Chemical Engineering Journal 171 (2011) 526531

Contents lists available at ScienceDirect

Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Enhanced removal of nitrate by a novel composite: Nanoscale zero valent iron supported on pillared clay
Yun Zhang a,b , Yimin Li b, , Jianfa Li b , Liujiang Hu b , Xuming Zheng a,
a b

Department of Chemistry and State Key Laboratory of ATMMT (MOE), Zhejiang Sci-Tech University, Hangzhou 310018, PR China College of Chemistry and Chemical Engineering, Shaoxing University, Zhejiang 312000, PR China

a r t i c l e

i n f o

a b s t r a c t
The nanoscale zero valent iron supported on pillared clay (NZVI/PILC) was prepared, and used for nitrate removal with the objective of enhanced efciency. The composite NZVI/PILC was characterized by transmission electron microscope (TEM), X-ray diffraction (XRD) and BrunauerEmmettTeller (BET). Good dispersion of NZVI particles (ca. 3070 nm) in the clay phase was observed. The removal efciency of nitrate by this composite was investigated, and compared with commercial iron powder and NZVI containing the same amount of iron. Results showed nitrate could be completely removed by NZVI/PILC within 120 min. This efciency was not only much higher than that (62.3%) by NZVI alone, but also superior to the sum (71.5%) of reduction by NZVI plus adsorption (9.19%) by PILC. The kinetic studies indicated that the rate of nitrate removal was positively related to the adsorption. So we suggested that the adsorption of nitrate by PILC enhanced the mass transfer of nitrate from solution to iron surface, therefore accelerated the reduction rate. The end-products of nitrate reduction by NZVI/PILC were identied as ammonium and nitrogen gas, implying NZVI/PILC may help cut down the total nitrogen amount in water. 2011 Elsevier B.V. All rights reserved.

Article history: Received 6 December 2010 Received in revised form 1 April 2011 Accepted 11 April 2011 Keywords: Pillared clay Supported Nanoscale zero valent iron Nitrate Removal

1. Introduction Recently, the application of zero valent iron (ZVI) in nitrate removal has been extensively studied, because it has advantages of low-cost and easy operation [15]. To improve its removal performance, nanoscale zero valent iron (NZVI) has been developed, which offers larger specic surface area and higher reactivity [69]. However, NZVI particles exhibit strong tendency to agglomerate into larger ones due to the high surface energy and intrinsic magnetic interaction [10]. This results in adverse effect on both effective surface area and removal performance. In addition, the separation and recycling of bare NZVI particles is extremely difcult [11]. To overcome these drawbacks, several solids such as graphite [12], surfactant-modied zeolite (SMZ) [13], porous silica [10,14], resin [15] and poly acrylic acid [11] have been introduced as carriers of NZVI. Most of these composites showed dramatic improvement on removal of contaminants. It has been speculated that the mass transfer of contaminants to iron surface was promoted because

Corresponding authors at: Department of Chemistry, Shaoxing University, Huancheng West Road 508, Shaoxing, Zhejiang 312000, China. Tel.: +86 575 8834 2386; fax: +86 575 8831 9253. E-mail addresses: liym@usx.edu.cn (Y. Li), zhengxuming126@126.com (X. Zheng). 1385-8947/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.cej.2011.04.022

of the adsorption by the carrier, thereby the reduction rate was enhanced [10,14]. This implies that the removal of nitrate by NZVI will be enhanced if a proper adsorbent serving as the carrier. However, the preparation of most above-mentioned composites was complex and the cost was high. Clays are naturally occurring materials, and have been widely used as adsorbents for pollution control due to their high surface area and uptake ability [16]. Bentonite is a kind of layered clay composed mainly of montmorillonite. Its interlayer cations are exchangeable with inorganic/organic cations, which serve as pillars between adjacent layers of montmorillonite. The resulting products, pillared clays (PILCs), usually offer higher sorption capacity toward contaminants in water due to their enhanced surface areas and more functional groups [1721]. PILCs are also advantageous over other solid carriers for its possibility to be designed according to various contaminants by choosing corresponding pillars (inorganic/organic cations) [2123]. Besides, PILCs may act as the catalyst for reduction of contaminants because of its surface acidity [5,2426]. Therefore, it is very interesting to probe the potential of PILCs as the carrier of NZVI for the removal of contaminants. In this paper, the PILC was prepared from bentonite by intercalation with poly(hydroxo Al (III)) cations, and used as the carrier of NZVI. The performance on removing nitrate of this novel composite NZVI/PILC was tested by batch experiments, and compared

