Chemical Engineering Journal 173 (2011) 480–485

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Chemical Engineering Journal

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

Removal of hexavalent chromium in aquatic solutions by iron nanoparticles

embedded in orange peel pith
Gustavo López-Téllez a , Carlos E. Barrera-Díaz a , Patricia Balderas-Hernández a,∗ , Gabriela Roa-Morales a ,
Bryan Bilyeu b
a
Centro Conjunto de Investigación en Química Sustentable UAEM–UNAM, Carretera Toluca-Atlacomulco, km 14.5, Unidad El Rosedal, C.P. 50200, Toluca, Estado de México, México,
Mexico
b
Department of Chemistry, Xavier University of Louisiana, Drexel Drive, Box 22, New Orleans, LA 70125, USA

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

Article history: The aim of this work was to create a biocomposite which coupled the reducing capability of iron nanopar-
Received 7 June 2011 ticles with the adsorption capacity of cellulose to effectively remove hexavalent chromium from industrial
Received in revised form 2 August 2011 wastewater. The iron nanoparticles were synthesized on the orange peel pith using a simple redox precip-
Accepted 4 August 2011
itation reaction to ensure the biocomposite was inexpensive and easy to produce. The nanoparticles were
characterized for size, composition, oxidation state, and distribution before and after the Cr(VI) expo-
Keywords:
sure. The nanoparticles were mostly 20 × 80 nm tubular shapes, but there were also some octahedral
Iron oxide nanoparticles
crystals around 20–40 nm. The biocomposite with the nanoparticles exhibited twice the Cr(VI) removal
Orange peel
Chromium removal
of the unmodified orange peel pith and also possesses over twice the adsorption capacity −5.37 mg/g vs.
1.90 mg/g.
© 2011 Published by Elsevier B.V.

1. Introduction orange peel [10–12], microorganisms [13,14] and several waste

Among heavy metals hexavalent chromium is well known for
its toxicity and carcinogenicity, as well as being a strong oxidiz-
ing agent which causes irritation of animal and plant tissues [1].
According to the US agency for toxic substances and disease reg-
istry (ATSDR), Cr(VI) primarily occurs in industrial wastewater as a
result of processes involving metal and mineral processing, leather
tanning, textile processing, and electroplating processes.
Traditional Cr(VI) removal involves lowering the pH of the
wastewater and adding a reducing agent, then raising the pH to
precipitate the Cr(III) as an oxide or hydroxide. However, this
technology is costly and the sludge disposal is an environmen-
tal problem. Therefore, new ways of removing metal ions from
wastewater are of great interest. Among these, adsorption tech-
niques represent a promising technology [2,3]. A key factor for
implementing a technology is cost; a sorbent can be considered
a low-cost material if it requires little processing and it is abundant
in nature.
In the case of Cr(VI) removal, several biosorbents have been
studied such as treated sawdust [4], Opuntia [5], Tamarindus indica
[6], wheat bran [7], agricultural waste [8], eucalyptus bark [9],
∗ Corresponding author.
E-mail address: patbh2003@yahoo.com.mx (P. Balderas-Hernández).
products [15–18]. Although, reasonable removal percentages have
been achieved, they seem only effective at low Cr(VI) concen-
trations. Therefore, new studies are being done with modified
biosorbents in hopes of increasing the removal capacity which will
encourage industrial use.
On the other hand, several studies have evaluated the traditional
Cr(VI) reduction using ferrous ion [19–21]. Recently, nanoparti-
cles of zero valent iron (nZVI) have been used for enviromental
remediation [22], and there is also research specifically concerning
the removal of hexavalent chromium using nZVI [23]. One of the
usual methods consists of injecting the nanoparticles directly into
the effluent, but the subsequent separation is difficult and time
consuming. These particles, supported in a solid matrix such as
activated carbon or zeolite, enhance the effectiveness of the iron
nanoparticles [24] and make separation from the effluent simple.
Indeed, nZVI supported in a polymeric resin showed better removal
of Cr(VI) and Pb(II) when compared to unsupported nZVI and to
commercial iron powders [25].
The present work focuses on the use of orange peel pith as
a support for iron and iron oxide nanoparticles for the removal
of Cr(VI). Since orange peel is a cheap, renewable, biodegradable
and readily available material often considered as waste [10,11],
its advantage over synthetic materials such as polymers is enor-
mous and contributes to the actual trend of green chemistry. The
nanoparticles are synthesized on the substrate using a simple

1385-8947/$ – see front matter © 2011 Published by Elsevier B.V.

