Journal of Contaminant Hydrology 114 (2010) 35–42

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Journal of Contaminant Hydrology

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 / j c o n h yd

Reduction of hexavalent chromium by carboxymethyl cellulose-stabilized

zero-valent iron nanoparticles
Qian Wang a, Huijing Qian a, Yueping Yang a,b, Zhen Zhang a, Cissoko Naman a, Xinhua Xu a,⁎
a
Department of Environmental Engineering, Zhejiang University, Hangzhou 310027, PR China
b
Zhejiang Chimey Environment Science & Technology Co., Ltd, Hangzhou 310030, PR China

a r t i c l e i n f o a b s t r a c t

Article history: The reduction of hexavalent chromium or Cr(VI) by zero-valent iron (Fe0) nanoparticles has
Received 5 March 2009 received increasing attention in recent years. However, Fe0 nanoparticles prepared using
Received in revised form 24 February 2010
conventional methods suffered several drawbacks due to their high reactivity towards
Accepted 24 February 2010
Available online 2 March 2010
surrounding media, which led to the formation of much larger flocs and significant loss in
reactivity. To overcome these problems, we synthesized Fe0 nanoparticles by applying water-
soluble carboxymethyl cellulose (CMC) as a stabilizer. CMC-stabilized Fe0 nanoparticles
Keywords:
Hexavalent chromium displayed much less agglomeration but greater Cr(VI) reduced power than those prepared
Iron nanoparticles without a stabilizer. At a dose of 0.15 g L−1, CMC-stabilized Fe0 nanoparticles were able to
Carboxymethyl cellulose reduce 100% of 10 mg L−1 Cr(VI) in minutes. Several factors that may affect the efficiency of Cr
Remediation (VI) removal were investigated. These included the concentration of CMC, the concentration of
Fe0 nanoparticles, the initial Cr(VI) concentration, the pH value, the reaction temperature and
the concentration of the calcium cation in the reaction mixture. Our study suggested that the
introduction of an innocuous stabilizer such as CMC could significantly improve the
performance of Fe0 nanoparticles for environmental remediation applications.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction much less toxic. Indeed, Cr(III) is a required nutrient for

Hexavalent chromium, Cr(VI), is a common contaminant in
soil and groundwater (Vainshtein et al., 2003). It is commonly
found in wastewater from electroplating and metal finishing
processes, pigment manufacturing, tannery facilities, and
chromium mining operations. Cr(VI) is carcinogenic to
human and animals. It can cause dermatitis, rhinitis even lung
cancer and nasopharynx cancer (Fendorf et al., 2000; Costa and
Klein, 2006). In an aqueous environment, Cr(VI) is highly
mobile and can impact large-volume aquifers. The mobile form
of Cr(VI) has the potential for increased exposure and harm to
human health and the environment (Vainshtein et al., 2003;
Costa and Klein, 2006). In contrast, the reduced form of
chromium, Cr(III), is less mobile in the environment and
⁎ Corresponding author. Tel.: +86 571 87951239; fax: +86 571
87952771.
E-mail address: xuxinhua@zju.edu.cn (X. Xu).
humans and animals (Kotas and Stasicka, 2000; Vainshtein et
al., 2003; Costa and Klein, 2006). Hence, the reduction of Cr(VI)
to Cr(III) is environmentally favorable, and can be used to
remediate Cr(VI) contaminated sites.
Much of the research has focused on the remediation of Cr
(VI) and many treatment processes have been developed. For
example, the remediation of Cr(VI) by physicochemical
adsorption has long been investigated (Hideaki et al., 2002;
Bowman, 2003), but its operational cost is high. Moreover, Cr
(VI) is often just transferred, but not removed. Bioremedia-
tion by strains of bacteria (Chen and Hao, 1998) is a cost-
effective alternative to reduce Cr(VI) to Cr(III), but a variety of
bactericidal toxicants (e. g. hydrocarbon) at many waste sites
may limit their growth and effectiveness (Hua and Deng,
2003). Chemical reduction is also known to transform Cr(VI)
to Cr(III) rapidly and effectively. Many reducing agents have
been reported, these include H2S, Fe2+, Fe0, etc (Buerge and
Hug, 1999; Hua and Deng, 2003). Cr(VI) reduction by Fe0

