Journal of Hazardous Materials 164 (2009) 1130–1136

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Journal of Hazardous Materials

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Removal of cationic heavy metal from aqueous solution by activated

carbon impregnated with anionic surfactants
Chi K. Ahn a , Donghee Park a , Seung H. Woo b,∗ , Jong M. Park a,∗∗
a
Advanced Environmental Biotechnology Research Center, School of Environmental Science and Engineering, Department of Chemical Engineering,
Pohang University of Science and Technology, San 31, Hyoja-Dong, Pohang 790-784, Republic of Korea
b
Department of Chemical Engineering, Hanbat National University, San 16-1, Deokmyeong-Dong, Yusung-Gu, Daejeon 305-719,
Republic of Korea

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

Article history: To increase their capacity to adsorb heavy metals, activated carbons were impregnated with the anionic
Received 18 June 2008 surfactants sodium dodecyl sulfate (SDS), sodium dodecyl benzene sulfonate (SDBS), or dioctyl sulfosuc-
Received in revised form 3 September 2008 cinate sodium (DSS). Surfactant-impregnated activated carbons removed Cd(II) at up to 0.198 mmol g−1 ,
Accepted 4 September 2008
which was more than an order of magnitude better than the Cd(II) removal performance of activated
Available online 19 September 2008
carbon without surfactant (i.e., 0.016 mmol g−1 ) even at optimal pH (i.e., pH 6). The capacity of the acti-
vated carbon to adsorb Cd(II) increased in proportion to the quantity of surfactant with which they were
Keywords:
impregnated. The kinetics of the adsorption of Cd(II) onto the surfactant-impregnated activated carbon
Activated carbon
Adsorption
was best described by a pseudo-second-order model, and was described better by the Freundlich adsorp-
Anionic surfactant tion isotherm than by the Langmuir isotherm. The surface charge of activated carbon was negative in all
Cadmium pH ranges tested (2–6). These results indicate that surface modification with anionic surfactant could be
Impregnation used to significantly enhance the capacity of activated carbon to adsorb cations.
© 2008 Published by Elsevier B.V.

1. Introduction of these groups might enhance the activated carbon’s capacity to

Removal of toxic heavy metals from the environment is an
important challenge. Ideally, a removal processes must be simple,
effective and inexpensive. Several processes have been suggested
to remove heavy metals from wastewaters. These processes include
chemical precipitation, ion exchange, cementation [1], coagulation
and flocculation [2], complexation, biosorption [3], and membrane
processes [4].
In this study, we focus on the adsorption process because it
is inexpensive, widely applicable, efficient, and creates relatively
little sludge [5]. Activated carbon is an effective and inexpensive
adsorbent [5–11] and has been widely used in various industries
to purify water [9,12–17]. Activated carbon removes heavy metals
by complexation or by electrostatic attraction of metal ions to var-
ious surface oxygen-containing functional groups [9]. However, in
commercial activated carbons, these functional groups cover only a
small portion of the carbon’s surface [11]; increase in the quantity
∗ Corresponding author. Tel.: +82 42 821 1537; fax: +82 42 821 1593.
∗∗ Corresponding author. Tel.: +82 54 279 2275; fax: +82 54 279 8299.
E-mail addresses: shwoo@hanbat.ac.kr (S.H. Woo), jmpark@postech.ac.kr
(J.M. Park).
adsorb metal cations.
To enhance the capacity of activated carbon to adsorb cations,
many functional/surface modification methods have been intro-
duced. These include chemical or physical treatment [18–20],
and surface modification [21–28]. Among these methods, sur-
face modification method using surfactants (i.e. impregnation)
can significantly enhance the capacities of activated carbons to
absorb heavy metals such as zinc, cadmium and chromium [24–28].
However, the mechanism by which the surfactant-impregnated
activated carbon (SIAC) adsorbs heavy metals more effectively than
unmodified carbon, is poorly understood [24,25].
In this study, we attempted to improve the capacity of a commer-
cial activated carbon to adsorb cadmium ions (Cd(II)). We modified
the surface of the activated carbon by impregnating it with the
anionic surfactants sodium dodecyl sulfate (SDS), sodium dodecyl
benzene sulfonate (SDBS) or dioctyl sulfosuccinate sodium (DSS).
Capacities of the SIACs to adsorb Cd(II) were examined under var-
ious conditions. We also measured the surfaces properties of the
activated carbons, and determined how these properties correlated
with the SIACs’ ability to adsorb cations. Finally, we proposed a
mechanism by which these SIACs remove Cd(II) from aqueous solu-
tion and discussed the surface charges of SIAC as an adsorbent to
be used for wastewater treatment.