Y. Zhang et al. / Chemical Engineering Journal 171 (2011) 526531

527

with that of the bare NZVI. Effect of dissolved oxygen on the removal efciency was investigated, and the kinetic of reactions and endproducts of reduction were also analyzed. 2. Materials and methods 2.1. Materials The original clay used was the bentonite purchased from Inner Mongolia, China. It is composed primarily of Na+ montmorillonite, with cation exchange capacity of 115 cmol/kg. Commercial iron powder and the following chemicals of analytical grade were purchased from Shanghai Chemical Co., China: ferrous sulfate heptahydrate (FeSO4 7H2 O), sodium borohydride (NaBH4 ), aluminum chloride hexahydrate (AlCl3 6H2 O) and sodium hydroxide (NaOH). The fraction of iron powder passing through a sieve of 100 mesh was used. Potassium nitrate of analytical grade was used to prepare aqueous nitrate solutions. 2.2. Preparation of PILC and NZVI samples The PILC was prepared from the original clay by intercalation with poly(hydroxo Al (III)) cations [5,22]. Firstly, 0.2 mol/L solution of aluminum hydroxide was prepared by dropwise addition of NaOH solution into a solution of AlCl3 6H2 O until the molar ratio [OH ]/[Al3+ ] = 2.2 was obtained. The resulting pillaring solution was slowly added in a suspension of 10 g bentonite in 500 mL of deionized water until the [Al3+ ]/bentonite ratio reached 10 mmol/g. The resulting mixture was heated at 70 C for 48 h and the modied clay was centrifuged, washed and dried to a constant weight. The sample was mechanically ground to pass through a sieve of 100 mesh and heated at 115 C for 120 min before use. The NZVI was prepared with a chemical reduction procedure. The 0.108 mol/L solution of NaBH4 was dropwise added into the 0.054 mol/L solution of FeSO4 7H2 O until the molar ratio [BH4 ]/[Fe2+ ] = 2.0 was reached. The solution was stirred for another 30 min under room temperature. The metal particles formed were settled and ltered. Then the solid was washed with ethanol for several times, and nally vacuum-dried. The NZVI/PILC composite was prepared by a similar procedure as described above, except that the PILC was uniformly mixed with solution of FeSO4 7H2 O before the addition of NaBH4 solution. 2.3. Nitrate adsorption on PILC The adsorption isotherms were determined by batch equilibration of 50 mg of each PILC sample with 50 mL of aqueous nitrate solutions of varied initial concentrations. Experiments were carried out in a thermostatic shaker bath at 25 0.1 C for 120 min. Preliminary experiments conrmed that the adsorption equilibrium time required was less than 120 min. After equilibration, the suspension was ltered through a 0.22 m membrane, and the nitrate concentration in supernatant (Ce ) measured. The amount adsorbed (Qe ) was calculated from the difference in concentration between the initial (C0 ) and the equilibrium (Ce ) solution. 2.4. Removal of nitrate Typically, each iron sample (iron powder, NZVI or NZVI/PILC) containing iron of 50 mg was added into the 250 mL conical ask containing 100 mL of nitrate solution (initial pH = 7.00) of 0.806 mmol/L (50 ppm, C0 ) under stirring. The nitrate solution was deoxygenated by a nitrogen stream for 20 min before adding iron sample, and kept sealed during the experiment (the schematic installation is shown in Fig. 1A). The removal experiment was carried out by putting the ask in a thermostatic shaker bath at

Fig. 1. Schematic installation for (A) batch experiments and (B) analysis of endproducts.