0169-7722/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jconhyd.2010.02.006
36 Q. Wang et al. / Journal of Contaminant Hydrology 114 (2010) 35–42
(Powell et al., 1995; Powell and Puls, 1997; Pratt et al., 1997;
Ponder et al., 2000; Alowitz and Scherer, 2002; Gheju and
Iovi, 2006) appears to be one of the most promising
technologies. Powell et al. (1995) suggested that the
mechanism of Cr(VI) reduction by Fe0 is a cyclic, multiple-
step electrochemical corrosion process and confirmed that
aluminosilicate minerals could enhance the rate of Cr(VI)
reduction. Alowitz and Scherer (2002) evaluated the effect of
the different type of iron metal, the Fe0 area concentration
and the pH value on the removal efficiency of Cr(VI)
reduction by Fe0. Fe0 nanoparticles, due to their extremely
high surface areas, can enhance the reduction efficiencies
remarkably. Typically, Fe0 nanoparticles are prepared by
reducing Fe(II) or Fe(III) in an aqueous solution using a strong
reducing agent (e.g., NaBH4). However, because of their high
surface area and high reactivity, Fe0 nanoparticles prepared
by this approach tend to react rapidly with their surrounding
media (e.g., dissolved oxygen, or water) or agglomerate
rapidly, resulting in the formation of much larger particles
and rapid loss in reactivity (He and Zhao, 2005; Xu and Zhao,
2007). As a result, new processes are being investigated to
prepare stable Fe0 nanoparticles using stabilizers such as
cetylpyridinium chloride (CPC) (Chen et al., 2004), starch (He
and Zhao, 2005), hydrophilic carbon, poly (acrylic acid)
(Schrick et al., 2002, 2004), as well as other surfactants and
polymers (Shen et al., 1999; Sousa et al., 2001; Wu et al.,
2005; Lu et al., 2007; Sun et al., 2007; Saleh et al., 2008;
Tiraferri and Sethi, 2008; Tiraferri et al., 2008; Bai et al., 2009;
Parshetti and Doong, 2009). Recently, carboxymethyl cellu-
lose (CMC) was used as a stabilizing agent for preparing
bimetallic nanoparticles in aqueous media (Raveendran et al.,
2003; Xu and Zhao, 2007).
A range of Fe(0) and Fe(II)-bearing materials can promote
the reduction and precipitation of Cr(VI). The net reactions of
Cr(VI) reduction with Fe0 and co-precipitation of Cr(III) and
Fe(III) can be written as below (Lee et al., 2003):
2− 0 þ 3þ 3þ
CrO4 þ Fe þ 8H →Fe þ Cr þ 4H2 O
3þ 3þ
ð1−xÞFe þ ðxÞCr þ 2H2 O→Feð1 − xÞ Crx OOH↓ þ 3H
To prepare physically more stable and chemically more
reactive Fe0-based nanoparticles, Mallouk et al. employed
carbon nanoparticles and poly (acrylic acid) (PAA) as
supports for iron and bimetallic nanoparticles (Ponder et al.,
2000, 2001; Schrick et al., 2002; Zhu et al., 2006). These
supports prevented iron particles from agglomerating and
thereby prolonged the reactivity of the particles. Generally,
polymers such as CMC, guar gum, chitosan, and PAA provide
steric stabilization that exhibit a larger repulsion force than
electrostatic repulsion (Geng et al., 2009), hence they can
help to stabilize Fe0 nanoparticles (Kanel et al., 2008; Tiraferri
and Sethi, 2008; Tiraferri et al., 2008) and superparamagnetic
ferrofluid (Lin et al., 2005) via carboxylate binding. CMC is a
commercial, environmentally friendly material and has
already been applied for stabilizing Fe0 nanoparticles (Xu
and Zhao, 2007; He et al., 2009).
The primary objective of this work was to prepare a new
class of Fe0 nanoparticles involving the use of an innocuous
stabilizer for the removal of Cr(VI). Specifically, water-soluble
CMC was used as the stabilizer during the preparation of the
Fe0 nanoparticles. The specific aims were (1) to prepare water
dispersed Fe0 nanoparticles stabilized by CMC under inert
conditions; and (2) to characterize the resulting CMC-
stabilized Fe0 nanoparticles with regard to their physical
stability and chemical reactivity for reductive removal of Cr
(VI) from water.
2. Experiments and methods
2.1. Chemicals
All chemicals, such as potassium dichromate (K2CrO4),
water-soluble carboxymethyl cellulose (CMC), ferrous sulfate
(FeSO4·7H2O), sulfuric acid (H2SO4) and acetone were of
analytical reagent grade. Waste iron filings (0.55–0.85 mm)
were obtained from the Machine Factory of Zhejiang Univer-
sity. The commercial Fe0 powder (N98%, size passing through
a mesh screen to maintain their diameter less than 0.075 mm)
was purchased from Jinshan Metallurgical Factory. Both types
of iron were pretreated by washing with acetone and a sulfuric
acid solution (pH = 2), which created fresh sites for oxidation
and made the surface more active. Deionized water was used
for preparing all solutions.
The Fe0 and CMC-stabilized Fe0 nanoparticles were freshly
synthesized before use. They were prepared by following the
methods reported by Wei et al. (2004) and He and Zhao
(2005). In brief, the iron nanoparticles were synthesized by
adding stoichiometric amounts of NaBH4 aqueous solution at
a BH4−/Fe2+ molar ratio of 2.0 dropwise to a 1000 mL three-
necked flask containing FeSO4·7H2O aqueous solution and
0.2% (w/w) CMC with electrical stirring at ambient temper-
ature. Before use, deionized water and the CMC solution were
purged with purified N2 to remove dissolved oxygen. The
ferrous iron was reduced to zero-valent iron according to the
following reaction:
ð1Þ
2þ − 0
FeðH2 OÞ6 þ 2BH4 →Fe ↓ þ 2BðOHÞ3 þ 7H2 ↑ ð3Þ
Cellulose is a carbohydrate consisting of a series of
þ hydroglucose units interconnected by an oxygen linkage
ð2Þ
(known as a beta linkage) to form a linear molecular chain
structure. Cellulose can easily be modified to become CMC by
replacing the native CH2OH group in the glucose unit with a
carboxymethyl group (He et al., 2007), the molecular
structure of CMC is shown below:
Another important reason for selecting CMC is that CMC is
a food-grade ingredient, nontoxic and biodegradable, likely
 Q. Wang et al. / Journal of Contaminant Hydrology 114 (2010) 35–42 37

due to the presence of highly biodegradable –OH, –CO–, and

–COOH groups.

