Desalination 279 (2011) 344352

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Desalination
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / d e s a l

Arsenic (V) removal with modiable bulk and nano p(4-vinylpyridine)-based hydrogels: The effect of hydrogel sizes and quarternization agents
Nurettin Sahiner a, b,, Ozgur Ozay a, Nahit Aktas c, Diane A. Blake d, Vijay T. John e
a

Canakkale Onsekiz Mart University, Faculty of Sciences and Arts, Chemistry Department, 17100-Canakkale, Turkey Nanomaterial and Nanotechnology Laboratory, Terzioglu Campus, 17100-Canakkale, Turkey Yuzuncu Yil University, Faculty of Engineering, Chemical Engineering Department, 65080, Van, Turkey d Tulane University, School of Medicine, Department of Biochemistry, New Orleans, LA 70112-2699, USA e Chemical and Biomolecular Engineering, Tulane University, New Orleans, 70118, LA, USA
b c

a r t i c l e

i n f o

a b s t r a c t
Macrogels and nanogels (5 6 mm and 370 nm dimensions, respectively) based on 4-vinylpyridine (p-(4VP)) were prepared using redox and microemulsion techniques. The p(4-VP)-based materials were quaternized with HCl/alkyhalides having different chain lengths to tune the charges (macro and nanogels) and size of nanogels. By developing positive charge on the p(4-VP) materials, they behaved as ion exchangers and used in removal of As(V) from aqueous environments. The prepared p(4-VP) materials were also rendered responsive to magnetic eld by in situ incorporation of magnetic metal nanoparticles inside macro p(4-VP) hydrogels and by encapsulation of separately prepared magnetic ferrites by nanosized p(4-VP) particles. Nanoparticles quaternized with HCl (p(4-VP)-HCl) (1 g) removed over 95% of As(V) from a stock solution (10 mg L 1, 1000 mL) in 15 min whereas bulk hydrogels removed N 82% of the As(V) from an equivalent solution in ~ 12 h. Parameters effecting the As(V) removal, including pH, temperature and ionic strength, were also investigated. The synthesized magnetic p(4-VP) composites could be reused after elution with NaOH and regeneration with quaternization agents; these procedures were facilitated using an externally applied magnetic eld. The Langmuir and Freundlich adsorption isotherms were also applied to study the removal of As(V) from aqueous environments. 2011 Elsevier B.V. All rights reserved.

Article history: Received 4 May 2011 Received in revised form 13 June 2011 Accepted 14 June 2011 Available online 2 July 2011 Keywords: Nanogel/microgel Hydrogel Modication Arsenic removal p(4-VP) magnetic-composites

1. Introduction Arsenic is a toxic and carcinogenic pollutant [1,2]. Long-term exposure to arsenic can cause severe problems in target organisms [3] and can lead to diseases such as anemia and anorexia [4]. According to World Health Organization guidelines, the maximum concentration of arsenic in the drinking water should be limited to 10 g L 1 [5,6]. Arsenic enters the aquatic environment from sources that include mining, agriculture, medicinal activities, soil erosion/leaching, industrial discharges, chemical processing and manufacturing of metals, fertilizers, pesticides, glass and ceramics [710]. The arsenic contamination occurs in the groundwaters of many countries including India, Bangladesh, Argentina, Mexico, Chile, Nepal, the United States, Taiwan, Thailand and Mongolia [1114]. Arsenic is a serious health hazard that is causing increasing concerns world-wide. Arsenic exists in different oxidation states depending on the pH of the environment [15]. The primary forms of arsenic found in natural waters are arsenate (As(V)) and arsenite (As(III)) [16]. Many
Corresponding author at: Canakkale Onsekiz Mart University, Faculty of Sciences and Arts, Chemistry Department, 17100-Canakkale, Turkey. Tel.: + 90 286 2180018x2041; fax: + 90 2862181948. E-mail address: sahiner71@gmail.com (N. Sahiner). 0011-9164/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.desal.2011.06.028

techniques have been developed to remove exogenous arsenic from the water used for drinking or agriculture [4,6,11]. The most commonly used techniques for the removal of arsenic are coagulation, ion exchange, membrane ltration, sedimentation, adsorption and absorption [17,18]. The most commonly employed adsorbents used for removal of arsenic include magnetites, goethite, magnetite nanoparticles [18], CeTi oxide [14], graphene oxide [19], iron titanium oxide [20], red mud and activated red mud [21], activated alumina [2024], iron-modied activated carbon [3], TiO2 [5], modied zeolites, and clays [7]. More recently, adsorbents with biological origin have also been used; these include iron-impregnated chitosan and hydrogels [7,8,25]. Hydrogels are insoluble hydrophilic polymeric networks [26] formed from crosslinking of synthetic and natural hydrophilic linear monomers and polymers. Due to hydrophilic groups, hydrogels can absorb water up to thousands of times their dry weight [27,28] and have been widely investigated as biomaterials in the applications such as drug delivery vehicles [29], sensors [30], matrix materials for tissue engineering [31], absorbents for environmental applications [26,32], and as antimicrobial materials [33]. In addition to these applications, hydrogels can also be used as support materials for the synthesis of metal and magnetic particles and nanostructures [26,3237]. The in situ