25 0.1 C. At the given time intervals, 2 mL of solution sample were withdrawn and ltered through a 0.22 m membrane. The nitrate concentrations at time t (Ct ) were determined. The percentage of nitrate removed was calculated as: Percentage of nitrate removed(%) = (C0 Ct ) 100%. C0

For analysis of the nitrogen species during the reaction, the installation was rebuilt as shown in Fig. 1B. At the given time, the N2 was rapidly bubbled into the reactor and then kept for 1 min, the off-gas was absorbed by 25 mL acidic solution for analysis of ammonia gas. Subsequently, the solution in reactor was ltered for analysis of nitrate, nitrite and ammonium. When analyzing the nitrogen gas generated, the anaerobic situation was created by argon gas instead of nitrogen gas. 2.5. Analytical methods Concentrations of nitrate, nitrite and ammonium species in solution samples were determined by using a UVvis spectrophotometer (SP-756P, Shanghai Spectrum, China). The nitrate concentration was calculated by UV absorbance at 220 nm and corrected by subtracting a second absorbance at 275 nm. The nitrite concentration was determined by visible absorbance measurement at 540 nm, due to the diazonium complex formed by reaction involving NO2 , sulfanilamide and N-(1-naphtyl)-ethylenediamine dihydrochloride. The Nesslers method was used to determine the ammonium concentration in both reaction solution and absorbed solution of ammonia gas, in this method the derivative of ammonium was measured by absorbance at 420 nm [27]. Nitrogen gas was detected by gas chromatography with a 180 cm 0.63 cm packed molecular sieve No.5A column and a thermal conductivity detector. Hydrogen was used as a carrier gas. The temperature of injector, detector and column was kept at 80, 90 and 50 C, respectively.

528

Y. Zhang et al. / Chemical Engineering Journal 171 (2011) 526531

Fig. 2. XRD images of NZVI, NZVI/PILC and PILC.

The dissolved oxygen was measured by a dissolved oxygen meter (LD-900-7, China). The BrunauerEmmettTeller (BET) specic surface areas of PILC, NZVI and NZVI/PILC were obtained from nitrogen adsorption data at 77 K in a Micromeritics ASAP 2020 system. The samples were degassed at 300 C under vacuum prior to the measurement. X-ray diffraction (XRD) measurement was performed with a Rigaku D/MAX-2500 system using Cu K radiation at 0.1542 nm. The iron content was measured with the atom absorption in a Shimadzu AA-6300 Spectrophotometer. TEM images were obtained in a JEM-1010 instrument using an accelerating voltage of 80 kV.

Fig. 3. TEM images of (A) NZVI and (B) NZVI/PILC samples.

3.2. Reactivity of NZVI/PILC on nitrate removal When the same dosage of iron of 50 mg was used, the efciency on nitrate removal by various irons (including commercial iron powder, NZVI and NZVI/PILC) was investigated. As can be seen in Fig. 4, the percentage of nitrate removed by the commercial iron powder was less than 5% within 120 min. A much higher result (62.3%) was obtained for NZVI treatment due to its higher reactivity [6,8]. The removal of nitrate by PILC alone was also investigated, in which the same amount of PILC as that used in the NZVI/PILC treatment was employed. In this treatment, only a small fraction (<10%) of nitrate was removed, which was due to the adsorption by PILC. In comparison, the NZVI/PILC composite showed a surprisingly high efciency on removing nitrate. The nitrate was completely removed within 120 min. The efciency is much higher than that (62.3%) by NZVI alone, and also higher than the sum (71.5%) of the reduction by NZVI plus the adsorption (9.19%) by PILC. The results indicated that the nitrate removal by NZVI/PILC is not a simple combination of adsorption and reduction. There must be some synergetic effect existing between PILC and NZVI. The nitrate reduction by ZVI is surface mediated, so close contact between nitrate and iron surface is required. As shown in the adsorption isotherm (Fig. 5), the PILC can adsorb a certain amount of nitrate. As a result, the concentration of nitrate in the vicinity of iron surface increased, which facilitated the mass transfer of nitrate from solution to iron surface. Therefore, the reduction rate was accelerated. The similar synergetic effect has been