2.2. Batch experiments

The batch experiments for the reduction of Cr(VI) were

performed in the same three-necked flask to which Fe0
nanoparticles were introduced, followed by the addition of
CrO2−
4 aqueous solution. The reaction solution was stirred
under a nitrogen atmosphere to maintain reducing conditions
and periodically sampled by a glass syringe. The samples
were filtered immediately through 0.22 µm membrane filters
before further analyses.
The experimental conditions were as follows: 4.0–10.0 mL
of 1.0 g L−1 Cr(VI) stock solution and deoxygenated deionized
water were added into the flask containing 0.03–0.075 g of
freshly prepared CMC-stabilized Fe0 nanoparticles, the total
reaction volume was 500 mL. The reaction solution was stirred
under a nitrogen atmosphere to simulate an anaerobic
environment in groundwater at 25 °C, the initial pH was 5.5,
and the hydraulic retention time was 1 h. The stirring speed
was 400 rpm. Samples were periodically collected at 0, 2, 5, 15,
and 60 min with glass syringes and the reaction was stopped by
passing the aliquots through 0.22 µm membrane filters, all the
samples were analyzed within 4 h. Conditional experiments
were c onduc ted under the si milar experimen tal
conditions. Table 1 provides the details of the experiment
parameters for the conditional experiments. Fe0 nanoparticles
of different sizes were compared at appropriate concentrations.

2.3. Characterization and analytical methods

Fresh Fe0 nanoparticles (including CMC-stabilized Fe0

nanoparticles) were examined under a JEOL JEM 200CX
transmission electron microscope (TEM) at 180 kV. Prior to
TEM analysis, the particles were dispersed by an ultrasonicator.
Cr(VI) concentrations were determined via the diphenyl
Fig. 1. TEM images of Fe0 nanoparticles prepared (a) without CMC, and (b)
carbazide colorimetric method by measuring the absorbance
with CMC.
at 540 nm using a UV–VIS spectrophotometer. The pH value
was measured by a JENCO-6173 pH meter.