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prepared metal nanostructures in hydrogel networks have been used as catalyst [3436]. The unique physical and chemical characteristics of micron and nanometer size hydrogel particles combined with tunable functionalities have led to valuable contributions to medicine, energy conversion and storage systems [37], and to the separations for environmental applications [27,28,32,3840]. 4-vinyl pyridine has appealing properties due to both the hydrophilic nature of the nitrogen atom on the ring and the hydrophobic nature of the vinyl group and the aromatic ring. Furthermore, 4-VP can be chemically modied to acquire a desired positive charge and functional groups by the reaction with various quarternization agents due to the nucleophilicity of the nitrogen atoms on the pyridine ring [31,33]. In this investigation, p(4-VP) hydrogels were prepared in bulk (macro) and nano dimensions. The prepared materials were characterized using scanning electron microscope (SEM), dynamic light scattering (DLS) and thermal gravimetric analysis (TGA). Both bulk and nano materials were rendered magnetic eld responsive by in situ preparation technique and by inclusion of separately prepared magnetic metal nano particles inside the polymeric network during synthesis. The composite materials were readily removed from water samples under an externally applied magnetic eld. When neutral p(4-VP) particles and the magnetic composites were quaternized (positively charged), they became an ion exchange material that could be employed for the removal of As(V) from aqueous environments. The aim of this study is to compare arsenate adsorption on 4-VP hydrogels with different sizes and charges. Various parameters affecting the As(V) absorption including the size of the absorbent, the nature of the quaternization agent, the initial concentration of As(V), pH, temperature and the ionic strength of the solution (chloride and sulfate ions) were examined. 2. Experimental 2.1. Materials and analysis methods The monomer, 4-vinylpyridine (4-VP) (95%, Acros), the cross-linkers, ethylene glycol dimethacrylate (EGDMA) (99%, Fluka) and N,NMethylenebisacrylamide (MBA), and N,N,N,N-tetramethylethylenediamine (TEMED) (Acros) used as an accelerator, the initiator ammonium persulfate (APS) (Aldrich, 99%) and the quaternization and/or alkylation agents: HCl (37%), bromoethane (BE), 1-bromobutane (1-BB), 1bromohexane (1-BH), 1-bromooctane (1-BO) and 2-bromoethylamine (2-BEA) (all 99%) were purchased from Acros and Sigma-Aldrich Chem. Co. and used as received. The surfactant, sodium dodecyl sulfate (SDS), was a product of Acros (95%). For the preparation of magnetic particles, iron (III) chloride hexahydrate (FeCI3.6H2O, Acros), iron (II) chloride tetrahydrate (FeCI2.4H2O, Fluka), NaOH (Sigma) and aqueous ammonia (26%) were used as received. All the reagents and solvents (NaCl, Na2SO4, acetone and ethanol) were of analytical grade or the highest purity available, and were used without further purication. Stock solutions of arsenic were prepared by dissolving sodium arsenate heptahydrate (Na2HAsO4.7H2O) (98.5%, Sigma) in puried water. Water puried to 18.2 M.cm (Millipore Direct Q-3) systems was also used in the preparation of SDS solutions, washing of hydrogels and nanoparticles and in absorption experiments. A Sartorius Documeter pH-meter was used for pH measurements. Inductively coupled plasma atomic emission spectroscopy (ICP-AES, Varian Liberty II AX Sequential) was used to quantify arsenic (V) during absorption and desorption studies. The instrument was calibrated by using 100 mg L 1 standard As(V) solution (Merck) by sequential dilutions. The minimum detection limit of ICP-AES for arsenic was 0.05 mg L 1. 2.2. Synthesis of bulk p(4-VP) hydrogel and magnetic hydrogels Bulk P(4-VP) hydrogels were synthesized via a redox polymerization technique. In brief, a 4-VP was mixed with 0.1 mol% MBA (with respect to

monomer as a crosslinking agent) by vortex mixing and to this solution, 20 L TEMED was added and mixed thoroughly. Finally, the initiator solution APS (1 mol% with respect to monomer) in 1 mL puried water was added to the hydrogel precursor. The homogenous solution was injected into plastic straws of 5 mm in diameter and allowed to simultaneously polymerize and crosslink for 24 h at ambient temperature (~2022 C). The hydrogels were then removed from the plastic straws, cut into 6 mm long cylindrical shapes and cleaned by placing them in puried water for 48 h. The bulk hydrogels were washed by replenishing the wash puried water every 8 h to remove unreacted species (monomer crosslinker, and the initiator). After the cleaning procedure, hydrogels were dried in a vacuum oven at 40 C to a constant weight and kept in sealed containers for swelling and absorption experiments. In-situ magnetic p(4-VP)-based macro hydrogels were prepared according to previously published studies, with some modication [26,28,32]. In brief, a known amount of dried and cleaned p(4-VP) hydrogel (~1 g) was placed in a nitrogen-purged mixture of 0.5 M Fe (II) and 1 M Fe (III) for 24 h (total volume 100 mL). At the end of this metal ion loading period, hydrogels were moved for a day to remove the unbound or physically absorbed metal ions. After cleaning, the metal-ion-absorbed hydrogels were transferred into nitrogen-purged in 100 mL NaOH (0.5 M) sodium hydroxide solution in a water-shaker for 12 h for in situ reduction of absorbed iron ions. The obtained hydrogel composites were subsequently cleaned by placing them in puried water for another 12 h at ambient temperature. The cleaned magnetic hydrogels were separated and dried in vacuum oven at 40 C. The dried hydrogels and composites were used for the characterization and absorption studies. 2.3. Synthesis of p(4-VP) and magnetic eld responsive p(4-VP) nanocomposites P(4-VP) nanoparticles were synthesized as reported previously [31,33], with some modications, by employing a microemulsion system using SDS as the surfactant. In brief, p(4-VP) particles were prepared in a 40 mL vial equipped with a magnetic stir bar using 0.1 M 15 mL SDS solutions in puried water. In a typical particle synthesis, 0.3 mL of 4-VP was dispersed in SDS solution with 10 mol% EGDMA (with respect to 4-VP). The simultaneous polymerization and crosslinking reaction was initiated by the addition of 1 mL of 1% APS (with respect to total monomer amount) aqueous solution. The reaction mixture was then placed in a temperature-controlled oil bath at 75 C with constant stirring (500 rpm) for 6 h. The reaction solution was subsequently ltered using Whatman lter paper (particle retention N 2.5 m) and the synthesized p(4-VP) nanoparticles were puried by centrifugation (14,000 rpm for 20 min) at 20 C. The supernatant solution was removed and the particles were re-dispersed with copious puried water; the process was repeated at least ve times to wash the low molecular weight contaminants from the nanoparticles. The p(4-VP) nanoparticles (a whitish powder) were collected, dried using a Freeze Dryer (Christ Alpha 12 LD plus) and stored in an airtight container for characterization and further quarternization and the absorption experiments. The synthesis of the magnetic eld responsive p(4-VP) nanoparticles (nanocomposites) were carried out in two steps. Firstly, the magnetic ferrite particles were prepared according to a previously reported procedure [41]. In short, FeCl2 (0.43 g) and FeCl3 (1.168 g) were dissolved in 20 mL puried water using an ultrasonic bath. The mixture was dynamically stirred (250 rpm) under nitrogen at 85 C, and 1.5 mL aqueous ammonia (NH3, 26%) solution was added slowly with vigorous stirring (250 rpm) to obtain dispersion of metal nanoparticles. As an indication of metal nanoparticle formation, the color of the solution turned from orange to black instantly upon addition of NH3. Stirring was then stopped and a strong magnet was used to separate the black precipitate from the supernatant solution. The magnetic precipitates were washed twice with puried water and once with 0.02 M sodium chloride using magnetic decantation. The Fe3O4 nanoparticles obtained

