You are on page 1of 8

Materials Research Bulletin 59 (2014) 341–348

Contents lists available at ScienceDirect

Materials Research Bulletin
journal homepage:

Lead removal by nano-scale zero valent iron: Surface analysis and pH
Nicolás Arancibia-Miranda a, *, Samuel E. Baltazar b , Alejandra García c,d,
Aldo H. Romero e, María A. Rubio a , Dora Altbir b

Facultad de Química y Biología, CEDENNA, Universidad de Santiago de Chile, USACH. Casilla 40, C.P. 33, Santiago,Chile
Departamento de Física and CEDENNA, Universidad de Santiago de Chile, USACH, Av. Ecuador 3493, C.P. 9170124, Santiago, Chile
CIMAV, S.C. Alianza Norte 202, Carretera Monterrey-Aeropuerto Km 10, Apodaca, Nuevo León C.P. 66600, Mexico
Physics and Astronomy Department, University of Texas at San Antonio, One UTSA Circle 78249, San Antonio, TX, USA
Physics Department, West Virginia University, Morgantown, 26506, VA, USA



Article history:
Received 11 April 2014
Received in revised form 22 July 2014
Accepted 23 July 2014
Available online xxx

The use of nano-scale zero valent iron (nZVI) in the removal of Pb2+ from aqueous solution is studied as a
function of pH, evaluating the structural and surface changes of the nZVI, as well as its magnetic
properties after the sorption process. The kinetics of the removal process of Pb2+ by nZVI was studied as a
function of pH, where the pseudo second order (PSO) kinetics model reproduces the experimental
results, with an initial adsorption (h) at pH 4 almost three times greater than at pH 6.0. From the sorption
isotherm results, we find an enhanced sorption capacity as pH is increased. The Langmuir model is in
good agreement with our experimental data, where a maximum sorption capacity is found to be
50.31  2.36 and 32.85  3.87 (mg g1) at pH 6 and 4, respectively, suggesting the formation of new active
sites on the external surface of the nZVI. The XRD results, obtained from the samples after removal of Pb2
, show new mineral phases of nZVI, which can be attributed to Fe and Pb polycrystals. These results
obtained from the samples, before and after Pb2+ sorption at different pH values, indicate that these
values conditioned the surface and morphological changes observed in nZVI, even modifying their
magnetic properties.
ã 2014 Elsevier Ltd. All rights reserved.

Sorption process
Surface reconstruction
Water pollution

1. Introduction
The recent use of nanoparticles for the removal of several
contaminants detected in aqueous systems has brought about an
important development of new methodologies in mineral removal
from water [1], where sorption and degradation capacities have
been evaluated under several scenarios [1–3]. The application of
these particles in this field is mainly due to their physicochemical
characteristics, where the surface area to volume ratio of particles
increases as particle size decreases [1], favoring their ability to
capture and react with other compounds. In recent years, nanoscale zero valent iron (nZVI) has been one of the most studied
materials, due to its versatility and simple synthesis [3–5]. These
particles have high reactivity to adsorb inorganic contaminants
such as CIO
4 , AsO4 , AsO3 , CrO2, Pb , Ba , Co , Cu , and Ni

* Corresponding author at: Facultad de Química y Biología, Universidad de
Santiago de Chile, Casilla 40, C.P. 33 Santiago, Chile. Tel.: +56 2 27181050.
E-mail address: (N. Arancibia-Miranda).
0025-5408/ ã 2014 Elsevier Ltd. All rights reserved.

[6–9] and to degrade organic contaminants present in groundwater [10–12].
Characterization techniques such as HR-TEM and HR-XPS have
established that the nZVI have multiple mechanisms of interaction
with different pollutants, such as adsorption, precipitation, and
redox reactions [4,5,13,14]. Additionally to these processes, the
corrosion of the nanoparticles in aqueous systems, caused by the
presence of oxygen and Fe3+(aq), accelerates the formation of iron
oxide and oxyhydroxide compounds on the surface of the nZVI. The
surface reconstruction changes the sorption capacity of the
nanoparticles, depending on their abundance and the Fe species
generated on the surface of the nZVI [4,15]. Some of the most
typical Fe species found on nZVI are Fe(OH)2, Fe(OH)3, Fe3O4, Fe2O3,
FeOOH, and Fe5HO84H2O, which protect the Fe0 core of the nZVI
against additional chemical attack [13,14]. This reconstruction
process, which depends on several factors such as pH, O2, and Fe3
(aq) concentrations, among others, continues until the total
oxidation of the nZVI occurs [16–18].
In general, the sorbed elements on the surface, or those that are
diffused into the nanoparticles, can be oxidized and reduced
[3,13,14] changing the toxicity of the adsorbed elements [19,20].