3. Results and discussion 3.1. Characterizations of NZVI and NZVI/PILC samples The XRD measurement conrmed the formation of zero valent iron with its major reection at 44.8 (2 ), which was observed on both NZVI and NZVI/PILC samples (shown in Fig. 2) [12]. The BET specic surface areas of various samples were determined to be: 0.35 m2 /g for commercial iron powder, 33.5 m2 /g for NZVI, 29.8 m2 /g for NZVI/PILC and 31.1 m2 /g for PILC. The iron contents in NZVI and NZVI/PILC samples were measured to be 53.5% and 23.9%, respectively. Microscopic morphology of NZVI and NZVI/PILC samples was investigated by TEM, and the images were shown in Fig. 3. The necklace-like aggregates of bare NZVI particles were observed in Fig. 3A. In comparison, as revealed in Fig. 3B, the NZVI particles (ca. 3070 nm) supported on PILC were clearly discrete and well dispersed in the PILC carrier, without aggregation. So PILC can prevent the NZVI particles from aggregating together.

Y. Zhang et al. / Chemical Engineering Journal 171 (2011) 526531

529

Fig. 4. Removal of nitrate by various iron samples and PILC.

Fig. 6. Effect of dissolved oxygen on removal of nitrate by NZVI and NZVI/PILC.

observed in some previous reports, in which the enhanced removal of contaminants by ZVI was obtained by using adsorbents together [5,13,15,28].

tron acceptor and competed with nitrate in the reaction [7,8], as depicted in Eq. (1): 2Fe0 + 2H2 O + O2 2Fe2+ + 4OH (1)

3.3. Effect of dissolved oxygen The removal efciency of nitrate was investigated under aerobic and anaerobic situation, respectively. The results were illustrated in Fig. 6. As revealed, for NZVI treatment, 62.3% of nitrate was reduced in the anaerobic system, but the removed percentage accounted for only 22.1% in the aerobic system within 120 min. For NZVI/PILC treatment, a complete removal was obtained in the anaerobic system, however, in the aerobic system, the residual nitrate was still observed. Therefore, for both NZVI and NZVI/PILC treatments, nitrate was reduced more facilely in the anaerobic system than in the aerobic system. The dissolved oxygen played a role of elec-

We measured the DO concentration in the aerobic system. For NZVI treatment, the DO concentration decreased from 3.92 mg/L to 3.56 mg/L within 20 min, and then gradually increased to 3.82 mg/L. For NZVI/PILC treatment, the DO concentration decreased from 3.92 mg/L to 1.05 mg/L within 20 min, and then rebounded to 3.61 mg/L with the reaction proceeding. Such a change may be related to the different reactivity between NZVI and NZVI/PILC. As NZVI/PILC offered higher reactivity, the DO concentration was reduced rapidly. 3.4. Kinetic study on nitrate removal by NZVI or NZVI/PILC Removal of nitrate by NZVI or NZVI/PILC was conducted as a function of initial concentrations, viz., 0.806, 1.16, 1.42 and 2.40 mmol/L. The results were shown in Fig. 7A and B, respectively. The efciencies of NZVI/PILC were all higher than those of NZVI alone at the same initial concentrations. Besides, it was found that the removal efciency increased with the decrease of initial concentration for both NZVI and NZVI/PILC treatments. The LangmuirHinshelwood model (Eq. (2)) for describing surface-catalyzed reactions [2931] was employed to investigate the kinetics of nitrate reduction by NZVI or NZVI/PILC. The r0 is the initial reaction rate, C0 is the initial concentration of nitrate, and k1 , k2 are the reaction rate constant and adsorption coefcient, respectively. The parameters describing the kinetics are given in Table 1. 1 1 1 1 = + r0 k1 k2 C0 k1 (2)

As can be seen, the correlation coefcients are both close to 1 (R > 0.990), indicating the nitrate reduction by NZVI or NZVI/PILC t
Table 1 Parameters for kinetics of nitrate reduction. Treatment NZVI NZVI/PILC k1 (mmol/(L min)) 0.163 0.323 k2 (L/mmol) 0.0488 0.160 R 0.997 0.990

Fig. 5. Adsorption isotherm of nitrate on PILC (25 C).