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were of 810 nm average size as previously reported [41]. In the second step, a certain amount of these prepared ferrite nanoparticles was dispersed in 10 mL puried water. A 100 L aliquot of these ferrites was added to the polymeric precursor solution of 4-VP containing EGDMA (10% with respect to monomer ratio) in SDS solution at 75 C prior to the addition of the initiator solution (APS). After allowing the reaction to proceed for 6 h, the composite p(4-VP) magnetic particles were puried by centrifugation as described above and dehydrated using a freeze dryer. 2.4. Quaternization/alkylation of the p(4-VP) hydrogels, nanoparticles and magnetic composites In order to generate positive charge (quaternize) with different alkyl chain lengths on the products synthesized as described above, p(4-VP) hydrogels and nanoparticles were reacted with HCl (in puried water) or with BE, 1-BB, 1-BH, 1-BO and 2-BEA in ethanol-acetone mixture (50:50 v/v) at ambient temperature. In short, 1 g of p(4-VP) bulk hydrogel or nanoparticles in acetone was mixed with an equal amount of ethyl alcohol and then with an excess of alkylation and/or quaternization agents (at least 3 excess, based on the 4-VP repeating unit) under continuous mixing (750 rpm) at room temperature for 24 h. Magnetic p(4-VP) based hydrogels or nanoparticles were quaternized only using BE. The N-alkyl quarternized p(4-VP) and magnetic p(4-VP) hydrogels were repeatedly washed with acetone, to ensure that all of the excess alkylation and quaternization agents were eventually removed. 2.5. p(4-VP) based bulk and nanoparticle hydrogel characterization and analysis methods The SEM images of the p(4-VP) nanoparticles were obtained from powder samples deposited on carbon tape attached SEM stubs after Au coating to a few nm thickness under vacuum with the operating at 1020 kV (SEM, Hitachi-4800). The Fourier transform infrared radiation (FT-IR) spectra of the macro hydrogels and nanoparticles were recorded with an FT-IR (Perkin Elmer Spectrum 100) instrument using an ATR apparatus with 4 cm 1 resolution between 4000 and 650 cm 1. Swelling experiments with p(4-VP) bulk hydrogels were performed in triplicate using puried water at room temperature. The mass increase was measured by weighing the hydrogels taken from the swelling medium at certain times after blot-drying with lter paper to remove the supercial water; after weighing the materials were placed back in the same swelling media. Hydrogels were kept in swelling medium for 12 h to determine the maximum % swelling value, %S. The swelling ratio (S) of the modied particles was estimated using the following equation: % S = MS MD = MD 100 1