stabilizer. Fig. 1a shows that the resulting particles without

3. Results and discussion
the stabilizer do not appear as discrete nanoscale particles,
rather, they form much bulkier dendritic flocs with varying
3.1. Characterization of both Fe0 nanoparticles
optical density. The size of some denser flocs can be much
larger than 1 μm. This type of aggregation could be attributed
Fig. 1 depicts transmission electron micrographs of the Fe0
to the electrostatic forces between nanoscale particles and
nanoparticles prepared (a) with and (b) without a CMC
small particles, as well as their surface tension interactions
(Cushing et al., 2004; Manning et al., 2007). As a result, a lower
surface area is likely and a poorer reactivity is expected. In
Table 1 contrast, the CMC-stabilized Fe0 nanoparticles shown in
Experimental parameters values. Fig. 1b appear to be clearly discrete and well-dispersed, the
particles are close to spherical in shape, and their sizes range
CMC Fe0 Cr initial pH Temperature Ca2+
concentration nanoparticles concentration from 20 to 100 nm in diameter. Evidently, the presence of
concentration CMC minimized agglomeration of the resulting iron particles
(g L−1) (g L−1) (mg L−1) (°C) (mM) and thus maintained the high surface area and potential
0 / / / / 0 reactivity of the particles. Fig. 1b shows the volume weighted
0.1 0.06 8 4.5 10 1 mean hydrodynamic diameter and size distribution of ZVI
0.3 0.08 10 5.5 15 2 nanoparticles synthesized in the presence of CMC with a fixed
0.5 0.10 15 8.5 25 5 Fe2+ concentration of 0.1 g L−1 and CMC:Fe2+ = 5:1, the
1.0 0.15 20 10.5 35
volume weighted distribution consisted primarily (about
38 Q. Wang et al. / Journal of Contaminant Hydrology 114 (2010) 35–42
80.0%) of particles 50 nm in diameter, and dispersed as a
colloidal suspension in solution. Conversely, in pristine Fe0 as
Fig. 1a, more than 95% of the ZVI particles formed aggregates
that were greater than 300 nm in length.
To further examine the stability of CMC-stablized Fe0
nanoparticles, precipitation experiments were carried out, in
which 20 mL of nanoparticle suspensions (i.e., bare- and
CMC-Fe0 nanoparticles) were transferred from the flask
reactor into 25-mL tubes with tapered bottoms as shown in
Fig. 2. The Fe0 nanoparticles prepared without the CMC
settled at the bottom of the tube in less than 30 min while the
CMC-stabilized Fe0 nanoparticles remained in suspension
over an extended period of time (N15 d) with no noticeable
sedimentation or flocculation (i.e., with stable particle sizes
and solution density). These results further confirmed that
the presence of CMC prevented agglomeration of the
resulting Fe0 nanoparticles and thus maintained the high
surface area and potential reactivity of the particles.
3.2. Effect of CMC concentration on Cr(VI) removal
Four different CMC concentrations were investigated in
this study (while other parameters were fixed and not
changed). Fig. 3a shows that the increasing concentration of
CMC greatly enhanced the removal efficiency when the
concentration of CMC was less than 0.5 g L−1. The removal
percentages of Cr(VI) at different CMC concentrations over a
period of 60 min were 52, 69, 77, 94 and 88%, for CMC
Fig. 2. Sedimentation experiments with two different types of Fe0
nanoparticles. (a) Common Fe0 nanoparticles, and (b) CMC-stabilized Fe0
nanoparticles, CMC = 0.5 g L−1, Fe0 = 0.1 g L−1.
concentrations of 0, 0.1, 0.3, 0.5 and 1.0 g L−1, respectively.
The addition of CMC to Fe0 nanoparticles significantly improved
the Cr(VI) removal efficiency. The removal efficiency is defined
as the fraction of Cr(VI) in the solution during the reaction time
as a fraction of the initial concentration. At a concentration of
1.0 g L−1 of CMC added, a lower removal efficiency was
observed. It is likely that the CMC occupied a part of the surface
of the Fe0 nanoparticles at that concentration, thus inhibiting
the reaction.
3.3. Effect of Fe0 nanoparticle concentrations on Cr(VI) removal
Four CMC–Fe0 nanoparticle concentrations were employed
in this study. Fig. 3b shows that increasing the concentration of
Fe0 nanoparticles greatly enhanced the Cr(VI) removal
efficiency. With Fe0 nanoparticles concentration increasing
from 0.06 to 0.08, 0.10 and 0.15 g L−1, the ratio of Fe0:Cr
changed from 6:1 to 8:1, 10:1 and 15:1. 100% of Cr(VI) was
removed when the Fe0 nanoparticles mass concentration was
0.15 g L−1, but only 67% was removed when the mass
concentration was 0.06 g L−1 over a 60 min period. When the
reaction proceeded, the pH quickly rose from 5.5 to between 6.0
and 6.3, and remained basically unchanged in the next reaction.
It is believed that the Cr(VI) reductive reaction occurs on the Fe0
nanoparticles' surfaces. As the Fe0 nanoparticles mass concen-
tration increases, the reactive Fe sites increase proportionally,
which lead to the increase of Cr(VI) removal efficiency.
3.4. Effect of initial Cr(VI) concentration on Cr(VI) removal
Aqueous Cr(VI) concentrations in the batch reactors at
room temperature (25 °C) as a function of elapsed time, with
different initial Cr(VI) concentrations, are shown in Fig. 3c.
The results show that for initial Cr(VI) concentrations
between 8 and 20 mg L−1, Cr(VI) removal efficiencies
decreased with increasing initial Cr(VI) concentration. The
removed fraction was 41% at a concentration of 20 mg L−1,
and 98% at the lowest initial concentration of 8 mg L−1. The
optimal mass ratio of Fe0 nanoparticles to Cr(VI) is about
10:1. The final removal rate of Cr(VI) decreased with the
increase of initial Cr(VI) concentration with the same amount
of the addition of CMC-stabilized Fe0 nanoparticles, but the
absolute removal amount increased with increasing initial Cr
(VI) concentration.
3.5. Effect of the initial pH values on Cr(VI) removal
Preliminary experiments indicated that Cr(VI) reduction
was very fast under acidic conditions (e.g., pH 4.5), but
proceeded slowly when the pH was increased up to 10.5. As
shown in Fig. 3d, the Cr(VI) removal efficiency increased
significantly with decreasing pH. When Cr(VI) was intro-
duced, the pH was changed quickly with the different intial
pH, and remained basically unchanged in the next reaction.
The final pH after the 60 min reaction were 5.9, 6.2, 8.6 and
10.5, for initial pH of 4.5, 5.5, 8.5 and 10.5, respectively. Acidic
conditions would accelerate the corrosion of CMC–Fe0, thus
enhancing Cr(VI) reduction. In the initial 5 min, Cr(VI)
removal was rapid for pH values below 5.0. It indicates that
the Fe0 nanoparticles have a high reactivity. In contrast, the
plots for pH N 8 show a less rapid removal. This may be
 Q. Wang et al. / Journal of Contaminant Hydrology 114 (2010) 35–42 39