0304-3894/$ – see front matter © 2008 Published by Elsevier B.V.

doi:10.1016/j.jhazmat.2008.09.036
 C.K. Ahn et al. / Journal of Hazardous Materials 164 (2009) 1130–1136
Table 1
Chemical properties of anionic surfactants used in this study.
Surfactant Formula and structure
SDS (sodium dodecyl sulfate)
SDBS (sodium dodecyl benzene sulfonate)
DSS (dioctyl sulfosuccinate sodium)
2. Experimental
2.1. Materials
In these experiments, we used a granular activated carbon (GAC;
Darco 20–40 mesh). This GAC, all reagents (Na2 CO3 , NaHCO3 , NaOH,
NaOC2 H5 , H2 SO4 , HNO3 , HCl) and the surfactants SDS, SDBS and
DSS (Table 1) were purchased from Sigma.
Cadmium solutions were prepared by dissolving analytical
grade CdCl2 ·2.5H2 O (Acros) volumetrically in deionized water.
2.2. Surface modification of activated carbon
The activated carbon was washed several times with deion-
ized water, then dried for several days in an oven at 60 ◦ C. The
resulting unmodified dried granular activated carbon (virgin GAC)
was modified by impregnating it with the anionic surfactants as
follows.
Ten grams of virgin GAC were mixed with 1 L of 0.035 mol L−1
SDS, 0.029 mol L−1 SDBS, or 0.023 mol L−1 DSS solutions. The mix-
tures were shaken at 100 rpm at 20 ± 1 ◦ C for 48 h, then washed and
redried as described above. The resulting SIACs were designated as
SDS-GAC, SDBS-GAC and DSS-GAC, respectively.
Further, to examine the effects of surfactant loading on the
capacity of SDS-GAC to adsorb Cd(II), five variants of this species
were prepared by mixing virgin GAC with SDS solutions of dif-
ferent concentrations of 0.000 mmol g−1 (S0GAC), 0.191 mmol g−1
(S1GAC), 0.385 mmol g−1 (S2GAC), 0.756 mmol g−1 (S3GAC) and
0.811 mmol g−1 (S4GAC).
2.3. Characterization of activated carbons
The capacity of activated carbon to adsorb metal ions depends
both on the surface area of the carbon particles and on the quan-
tity of surface functional groups [9]. The specific surface areas
and pore volumes of virgin GAC and the SIACs were determined
from the N2 gas adsorption isotherm at 77.3 K using an ASAP 2010
(Micromeritics, USA). Specific surface areas were calculated by the
Brunauer–Emmett–Teller method.
1131
MW (g mol−1 ) Surfactant loading (mmol g−1 )
288.38 0.728
348.48 0.545
444.56 0.472
The identities of the functional groups on activated carbon were
determined using Boehm titration to determine their acidities and
basicities [29]. For measurement, 0.1 g of virgin GAC or SIAC was
mixed with 10 mL of basic or acidic solutions in 50 mL capped
conical tubes. The mixtures were shaken at 160 rpm at 20 ± 1 ◦ C
for 72 h, and then passed through 0.45 ␮m PTFE syringe filters
(Whatman).
To measure acidities, the solutions were 0.025N NaHCO3 ,
Na2 CO3 , NaOH or NaOC2 H5 . The filtrates were titrated up to pH
4.5 using a 0.025N H2 SO4 solution. To measure basicities, the solu-
tion was 0.025N HCl. The filtrates were titrated up to pH 11.5 using
a 0.025N NaOH solution.
The surface charges of the activated carbons were examined
using a zeta-potential analyzer (ELS-8000, Photal, Ostsuka Elec.).
For this measurement, the activated carbons were milled in a mor-
tar. Surface charges were measured at several pHs from 2.0 to
12.5.
2.4. Batch experiment for Cd(II) adsorption
The capacities of virgin GAC and SIACs to adsorb Cd(II) were
examined by measuring the initial and final concentrations of Cd(II)
in a batch system. Experiments were conducted in 250 mL Erlen-
meyer flasks with a working volume of 100 mL. To examine the
effect of pH on Cd(II) removal by the activated carbons, solutions
of each SIAC were obtained by adding 0.1 g samples to 100 mL of
0.89 mmol L−1 Cd(II) solution, then adjusting the pH to 2, 3, 4, 5
or 6 by adding 1N NaOH or H2 SO4 as required. The solutions were
shaken at 100 rpm at 20 ± 1 ◦ C for 48 h. The batch adsorption exper-
iments were conducted in duplicate; results differed by ≤5%. The
changes of pH during adsorption of Cd(II) were monitored using a
pH meter (Orion, USA) in a solution of 0.89 mmol-Cd L−1 that had
an initial pH of 6.0.
2.5. Analysis
After equilibrium was reached, the residual Cd(II) concentra-
tion was analyzed using an atomic absorption spectrophotometer
(SpectrAA-800, Varian) at a wavelength of 228.8 nm. The Cd(II)
1132 C.K. Ahn et al. / Journal of Hazardous Materials 164 (2009) 1130–1136