behavior of bare and magnetic p(4-VP) materials. Samples (~ 3 mg) were heated from 50 to 750 C under nitrogen ow of 100 mL/min with a 10 C/min heating rate. 2.6. Batch absorption/desorption experiments The ability of the hydrogels to absorb As(V) from an aqueous solution was determined in triplicate at 30 C and under a constant stirring rate (300 rpm). The p(4-VP) bulk hydrogels and the bulk magnetic composites (~1 g) were placed in 1000 mL of a solution containing 10 mg L 1 As(V) at pH 6 for 12 h. The quaternized hydrogel materials (p (4-VP)-HCl, p(4-VP)-BE, p(4-VP)-1-BB, p(4-VP)-1-BH, p(4-VP)-1-BO, p (4-VP)-2-BEA, and p(4-VP)-2-BEA-HCl) were also assessed by this method. The amount of absorbed As(V) remaining after 12 h was calculated directly from the ICP-AES measurements. The same absorption conditions were used to assess the absorption properties of the p(4-VP) nanoparticles, except the absorption time was shortened to 1 h. Absorbed As(V) was determined after centrifugation of the solution containing the particles at 14,000 rpm (20 min). The centrifuged solutions were also ltered through 0.22 m syringe (PTFE) lters before ICP-AES measurements. The lter only absorbed 2% of the As(V) measured by ICP-AES. To determine the effect of the initial As(V) concentration on absorption, the bulk or nano p(4-VP)-HCl was added at 1 g/L to aqueous As(V) (pH 6.0) at concentrations between 5 and 100 mg L 1 (5, 10, 25, 50, and 100 mg L 1). As in previous experiments, these solutions were mixed constantly at 300 rpm at 30 C. The effect on pH was determined in a similar manner, by varying the pH between 2 and 8 aqueous solutions of As(V) at a concentration of 10 mg L 1 and maintaining the concentration of the hydrogel at 1 g/L. The effect of temperature was also determined similarly; three different solution temperatures, 30, 35 and 40 C were studied, at pH 6 under the same absorption conditions (10 mg L 1 As(V) and 1 g/L (p(4-VP)-HCl) as absorbent). The inuence of ionic strength on the absorption process was investigated by amending the standard test solution (10 mg L 1 As(V) in aqueous solution at pH 6) with 020 mg L 1 NaCl or Na2SO4. As before, the solutions were stirred at 300 rpm and 30 C, and the hydrogel concentration was maintained at 1 g/L. Finally, the kinetics of As(V) absorption were investigated by using standardized conditions (pH 6, 30 C, 10 mg L 1 As(V), 1 g/L absorbent, 300 rpm mixing). The amount of absorbed As(V) was determined by ICP-AES on samples taken at varying time intervals during absorption process. The maximum amount of absorption was calculated using Eq. 2: qe = CI Ce V = W 2

where, MS = weight of the swollen hydrogel, and MD is the weight of the dried hydrogel. Dynamic light scattering (DLS) studies were performed with a 90 Plus particle size analyzer (Brookhaven Instrument Corp.) to determine the sizes of the particles for p(4-VP) based materials using particle suspensions in 10 2 M KNO3 aqueous solution with 20 s integration time. The DLS experiments were conducted at a 90 angle using 35 mW solid state laser detectors operating at 658 nm. The Zeta potential measurements were performed with a ZetaPals Zeta Potential Analyzer BIC (Brookhaven Inst. Corp.) to determine the charge of the particles, using a dilute aqueous solution of p(4-VP) based nanoparticles. Both zeta potential and DLS measurements were performed in triplicate. Thermogravimetric analysis (Seiko, SII TG/DTA 6300 Thermal Analyzer)) was carried out in order to determine the thermal

where CI and Ce are the initial and equilibrium arsenate ion concentrations (mg L 1), V is the volume of arsenate ion solution and W is the weight (as g) of the nanoparticle or hydrogel used. In addition to maximum absorption capacity, the Langmuir adsorption equilibrium constant, KL [42] and Freundlich parameters KF and n [43] were also determined using the equations below; Ce = qe = Ce = qmax + 1 = qmax KL 3

where; Ce is the equilibrium concentration of arsenate ions (mg/L), qe is the amount of arsenate ions adsorbed (mg/g), qmax is the maximum adsorption capacity of metal ions (mg/g), and KL is the Langmuir adsorption equilibrium constant (L/mg). log qe = log KF + 1 = n log Ce 4

where; qe (mg/g) is the adsorption capacity at equilibrium, Ce (mg/L) the equilibrium concentration of arsenate ions in solution, and KF and n are the physical constants of the Freundlich adsorption isotherm. The KF and n are the indicators of the adsorption capacity and adsorption intensity, respectively.

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Desorption studies were carried out by treatment of 1 g of bulk or nano hydrogels recovered from absorption experiments with 100 mL of 2 M NaOH at 30 C and 300 rpm mixing. (Preliminary studies showed that desorption of As(V) from the p(4-VP) hydrogels with (2 M) NaOH was most efcient for the p(4-VP)-HCl bulk gel and nanoparticles (data not shown). Further characterization of the absorption behaviors were therefore conducted on these materials.) The quantity of As(V) desorbed from the hydrogel was determined after 2 h and 24 h of treatment. After desorption, the bulk and the nano hydrogels were treated with HCl to requaternize the material.

Table 1 The hydrodynamic radius and zeta potentials of p(4-VP) based nanoparticles. Particle p(4-VP) p(4-VP)-BE p(4-VP)-BB p(4-VP)-BH p(4-VP)-BO p(4-VP)-HCl p(4-VP)-2-BEA-HCl Hydrodinamic radius (nm) 370 6 501 15 463 14 420 12 389 22 562 19 1086 57 Zeta potential (mV) 1.8 0.4 29.6 1.7 35.9 2.8 21.9 2.3 15.2 3.5 39.8 2.1 42.6 3.8