530

Y. Zhang et al. / Chemical Engineering Journal 171 (2011) 526531

Fig. 8. Amount of various nitrogen species during the nitrate reduction by (A) NZVI and (B) NZVI/PILC.

mainly consisted of ammonium. In view of this, it was proposed that the nitrate may be reduced by NZVI/PILC through a pathway including nitrite as an intermediate [2]. The nitrate was converted to nitrite in the rst stage, and then, further transformed into ammonium [32] as described in Eqs. (3)(5). Fe0 + NO3 + 2H+ Fe2+ + H2 O + NO2
Fig. 7. Removal of nitrate at various initial concentrations by (A) NZVI and (B) NZVI/PILC.

(3)
+

3Fe + NO2 + 8H 3Fe

0 +

2+

+ 2H2 O + NH4

(4) (5)

3Fe + 2NO2 + 8H 3Fe

2+

+ 4H2 O + N2(g)

well to the LangmuirHinshelwood model. The reaction rate constant k1 for the NZVI/PILC treatment was two times larger than that for the NZVI alone. The adsorption coefcient k2 for the NZVI/PILC treatment was three times larger than that for the NZVI alone, indicating that the reaction rate is positively related to the adsorption. We proposed that, in the NZVI/PILC treatment, the adsorption by PILC enhanced the mass transfer of nitrate from solution to iron surface, which accelerated the rate of nitrate removal. 3.5. End-products of nitrate reduction by NZVI or NZVI/PILC Most of the reports have indicated ammonium (NH4 + ) is the main product of nitrate reduction by iron [7,8]. Fig. 8 shows the concentration change of nitrogen species in the NZVI or NZVI/PILC treatment under our experimental condition (pH = 7, C0 = 0.806 mmol/L). As can be seen, for NZVI treatment, some nitrate still existed in the solution and the end-products were mainly composed of ammonium and nitrite (as shown in Fig. 8A). However, in the NZVI/PILC treatment (as shown in Fig. 8B), the nitrite was detected only in the rst stage. It reached a peak concentration at 5 min, and then disappeared after 60 min. The nal solution was

In the solution of NZVI/PILC treatment, the overall amount of nitrogen species decreased a lot compared with the initial amount. This implies that part of nitrogen was converted from the aqueous phase into the gas phase. The decreased amount of nitrogen species in the solution is probably due to the formation of ammonia gas or/and nitrogen gas. As illustrated in Fig. 8B, with the reaction proceeding, the solution pH increased from 7.00 to 9.68. As a result, about 0.0048 mmol ammonia gas was generated within 120 min. This may be responsible for the decrease of ammonium after 20 min in the aqueous phase [33]. The analytical result showed that 0.0243 mmol of nitrogen gas was generated during the reaction. The similar conversion of nitrate into nitrogen gas has also been observed in some previous reports [6,8,32] (as described in Eqs. (5) and (6)). 5Fe0 + 2NO3 + 6H2 O 5Fe2+ + N2(g) + 12OH (6)

In view of the mass balance of total nitrogen species (including both aqueous and gaseous species) in the NZVI/PILC treatment (Fig. 8B), the small decease of the total nitrogen amount may be related to the escaped gas, or to a little adsorption by solid residues. This also indicated that, for NZVI/PILC treatment, almost all nitrate