and mental retardation among other consequences. is an interesting case to study and to evaluate the superficial and structural changes occurring during the sorption process [21.23]. that occur after the removal of Pb2+. We expect to identify new mineralogical phases of iron and lead. oxygen (c) and lead (d) on the sample. HCl. infertility. . Pb is slightly more electropositive than Fe.14. under different pH conditions.342 N. generated by the oxidation of the nanoparticles in contact with water and the Pb2+. This process leads to the formation of new Pb species. 1. in order to determine possible interaction mechanisms between lead and nZVI.22]. at surface and structural levels. a heavy metal of well-known toxicity and responsible for liver and kidney damage. and NaBH4) are analytical grade from Merck and were used without further purification. The main purpose of this work is to study and to identify the structural and magnetic changes in nZVI. a similar phenomenon recently reported in As(V) and nZVI [13. anemia. 2. Methodology 2. Fig. X-ray diffraction peaks associated with (a) pristine nZVI. The obtained information can be used to understand the interaction between nZVI and several heavy metals while they are present in water. mainly due to the specific interaction among the surface sites of the nZVI (RFe OH). SEM image shows (a) the formation of aggregated iron clusters followed by a distributed concentration of iron (b). (b) nZVI after treatment with Pb at pH 4. Pb2+ in water. In this context. as well as modifications in the magnetic properties of nZVI. NaOH. Additionally we investigate the impact of pH conditions in the kinetics and isotherms of Pb2+ adsorption. Materials The chemical reagents used in the study (FeCl36H2O. 2. lead (Pb). Arancibia-Miranda et al. Elemental mapping of nZVI particles after Pb sorption at pH 4. and (c) treatment with Pb at pH 6. / Materials Research Bulletin 59 (2014) 341–348 described by the following reaction [16]: 2þ Pb Fig. so their interaction with the nZVI is generated by a partial reduction of Pb2+ that can be 0 þ Fe0 ! Pb þ Fe2þ E0 CellðVÞ : 2:8:: This reaction might alter the corrosion process of the nZVI.1.

using oriented aggregate preparations after drying on glass slides the samples suspended in water. For the high resolution transmission electron microscopy analysis.4. The XRD analysis was carried out in a Shimadzu XRD-6000 diffractometer with graphite-monochromated CuKa radiation. the sorption of iron (b) and lead (c) on the structure. / Materials Research Bulletin 59 (2014) 341–348 2. Arancibia-Miranda et al. The resultant solution was centrifuged at 9000 rpm for 5 min. The SEM image of the sample (d) shows a formation of aggregated iron clusters. The concentration of Pb2+ in solution was determined at 5.01 M of NaCl as a background electrolyte. In the case of lead. . 10. SEM micrographs were obtained from an FE-SEM (field emission scanning electron microscope) Nova NanoSEM-200 from FEI Company. The isoelectric point (IEP) was determined by measuring the electrophoretic mobility (EM) of particles on a Zeta Meter ZM-77 apparatus. In order to consider the reactivity of the nanoparticles we have measured their specific surface area by the N2 method of Brunauer–Emmett–Teller (BET). The nZVI particles were stored in a N2-purged desiccator [10]. Fig. pore size was measured by the Barrett. The magnetic response of the samples was investigated with a cryogenic system. SEM. and a sensitivity of 104 emu.2 T.N. The kinetic studies have considered two sets of solutions of 200 mg L1 of Pb2+ in pure water (MilliQ quality) at initial pH values of 4 and 6. leading to a fine black powder product after freeze-drying. and the supernatant solution was replaced by acetone. 20. Magnetization loops were then obtained as a function of the external applied field.01 M NaCl solution and the EM was determined as a function of pH. and Halenda (BJH) analysis of an N2 adsorption/desorption isotherm at 77 K using an automatic analyzer (Quantachrome Nova Station A). a drop of the suspension was deposited onto a holey 343 carbon grid. 3. The elemental mapping identifies (a) the oxygen. The systems were mixed mechanically with glass rods at 300 rpm for 120 min. a uniform distribution is seen over the whole sample. Elemental mapping of nZVI particles after Pb sorption at pH 6. 30. set up in vibrating sample magnetometer (VSM) mode and operated at room temperature with a maximum magnetic field of 1. Characterization of nZVI The structure and surface of nZVI particles were characterized by X-ray diffraction (XRD). Preparation of iron materials The synthesis of nZVI was carried out at room temperature in a 500-mL borosilicate glass flask containing 100 mL of Fe3+ solution. Joyner.63 was reached. The IEP was obtained from the EM versus pH graph as the pH at which EM = 0. Batch experiments A standard batch sorption experiment was carried out in triplicate in order to obtain more reliable results. 2.2. acetone-washing was applied during purification. and HRTEM. The samples were characterized using a JEOL JEM2010F (FEG-TEM) operated at 200 kV with a 0. using 0. adding a NaBH4 solution dropwise with constant mechanical stirring under an N2 atmosphere until an Fe/NaBH4 ratio of 0. 2.3. Energy dispersive microanalysis X-ray (EDX) was obtained by Nova NanoSEM 200 coupled with a microanalysis system Oxford INCA X-Sight Model. Besides this. In order to avoid oxidation of nZVI. An amount of about 100 mg of each sample was suspended in 200 mL of a 0.1 nm lattice resolution.