Fig. 1. Distribution of cadmium species in aqueous system as a function of pH.
uptake (q) was calculated from the mass balance as follows:
V (C0 − Cf )
q=
M surfactants can be dissociated, and then the protons bind to the
where V is the solution volume (L) and M is the weight of activated
carbon (g) used. C0 and Cf are the initial and final concentrations of
Cd(II) (mmol L−1 ), respectively.
Final concentrations of the surfactants desorbed from activated
carbon during batch adsorption experiments were determined
using a TOC analyzer (TOC-VCSH , Shimadzu). The desorption ratios
of the surfactants were calculated as follows:
released surfactant (mg)
desorption ratio (%) = × 100
initially bound surfactant (mg)
3. Results and discussion
3.1. Distribution of cadmium species
The distributions of cadmium species were determined using
Visual MINTEQ (V 2.15) [16,17]. The effect of pH on the pro-
portion of cadmium species present was determined at 0.001 M
of ionic strength at 20 ◦ C. Hydrated precipitate of cadmium,
Cd(OH)2(s) , can be formed at pH > 9 (Fig. 1). Therefore, in this
study, we conducted all batch adsorption experiments at pH ≤ 6.0.
The divalent cadmium cation (Cd2+ ) was most abundant at
pH < 8.
3.2. Characterization of activated carbons
Several functional groups occurred at varying amounts present
on the surface of the virgin GAC and SIACs (Table 2). The virgin
GAC contained carboxylic and phenolic hydroxyl groups, resulting
in 212.5 ␮eq g−1 of total acidity. Total basicity of the virgin GAC was
417.9 ␮eq g−1 , but the identity of the groups causing its basicity
could not be determined.
Treatment with SDS resulted in SIACs with the lowest acid-
ity (125.0 ␮eq g−1 ) and highest basicity (587.5 ␮eq g−1 ). Treatment
with DSS only slightly changed total acidity (16.8% reduction) and
total basicity (6.4% increase) compared to the virgin GAC. This result
might be due to the more complex molecular structure of DSS,
which has two hydrophobic branches (Table 1). Treatment with
SDS or SDBS significantly decreased the amounts of carboxylic and
phenolic hydroxyl groups, but induced formation of lactonic and
carbonylic groups (Table 2).
Acidic functional groups sequester heavy metals ions mainly by
adsorption [7,9,30–32]. For this reason, many researchers have tried
to increase the total quantity of surface functional groups and to
make the surface charge more favorable for adsorption of cationic
heavy metals [11,31,33]. In this study, impregnation of GAC with
anionic surfactants reduced its total acidity and increased its total
basicity (Table 2). This result means that these anionic surfactants
successfully covered the surface of the virgin GAC. Specifically, total
acidity of the activated carbon was decreased because the surfac-
tants covered surface acidic groups, especially carboxylic groups.
Meanwhile, the hydrophilic head(s) of the surfactants can act as
(1) basic functional groups. In aqueous solutions, the bound anionic
hydrophilic head(s), resulting in the increase of the GAC’s total
basicity.
3.3. Removal behaviors of Cd(II) by activated carbons at various
pHs
Because the solution pH has an important effect on the
interactions between adsorbent and adsorbate, batch adsorption
(2)
experiments with virgin GAC and SIACs were conducted at vari-
ous pHs from 2 to 6 (Fig. 2a). The virgin GAC removed Cd(II) poorly
at all pHs, i.e., <0.016 ± 0.007 mmol g−1 even at pH 6. Activated car-
bon removes Cd(II) ions by surface complexation or by ion exchange
with other ions bound to acidic functional groups, or by both mech-
anisms [9,31,33]. Commercial activated carbons have few acidic
functional groups on their surface where cationic heavy metal ions
can encounter them [11]. Thus, the low capacity of virgin GAC to
adsorb Cd(II) is a result of its low acidity.
SDS-GAC, SDBS-GAC and DSS-GAC all removed Cd(II) well even
at pH 2 (Fig. 2a). Impregnating activated carbon with anionic sur-
factants increased the number of active sites capable of binding
the Cd(II) ions. These active sites may exist on the head(s) of the
anionic surfactants. Of course, the surfactants covered acidic groups
and therefore significantly reduced total acidity and increased total
basicity of the GAC (Table 2). Owing to these effects, Cd(II) ions
could react easily or favorably with active sites on the surface of
the activated carbon.
Cd(II) uptakes of the SIACs increased linearly with pH (Fig. 2a).
This effect is due to reduced competition between Cd(II) ions and H+
ions for anionic surface functional groups as pH increases [19,33].