Y. Zhang et al. / Chemical Engineering Journal 171 (2011) 526531

531

was converted to other nitrogen species, so the removal of nitrate by NZVI/PILC was dominantly attributed to the reduction by NZVI instead of adsorption by PILC. 4. Conclusions The results indicate that the PILC is an excellent candidate as the carrier of NZVI. Effectively, it prevented the NZVI particles from aggregating together. The PILC also promoted the mass transfer of nitrate from solution onto iron surface, leading to the enhanced removal efciency. The kinetic of nitrate removal by NZVI or NZVI/PILC tted well with the LangmuirHinshelwood model. The reaction constant and adsorption constant of NZVI/PILC treatment are both much higher than those of NZVI alone, indicating the reaction rate is positively related to the adsorption. Besides, the end-products of nitrate reduction by NZVI/PILC were identied as ammonium and nitrogen gas, implying NZVI/PILC may help cut down the total nitrogen amount in water. In view of this, the NZVI/PILC composite is obviously advantageous on removing nitrate over NZVI alone, and offers a great potential to the removal of other contaminants in water. Acknowledgements This work was supported by the National Science Foundation of China (Grant No. 20977063, 21047005) and by the Natural Science Foundation of Zhejiang Province, China (Grant No. Y506288). References
[1] F. Cheng, R. Muftikian, Q. Fernando, N. Korte, Reduction of nitrate to ammonia by zero valent iron, Chemosphere 35 (1997) 26892695. [2] C.P. Huang, H.W. Wang, P.C. Chiu, Nitrate reduction by metallic iron, Water Res. 32 (1998) 22572264. [3] J.M. Rodrguez-Maroto, F. Garca-Herruzo, A. Garca-Rubio, C. Gmez-Lahoz, C. Vereda-Alonso, Kinetics of the chemical reduction of nitrate by zero-valent iron, Chemosphere 74 (2009) 804809. [4] X. Fan, X. Guan, J. Ma, H. Ai, Kinetics and corrosion products of aqueous nitrate reduction by iron powder without reaction conditions control, J. Environ. Sci. 21 (2009) 10281035. [5] J. Li, Y. Li, Q. Meng, Removal of nitrate by zero valent iron and pillared bentonite, J. Hazard. Mater. 174 (2010) 188193. [6] S. Choe, Y.Y. Chang, K.Y. Hwang, J. Khim, Kinetics of reductive denitrication by nanoscale zero-valent iron, Chemosphere 41 (2000) 13071311. [7] Y.H. Liou, S.L. Lo, C.J. Lin, W.H. Kuan, S.C. Weng, Chemical reduction of an unbuffered nitrate solution using catalyzed and uncatalyzed nanoscale iron particles, J. Hazard. Mater. B127 (2005) 102110. [8] G.C.C. Yang, H.L. Lee, Chemical reduction of nitrate by nanosized iron: kinetics and pathways, Water Res. 39 (2005) 884894. [9] J. Zhang, Z. Hao, Z. Zhang, Y. Yang, X. Xu, Kinetics of nitrate reductive denitrication by nanoscale zero valent iron, Process Saf. Environ. 88 (2010) 439445. [10] T. Phenrat, N. Saleh, K. Sirk, R.D. Tilton, G.V. Lowry, Aggregation and sedimentation of aqueous nanoscale zerovalent iron dispersions, Environ. Sci. Technol. 41 (2007) 284290.

