption experiments were carried out at room temperature for 120 min contact time. For this aim, 0.5, 1, 2, 3 and 4 mL of 0.05 g magnetic adsorbent was added to the standard solution of As (V) and their adsorptions were recorded. Based on Figure 6, it is found that for MMCM-41-SO3 H, the optimum dose

Figure 7. reaction.

Adsorbent recovery procedure at the end of the


Scheme 2.

Schematic representation of As (V) adsorption by MMCM-41-SO3 H in optimal conditions. Table 2.


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Comparison of As (V) removal capacities of various adsorbents.

Adsorbent Ferric hydroxide Ti-Ce oxide

surface area/ m2 g−1 240–300 137.4

Aminated fibre ZrO2 sphere Granular ferric hydroxide Hydrous cerium oxide nanoparticles Aluminium loaded lime stone MnO2 Red mud Al2 O3 /Fe (OH)3 Granular ferric hydroxide Hematite Activated alumina Alginate bead (coated and loaded with iron) Activated alumina graine Modified calcined bauxite Methylated biomass TiO2 loaded amberlite α-Fe2 O3 -nanoparticles Maghemite-Fe2 O3 -nanoparticles MMCM-41-SO3 H

changed from colourless to brown within 1 min. It indicates that the As (V) was quickly and strongly adsorbed on MMCM-41-SO3 H while mesoporous-As could be separated using a magnet. It was found that As (V) totally disappeared after 1 min by a magnet. This result demonstrates that MMCM-41-SO3 H has a magnetic property and can potentially be used as a magnetic adsorbent to remove As (V) from the aqueous solution for the groundwater treatment processes. It is important to note that the magnetic property of this adsorbent facilitates its efficient recovery from the adsorbent-desorption agent mixture during work-up procedure. In the presence of an external magnet, recoverable MMCM-41-SO3 H moved onto the magnet steadily and the reaction mixture turned clear within 10 s. Thus, the adsorbent effectively collected and the recovered adsorbent was used in subsequent runs without observation

– 32 236 198 – – – – – – – – – – – 162 203 1213

pH

Adsorption capacity/mg g−1

6.5 6.5 6.5 7.0 7.3 7.0 7.0 2–11 7.9 3.5 8.2–8.9 7.0 4.2 7.0 7.0 5.2 7.0 6.5 1–5 7 5 2–12

1.4 – – – 1.1 – > 40 0.15 0.17 0.51 0.09 0.004 0.2 9.2 0.014 15.9 1.57 3.75 4.72 47 9.20 65

Ref. 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 This work

of a significant decrease in activity even after 5 runs (Figure 7). Adsorption of As (V) on MMCM-41-SO3 H indicated that SO3 H groups were accessible for the binding of As (V) ions. It can be ascribed to the combination of the electronacceptor ability of As (V) and confinement effects due to the attachment to the SO3 H group. On the basis of the previous considerations,[37] this must result from the superposition of the effect associated with more external SO3 H units and that due to boundary-associated ones. It is noteworthy that the present response of As (V) was dramatically improved when chlorosulphonic acid was introduced into the surface of MMCM-41. This can be attributed to the hydrogen bonding between the SO3 H and As (V). This leads to a greater amount of As (V) accumulation on the surface of MMCM41-SO3 H. Therefore, As (V) could be more accumulated

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on the surface of adsorbent due to their interaction with chlorosulphonic acid groups.[37] In addition, their superior adsorption effect on arsenic concentrations is comparable to or even better than the adsorption capacities of various As (V) adsorbents. The performance of various adsorbents at low arsenic concentration iss compared in Table 2.[38–57] There are many studies about sorption of As (V) with magnetic materials. For example, Tang et al. [56] and Tuutijärvi et al. [57] estimated the As (V) sorption capacity of Fe2 O3 nanoparticles as ∼47 mg/g. It is established that the sorption capacity of an adsorbent depends on the particle size (or surface area) of the adsorbent.[58] The Langmuir adsorption capacity of proposed mesoporous was higher than that of other reports (65 mg g−1 ). This result is due to the lower particle size and higher surface area of mesoporous material (Table 1).