Table 2
Quantities of various functional groups on the virgin and surfactant-impregnated activated carbons.

Acidity (␮eq g-AC−1 ) Basicity (␮eq g-AC−1 )

Carboxylic Lactonic Phenolic hydroxyl Carbonylic Total acidity

Virgin GAC 160.7 NDa 51.8 NDa 212.5 417.9

SDS-GAC 75.0 26.8 1.8 21.4 125.0 587.5
SDBS-GAC 67.9 32.1 16.1 8.9 125.0 533.9
DSS-GAC 92.9 7.1 76.8 NDa 176.8 444.6
a
Not detected.
 C.K. Ahn et al. / Journal of Hazardous Materials 164 (2009) 1130–1136 1133

Fig. 3. Equilibrium isotherms of Cd(II) by surfactant-impregnated activated carbons

at pH 6.

3.4. Isotherm study

The Cd(II) uptakes of the SIACs increased with equilibrium Cd(II)

concentration and eventually reached an equilibrium value that
depended on the surfactant used (Fig. 3). The Freundlich and Lang-
muir isotherms were used to describe adsorption of Cd(II) from
bulk solution onto SIACs, assuming no interaction among adsorbed
molecules.
The Freundlich isotherm is expressed as follows
1/n
qe = KF Ce (3)