(a) HRTEM image of Fe nanoparticles before lead sorption. which allowed the determination of the rate at which a given substrate is removed from a surface. 90. 150. 20. (2)): Fig. and 180 min. The sample has a polycrystalline structure with a diameter around 10–20 nm. 120. 5. the collected samples (nZVI-Pb) were dried in a vacuum oven at 50  C and stored in a refrigerator at 4  C for further analysis.1. An inset for low magnetic field is shown in each case for better comparison. and k1 is the pseudo-first order adsorption rate constant (min1). Magnetic hysteresis loop of zero-valent nanoparticles before and after Pb sorption. using 0. The initial concentrations used in the adsorption isotherms were 1. Fig. 5. The graphs show the magnetization behavior of the particles at pH 4 (top) and and at pH 6 (bottom). The pH of the solution was adjusted to the desired pH value using 1 M NaOH or HCl. Sorption kinetics models We studied the kinetic process considering two models. . and 200 mg L1. 50. 150. 100. Reactions proceeded for 24 h at 25  C (unless otherwise specified) in a shaken water bath (200 rpm) kept in the dark by covering with aluminum foil. 10. Adsorption isotherms were produced as a function of the Pb2+ initial concentration. 4. 2. 2. 6. 45. Arancibia-Miranda et al.344 N. The inset shows a magnification of one of the polycrystals on the surface (A zone) and surrounding the iron core (B zone). Pseudo first order equation model (PFO) In this model the kinetic rate equation is (Eq. (1)) dqt ¼ k1 ðqe  qt Þ dt (1) where the solution obtained at the boundary conditions q = 0 and q = qt leads to (Eq. All experiments were performed in triplicate. 70.5. providing information about the specific adsorption within the condition of the reactive sites. logðqe  qt Þ ¼ logðqe Þ  k1 2:303 (2) where qe and qt correspond to the adsorbed amount of lead (mg g1) at equilibrium and at time t. measured by an Orion (model 250 A) pH meter. Electrophoretic mobility of nZVI in the presence and absence of Pb2+ with respect to pH (pH 5–9).01 M NaCl as a background electrolyte. / Materials Research Bulletin 59 (2014) 341–348 Fig. 60. respectively. Finally. which combines the adsorption (ka) and desorption (kd) constants [23]. (b) HRTEM image of nZVI particles after lead sorption at pH 6.5. The residual concentrations of Pb2+ in the supernatant solutions obtained from the sorption studies were determined in a Thermo atomic absorption spectrometer with an air-acetylene flame.