Fig. 3. Factors influencing the Cr(VI) removal efficiency by CMC-stabilized Fe0 nanoparticles. (a) CMC concentration changes, Fe0 = 0.1 g L−1, CMC = 0–1.0 g L−1,
Cr(VI) = 10 mg L−1, pH = 5.5, T = 25 °C, ω = 400 rpm; (b) Fe0 nanoparticles concentration changes, Fe0 = 0.06–0.15 g L−1, CMC:Fe0 = 5:1, Cr(VI) = 10 mg L−1,
pH = 5.5, T = 25 °C, ω = 400 rpm; (c) initial Cr(VI) concentration changes, Fe0 = 0.1 g L−1, CMC = 0.5 g L−1, Cr(VI) = 8–20 mg L−1, pH = 5.5, T = 25 °C,
ω = 400 rpm; (d) pH changes, Fe0 = 0.1 g L−1, CMC = 0.5 g L−1, Cr(VI) = 10 mg L−1, pH= 4.5–10.5, T = 25 °C, ω = 400 rpm; (e) temperature changes, Fe0 = 0.1 g L−1,
CMC = 0.5 g L−1, Cr(VI)= 10 mg L−1, pH= 5.5, T = 10–35 °C, ω = 400 rpm.

because of the formation of mixed Fe and Cr oxyhydroxides at
high pH values on the iron surfaces (Powell et al., 1995; Lee
et al., 2003). The near plateau segment of the plots after
60 min was probably due to the passivation of the surface
with the consequent loss of reactivity (Rivero-Huguet, and
Marshall, 2009a,b; Wu et al., 2009). This is also in accordance
with the stoichiometry of this reaction (Eq. (1)) which
requires 8 mol of hydrogen ions for each mol of Cr(VI) and is
highly dependent on H+ concentration.
3.6. Effect of the reaction temperature on Cr(VI) removal
The effect of the reaction temperature on the reduction of
Cr(VI) by CMC-stabilized Fe0 nanoparticles was examined at
40 Q. Wang et al. / Journal of Contaminant Hydrology 114 (2010) 35–42
pH 5.5 and an initial Cr(VI) concentration of 10 mg L−1, for
temperature values ranging from 10 to 35 °C, using a
temperature-controlled water bath. The results, presented
in Fig. 3e, show an important dependence of the Cr(VI)
removal efficiencies on the reaction temperature. The Cr(VI)
removal efficiency is 97% at 35 °C, but just 75% at 10 °C.
3.7. Comparison of different types of Fe0 nanoparticles
Fig. 4 shows that the removal of Cr(VI), especially for Fe0
nanoparticles and CMC-stabilized Fe0 nanoparticles, was rapid
in the first minutes. This indicates that the predominant
mechanism for the removal of Cr(VI) is most likely due to the
adsorption to the Fe0 nanoparticles surface rather than the
reductive transformation (Geng et al., 2009). After the first
minutes till the end of the experiment, the Cr(VI) concentration
decreased gradually. In aqueous solutions, Fe0 nanoparticles
will react with water to generate Fe(II) which then reacts with
Cr(VI) rapidly (Kieber and Helz, 1992; Kendelewicz et al., 2000)
resulting in the disappearance of Cr(VI) from water in the
second phase(Geng et al., 2009). The removal efficiency was
just 8% and 9% for Fe0 filings and powder after 60 min, but was
22% and 94% for Fe0 nanoparticles and CMC-stabilized Fe0
nanoparticles, respectively. CMC-stabilized Fe0 nanoparticles
had a greater reactivity than Fe0 nanoparticles, and Fe0
nanoparticles had a greater reactivity than Fe0 powder. Fe0
filings had the least reactivity. The comparison shows that Fe0
nanoparticles had a greater removal efficiency than Fe0 filings
or powder, but the removal of Cr(VI) from the solution ceased
quickly, this may be due to aggregation. The CMC-stabilized Fe0
nanoparticles apparently did not aggregate as much, yielding a
much increased removal efficiency. It has been proposed that
Fe0 nanoparticles reduce Cr(VI) primarily to Cr(III). Then Cr(III)
can also precipitate as Fe(III)–Cr(III) hydroxides on the Fe0
nanoparticles surface. The formation of this surface passivation
layer on Fe0 nanoparticles accordingly blocked Cr(VI) reduction
(Alowitz and Scherer, 2002). For the CMC-stabilized Fe0
nanoparticles system, CMC, can inhibit aggregation of the iron
nanoparticles and possibly inhibit the formation of Fe(III)–Cr
(III) precipitation, as was reported for chitosan by Geng et al.
2009.
Fig. 4. Comparison of different Fe0 types on the Cr(VI) removal efficiency,
CMC = 0.5 g L−1, Fe0 = 0.1 g L−1, CMC:Fe0 = 5:1, Cr(VI) = 10 mg L−1,
pH = 5.5, T = 25 °C, ω = 400 rpm.
3.8. Effect of Ca2+ on Cr(VI) removal
Four different Ca2+ concentrations were studied in this
study. Fig. 5 shows that the increased Ca2+ concentration has
an obvious inhibitory effect on Cr(VI) removal. The removal
efficiencies of Cr(VI) at different Ca2+ concentrations in
60 min were determined to be 94, 47, 56 and 61%, for Ca2+