where qe is the amount of adsorbate that can be adsorbed

(mmol g−1 ), KF is the Freundlich adsorption constant (mmol g−1
(L mmol−1 )1/n ) and Ce is the equilibrium concentration of the adsor-
Fig. 2. Effect of solution pH on Cd(II) uptakes of activated carbons (a) and desorption bate (mmol L−1 ).
ratios of anionic surfactants bound on their surface (b). The Langmuir isotherm is expressed as:
Q0 bCe
qe = (4)
SDS-GAC had the highest uptake value, 0.198 ± 0.003 mmol g−1 ,
at 1 + bCe
pH 6. Thus, further batch experiments were performed using SDS- where qe is amount of adsorbate adsorbed per unit weight of
GAC at pH 6. adsorbent (mmol g−1 ), Q0 is the monolayer adsorption capacity
During adsorption of Cd(II) to the activated carbons, anionic (mmol g−1 ), and b is the Langmuir constant (L mmol−1 ).
surfactants were desorbed from their surfaces into the solution The Freundlich and Langmuir parameters were estimated by
(Fig. 2b). As the pH increased, the proportion of SDS desorbed nonlinear regression (Table 3). The Freundlich model agreed better
increased slightly, but that of DSS decreased remarkably. Among with experimental data than did the Langmuir model (Fig. 3.). This
the three impregnated activated carbons tested, stability of the result suggests that the heterogeneity of SIAC surface and bidentate
bound surfactant was greatest in DSS-GAC. Anionic surfactant is type adsorption process might be conducted between the Cd(II)
bound to activated carbon by a hydrophobic reaction in which ions and the negative charged groups of surfactant onto SIACs.
hydrophobic alkyl chain(s) of the surfactant interact with the non- The KF value of the Freundlich model and the Q0 value of the
polar portion(s) of the activated carbon’s surface [34]. Because DSS Langmuir model both indicate that the capacity SIACs to adsorb
has two hydrophobic alkyl chains, it might bind more strongly to
the surface of activated carbon than do SDS and SDBS, which each Table 3
have only one such chain. However, DSS-GAC had the poorest Cd(II) Freundlich and Langmuir adsorption isotherm parameters for Cd(II) adsorption by
removal performance among the surfactants used in this study. This surfactant-impregnated activated carbons at pH 6.
result indicates that strong binding of the anionic surfactant to the Isotherm model Parameter SDS-GAC SDBS-GAC DSS-GAC
GAC does not necessarily translate to increased capacity to adsorb
KF 0.203 0.155 0.138
Cd(II).
Freundlich isotherm 1/n 0.104 0.076 0.063
Of the anionic surfactants tested in this study, SDS was the R2 0.998 0.996 0.996
most efficient surfactant at enhancing capacity of the activated
Qo 0.170 0.139 0.127
carbon to adsorb Cd(II). The adsorptive capacity for Cd(II) on b 3408.7 1713.9 1673.2
SIACs ranked SDS-GAC > SDBS-GAC > DSS-GAC. This order corre- Langmuir isotherm
R2 0.937 0.986 0.990
sponds to the amount of surfactant on the activated carbons, RL a 1.7 × 10−3 4.2 × 10−3 4.7 × 10−3
which was 0.728 mmol g−1 for SDS, 0.545 mmol g−1 for SDBS, and a
Separation factor was calculated at the initial Cd(II) concentration of
0.472 mmol g−1 for DSS (Table 1). 8.9 × 10−1 mmol L−1 .
1134 C.K. Ahn et al. / Journal of Hazardous Materials 164 (2009) 1130–1136

Table 4
Comparison of kinetic parameters for the adsorption of Cd(II) onto anionic-
surfactant-impregnated GAC at 8.9 × 10−1 mmol-Cd L−1 and pH 6.

Kinetic model Parameters SDS-GAC SDBS-GAC DSS-GAC

−1
Experimental qe (mmol g ) 0.198 0.156 0.154

q1 (mmol g−1 ) 0.135 0.112 0.094

Pseudo-first-order k1 (1 min−1 ) 0.033 0.091 0.039
r12 0.847 0.956 0.839

q2 (mmol g−1 ) 0.190 0.150 0.146

k2 (g mmol−1 min−1 ) 0.761 2.527 1.553
Pseudo-second-order
h (mmol g−1 min−1 ) 0.028 0.057 0.033
r22 0.978 0.984 0.967