3. Results and discussion 3.1. Characterization of bulk/nano p(4-VP) based hydrogels The macro and nano sized p(4-VP) hydrogels quaternized with HCl, BE, 1-BB, 1-BH, 1-BO, and 2-BEA have the characteristic R3NH + groups and have the typical bands for all the hydrogels' system in their FT-IR spectra at about 36002400 cm 1 due to positive charges on pyridinium cations. The FT-IR spectra of macro and nano hydrogels quaterized with alkylhalides (p(4-VP)-BE, p(4-VP)-BB, p(4-VP)-BH, p (4-VP)-BO and p(4-VP)-2-BEA-HCl) have the aliphatic stretching frequency at 2924 cm 1 belonging to C\H due to aliphatic chains on these modifying agents; the intensity of this frequency increased with the increase in the alkyl chain length [44]. Furthermore, the peak at 1636 cm 1 for the quaternized nitrogen atom for pH responsive p(4VP) based hydrogels is the proof for readily charge formation [31,33,44]. The particles prepared using the microemulsion technique had a size of about 200 nm in dry state as shown in SEM images of Fig. 1(a). A schematic representation of the quaternization reaction with 2-BEA is shown in Fig. 1(b). This representation demonstrates that 2-BEA can be further quaternized to generate an additional positive charge on the pyridinyl ring of the polymer. This is very important in the environmental application e.g., in the removal of negatively charged arsenic oxyanions (As(V)) from aqueous environments [25]. Table 1 shows the zeta potentials and hydrodynamic radius (as determined by DLS measurements) of the p(4-VP) based particles modied with alkylating agents of different chain lengths. Without a treatment, p(4-VP) particles were almost neutral, with a zeta potential of 1.8 0.4 mV; after treatment with alkylhalides, the zeta potential increased to 15.242.6 mV. There was no discernible correlation between alkyl chain length and the increase in the zeta potential, although the particles treated with 2-BEA followed by HCl had the most positive zeta potential, as expected to be due to the additional positive charge present on the p(4-VP)-2BEA-HCl particles (as shown in Fig. 1(b)). Increasing the alkyl chain length up to 8 carbons, made the particles more hydrophobic and resulted in a decrease in the particle diameters (also shown in Table 1). The bare p (4-VP) is 370 6 nm in size whereas particles treated with BE, 1-BB, 1-BH, and 1-BO were in the order of 501 15, 463 14, 420 12 and 389 22 nm in hydrodynamic diameter. In contrast, quaternization of p(4-VP) particles with HCl and 2-BEA-HCl caused an increase in particle size; the hydrodynamic radii and the p(4-VP)-HCl and p(4VP)-2-BEA-HCl particles were 562 19 and 1086 57 nm, respectively. Fig. 2(a) demonstrates the ~3-fold increase in particle size that occurs when the p(4-VP) particles are treated with 2-BEA and HCl. This demonstrates how a simple chemical modication procedure can transform the particles from nano- to microscale. This feature (swelling characteristic) may also have advantages in the absorption

(a)

2 m

(b)
:
:N
H2N N N

Br N

H2N N

Br Br H3N N

H3N N

Cl Br

2-BEA
Br N NH2 N Br

N Br NH2

HCl

Cl Br N Cl NH3 N N Br NH3 Cl

p(4-VP)

Fig. 1. (a) SEM images of p(4-VP) nanoparticles (scale bar: 2 m). (b) The schematic representation of the double quaternization of p(4-VP) nanoparticles.

NH2

Br NH3 Cl

p(4-VP)-2-BEA

p(4-VP)-2-BEA-HCl

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(a)
100 75 Intensity 50 25 0
2-BEA + HCl

lengths increased because of the hydrophobicity of the alky group [31,44]. 3.2. Effect of quarternization/modication agent and hydrogel size on As (V) removal In the absorption of As(V) by quaternized p(4-VP) materials via ion exchange mechanism, the Br or Cl anion is assumed to exchange with the negatively charged As(V) [45]. Therefore, the extent and the nature of the charge is very important in the use modied p(4-VP) particles. In general, the quantity of As(V) absorbed from the solution correlated with hydrogel charge and the particle size. Fig. 3(a) compares the ability of quaternized p(4-VP) particles and 5 6 mm bulk hydrogels for their ability to remove As(V) under standard conditions. The highly water swollen p(4-VP)-HCl particles removed 97.1% of the As(V) in ~15 min, while HCl-treated bulk p(4-VP) removed only 87.6% of As(V) after 12 h. As the chain length of the modifying agent was increased, the hydrophilic character of the p(4-VP) based materials were decreased, as was its ability to absorb As(V). The lowest amounts of As(V) removal were observed for p(4-VP)-BO based materials in both bulk and particle formulation (~21% and ~42%, respectively). The ability of the p(4-VP) polymers quaternized with 2-BEA or 2-BEA followed by HCl to remove

200

400 600 800 1000 Hydrodynamic Radius (nm)

1200

1400

(b)
7500 6000 4500

%S

Number of Carbon 0: HCl 3000 2:Ethane 4:Buthane 6:Hexane 1500 8:Octane

2 4 6 Number of Carbons in alkyl halide

(a)
40 30 qe (mg/g) 20 10 0

Fig. 2. (a) The change in the p(4-VP) nanoparticle sizes with quarternization by using 2BEA and HCl in 10 2 M KNO3. (b) Swelling characterization of quarternized p(4-VP) bulk hydrogels in DI water.

of toxic species such as arsenic from aqueous environments by allowing greater diffusion into the interior of the particle. As shown in Fig. 2(b), the %S values of the quaternized bulk p(4VP) hydrogels decreased signicantly as the alkylation agents' chain

p(4-VP)-HCl Nanoparticle p(4-VP)-HCl Bulk hydrogel

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100
p(4-VP) Nanoparticle p(4-VP) Bulk hydrogel

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40 Ce(ppm)

60

80

(b) 4
3
p(4-VP)-HCl Nanoparticle p(4-VP)-HCl Bulk hydrogel

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50 Number of Carbon
0: HCl 2:Ethane 4:Buthane 6:Hexane 8:Octane

Ce/qe 2 4
Number of Carbon

2 1

25

20

(b)
100
p(4-VP)-2-BEA p(4-VP)-2-BEA-HCl

40 Ce (ppm)

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80

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2
p(4-VP)-HCl Nanoparticle p(4-VP)-HCl Bulk hydrogel

75
% Removal

log qe

50

25 0 0 Bulk hydrogel Nanoparticle -1 0 1 2

log Ce

Fig. 3. The percent removal of As(V) from aqueous environments by alkyl (a) and 2-BEA (b) quarternized p(4-VP)-based bulk hydrogels and nanoparticles. [(As(V) concentration = 10 mg L 1 (1000 mL), absorbent dosage 1 g/L, pH = 6, 30 C, time: nanoparticle = 1 h, hydrogel = 12 h)].