synthesized at nearly neutral conditions. reducing and controlling the oxidation of nZVI. with peaks associated with the presence of Fe3O4. Fig.27]. and FeO(OH) on the surface (A zone in Fig.2 (0.321 66. 2).2.5.N. c) the diffraction patterns reveal the formation of mineral phases of Fe. Fe3O4. compared to the other samples. The kinetic rate equation is written as dqt ¼ k2 ðqe  qt Þ2 dt (3) where k2 is the reaction-rate constant (g mg1 min1). The second case corresponds to the Fe core covered by a highly disordered layer of amorphous Fe oxide/hydroxide degenerated as a byproduct of the corrosion and with a thickness of approximately 5 nm (Fig. The removal of Pb at pH 6 magnifies the thickness of the samples along with an increase of the SBET and a greater distribution of lead seen in the EDX images (Figs. 65.997 0.97 (0.991 0. 4b). At pH 4 (Fig. The second phenomenon is the protecting role of the adsorbed lead at pH 6. and 13. 3 the treatment at pH 6 shows the mapping distribution with 29. In Fig. which is consistent with the observed XRD analysis [25]. Similar results were reported by Manning et al.26] (Fig.160 (0.93 (2. depending on the experimental conditions.90 Pseudo first order qe (mg g1) k1 (min1) r2 RMSE 55. which could explain the increased content of oxygen at pH 4 [28].4 (0.2% (Fe). partially due to the increase of the SBET surface area and the decreased surface charge of the nZVI [4. but also of polycrystals of Pb surrounding the iron core (B zone in Fig. 3. The first one is the formation of Fe oxides and oxyhydroxides as well as Pb oxides. where the characteristic peaks of Fe appear at 2u = 44. Pseudo second order equation model (PSO) In this case the driving force (qe  qt) is proportional to the portion of available active sites on the sorbent [24] (Eq.3% (Fe). in studies of arsenic removal by nZVI [4. 1b) we see the presence of Fe. In the case of the nZVI particles used to capture Pb.04) 0.99 (1. The first one is a core structure corresponding to a highly ordered atomic distribution that can be attributed to the crystalline Fe. and Kanel et al.5. and Pb0 [26]. The different percentage of O obtained for the samples after Pb sorption can be attributed to two phenomena.09 (1.0.284 1 . The combined analysis of XRD and HRTEM confirms the presence of not only iron oxide compounds such as Fe3O4.9% (Pb). EDX images confirm changes on the surface of nZVI particles.t) along with the boundary conditions results in the adsorption equation (Eq.122 (0. Pb-nZVIpH 4. 2 shows the case at pH 4. After Pb sorption.04) 3. The diffractogram of the treated samples at pH 6 shows a lower crystalline degree. and 19. 