doi:10.1016/j.cej.2011.08.018
 G. López-Téllez et al. / Chemical Engineering Journal 173 (2011) 480–485
precipitation reaction. In addition to characterizing the adsorption
behavior compared to unmodified orange peel, the biocomposite
and the embedded nanoparticles before and after the sorption were
characterized for particle size, composition, and chemical oxidation
state.
2. Materials and methods
2.1. Preparation of biomass
Orange peel samples of about 5 mm × 5 mm squares were
treated for 3 h with 5% ethanol to remove the color, then triple
rinsed with deionized water. Afterwards, they were dried under
vacuum in a desiccator for 24 h at room temperature (25 ◦ C), then
milled and sieved through a no. 40 mesh (420–600 ␮m). The pow-
der was stored under vacuum until use.
2.2. Preparation of biocomposite
A mixture of 0.6 g orange peel powder and 15 mL of 1 × 10−2 M
iron(II) acetate was stirred while 1 × 10−2 M sodium borohydride
was added dropwise. Afterwards, the mixture was stirred for an
additional 20 min, filtered, washed five times in ethanol, and dried
at room temperature for 48 h in a homemade desiccator.
2.3. Effect of pH
In order to evaluate the effect of pH on the adsorption capacity of
the biomass and the biocomposite, batch studies were performed
on each at 7 pH values between 1 and 7. This pH selection was
selected because a redox reaction between iron and Cr(VI) species
was expected and is favored at low values of pH [26]. For each
material, 25 mg of sorbent was added to 7 test tubes with 5 mL
of a 20 mg/L Cr(VI) solution which had been adjusted to pH values
between 1 and 7 with dilutions of concentrated sulfuric acid or 5 M
sodium hydroxide.
2.4. Effect of concentration on adsorption effectiveness
Batch studies were performed to determine the effectiveness
of the biomass and the biocomposite at five different initial con-
centrations of Cr(VI) solutions (10, 20, 30, 40, and 50 mg/L). For
each concentration, 25 mg of sorbent was added to 3 test tubes
with 5 mL of Cr(VI) solution, the pH used was 1 according to the
results obtained from the effect of pH studies, then left for a con-
tact time of 60 min in order to obtain the maximum adsorption
Fig. 1. Kinetics of the Cr(VI) removal at initial concentration Cr(VI) of (a) 10 mg/L, (b) 20 mg/L. pH 1, T = 25 ◦ C, biocomposite and orange peel quantities of 25 mg each and
after 60 min of equilibrium time.
481
capacity. The mixtures were filtered and the supernatant analyzed
for Cr(VI) concentration.
2.5. Chromium adsorption kinetics and adsorption isotherms
Batch studies were performed to determine the adsorption
kinetics and the sorbent adsorption isotherms in a series of test
tubes with 25 mg of sorbent (biomass or biocomposite) and 5 mL
of chromium solution, according to the results obtained from the
effect of pH studies an optimum pH of 1 was selected, since at that
pH the maximum adsorption capacity was obtained. The mixtures
were filtered and the supernatant analyzed for Cr(VI) concentra-
tion. In the kinetics experiments, both sorbents were evaluated
in 10 and 20 mg/L Cr(VI) solutions in 5–10 min increments. In the
adsorption isotherms studies, each sorbent was mixed with Cr(VI)
solutions varying between 10 and 50 mg/L in 10 mg/L increments
at pH 1 for 1 h.
2.6. Chromium detection in aqueous solution
The colorimetric method according to the NMX-AA-044-SCFI-
2001 test method was used to measure the concentration of Cr(VI).
A solution of 1–5 diphenylcarbazide in acid forms a pink complex
with Cr(VI), which was spectrophotometrically analyzed at 540 nm
in a single wavelength HACH DR/4000U spectrophotometer.
2.7. Scanning electronic microscopy
Images were obtained in a JEOL JSM 6510LV at 15 KV and 10 mm
WD, using both secondary and backscattered electron signals. Sam-
ples were sputtered with about 20 nm of gold using a Denton
Vacuum DESK IV.
2.8. Energy dispersive X-ray spectroscopy
EDS analysis was performed with an Oxford PentaFetx5 probe
attached to the microscope detailed above, the probe was calibrated
prior to the analysis with a copper standard.
2.9. Transmission electronic microscopy
Images were obtained in a JEOL JEM-2100 at 200 KV. Samples of
the nanoparticles were isolated by ultrasonically treating the sor-
bent in acetone and drying the residual solvent on formvar-coated
copper TEM grids.
482 G. López-Téllez et al. / Chemical Engineering Journal 173 (2011) 480–485

2.10. X-ray photoelectron spectroscopy

The XPS wide and narrow spectra were aquired using a JEOL
JPS-9200, equipped with a Mg X-ray source (1253.6 eV) at 200 W,
over an analysis area of 1 mm2 , under vacuum on the order of
10−8 Torr for all samples. The spectra was analyzed using the
specsurfTM software included with the instrument and all spec-
tra were charge corrected by means of the adventitious carbon
signal (C1s) at 284.5 eV. The Shirley method was used for the back-
ground substraction, whereas the curve fitting was done with the
Gauss-Lorentz method.