Fig. 4. (a) qe vs Ce graph of p(4-VP)-HCl hydrogels at different As(V) concentrations, and the application of (b) Langmuir, and (c) Freundlich isotherms, respectively. [(As(V) concentration: 5100 mg L 1 (1000 mL), absorbent dosage 1 g/L, pH = 6, 30 C, time: nanoparticle = 1 h, hydrogel = 12 h].

N. Sahiner et al. / Desalination 279 (2011) 344352 Table 2 Langmuir and Freundlich adsorption isotherm data for the p(4-VP)-HCl hydrogels and nanoparticles. Hydrogel Langmuir isotherm constants KL (L/mg) p(4-VP)-HCl bulk hydrogel p(4-VP)-HCl Nanoparticle 11.07 25.45 qm (mg/g) 23.26 31.75 R2 0.998 0.998 Freundlich isotherm constants KF 7.680 11.45 n 3.468 3.518 R2 0.962 0.940

349

(a)
100 75 % Removal 50 25 0
p(4-VP)-HCl Nanoparticle p(4-VP)-HCl Bulk hydrogel

pH

10

As(V) under standard conditions is shown Fig. 3(b). The double quaternized p(4-VP)-2-BEA-HCl bulk and nanoparticles removed 92.7 and 98.1% of As(V), respectively under our standard test conditions. This is plausible, because these quaternization agents generate double charges for every pyridinyl ring, and thus should be able to absorb more As(V). Because the particles have a higher surface area than the bulk gels, As(V) removal by the particles was both faster and more efcient, regardless of the charge on the particles. Amongst the modifying agents, HCl, BE, 1-BB, 1-BH, 1-BO, and 2-BEA, the double charge forming agent (2-BEA) treated particles and macrogels showed the highest removal efciency as shown in Fig. 3 (a) and (b).

(b)
100 75 % Removal 50 25 0 25

p(4-VP)-HCl Nanoparticle p(4-VP)-HCl Bulk hydrogel

30

35 T (C)

40

45

3.3. Effect of initial concentration of As(V) As can be seen in Fig. 4(a), the maximum absorption capacity for p (4-VP)-HCl is 22.6 mg/g As(V) for macro hydrogels at 12 h contact time; the same hydrogels of nanosized materials showed a maximum absorption capacity of 31.2 mg/g As(V) in 1 h. For both materials, the further contact times (24 h for macro and 12 h for nano hydrogels) did not provide any increase in the absorption capacity. Upon the application of absorption processes to Langmuir (Fig. (4b)) and Freundlich (Fig. 4(c)) models, the As(V) ion absorption by p(4-VP)HCl macro and nanohydrogels is said to be monolayer. The Langmuir and Freundlich isotherm constants for As(V) absorption by macro and nano p(4-VP)-HCl hydrogels are provided in Table 2. To assess the effect of the initial As(V) concentration on absorption process by p(4-VP)-HCl macro and nanogels using 1 g of each, the concentration of the As(V) solutions was varied between 5 and 100 mg L 1 (1000 mL volume of each). The dependence on As(V) absorption on the initial As(V) concentration is shown in Fig. 5. From the gure it is clear that, regardless of the material size, the % removal efciency is decreased with the increase in the As(V) concentrations. At low initial concentrations (10 mg L 1) 97.8% of As(V) was removed; however, at high concentration (100 mg L 1) the removal ratio was reduced to 31.2% for even nano sized hydrogels. The %

Fig. 6. (a) Absorption of As(V) onto p(4-VP)-HCl nanoparticles and bulk hydrogels as a function of solution pH. [(As(V) concentration: 10 mg L 1 (1000 mL), absorbent dosage 1 g/L, 30 C, time: nanoparticle = 1 h, bulk hydrogel = 12 h)], (b) the absorption isotherms of p(4-VP)-based hydrogels for As(V) at different temperatures. [(As(V) concentration: 10 mg L 1 (1000 mL), absorbent dosage 1 g/L, pH = 6, time: nanoparticle = 1 h, bulk hydrogel = 12 h)].

removal capacities were 94.6%22.6% for macro (bulk) p(4-VP)-HCl as shown in Fig. 5.

3.4. Effect of pH and temperature on As(V) removal The effect of pH and temperature on As(V) removal was determined and the corresponding data are shown in Fig. 6(a) and (b), respectively. As(V) can be found at different oxidation states: for 2 pH = 02 in H3AsO4, pH = 27 in H2AsO4 , pH = 712 in HAsO4 , and 3 in pH = 1214 AsO4 [46]; therefore, the pH has a signicant effect on the As(V) absorption processes. As can be seen in Fig. 6(a), as the removal of As(V) was stable between pH 5 and 7, but it decreased when the pH fell below 4 or rose above 7. The highest absorption values were obtained for pH 5 and 6 which corresponds to negatively charged As(V) compounds that can interact electrostatically with the positively charged p(4-VP)-HCl bulk or nanohydrogels via an ion exchange mechanism. As the pH values decrease below 5 and/or above 6, the ionic type and the charge of As(V) was changed resulting in decrease in % removal. As the quaternized bulk and nano p(4-VP) hydrogels become neutral in the basic medium [47], the absorption falls sharply. To explore the effect of temperature on As(V) absorption by p(4-VP) based materials, the absorption studies were also performed at 30, 35 and 40 C, and the data is shown in Fig. 6(b). As the gure clearly shows, there is very little decrease in % removal of As(V) by p(4-VP)-HCl with the increase in the temperature. This can be attributed to the existence of very small secondary interactions (iondipole and dipoledipole) between As(V) and the absorbents [26]. The removal efciency decreased from 97.1% at 30 C to 93.8% at 40 C for p(4-VP)-HCl for nanoparticles and these values were 87.6 and 79.1% for bulk hydrogels, for the corresponding temperatures, respectively.