ki (mmol g−1 min−0.5 ) 0.028 0.026 0.023

Intra-particle diffusion
ri2 0.898 0.619 0.589

in Table 4. The correlation coefficients (r2 ) for the pseudo-first-

order kinetic model were relatively low compared with those for
Fig. 4. Cd(II) uptake during adsorption onto surfactant-impregnated activated car- the pseudo-second-order kinetic model, and the value of q1 from
bon with pseudo-second-order kinetic model fitting.
the pseudo-first-order kinetic model differed from the experimen-
tal data (Table 4). Therefore, the pseudo-first-order kinetic model
Cd(II) ranked SDS-GAC > SDBS-GAC > DSS-GAC; this is the same dose not adequately describe the adsorption process of Cd(II) on
order as the observed Cd(II) absorptive capacity of these three these SIACs.
SIACs. The intra-particle diffusion kinetic model provides information
The essential characteristic of the Langmuir isotherm model can about the nature of the adsorption process. If a plot of the lin-
be described by the separation factor, RL , as follows [35]: earized form of the intra-particle diffusion model passes through
1 the origin, the process is affected by only intra-particle diffusion;
RL = (5) otherwise, adsorptive processes other than intra-particle diffusion
1 + bC0
might occur [36]. Our linearized plots did not pass through the ori-
where b is the Langmuir constant (Eq. (4)) and C0 is initial concen-
gin (data not shown). Therefore, non-diffusion reactions probably
tration of Cd(II) (mmol L−1 ) at the same pH. RL indicates the shape of
occur between Cd(II) and SIACs.
the isotherm and the nature of adsorption process. The adsorption
In the pseudo-second-order kinetic model, the r2 values of lin-
process is thermodynamically unfavorable if RL > 1, linear if RL = 1,
ear plots of t/qt vs. t (pseudo-second-order kinetic equation) were
thermodynamically favorable if 0 < RL < 1, and irreversible if RL = 0
0.978 for SDS-GAC, 0.984 for SDBS-GAC and 0.967 for DSS-GAC;
[35]. For the SIACs used in this experiment, calculated RL ranged
these were greater than the r2 value of the other kinetic models
from 1.7 × 10−3 to 4.7 × 10−3 (Table 3), therefore the adsorption
tested in this study (Table 4). Moreover the adsorptive capacity val-
process is thermodynamically favorable.
ues (q2 ) from the pseudo-second-order kinetic model agreed well
with experimentally determined adsorptive capacity values (qe ).
3.5. Sorption kinetics of Cd(II)
This result indicates that the adsorption of Cd(II) ions on SIAC fol-
lows a pseudo-second-order reaction. Thus the adsorption of Cd(II)
Various models have been suggested to express the kinetics of
onto SIAC appears to occur by chemical processes involving valence
adsorption of solute molecules onto a sorbent [36]. We tested the
forces due to sharing or exchange of electrons between cadmium
abilities of three kinetic models to describe the process of Cd(II)
and SIACs [36].
adsorption onto SIACs. These models were a pseudo-first-order
model, a pseudo-second-order model, and an intra-particle diffu-
3.6. Effect of surfactant loading
sion model.
The pseudo-first-order kinetic model used was [36,37]:
To understand the effect of anionic surfactants on Cd(II) removal,
k1 virgin GAC was impregnated with five different amounts of SDS
log(qe − qt ) = log q1 − t (6)
2.303 (Table 5). As the amount of SDS on the surface of activated car-
The pseudo-second-order kinetic model used was bon increased, its specific surface area decreased from 643.5 to
121.4 m2 g−1 . This decrease means that SDS covered most of the
t 1 1
= + t (7) micro-pores of the GAC. This phenomenon may seem to be very
qt 2
k2 q2 q2
unfavorable for the adsorptive capacity of the SDS-impregnated
The intra-particle diffusion model used was: activated carbon, because the capacity of activated carbon to adsorb