3. Results and discussion

3.1. Chromium sorption kinetics

Fig. 1 shows the concentration of Cr(VI) as a function of time

when mixed with the biomass or the biocomposite for initial Cr(VI)
concentrations of 10 and 20 mg/L. With both sorbents at both
concentrations, the Cr(VI) concentration decreases rapidly, then
stabilizes after about 50 min. This indicates that the biocomposite
reaches its maximum adsorption capacity at 50 min. Thus, 60 min
of treatment was used in all subsequent experiments. Fig. 2. Effect of pH on q (maximum capacity of adsorption).

3.2. Effect of aqueous pH on Cr(VI) adsorb

The maximum capacity of each sorbent as a function of pH is
shown in Fig. 2. The optimal pH for maximum capacity within the
range of 1–7 is at pH 1, so subsequent experiments were performed
at pH 1.
3.3. Effect of concentration on adsorption effectiveness
As shown in the results in Table 1, the biocomposite showed
significantly higher capacity than the biomass at all concentrations.
Additionally, both sorbents were more effective at lower concen-
trations, which is consistent with other sorption studies. At the
lowest concentration of 10 mg/L, the biocomposite adsorbed 71%
of the Cr(VI), while the biomass only removed 34%. It can be seen
that for all concentrations there is a similar behavior where the
biocomposite consistently removes a greater percentage of Cr(VI).
3.4. Adsorption isotherms
The adsorption data for both sorbents was fitted to both Lang-
muir and Freundlich models, with the Langmuir model showing
better correlation. The Langmuir model assumes homogeneous
adsorption sites, whereas the Freundlich model takes into account
heterogeneity in sites. Since the data fit the Langmuir model, the
active sites appear to be homogeneous for both materials. The Lang-
muir model parameters were calculated from the curve fit of the
experimental data, as listed in Table 2. The capacity of the biocom-
posite (5.37 mg/g) is significantly higher than that of the biomass

Fig. 3. (a) SEM image of the biocomposite formed with orange peel, iron(II) acetate and sodium borohydride. (b) EDS qualitative results of the biocomposite formed with
orange peel, iron(II) acetate and sodium borohydride. (c) SEM image of biocomposite after contact with a Cr(VI) solution, (d) EDS spectra of biocomposite after contact with
a Cr(VI) solution.
 G. López-Téllez et al. / Chemical Engineering Journal 173 (2011) 480–485 483

Fig. 4. (a)TEM image of a tube shaped iron oxide nanoparticle, (b) TEM image of an octahedral shaped iron oxide nanoparticle.

Table 1 binding to or near the iron nanoparticles, since both metals appear
Comparison of Cr(VI) removal between orange peel and biocomposite, pH 1,
bright in the image.
T = 25 ◦ C, biocomposite and orange peel quantities of 25 mg each and after 60 min of
equilibrium time.
3.6. TEM analysis
Cr(VI) concentration (mg/L) Orange peel Biocomposite

10 34.3% 71% TEM was used to determine the size and shape of the nanopar-
20 23.7% 43.4%
ticles. As shown in Fig. 4, two different iron oxide nanoparticles
30 19.4% 32.2%
40 17.2% 28%
50 13.8% 25%

(1.90 mg/g). Since the substrate (orange peel) is the same in both
materials, the iron nanoparticles in the biocomposite must play a
strong role in the process.

3.5. SEM and EDS analysis

The SEM image of the nanoparticle-containing biocomposite is

shown in Fig. 3a and the EDS spectra showing the elemental anal-
ysis is shown in Fig. 3b. The SEM image was taken in backscatter
mode to enhance the contrast between the nanoparticles and the
substrate, i.e. the iron appears brighter than the organic substrate.
It is apparent in the image that the nanoparticles tend to agglomer-
ate on the surface of the biocomposite in small (100 nm) and large
(400–500 nm) aggregates. The aggregates are evenly distributed
across the surface. The EDS spectrum showing the elemental anal-
ysis of the surface of the biocomposite, confirms the presence of
iron (about 1%) on the surface.
The SEM backscatter image of the biocomposite after it has been
in contact with a Cr(VI) solution is shown in Fig. 3c. The aggregates
are similar to the ones in the unexposed biocomposite in Fig. 3a,
but the aggregates appear to be somewhat larger.
The EDS spectrum of this area of the surface indicates the pres-
ence of iron (about 1%) as the previous one, but chromium also
appears (about 0.4%). The presence of chromium on the surface con-
firms that it is binding to the surface, as expected from the solution
concentration change, but the image implies that the chromium is