100 75 50 25 0 0 20 40 60 80 Initial As(V) Concentration (ppm) 100 120

p(4-VP)-HCl Nanoparticle p(4-VP)-HCl Bulk hydrogel

Fig. 5. Effects of initial concentration As(V) on removal (%). [(As(V) concentration: 5 100 mg L 1 (1000 mL), absorbent dosage 1 g/L p(4-VP)-HCl nanoparticles and bulk hydrogels , pH = 6, 30 C, time: nanoparticle = 1 h, hydrogel = 12 h)].

% Removal

350

N. Sahiner et al. / Desalination 279 (2011) 344352

100
% Removalof As(V)

(a)
100 80
p(4-VP)-HCl Nanoparticle-NaCl p(4-VP)-HCl Nanoparticle-Na2SO4 p(4-VP)-HCl Bulk hydrogel-NaCl p(4-VP)-HCl Bulk hydrogel-Na2SO4 Magnetic p(4-VP) Bulk hydrogel Magnetic p(4-VP) Nanoparticle p(4-VP) Nanoparticle p(4-VP) Bulk hydrogel

75 50 TG % 25 20 25 0

60 40

10 15 Salt Concentration (ppm)

20

23.7% 6.8 %

Fig. 7. Chloride and sulfate effect on As(V) removal. [(As(V) concentration: 10 mg L 1 (1000 mL), absorbent dosage 1 g/L, pH = 6, 30 C, contact time: nanoparticle = 1 h, bulk hydrogel = 12 h)].

0 100 200 300 400 500 Temp. Cell 600 700

3.5. Effect of salts on As(V) removal Anions such as sulfate, chloride, nitrate, and phosphate exist in the ground and surface water. Especially, sulfate and chloride ions are the most commonly found ions with high concentration, and many investigations for the removal of As(V) were performed in presence of these ions [48,49]. As illustrated in Fig. 7, neither chloride nor sulfate signicantly affected the removal of As(V) at concentrations up to 15 mg L 1. When the salt concentration was increased to 20 mg L 1 there was a small decrease in the % removal; for example, the As(V) solution containing 20 mg L 1 Na2SO4 and NaCl reduced the % As(V) removal to 74.3 from 82.2% for macro p(4-VP)-HCl and to 89.3 from 94.6% for nano p(4-VP)-HCl particles, respectively. This results are reasonable as the ions from the corresponding salts can also compete with the active sites from hydrogels, and due to the salt screening effect there is almost always reduction in absorption capacity of As(V) as the concentration of salts are increased (increases the ionic strength of the medium). 3.6. Effect of magnetic particle and contact time on As(V) removal The utilization of nano size materials in real environmental applications has some problems due to the difculty in removing the nanoparticles from the environments after their use. To overcome this problem, we introduced magnetic eld responsiveness to the p(4-VP) materials. To determine the inorganic parts of these composite materials, as shown Fig. 8(a), thermogravimetric analyses were done and they revealed that p(4-VP) nanoparticles have 8.6% and macro hydrogels have 23.7% magnetic metal nanoparticles by weight. The magnetic particle content of the bulk p(4-VP) hydrogel composites can be determined by material property (the iron ion absorption capacity of pyridine), the magnetic particle content of the nanosized p(4-VP) composite could be controlled by simply changing the quantity of magnetic particles added during synthesis. As can be seen from the TGA thermogram, the degradation behaviors for non-magnetic p(4-VP) materials are very similar; degradation starts at ~260 C and ends at ~400 C. On the other hand, the degradation temperatures for both composites (macro and nano) p(4-VP) continues up to 404 C and 452 C. Fig. 8(b) and (c) is the clear visualization of the ease with which the bulk and nano sized p(4-VP) composites can be recovered after completion of their missions e.g., removing As(V) from aqueous environments; they can be easily collected using an externally applied magnetic eld. Another advantage of the utilization of magnetic particles in the removal of As(V) is the synergic effect of the magnetite or maghemite, which also have the ability to absorb As(V) [1,18,50]. As was observed in this investigation, the addition of magnetic eld responsive materials to nano size particles increased their As(V) removal capacity by 3.6%, while the addition of the particles to the bulk composite increased absorption by 6.9%. Therefore, the utilization of magnetic eld responsive materials may be of great practical value in water treatment.

(b)

(c)

(d)
100 %Removal of As (V) 75 50 25 0 0 100 200 300 Time (min) 400 500 600
Magnetic p(4-VP)-BE Nanoparticle p(4-VP)-BE Nanoparticle Magnetic p(4-VP)-BE Bulk hydrogel p(4-VP)-BE Bulk hydrogel Bulk p(4-VP) Hydrogel

Fig. 8. (a) Thermogravimetric analysis of bare p(4-VP) and magnetic p(4-VP) materials. (b) and (c) are the digital camera images of magnetic p(4-VP)-BE nanoparticles, and p (4-VP)-BE bulk hydrogels, under applied external magnetic eld. (d) Effect of contact time on As(V) absorption on the p(4-VP) based materials and their composites. [(As(V) concentration: 10 mg L 1 (1000 mL), absorbent dosage 1 g/L, pH = 6, 30 C].