51. and/or lepidocrocite (g -FeOOH) [4. Integration of the equation between (0. The crystalline structure of the nZVI nanoparticles was confirmed by XRD analysis.08) 0. which are granular structures of chain-like nanoparticles before the removal of Pb that evolve to more irregular structures after both treatments (Figs.87 (2. the coercivity of the nanoparticles is 550 Oe. in agreement with previous results [4. The corrosion by-products determined from the XRD spectra are identified as magnetite (Fe3O4).718 67. FeO(OH) as well as Pb0. Results and discussion 3. without clear presence of other lead compounds. (4)): t 1 1 ¼ þ t qt q2e k2 qe (4) from which the initial adsorption rate is obtained defining h = kqe2 directly from the intercept of the curve.987 0. 1/N  2 i = 1(Ccal  Cexp)2)1/2. confirming the XRD results (Fig.01) 0. Effect of pH on the amount of Pb2+ removed on nZVI. after the sorption of Pb (Fig.979 1.54 (0.0% (O). the coercivity at pH 4 is 140 Oe while at pH 6 it is 1125 Oe. and Pb-nZVIpH 6 were analyzed by SEM and HRTEM. The images obtained by SEM show nanoparticles with diameters around 50–100 nm forming thermodynamically stable chain-like structures (Fig.25.5.81) 2. They can be attributed to the 345 formation of Fe oxides/hydroxides phases on the nZVI evolved.622 Pseudo second order qe (mg g1) k2 (x103g mg1 min1) h(mg g1 min1) r2 RMSE 57. Characterization of nZVI Fig.5. whose origin corresponds to the corrosion process at specific pH and Pb2+ concentration. Standard error for each parameter is included in parenthesis. Cexp = experimental concentration). P RMSE (root mean square of error. 2. XRD analysis revealed differences at each pH. 4b) [26.25. Structural and surface reconstructions in the samples of pristine nZVI. and 82. generating a particular Fe oxide (Fe3O4). The higher saturation magnetization is found when the Table 1 Kinetic parameters predicted from pseudo-first and pseudo second order models. with the new Pb species dominating the surface of nZVI. Arancibia-Miranda et al. 1b–c). 2 and 3). 1a [4. 5 illustrates the magnetic hysteresis of our synthesized nanoparticles before and after lead sorption under an external field at room temperature. 1 shows the diffraction patterns of three samples: pristine nZVI.003) 0. FeO. 7.25].. The coercivity (Hc) and remanence (Mr) of the samples depend on the applied conditions.1.8% (O).13.45 68.8% (Pb). The elemental mapping of Pb-nZVIpH 4 and PbnZVIpH 6 reveal significant differences in the superficial distribution of O and Pb.01) 11. Fig. In the case of the nZVI.18) 72. where the distribution was 27. / Materials Research Bulletin 59 (2014) 341–348 Fig. These results suggest an adsorption enhancement at higher pH values.4 and can be clearly seen in Fig.98) 0. which is higher than the values obtained at pH 6 (480 Oe) and pH 4 (30 Oe).92 (1.7.23) 61. Kinetic parameters pH 4 pH 6 qexp (mg g ) Total Pb2+ removal (%) 59.54 (2. (3)). 1) [3–5]. The experimental data were adjusted following the kinetic models: pseudo first order (PFO) and pseudo second order (PSO). These conditions impact the crystalline degree of the new products [25]. Ccal = calculated concentration. In the case of our initial Fe particles. 4a) [28]. from Fe0 ! Fe2+ ! Fe3+. 1b.26]. respectively. Fe0.001) 0.23) 1.14]. 2 and 3).29]. 58. Pb-nZVIpH4 and Pb-nZVIpH6.