qt = ki t 1/2 (8)
Table 5
In these models, k1 is the rate constant for the pseudo-first-order Chemical properties and Cd(II) uptakes of SIACs with impregnated with different
model, k2 is the rate constant for the pseudo-second-order model amounts of SDS.
and ki is an intra-particle diffusion rate constant, qe is the amount SDS loading Surface area Total acidity Cd(II) uptake
of solute adsorbed at equilibrium and qt is the amount of solvent (mmol-SDS g-AC−1 ) (m2 g−1 ) (␮eq g−1 ) (mmol g−1 )
adsorbed at time t. The initial adsorption rate in the pseudo-second- S0GAC 0.000 643.5 ± 8.4 206.6 ± 7.6 0.022 ± 0.012
order kinetic model is h = k2 q22 . S1GAC 0.191 466.2 ± 4.2 150.0 ± 22.7 0.045 ± 0.015
At pH 6, the amount of Cd(II) adsorbed onto SIACs increased S2GAC 0.385 306.6 ± 0.8 110.7 ± 7.6 0.088 ± 0.004
rapidly for 120 min and thereafter increased only slightly (Fig. 4). S3GAC 0.756 129.8 ± 0.4 77.7 ± 1.3 0.178 ± 0.013
S4GAC 0.811 121.4 ± 0.5 80.4 ± 0.0 0.198 ± 0.004
The kinetic constants for the three kinetic models are summarized
 C.K. Ahn et al. / Journal of Hazardous Materials 164 (2009) 1130–1136
Fig. 5. Zeta-potentials of surfactant-impregnated activated carbons as a function of
pH.
ions is proportional to its surface area [15]. However, the quan-
tity of active functional groups and the surface charge are also
important variables that affect the adsorptive capacity of activated
carbon.
Total acidity of the SDS-impregnated activated carbon decreased
as the amount of SDS on the SIAC increased (Table 5), i.e.,
206.6 ␮eq g−1 for the virgin GAC vs. 80.4 ␮eq g−1 for the GAC treated
with the highest concentration of SDS (i.e., 0.811 mmol g−1 ). This
result means that acidic groups of the virgin GAC were covered by
the SDS, resulting in a reduced possibility of interactions between
these groups and Cd(II) ions. However, the virgin GAC, which has a
large quantity of acidic groups, showed very poor capacity to adsorb
Cd(II) (Fig. 4). This result indicates that most of the acidic groups
in the virgin GAC were not active ones capable of interacting with
Cd(II) ions. Thus, impregnation with SDS can provide the activated
carbon with active functional groups. As a result, the capacity of
the GAC to adsorb Cd(II) was significantly increased from 0.022 to
0.198 mmol g−1 by impregnation with SDS (Table 5); this trend was
in proportion to the quantity of surfactant onto SIAC.
3.7. Mechanism of Cd(II) adsorption
Cationic heavy metals including Cd(II) are removed from aque-
ous solution due to their interaction with anionic functional groups
on the surface of activated carbon [9,28]. Thus, the surface charge
of the activated carbon significantly influences its interaction with
Cd(II) ions, and this charge varies according to the solution pH
[8,20,29]. To examine the surface charges of the virgin GAC and the
SIACs, zeta potentials of the solutions containing virgin GAC or SIAC
were measured as a function of pH in the range of pH 2.0 to 12.5
(Fig. 5). In the virgin GAC the point of zero charge (pHpzc ) occurred
at pH 4.71; the virgin GAC was positively charged below this pH
and negatively charged above it. On the contrary, SIACs showed
negative values of zeta potential even at pH 2.0. Other researchers
reported that surface charges of the activated carbons impregnated
with other anionic surfactants (i.e. linear alkyl benzene sulfonate)
were negative at all pHs tested because the hydrophilic negatively
charged head groups of the surfactants are arranged toward the
aqueous phase [26]. These results suggest why SIACs effectively
remove Cd(II) even at pH 2. At pH ≥ pHpzc , the surface charge of
activated carbon is negative, so Cd(II) ions, which are positively
charged, can easily bind to negatively dissociated forms of the sur-
factant’s active groups and can form complexes with its surface
1135
Fig. 6. The pH profile during Cd(II) adsorption onto surfactant-impregnated acti-
vated carbon.
groups, as indicated in Eq. (9) [7].
2ROH + M2+ ↔ (RO)2 M + 2H+
(surface functionals groups on AC) (9)
Because activated carbon is highly hydrophobic, exterior
molecules with hydrophobic groups can be strongly bound to its
surface by the van der Waals interaction and then can influence the
characteristics of the activated carbon’s surface. In anionic surfac-