The absorption time is also one of the other important parameters that will affect the real utilization of these absorbents. Therefore, we carried out the % removal of As(V) experiments with time for all the
Table 3 Comparison of the adsorption/absorption values of As(V) with various materials. Adsorbent/absorbent Activated CO2-neutralized red mud Magnetite-maghemite nanoparticles Fe3O4 loaded active carbon Fe (III) treated biomass CuO nanoparticles Zero-valent iron/activated carbon Synthetic siderite p(4-VP)-BEA-HCl bulk hydrogel p(4-VP)-BEA-HCl nanoparticle Magnetic p(4-VP)-E bulk hydrogel Magnetic p(4-VP)-E nanoparticle
a

Initial con. Dosage % removal References (ppm) (g/L)a As(V) 10 1.5 40 50 0.9 5.0 1.0 10 10 10 10 0.2 0.4 0.2 1.0 2.0 0.5 2.0 1.0 1.0 1.0 1.0 99 99 95 83 99.7 100 99.93 92.7 98.1 87.2 97.1 [21] [50] [51] [52] [53] [54] [55] This This This This

study study study study

Adsorbent or absorbent concentration.

N. Sahiner et al. / Desalination 279 (2011) 344352 Table 4 Desorption of As(V) from p(4-VP)-HCl hydrogels and nanoparticles. Desorption % Number of cycle p(4-VP)-HCl Bulk hydrogel p(4-VP)-HCl nanoparticle 1 90 97 2 90 96 3 86 96 4 84 93 5 82 95

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4. Conclusion In this investigation, macro and nanosized p(4-VP) materials were prepared and quaternized to have positive charged macro and nanogels using different quaternization agents such as HCl, BE, 1-BB, 1-BH, 1-BO and 2-BEA. The materials were also made magnetic eld responsive by in situ preparation method for bulk and by encapsulation techniques of magnetic metal nanoparticles for nano p(4-VP). And it was demonstrated that these materials can be used for the effective and efcient removal of As(V). It was also proven that the incorporated magnetic particles, in addition to providing a simple route of absorbent recovery, also increased the absorption capacity of materials for As(V). The absorption time of the modied nanoparticles was much faster than that determined for macro p(4-VP) hydrogels. These materials can be used up to 5 times and very high desorption rate (N 80% for macro and 90% for nano materials). Basic medium (2 M NaOH) can be used for elution of the absorbed As(V) by neutralizing the quaternized materials and bulk/nano p(4-VP)-HCl can make desorption N 90% becoming neutral and can be regenerated by requaternization. The p(4-VP) based materials prepared here are comparable with some of the other materials reported in the literature with some additional advantages such as modiable charges with various quaternization agents, and sizes and with magnetic responsive behaviors. To sum up, the synthesized p(4-VP) materials are resourceful and promising candidates for effective and fast removal of As(V) from aqueous medium for real application and also have great potential for other potential applications. Acknowledgments N. Sahiner is grateful to the Turkish Academy of Science for nancial support under the 2008 TUBA-GEBIP program. This work is partially supported by Canakkale Onsekiz Mart University (COMU-2010/187). References

Absorption medium: pH = 6, 30 C, 10 ppm (1000 mL) As(V), 1 g p(4-VP)-HCl nanoparticle and hydrogel, release medium: 2.0 M NaOH (100 mL).

synthesized materials. In preliminary experiments, we discovered that p(4-VP) materials quaternized with HCl lost their magnetic behavior (data not shown). For the magnetic eld-assisted removal of As(V), we therefore employed composite BE quaternized p(4-VP) material, as shown in Fig. 8(d). It is obvious from Fig. 8(d) that without quaternization, p(4-VP) bulk hydrogels removed only 10.6% of 10 mg L 1 As(V) in 500 min, whereas the bulk magnetic p(4-VP)BE removed 87.2% of As(V) during the same contact time. The very best results were obtained with nano sized quaternized p(4-VP)-BE. These particles removed 97.1% of the As(V) in about 15 min. The particles could be subsequently removed via an external magnetic eld, and can be reused in absorption experiments as will be shown in the next section. Table 3 provides a comparison of properties of the p (4-VP) materials described in this study with some of the materials previously reported in the literature [5055]. Upon investigation of the Table, p(4-VP) materials are great contribution to arsenic absorption studies as they offer tunable charge and sizes as well as the magnetic eld responsive ability. Additionally, the As(V) removal capacities are comparable and even better in some cases than the reported materials in the literature. 3.7. Desorption studies of As(V) The reusability is another important factor for the widespread usage of the absorbent materials in the environmental applications. Hence, we investigated the desorption capability of the As(V) absorbed onto bulk and nano p(4-VP)-HCl materials. For the elution medium 100 mL 2 M NaOH was used. As summarized in Table 4, the desorption ratio % was determined for 5 consecutive absorption/desorption cycles. The absorption and desorption times for bulk and nano hydrogels were 6 h and 15 min respectively and the following equation was used in the calculation of the desorption ratio (DR) %.

DR% = Amount of desorbed As V = Amount of absorbed As V 100

The desorption medium that is basic that can neutralize quaternized the p(4-VP)-HCl bulk and nanomaterials [47]; this material that can then be re-quaternized and used repetitively. The nature of quaternizing agents are also very important in the desorption processes. As mentioned in Section 3.2, the most effective agent in the absorption of As(V) is p(4-VP)-2-BEA-HCl hydrogels and their particles release 44 and 51% of the absorbed As(V) respectively upon treatments with NaOH. The lower releasing DR% can be due to the existence of \NH2 and between two carbon chain lengths. As the carbon numbers in chain length of the quaternization agents were increased, the DR% ratio was decreased as the quaternized structures can hardly be neutralized to requaternize. The exchange of H+ in basic medium is easier (when HCl was used as quaternization agent) than the other quaternized structures. As given in Table 4, even after the 5th reuse, 93% DR for p(4-VP)HCl particles and DR>82% for macro gels were obtained. And due to the smaller sizes of nanoparticle these results are conceivable.

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