2 and suggesting that a fraction of the offered Pb2+. The adsorption of Pb2+ on the nZVI causes an increase of the net charge of the nZVI as well as of the IEP. 7).02) 0. leads to different interaction mechanisms with Pb2+ and with distinct degrees of affinity [3. the coercivity is decreased due to the formation of other iron oxide phases. and coprecipitation processes. and the lower magnetic response is obtained after Pb sorption at pH 4 and 6 (5. (5)) and Freundlich (Eq.29 (0.26. C(mg L1) is the equilibrium Pb2+ concentration. we observe a positive net charge of the pristine nZVI with an IEP of 7.25. Electrophoretic mobility q ¼ K F C 1=n The electrophoretic mobility. The formation of different corrosion products of nZVI might favor a specific removal mechanism [16. The saturation remanence is also decreased after Pb sorption at pH 4 (1.25]. In this context the nZVI removed the Pb2+ by reduction.87) 0. from neutral to pH 6 and 4. adsorption. At pH 6. 8).0) were considered for the removal of Pb2+ (Fig.09) 3.85 (3.5 and 7. where the sorption capacity (qe) was similar to the experimentally found results. when qt/t approaches 0.2 emu g1) and pH 6 (1.23 (0.0).0 than at pH 4. Adsorption isotherms of Pb2+ to nZVI at two different pH (4.0.25. KL is the Langmuir constant.325 samples are exposed to lower pH values before the sorption process. when adsorbed by the surface groups on the nZVI.29]. In Fig. which could explain the increase of the zeta potential (ZP) at the studied conditions (pH 4. we consider the analysis of the residual root mean square error (RMSE). The results of fitting Freundlich and Langmuir equations to isotherm curves are summarized in Table 2. RMSE (root mean square of error. shifting its pH value to 8.7  0. 3. Effect of pH on the kinetic removal of Pb2+ from nZVI Two different pH values (pH 4. 3 based on the correlation coefficient (R2). (6)) adsorption equations: q¼ qm  K L  C 1 þ KL  C (5) (6) 1 1 where qm (mg g ) is the maximum adsorption capacity. The higher sorption was found at pH 6. In contrast.99) 3. In general.4 emu g1). . where small RMSE values indicate a better fit of the curve [29]. respectively). 1/N  2 i = 1(Ccal  Cexp)2)1/2. Standard error for each parameter is included in parenthesis. as reflected in the low qe values (Table 1) [3.29]. However.991 0. Pb). This parameter is almost three times larger at pH 6.0 and pH 6. promoting an almost anhysteretic response to an external magnetic field.5. the adsorption intensity does not vary in both treatments.26. were measured to determine the changes on the surface charge and the IEP due to the presence of Pb2+. 6). could form inner sphere complexes or new mineralogic phases (PbO. The best description of the experimental data was obtained with the PSO model.34 (0. Arancibia-Miranda et al. If we impose acidic conditions. Cexp = experimental concentration). These products possess IEP values higher than those reported for nZVI [30].4  0. The time to reach equilibrium was close to 60 min in both cases.0 Pb2+ removal is higher (72.31. Effect of pH on Pb2+ adsorption The equilibrium adsorption isotherm data at varying pH were analyzed using the Langmuir (Eq.32]. as well as the pH of the samples. The Langmuir isotherm correlated better than Freundlich with the experimental data (Fig. The formation of new active sites such as RFeOH and 3.25–27]. The Freundlich and Langmuir parameters were obtained by nonlinear least-squares regression analysis. precipitation.005 13.199 0.02) 8. and KF and n are the Freundlich constants.38 (1.0) (Fig. 5 we observe the presence of iron oxides phases on the nanoparticles.0 emu g1.0 and 6.2. 7). Table 1 The application of the PSO model allows the calculation of the values of the initial removal rate of Pb2+ (h) defined as h = k  qe2.004 0.31 (2.891 0. where changes in the mineralogical phase and magnetic behavior are observed [3.23 (0. Ccal = calculated concentration. 3.0 and the sorption parameters fitted from equilibrium (from the Langmuir and Freundlich models) are listed in Table 2.01) 50.4.0 and 6. q(mg g ) is the amount of adsorbed Pb2+. 8. the PFO predicted with lower fit of the curve and high RMSE values. Several reports indicate a partial reduction of Pb occurring in the presence of nZVI as a consequence of the different electronegativity of the involved elements. regardless of the model applied. RFe O OH. while the sample treated at pH 4 reached only 61.346 N.992 0.36) 32.12 (0. / Materials Research Bulletin 59 (2014) 341–348 Table 2 P Related parameters for the adsorption of Pb2+ on nZVI at different pH. Sample nZVI-pH 6 nZVI-pH 4 Langmuir Freundlich KL qmax r2 RMSE KF n r2 RMSE 0. In order to choose a suitable kinetic model to describe the removal of Pb2+. indicating that higher pH values promote a faster and more dramatic surface reconstruction.3. The sorption isotherms of Pb2+ on nZVI under both pH conditions are shown in Fig. This is confirmed by the XRD and VSM results. suggesting a monolayer sorption [4. 6). Fig.2 (Fig.03) 0. 3.5% (Table 1 and Fig. Only the Langmuir curves are shown in Fig.9%). suggesting that the newly formed groups on the surface of nZVI have similar affinities for Pb2+ (Table 2).895 0.