concentrations of 0, 1, 2 and 5 mM, respectively. The probable
reason was with the increasing of Ca2+ concentration in the
solution, Na+ ions are replaced by the divalent cations,
resulting in CMC-metal precipitates, which accordingly
blocked the Cr(VI) reduction (He and Zhao, 2007). The
concentration of Ca2+ further increased, thus may lead to the
formation of Ca(OH)2 and the absorption of Cr(VI) by Ca
(OH)2 may also take place.
3.9. Electrochemical analysis of the reaction process
The standard reduction potentials of E Fe(II)/Fe(0) and E Cr
are −0.44 and 1.33 V, respectively. When mixed
(VI)/Cr(III)
with Cr2O2− 0
7 , Fe would be corroded and dissolved, causing
the reduction of Cr(VI) to Cr(III). The standard reduction
potential of E Cr(III)/Cr(0) is −0.74 V, which is lower than that of
Fe0. This suggests that the Cr(III) or Cr(III) hydroxide might be
the steady product in the reaction. In fact, several investiga-
tors have reported that the removal mechanism involves the
reduction of highly soluble Cr2O2− 7 to sparingly soluble Cr(III)
compounds at the surface of the iron (Powell et al., 1995; Lee
et al., 2003). Spectroscopic data have also shown that Cr(OH)3
and mixed Cr(III)/Fe(III) hydroxides are precipitated on the
iron surface (Powell et al., 1995; Pratt et al., 1997; Ponder
et al., 2000). The net reactions of Cr(VI) reduction with Fe0
and the co-precipitation of Cr(III) and Fe(III) could be
expressed by Eqs. (1) and (2). No dissolved Cr(III) was
detected during the reaction, which suggests that all the Cr
(III) was co-precipitated with Fe(III). This observation is
consistent with those reported previously (Pratt et al., 1997;
Williams and Scherer, 2001; He and Trainas, 2005).
Insight into the process of Cr(VI) removal can also be
evaluated by determining the reduction potential E and pH
values in solution. The E and pH values of the Cr2O2− 7 solution
(0.1 mM) were 0.239 V and 7.00, respectively. The reduction
Fig. 5. Effect of Ca2+ on the Cr(VI) removal efficiency, CMC = 0.5 g L−1,
Fe0 = 0.1 g L−1, CMC:Fe0 = 5:1, Cr(VI) = 10 mg L−1, pH = 5.5, T = 25 °C,
ω = 400 rpm.
 Q. Wang et al. / Journal of Contaminant Hydrology 114 (2010) 35–42
potential E decreased with increasing initial pH in the
reaction, which indicates that Cr(VI) would be converted to
Cr(OH)3 gradually. After achieving its minimum, E increased
with the decreasing pH due to the likely formation of Cr(III)/
Fe(III) hydroxides. These would cover the surface of Fe0
nanoparticles and reduce their activity. The reaction was in
the sample area where the Cr(OH)3 was dominant. Based on
the afore-mentioned observation and previously documented
results (Pratt et al., 1997; Williams and Scherer, 2001; He and
Trainas, 2005), it can be concluded that iron hydroxide and
chromium hydroxide could be the final and predominant
products of Cr(VI) reduction by CMC-stabilized Fe 0
nanoparticles.
4. Conclusions
The reduction of Cr(VI) by CMC-stabilized Fe0 nanoparti-
cles was studied using potassium dichromate (K2CrO4) as the
model contaminant. The concentration of CMC-stabilized Fe0
nanoparticles had a significant effect on the reduction of Cr
(VI). When the mass ratio of Fe0 to Cr(VI) was about 10:1, a
maximum Cr(VI) removal efficiency of 100% was achieved.
The reaction occurred within a broad pH range and the
reaction efficiency increased significantly with decreasing
initial pH. The CMC-stabilized Fe0 nanoparticles exhibited a
higher removal efficiency than those prepared without a
stabilizer because the CMC acted as a good dispersant to prevent
Fe0 nanoparticles from agglomerating. The electrochemical
analysis of the reaction process suggested that iron hydroxide
and chromium hydroxide should be the final and predominant
products of Cr(VI) reduction by Fe0 nanoparticles. This study
demonstrated that Fe0 nanoparticles, especially those stabilized
by CMC, could lead to a high removal efficiency for applications
such as in-situ remediation of Cr(VI)-contaminated soils and
groundwater.
Acknowledgements
The authors are grateful for the financial support of the
Zhejiang Provincial Natural Science Foundation of China (No.
R5090033), the Zhejiang Provincial Water Pollution Control
and Management Project of China (2008C13007-1) and the
National Water Pollution Control and Management Project of
China (2008ZX07101-006).
References