[11] X. Wang, C. Chen, H. Liu, J. Ma, Preparation and characterization of PAA/PVDF membrane-immobilized Pd/Fe nanoparticles for dechlorination of trichloroacetic acid, Water Res. 42 (2008) 46564664. [12] H. Zhang, Z. Jin, L. Han, C. Qin, Synthesis of nanoscale zero valent iron supported on exfoliated graphite for removal of nitrate, Trans. Nonferrous Met. Soc. Chin. 16 (2006) 345349. [13] P. Zhang, X. Tao, Z. Li, R.S. Bowman, Enhanced perchloroethylene reduction in column systems using surfactant-modied zeolite/zero-valent iron pellets, Environ. Sci. Technol. 36 (2002) 35973603. [14] T. Zheng, J. Zhan, J. He, C. Day, Y. Lu, G.L. McPerson, G. Piringer, V.T. John, Reactivity characteristics of nanoscale zero valent ironsilica composites for trichloroethylene remediation, Environ. Sci. Technol. 42 (2008) 44944499. [15] A. Li, C. Tai, Z. Zhao, Y. Wang, Q. Zhang, G. Jiang, J. Hu, Debromination of decabrominated diphenyl ether by resin-bound iron nanoparticles, Environ. Sci. Technol. 41 (2007) 68416846. [16] G.J. Churchman, W.P. Gates, B.K.G. Theng, G. Yuan, Clays and clay minerals for pollution control Handbook of Clay Science, Developments in Clay Science, vol. 1, 2006, pp. 625675. [17] B. Lothenbach, G. Furrer, R. Schulin, Immobilization of heavy metals by polynuclear aluminium and montmorillonite compounds, Environ. Sci. Technol. 31 (1997) 14521462. [18] D.M. Manohar, B.F. Noeline, T.S. Anirudhan, Adsorption performance of Alpillared bentonite clay for the removal of cobalt (II) from aqueous phase, Appl. Clay Sci. 31 (2006) 194206. [19] O. Bouras, J.C. Bollinger, M. Baudu, H. Khalaf, Adsorption of diuron and its degradation products from aqueous solution by surfactant-modied pillared clays, Appl. Clay Sci. 37 (2007) 240250. [20] L. Zhu, R. Zhu, Simultaneous sorption of organic compounds and phosphate to inorganicorganic bentonites from water, Sep. Purif. Technol. 54 (2007) 7176. [21] J. Li, Y. Li, J. Lu, Adsorption of herbicides 2,4-D and acetochlor on inorganicorganic bentonites, Appl. Clay Sci. 46 (2009) 314318. [22] J. Li, Y. Li, H. Dong, Controlled release of herbicide acetochlor from clay/carboxyl-methylcellulose gel formulations, J. Agric. Food Chem. 56 (2008) 13361342. [23] L. Zhu, Y. Li, J. Zhang, Sorption of organobentonites to some organic pollutants in water, Environ. Sci. Technol. 31 (1997) 14071410. [24] T. Mishra, K.M. Parida, S.B. Rao, Transition metal oxide pillared clay. 1. A comparative study of textural and acidic properties of Fe (III) pillared montmorillonite, J. Colloid Interface Sci. 183 (1996) 176183. [25] M. Kurian, S. Sugunan, Characterisation of the acidbase properties of pillared montmorillonites, Micropor. Mesopor. Mater. 83 (2005) 2534. [26] F. Belkhadem, A. Maldonado, B. Siebenhaar, J.M. Clacens, M.J. Perez Zurita, A. Bengueddach, F. Figueras, Microcalorimetric measurement of the acid properties of pillared clays prepared by competitive cation exchange, Appl. Clay Sci. 39 (2008) 2837. [27] O. Brylev, M. Sarrazin, L. Rou, D. Blanger, Nitrate and nitrite electrocatalytic reduction on Rh-modied pryolytic graphite electrodes, Electrochim. Acta 52 (2007) 62376247. [28] H.H. Cho, T. Lee, S.J. Hwang, J.W. Park, Iron and organo-bentonite for the reduction and sorption of trichloroethylene, Chemosphere 58 (2005) 103108. [29] V. Janda, P. Vasek, J. Bizova, Z. Belohlav, Kinetic models for volatile chlorinated hydrocarbons removal by zero valent iron, Chemosphere 54 (2004) 917925. [30] G.A. Loraine, Effects of alcohols, anionic and nonionic surfactants on the reduction of PCE and TCE by zero-valent iron, Water Res. 35 (2001) 14531460. [31] B. Zhu, T. Lim, J. Feng, Inuences of amphiphiles on dechlorination of a trichlorobenzene by nanoscale Pd/Fe: adsorption, reaction kinetics, and interfacial interactions, Environ. Sci. Technol. 42 (2008) 45134519. [32] W. Wang, Z. Jin, T. Li, H. Zhang, S. Gao, Preparation of spherical iron nanoclusters in ethanolwater solution for nitrate removal, Chemosphere 65 (2006) 13961404. [33] Y. Hwang, D. Kim, H. Shin, Mechanism study of nitrate reduction by nano zero valent iron, J. Hazard. Mater. 185 (2011) 15131521.