Ind. Q. and Basal Funding for Scientific and Technological Centers under project FB0807. If the pH is increased (6. the structure of the nZVI can show passivation or dissolution. Zhang. C 115 (2011) 24. Boparai. According to the specific pH conditions. Üzüm.Q. such as Ni2+. Hazard. Mater. 148 (2007) 761–767. Clay Sci. Synthesizing nanoscale iron particles for rapid and complete dechlorination of TCE and PCBs. 143–24152. The structural characterization performed with XRD. Charlet. Shahwan. E.0. H.B. 9). Mater. Greneche. Krol. Nanoscale zero valent iron and bimetallic particles for contaminated site remediation. Korte. 3. / Materials Research Bulletin 59 (2014) 341–348 347 Fig. C. or redox reactions (presence of Pb0). These byproducts promote a significant increase of the surface area and. Environ. at the University of Texas. 3. T. affecting stability and sorption capacity. Sethi. I. Special thanks to Prof.F. ^lu. Çelebi. the increase of the removal capacity of the nZVI is given by sorption processes as well as precipitation.R. Arsenic(V) removal from groundwater using nanoscale zerovalent iron as a colloidal reactive barrier material. an increase of pH from 4. Choi. controlled by pH. 2. In the case of metals with high reduction potentials. Kocur. Chem. and 4). Conclusions In this study we have evaluated the structural and superficial changes taking place on nanoparticle zero valent iron under different pH conditions during the removal of Pb2+ from an aqueous solution. [8] O. Choi.S.E. Adv. 43 (2009) 172–181. Sleep. T. Chem. Technol. Chemosphere 35 (1997) 2689–2695.Q. from the International Center for Nanotechnology and Advanced materials (ICNAM). Wang. Several reports have shown the transformations occurring on the surface of the nZVI as a consequence of the sorption of several trace elements (Fig. L. Stoichiometry of Cr(VI) immobilization using nanoscale zerovalent iron (nZVI): a study with high-resolution X-ray photoelectron spectroscopy (HR-XPS). C.0). Water Resour. 51 (2012) 104–122. Eng. H. W. Environ. 11130157. In the case of neutral conditions. N. Scott. Zero-valent iron nanoparticles for abatement of environmental pollutants: materials and engineering aspects. ionic strength and temperature.H. Solid State 31 (2006) 111–122.0 leads to an increase of Pb2+ removal. indicating the application of monolayer coverage of Pb2+ on the nZVI surface. J. Based on the analysis of the results obtained from the characterization techniques it is shown that Pb2+ is removed from the aqueous solution by various physicochemical processes such as adsorption. Perspectives and directions. Cao. [10] C. Hg2+. Belluso. [2] J. [12] F. D. 9). Jortner. 212 (2012) 112–125. Arancibia-Miranda et al. ICM P10-061-F by Fondo de Innovación para la CompetitividadMinecon. W. Besides. W. H. Freyria. A. Sci. Sci. Lieberwirth. Hazard.0 to 6. H. Sci. generating several Fe byproducts such as Fe3O4. regardless of pH. Uzum. Fernando. Zhang.B. 31 (1997) 2154–2156. and 1120356. Nanoscale zero-valent iron: future prospects for an emerging water treatment technology. reduction. B. the removal mechanism is described as a reduction after the adsorption process. Manning. Bonelli. A. The magnetization of Fe nanoparticles after Pb sorption shows different magnetic behavior associated with different concentrations of iron oxides. Celebi.C.0 compared to pH 4. In spite of the reduced magnetic response after Pb sorption. and for facilities and assistance with SEM and HRTEM characterization. 47 (2008) 2131–2139. Conicyt Grant 79090022.N. San Antonio. Ç. Reduction of nitrate to ammonia by zero-valent iron.B. Hallam. Armandi.S. Cheng. EDX and HRTEM indicates that the pH is one of the main factors that modify the surface of the nZVI. Pb2+ can be removed by adsorption. then a highly porous layer of iron oxides and hydroxides is generated. O'Carroll.A.N. R. Yacaman. Li. N. Erog Synthesis and characterization of kaolinite-supported zero-valent iron nanoparticles and their application for the removal of aqueous Cu2+ and Co2+ ions. Removal of arsenic(III) from groundwater by nanoscale zero-valent iron. Rao. which is the main process under acidic conditions (pH 4. E. Chem. [3] D. Reactions of acid orange 7 with iron nanoparticles in aqueous solutions. therefore. 9. Crit.0) [3].5. Erten.R. [9] O. precipitation (formation of polycrystals).R. J.R. Crane. J. g -FeOOH. (5 and 6). B. and a pseudo second order kinetic model was found to describe the experimental data quite accurately. the Pb2+ removal. Appl. in accordance with the higher sorption obtained at pH 6. SBET. Muftikian. or coprecipitation (1. Nanostructured advanced materials. 39 (2005) 1291–1298. 74 (2002) 1491–1506. [6] X. T. Miguel J. 40 (2006) 2045–2050. such as Fe3O4 or FeO. acknowledges the support of the Marie-Curie Intra-European Fellowship. [7] X. [5] S. J. R. Phys. A radiotracer study of the adsorption behavior of aqueous Ba2+ ions on nanoparticles of zero-valent iron. Schematic representation of the possible mechanisms of Pb2+ removal and structural changes on the nZVI. Elliot.M. [11] I. Zhang. Rev. Implications of the use of nZVI in the removal of metals The large spectrum of applications of nZVI as removal agents of different contaminants considers several aspects such as pH. The Langmuir isotherm have shown a better fit than the Freundlich isotherm. Kanel. Cu2+. . Acknowledgments The authors thank the support of FONDECYT under grants 11100439. Garrone. Technol. J. and Pb2+.X. T. Li.W. [4] S.X. Environ. M. enhancing the diffusion process of the elements toward the Fe0 core and therefore increasing the sorption capacity of the nZVI. Res.X. precipitation. iron nanoparticles can still be envisaged as part of a control mechanism for aqueous systems. B. SEM. M. Shahwan. Pure Appl. References [1] R. Technol. coprecipitation and partial reduction (Fig. Depending on pH. 4. Kanel.