Analytical performance of the proposed method In order to estimate the possibility of using the proposed method based on strong hydride-generation conditions (10% HCl and 0.4% W/V NaBH4 ) for arsenic determination, the calibration curve of aqueous As (V) standard solutions was statistically compared with other reports. Figure 8 demonstrates the calibration curve for the determination of arsenic adsorbed by MMCM-41-SO3 H at low equilibrium arsenic concentration. The analytical performance data of the proposed method for selective determination of As (V) and using the optimized conditions are presented in Table 3. It is found that MMCM-41-SO3 H is very effective in removing arsenic from ground natural water with low As (V) concentrations as most cases in the natural environment. The method was also applied to the analysis of local natural groundwater samples. Table 4 gives the possibility for accurate analysis of low concentration of arsenic in natural groundwater and river samples by HG-AAS and based on the proposed adsorbent.

Table 3. Analytical performance data of the proposed method for As (V) determination. Regression equation

0.012 C (ppb)–0.0107

Correlation coefficient (R2 ) LOD (ppb) LOQ (ppb) Linear range (ppb) Precision (%)

0.998 0.6 1.5 5–100 1.5

Table 4. Amount As (V) in natural water samples analysed by the proposed method. Sample River water (near of ground water) Local natural ground water

Found (ppb) 60 250

Conclusion In summary, MMCM-41-SO3 H was found to be a new, efficient and magnetically recyclable adsorbent for the removal of As (V) from waters. The adsorbent was separated with an external magnet and was used in subsequent runs without the observation of a significant decrease in efficiency after five runs. Recovery and reusability of the adsorbent, simple work-up and the ecologically clean procedure make this method attractive and useful. In addition, it showed high efficiency in preconcentration of As (V) from aqueous samples to improve the analytical performance of the HG-AAS method. Therefore, MMCM-41-SO3 H can be potentially employed as recoverable adsorbents in large-scale plants of groundwater treatment due to their facile separation and high adsorption capacity. It is important to point out that we also examined magnetic aminopropyl functionalized MCM-41 (MMCM-41-nPrNH2 ) for adsorption and removal of As (V) from water and no absorbance signals were detected by Fe2 O3 -MCM-41-nPrNH2 . It could be attributing to no interaction of functionalized group (NH2 ) with As (V). Acknowledgements We gratefully acknowledge the support of this work by Drug Applied Research Center, Tabriz University of Medical Sciences. The authors are also grateful to Jafar Soleymani and Vahid Panahi-Azar for their assistance on experimental works.

Supplemental data Supplemental data for this article can be accessed at http://dx.doi.org/10.1080/09593330.2014.934744.

References Figure 8.

Calibration curve of As (V).

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Supplementary

Data for Manuscript

Mesoporous (organo) silica decorated with magnetic nanoparticles as reusable nanoadsorbent for arsenic removal from water samples

Mohammad Hasanzadeh a*, Farzad Farajbakhsh b, Nasrin Shadjou c, Abolghasem Jouyban a

a

Drug Applied Research Center and Faculty of Pharmacy, Tabriz University of Medical Sciences, Tabriz 51664, Iran. b

Liver and Gastrointestinal Diseases Research Center, Tabriz University of Medical Sciences, Tabriz 51664, Iran. c

Department of Chemistry, Faculty of Science, Urmia University, Urmia, Iran.

Corresponding Author: E-mail address: [email protected] Tel.: +98 411 3379323; fax: +98 411 3363231.

a

b

Fig. S1: The IR spectra of the (a) MMCM-41; (b) MMCM-41-SO3H

A

B

Fig. S2: A) The XRD patterns of the MMCM-41-SO3H in the region of 1.0° (2θ) to 10.0° (2θ). B) The XRD patterns of the MMCM-41-SO3H in the region of 1.0° (2θ) to 90.0° (2θ).

A

Fe2O3 nanoparticles

B

Fig. S3: The TEM image of MCM-41-SO3H (A) and MMCM-41-SO3H (B).