Alowitz, M.J., Scherer, M.M., 2002. Kinetics of nitrate, nitrite, and Cr(VI)
reduction by iron metal. Environ. Sci. Technol. 36, 299–306.
Bai, X., Ye, Z.F., Qu, Y.Z., Li, Y.F., Wang, Z.Y., 2009. Immobilization of nanoscale
Fe0 in and on PVA microspheres for nitrobenzene reduction. J. Hazard.
Mater. 172, 1357–1364.
Bowman, R.S., 2003. Applications of surfactant-modified zeolites to envi-
ronmental remediation. Micropor. Mesopor. Mat. 61, 43–56.
Buerge, I.J., Hug, S.J., 1999. Influence of mineral surfaces on chromium(VI)
reduction by iron(II). Environ. Sci. Technol. 33, 4285–4291.
Chen, J.M., Hao, O.J., 1998. Microbial chromium(VI) reduction. Critical Rev.
Environ. Sci. Teechnol. 28, 219–251.
Chen, S.S., Hsu, H.D., Li, C.W., 2004. A new method to produce nanoscale iron
for nitrate removal. J. Nanopart Res. 6, 639–647.
Costa, M., Klein, C.B., 2006. Toxicity and carcinogenicity of chromium
compounds in humans. Crit. Rev. Toxicol. 36, 155–163.
Cushing, B.L., Kolesnichenko, V.L., O'Connor, C.J., 2004. Recent advances in the
liquid-phase syntheses of inorganic nanoparticles. J. Chem. Rev. 104 (9),
3893–3946.
41
Fendorf, S., Wielinga, B.W., Hansel, C.M., 2000. Chromium transformations in
natural environments: the role of biological and abiological processes in
chromium(VI) reduction. Int. Geol. Rev. 42, 691–701.
Geng, B., Jin, Z.H., Li, T.L., Qi, X.H., 2009. Preparation of chitosan-stabilized Fe0
nanoparticles for removal of hexavalent chromium in water. Sci. Total
Environ. 407, 4994–5000.
Gheju, M., Iovi, A., 2006. Kinetics of hexavalent chromium reduction by scrap
iron. J. Hazard. Mater. B135, 66–73.
He, Y.T., Trainas, S.J., 2005. Cr(VI) reduction and immobilization by magnetite
under alkaline pH conditions: the role of passivation. Environ. Sci.
Technol. 39, 4499–4504.
He, F., Zhao, D., 2005. Preparation and characterization of a new class of
starch-stabilized bimetallic nanoparticles for degradation of chlorinated
hydrocarbons in water. Environ. Sci. Technol. 39, 3314–3320.
He, F., Zhao, D., 2007. Manipulating the size and dispersibility of zerovalent
iron nanoparticles by use of carboxymethyl cellulose stabilizers. Environ.
Sci. Technol. 41, 6216–6221.
He, F., Zhao, D., Liu, J., Roberts, C.B., 2007. Stabilization of Fe–Pd nanoparticles
with sodium carboxymethyl cellulose for enhanced transport and
dechlorination of trichloroethylene in soil and groundwater. Ind. Eng.
Chem. Res. 46, 29–34.
He, F., Zhang, M., Qian, T.W., Zhao, D.Y., 2009. Transport of carboxymethyl
cellulose stabilized iron nanoparticles in porous media: column experi-
ments and modeling. J Colloid. Interface Sci. 334, 96–102.
Hideaki, Y., Toshiiyuki, Y., Takashi, T., 2002. Adsorption of chromate and arsenate
by amino-functionalized MCM-41 and SBA-1. Chem. Mater. 14, 4603–4610.
Hua, B., Deng, B., 2003. Infulences of water vapor on Cr(VI) reduction by
gaseous hydrogen sulfide. Environ. Sci. Technol. 37, 4771–4777.
Kanel, S.R., Goswami, R.R., Clement, T.P., Barnett, M.O., Zhao, D., 2008. Two
dimensional transport characteristics of surface stabilized zero-valent
iron nanoparticles in porous media. Environ. Sci. Technol. 42, 896–900.
Kendelewicz, T., Liu, P., Doyle, C.S., Brown, G.E., Nelson, E.J., Chambers, S.A.,
2000. Spectroscopic study of the reaction of aqueous Cr(VI) with Fe3O4
(111) surfaces. Surf. Sci. 469, 144–163.
Kieber, R.J., Helz, G.R., 1992. Indirect photoreduction of aqueous chromium
(VI). Environ. Sci. Technol. 26, 307–312.
Kotas, J., Stasicka, Z., 2000. Chromium occurrence in the environment and
methods of its speciation. Environ. Pollut. 107, 263–283.
Lee, T., Lim, H., Lee, Y., Park, J., 2003. Use of waste iron metal for removal of Cr
(VI) from water. Chemosphere 53, 479–485.
Lin, C.L., Lee, C.F., Chiu, W.Y., 2005. Preparation and properties of poly(acrylic
acid) oligomer stabilized superparamagnetic ferrofluid. J. Colloid
Interface Sci. 291, 411–420.
Lu, A.H., Salabas, E.L., Schuth, F., 2007. Magnetic nanoparticles: synthesis,
protection, functionalization, and application. Angew. Chem. Int. Edit. 46,
1222–1244.
Manning, B.A., Kiser, J.R., Kwon, H., Kanel, S.R., 2007. Spectroscopic
investigation of Cr(III)- and Cr(VI)-treated nanoscale zerovalent iron.
Environ. Sci. Technol. 41, 586–592.
Parshetti, G.K., Doong, R., 2009. Dechlorination of trichloroethylene by Ni/Fe