tants a long (hydrophobic) alkyl chain binds to the surface of the
activated carbon, while its negatively charged (hydrophilic) head
group is arranged toward the surrounding water. As a result, the
hydrophilic part(s) of the surfactant contribute a large quantity of
anionic functional groups to the SIAC. For this reason, the capacity
of activated carbon to adsorb positive ions increases in proportion
to the quantity of anionic surfactant attached to its surface (Eq.
(10)).
2RSO3 Na + M2+ ↔ (RSO3 )2 M + 2Na+ (10)
Another possible reaction is a competitive or inhibition mecha-
nism between Cd2+ and H+ ion (Eq. (11)) [38]:
RSO3 Na + H+ ↔ RSO3 H + Na+ (11)
Eq. (10) indicates that Cd(II) ions can easily approach and bind
to the negatively charged group(s) of the anionic surfactant that is
bound to the surface of activated carbon. In addition, the Cd(II) ions
can bind to other active groups which were originally present on
the surface of the activated carbon and which were not covered by
the surfactant (Eq. (9)). However, it is obvious that the former is the
primary reaction in this system.
The pH changes that were observed (Fig. 6) during Cd(II)
adsorption onto SIACs could be also explained by our proposed
adsorption mechanism (Eq. (11)). The pHs of each SIAC slightly
increased during the first 60 min of Cd(II) adsorption (Fig. 4). These
results are in good agreement with the increments of basicity of
the SIACs (Table 2). In the early stages of adsorption, the acidic
functional groups of activated carbons might have been dissoci-
ated in the aqueous phase by de-protonation (Eq. (9)) causing
rapid drop of pHs. After that, a slight increase in pH occurred,
which might be due to the binding of the protons to hydrophilic
heads of the anionic surfactant on the SIACs (Eq. (11)). In SIACs,
however, the pH drops were smaller than in virgin GAC. This
difference probably occurs because in SIACs most of the disso-
ciable acidic functional groups on the activated carbon surface
1136 C.K. Ahn et al. / Journal of Hazardous Materials 164 (2009) 1130–1136
were covered by surfactant, resulting in less dissociation of these
groups.
Although fewer dissociable acidic functional groups occur in
SIACs than in virgin GAC, SIACs had much greater Cd(II) adsorption
capacities than did virgin GAC. This result clearly indicates that in
SIACs, the negatively charged surfactant head groups were the main
sites of Cd(II) adsorption, and that the original functional groups of
activated carbon do contribute to Cd(II) adsorption.
4. Conclusion
To develop a new type of activated carbon capable of removing
cationic heavy metal more specifically and effectively, we cre-
ated SIACs in which the surface of activated carbon was modified
by impregnating it with anionic surfactants. Among the surfac-
tants tested, SDS most effectively enhanced the activated carbon’s
capacity to adsorb Cd(II). The capacity of the SIAC to adsorb Cd(II)
increased in proportion to the quantity of the surfactant with which
the activated carbon was impregnated.
The pH-stat equilibrium data of Cd(II) adsorption onto
surfactant-impregnated activated carbon was well fitted by the
Freundlich isotherm. The maximum Cd(II) uptake of the SDS-
impregnated activated carbon was 0.198 mmol g−1 at pH 6.
Separation factor values (RL ) of 1.7 × 10−3 –4.7 × 10−3 from the
Langmuir isotherm indicated that the process of Cd(II) adsorption
by the SIAC was very favorable thermodynamically. The adsorption
of Cd(II) ions on SIAC was well described by a pseudo-second-order
reaction.
The investigations on the surface functional groups of the SIACs
revealed that their enhanced adsorptive capacity was due to the
negatively charged groups in the hydrophilic head of the anionic
surfactant. These groups made the surface charge of the activated
carbon more negative, resulting in more favorable conditions for
Cd(II) adsorption. Therefore, we conclude that surface modifica-
tion method using anionic surfactants can be used to enhance the
capacity of activated carbon to adsorb cationic heavy metal ions.
Acknowledgment
This work was supported by grants from the Korea Science and
Engineering Foundation (KOSEF) through the Advanced Environ-
mental Biotechnology Research Center (AEBRC, R11–2003–006).
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