Table 2
Langmuir parameters obtained for the orange peel and biocomposite, pH 1, T = 25 ◦ C,
biocomposite and orange peel quantities of 25 mg each and after 60 min of equilib-
rium time.

q = 1/m 1/Kq K = 1/bq

Fig. 5. XPS curve fitting spectra corresponding to: (a) Fe 2p3/2 narrow scan of the
Orange peel 1.90 7.52 0.07
biocomposite before and (b) after contact with Cr(VI) solution, (c) Cr 2p3/2 narrow
Biocomposite 5.37 0.94 0.19
scan of the Chromium adsorbed in the surface of the biocomposite.
484 G. López-Téllez et al. / Chemical Engineering Journal 173 (2011) 480–485

H
Cr6+ H
O
O H
Fe
O
Cr6+
Fe
O H

O H
Fe Cr6+
O H

Step 1

6Fe2++Cr2O72-+14H+ 6Fe3++2Cr3++7H2O

Step 2

H H H
H H H H
O O O O O O O

CrOH(s) Cr2O3(s) Fe2O3(s) Cr2O3(s) Fe2O3(s) Cr2O3(s) CrOH(s)

Step 3

Fig. 6. Stepwise mechanism of the chromium(VI) reduction by the biocomposite.

were found. The majority of the nanoparticles were tubular struc-
tures of about 20 nm in diameter and 80 nm in length. However,
there were also some octahedral nanoparticles varying in size from
20 to 40 nm. Both shapes are consistent with expected structures
of iron oxides. Since both structures have dimensions well below
100 nm the synthesis process was successful in forming iron oxide
nanoparticles.
3.7. XPS analysis
XPS analysis was performed in order to corroborate the presence
of iron and chromium on the biocomposite surface and to identify
their chemical state. The XPS spectrum corresponding to the Fe
2p3/2 narrow scan region of the biocomposite before contact with
the chromium solution is shown in Fig. 5a. The deconvolution of the
Fe 2p3/2 signal separates into 3 components, each corresponding
to the following chemical states of iron: Fe metallic (28.4%), FeO
(25.3%) and Fe2 O3 (46.3%).
The iron oxides are expected due to the high reactivity of metal-
lic iron [27,28]. Since one of the possible chromium(VI) removal
mechanisms is the reduction to Cr(III), the metallic and Fe(II) com-
ponents are very important reducing agents.
The XPS analysis of the biocomposite after contact with a Cr(VI)
solution is shown in Fig. 5b, the curve fitting results are as fol-
lows: FeO (25.5%), Fe2 O3 (65.6%) and FeSO4 (8.8%). After contact
with chromium solution, the metallic Fe signal is no longer present
due to its high reactivity, the ratio of iron(III) oxide increases as
a result of the redox reaction with chromium(VI) since iron is oxi-
dized in reducing Cr(VI) to Cr(III). To corroborate this, the chromium
region was also analyzed. Finally there is a signal related to FeSO4
which is attributed to the reaction of iron with H2 SO4 present from
acidification of the solution.
The XPS spectrum of the biocomposite after Cr(VI) contact in
the chromium binding energy range exhibits a peak that can be
separated into two components (Fig. 5c). The two components are
chromium (III) oxide (56.7%) and chromium (III) hydroxide (43.3%).
It is interesting to note that there is no chromium(VI) sig-
nal in the spectra. Both signals correspond to chromium(III) with
chromium(III) oxide in a slightly higher ratio than the hydrox-
ide [29,30]. The results show that the redox reaction between
chromium and iron oxide nanoparticles, proceeds practically to
completion, and that it occurs mainly on the surface of the bio-
composite (Fig. 6), this is in good agreement with the assumption
that there is a binding of metal ions to the surface via the functional
groups [31–34].
4. Conclusions
The biocomposite of iron/iron oxide nanoparticles embedded
in a porous orange peel pith matrix demonstrates effectiveness in
adsorbing and reducing Cr(VI) in solution, making it a promising
material for heavy metal bearing industrial wastewater. The bio-
composite adsorbs up to 71% of Cr(VI) from a 10 mg/L solution and
has a capacity of 5.37 mg/g. This is an improvement over unmod-
ified orange peel pith, which only removes 34% of Cr(VI) from a
10 mg/L solution with a capacity of 1.90 mg/g. The adsorption pro-
cess appears to involve two processes: reduction of Cr(VI) to Cr(III)
by Fe or Fe(II) and adsorption of the Cr(III).
 G. López-Téllez et al. / Chemical Engineering Journal 173 (2011) 480–485
Acknowledgement
We thank Universidad Autonoma del Estado de Mexico for sup-
port in the realization of this research.
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