nanoparticles immobilized in PEG/PVDF and PEG/nylon 66 membrane.
Water Res. 43, 3086–3094.
Ponder, S.M., Darab, J.G., Mallouk, T.E., 2000. Remediation of Cr(VI) and Pb(II)
aqueous solutions using supported, nanoscale zero-valent iron. Environ.
Sci. Technol. 34, 2564–2569.
Ponder, S.M., Darab, J.G., Bucher, J., Caulder, D., Craig, I., Davis, L., Edelstein, N.,
Lukens, W., Nitsche, H., Rao, L., Shuh, D.K., Mallouk, T.E., 2001. Surface
chemistry and electrochemistry of aqueous metal contaminants. Chem.
Mater. 13, 479–486.
Powell, R.M., Puls, R.W., 1997. Proton generation by dissolution of intrinsic or
augmented aluminosilicate minerals for in situ contaminant remediation
by zero-valence-state iron. Environ. Sci. Technol. 31, 2244–2251.
Powell, R.M., Puls, R.W., Hightower, S.K., Sabatini, D.A., 1995. Coupled iron
corrosion and chromate reduction: mechanisms for subsurface remedi-
ation. Environ. Sci. Technol. 29, 1913–1922.
Pratt, A.R., Blowes, D.W., Ptacek, C.J., 1997. Products of chromate reduction on
proposed subsurface remediation material. Environ. Sci. Technol. 31,
2492–2498.
Raveendran, P., Fu, J., Wallen, S.L., 2003. Complete ‘green’ synthesis and
stabilization of metal nanoparticles. J. Am. Chem. Soc. 125, 13940–13941.
Rivero-Huguet, M., Marshall, W.D., 2009a. Reduction of hexavalent chromi-
um mediated by micro- and nano-sized mixed metallic particles. J.
Hazard. Mater. 169, 1081–1087.
Rivero-Huguet, M., Marshall, W.D., 2009b. Reduction of hexavalent chromium
mediated by micron- and nano-scale zero-valent metallic particles. J.
Environ. Monit. 11, 1072–1079.
Saleh, N., Kim, H.J., Phenrat, T., Matyjaszewski, K., Tilton, R.D., Lowry, G.V.,
2008. Ionic strength and composition affect the mobility of surface-
modified Fe0 nanoparticles in water-saturated sand columns. Environ.
Sci. Technol. 42, 3349–3355.
42 Q. Wang et al. / Journal of Contaminant Hydrology 114 (2010) 35–42
Schrick, B., Blough, J.L., Jones, A.D., Mallouk, T.E., 2002. Hydrodechlorination
of trichloroethylene to hydrocarbons using bimetallic nickel-iron
nanoparticles. Chem. Mater. 14, 5140–5147.
Schrick, B., Hydutsky, B.W., Blough, J.L., Mallouk, T.E., 2004. Delivery vehicles
for zerovalent metal nanoparticles in soil and groundwater. Chem.
Mater. 16, 2187–2193.
Shen, L., Laibinis, P.E., Hatton, T.A., 1999. Bilayer surfactant stabilized magnetic
fluids: synthesis and interactions at interfaces. Langmuir 15, 447–453.
Sousa, M.H., Tourinho, F.A., Depeyrot, J., da Silva, G.J., Lara, M.C.F.L., 2001.
New electric double-layered magnetic fluids based on copper, nickel, and
zinc ferrite nanostructures. J. Phys. Chem. B 105, 1168–1175.
Sun, Y.P., Li, X.Q., Zhang, W.X., Wang, H.P., 2007. A method for the
preparation of stable dispersion of zero-valent iron nanoparticles.
Colloids Surf., A Physicochem. Eng. Aspects 308, 60–66.
Tiraferri, A., Sethi, R., 2008. Enhanced transport of zerovalent iron
nanoparticles in saturated porous media by guar gum. J. Nanopart. Res.
11, 635–645.
Tiraferri, A., Chen, K.L., Sethi, R., Elimelech, M., 2008. Reduced aggregation
and sedimentation of zero-valent iron nanoparticles in the presence of
guar gum. J. Colloid Interface Sci. 324, 71–79.
Vainshtein, M., Kuschk, P., Mattusch, J., Vatsourina, A., Wiessner, A., 2003.
Model experiments on the microbial removal of chromium from
contaminated groundwater. Water Res. 37, 1401–1405.
Wei, J.J., Xu, X.H., Liu, Y., 2004. Kinetics and mechanism of dechlorination of
o-chlorophenol by nanoscale Pd/Fe. Chem. Res. Chin. Univ. 20, 73–76.
Williams, A.G.B., Scherer, M.M., 2001. Kinetics of Cr(VI) reduction by
carbonate green rust. Environ. Sci. Technol. 35, 3488–3494.
Wu, L., Shamsuzzoha, M., Ritchie, S.M.C., 2005. Preparation of cellulose
acetate supported zero-valent iron nanoparticles for the dechlorination
of trichloroethylene in water. J. Nanopart. Res. 7, 469–476.
Wu, Y.J., Zhang, J.H., Tong, Y.F., Xu, X.H., 2009. Chromium (VI) reduction in
aqueous solutions by Fe3O4-stabilized Fe0 nanoparticles. J. Hazard.
Mater. 172, 1640–1645.
Xu, Y.H., Zhao, D.Y., 2007. Reductive immobilization of chromate in water
and soil using stabilized iron nanoparticles. Water Res. 41, 2101–2108.
Zhu, B.W., Lim, T.T., Feng, J., 2006. Reductive dechlorination of 1, 2, 4-
trichlorobenzene with palladized nanoscale Fe0 particles supported
on chitosan and silica. Chemosphere 65, 1137–1146.