J. Shin. Nature 397 (1999) 483–484. Sci. Kirsch.T. Naidu.C. Environ. [17] T. [21] E. Chem. Arancibia-Miranda. R.E. Scott. P. Crane. Res. Popescu. [24] S. Samadi.T. T. Hazard. J. E. H. M. Zhang. 28 (2011) 164–173. Ramos. I. Zhang. Water Res. Colloid. Z.J. Rubio. Desalin. C 116 (2012) 5303–5311. Kaolinite-supported nanoscale zero-valent iron for removal of Pb2+ from aqueous solution: reactivity.H. C. Bréniaux. Raj Mohan. Rev. M. [16] C. Kinetic models of sorption: a theoretical analysis. R. A critical review on the process of contaminant removal in Fe0–H2O systems. [30] M. 256 (2012) 2147–2163. Feller. M. Biochem. B. Guan. Desalination 223 (2008) 212–220. Yang. Xi.A. 153 (2008) 221–228. Arancibia-Miranda et al. D. Arsenic(III) and arsenic(V) reactions with zerovalent iron corrosion products. Rossi. Vasic. Fate of As(V)-treated nano zero-valent iron: determination of arsenic desorption potential under varying environmental conditions by phosphate extraction. B. Baveye. A. New York. [20] L. Stone. Yan. A.K. J. Rahmani.R. R. [15] H. Scott. [28] X. Hunt. C.C. McKay. Magnetite and zero-valent iron nanoparticles for the remediation of uranium contaminated environmental water. J. Environ. Hazard.A.C. Megharaj. Lee. Mater. Coord. Neurodegenerative diseases and exposure to the environmental metals Mn. Bull. Baltazar. M. I. Clin. Chen. Nano-scale metallic iron for the treatment of solutions containing multiple inorganic contaminants. Dong. M.R. M. Adsorption of reactive dye from aqueous solutions by compost. C. Environ. [23] S. Nazemi. Tsoucaris. TEM and XPS study. Koel. [31] G. Sci. Mahalik. Frenkel. P. Naidu. J. McKay.B. Studies on the removal of Pb(II) from wastewater by activated carbon developed from Tamarind wood activated with sulphuric acid.348 N. Environ.E. Technol. Lo. 45 (2011) 3481–3488. 34 (2000) 2564–2569. Technol. A. 29 (2008) 909–920. R.E.I. Surface rearrangement of nanoscale zerovalent iron: the role of pH and its implications in the kinetics of arsenate sorption. Y. Koel. 34 (2000) 735–742.J. Technol. Azizian. nanoscale zero-valent iron. Ho. Chapron. Y. Technol. Aminabad. [19] P. As(III) sequestration by iron nanoparticles: study of solid-phase redox transformations with X-ray photoelectron spectroscopy. Intraparticle reduction of arsenite (As (III)) by nanoscale zerovalent iron (nZVI) investigated with in situ X-ray absorption spectroscopy.X.V. 45 (2010) 1361–1367. Water Res. Amrhein. Noubactep. J. Environ. 2001.B. Chem. Walter. characterization and mechanism. The kinetics of sorption of divalent metal ions onto sphagnum moss peat. Ponder. J. [29] B. K. Mallouk. [25] Y. [27] S. Yan. [22] C. M. S. A. / Materials Research Bulletin 59 (2014) 341–348 [13] W. B. Meikap. Making make-up in ancient Egypt. 35 (2014) 2365–2372.R. M. M. and Hg. J. G. García. M. X. Mater. Manning. Noubactep. Hadi. Hong.A. Altbir. I. Kim.A. Technol. [18] R. Reduction and adsorption of Pb2+ in aqueous solution by nano-zero-valent iron—a SEM.E. Low level environmental lead exposure – a continuing challenge. Lin. Lefebvre. J. Popescu. Rev.A.H. P. 276 (2004) 47–52.N. [26] Y. Mallavarapu. G.C. 186 (2011) 280–287.S. W. R. 36 (2002) 5455–5461. .G. F. 45 (2011) 2931–2942. Dooryhee. Water Treat. Sci. H. Darab. Water Res. A. Richard.M. Charlet. 46 (2012) 7018–7026. N.K. Singh. Martinetto. G. Sahu. J.A.C. Interface Sci. Chemical Properties of Material Surfaces. [32] H. Dickinson. Dekker. Degradation of trichloroethylene by zero-valent iron immobilized in cationic exchange membrane. Crane. B. Yarmoff.M. R. [14] W. 29 (2008) 63–70. 46 (2012) 4071–4080.S. Water Res. T. Remediation of Cr(VI) and Pb(II) aqueous solutions using supported. Kosmulski. Phys. Romero. Mater. Pb. Mohanty.A. Talabot.