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Adsorption of Pb(II) Ions from Aqueous Solutions by Pyrolusite-modified


Activated Carbon Prepared from Sewage Sludge†
Lu Fan, Yao Chen, Li Wang and Wenju Jiang* College of Architecture and Environment, Sichuan
University, Chengdu 610065, P. R. China.

(Received 9 April 2011; accepted 1 June 2011)

ABSTRACT: In this study, activated carbons were prepared from sewage sludge
by chemical activation, and modified with pyrolusite as a catalyst during
activation and carbonization. The influence of the addition of the mineral on the
properties of the produced activated carbons was evaluated. The modified
activated carbons exhibited BET surface areas which were 11.31% higher than
ordinary sludge-based activated carbons and had larger pore volumes. The results
of adsorption experiments showed that the pyrolusite-added adsorbents
performed better towards the removal of Pb(II) ions than those without pyrolusite
addition. At an initial pH of 5.4 for the Pb(II) ion solution, addition of the
pyrolusite-added activated carbon led to the effective removal of Pb(II) ions with
an adsorption capacity of ca. 70 mg/g. The adsorption capacity towards Pb(II) ion
removal also increased with increasing contact time and adsorbent dosage.
Compared to adsorbents derived from various other materials, the pyrolusite-
modified adsorbent had a relatively high Pb(II) ion adsorption capacity.
Adsorption isotherm and kinetics studies showed that the adsorption of Pb(II)
ions onto the pyrolusite-modified adsorbent was well fitted by the Langmuir
isotherm and could be described by the pseudo-second-order kinetic model.

INTRODUCTION

The presence of heavy metal ions, such as Cu(II), Cd(II), Zn(II), Hg(II), Pb(II), etc., in the aquatic
environment has been a big issue for scientists and engineers due to their increasing discharge,
toxic nature and other adverse effects on receiving waters (Gerçel and Gerçel 2007). Lead ions
[Pb(II) ions] are an example of one such potentially toxic heavy metal ion. They are found in
waste waters from industries engaged in the production of lead–acid batteries, paint, oil, metal,
phosphate fertilizer and electronics, in wood processing and also in the combustion of fossil fuel,
forest fires, mining activity, automobile emissions, etc. Lead is also used in storage batteries,
insecticides, plastic water pipes, food, beverages, ointments and medicinal concoctions, and for
flavouring and sweetening (Singh et al. 2008). Lead(II) ions are non-biodegradable and can
accumulate in living tissues, thereby concentrating throughout the food chain and eventually
being readily absorbed into the human body (Dwivedi et al. 2008), causing severe damage to
human kidneys, nervous system, reproductive system, liver and brain, and causing sickness or
death. Severe exposure to lead may cause sterility, abortion, still-births and neonatal death.


Published in the Festschrift of the journal dedicated to Professor Giorgio Zgrablich on the occasion of his 70th birthday
and to celebrate his 50 years as a faculty member at the National University of San Luis in Argentina.
*
Author to whom all correspondence should be addressed. E-mail: wenjujiang@scu.edu.cn.
496 Lu Fan et al./Adsorption Science & Technology Vol. 29 No. 5 2011

Adsorption by activated carbon is the most common method for treating such wastewater due
to its extremely high surface area, micropore structure, large adsorption capacity, rapid adsorption
behaviour and relatively easy regeneration (Kurniawan et al. 2006). Activated carbon can be
produced from coal but also from other inexpensive material with a high carbon content, such as
peanut hulls (Periasamy and Namasivayam 1996), coconut shells (Song et al. 2010), plantain peel
(Oluyemi et al. 2009) and even sewage sludge (Seredych and Bandosz 2007), which would help
in the disposal of sludge and also exploit the economic value of wastes.
The adsorption of metal ions by activated carbon is a complex process and may involve ion
exchange, electrostatic effects and coordination with functional groups on the surface of the
activated carbon. Several factors, such as the specific surface area, pore-size distribution, pore
volume, surface charge and the presence of surface functional groups, can affect the adsorption of
metal ions onto activated carbon. Special modification of activated carbon using suitable
chemicals is necessary in order to enable this adsorbent to develop an affinity for metal ions and
remove them effectively from aqueous solution (Song et al. 2010). Many investigations have been
undertaken in this area. Thus, Yanagisawa et al. (2010) used a magnesium/coconut shell activated
carbon composite to remove Zn(II) and Cd(II) ions from aqueous solution, the results indicating
that the composite material adsorbed greater amounts of such metal ions than its counterpart
without magnesium addition. Kikuchi et al. (2006) found that ZnO-loaded activated carbon was
effective for the adsorption of Pb(II) ions, with the hydroxyl groups created by the addition of
ZnO being most likely responsible for the higher Pb(II) ion adsorption capacity.
In addition to the above methods, the modification of natural minerals also has a great potential
because the complex compositions of various transition metals which they contain can act as
catalysts during the carbonization and activation process. Thus, pyrolusite, an ordinary and
economical mineral resource in Sichuan Province, P. R. China, has been chosen as a catalyst for
modifying activated carbon in the present study. Liu et al. (2010) used an activated carbon from
sewage sludge treated by the addition of pyrolusite for the adsorption of dyes and achieved a
maximum adsorption capacity of 50 mg/g. However, there is only limited information on the removal
of metal ions by activated carbon generated by pyrolusite modification on sewage sludge. For this
reason, this study has been devoted to an examination of the adsorption of Pb(II) ions using sewage
sludge-derived activated carbon produced with and without the addition of pyrolusite.

EXPERIMENTAL

Materials

The raw materials were obtained from a local municipal wastewater treatment plant. Their properties
and analytical results are listed in Table 1. The main constituents (wt%) of the pyrolusite used in this
study were: MnO2, 41.33%; SiO2, 30.20%; Fe2O3, 13.80%; CaO, 3.62%; Al2O3, 3.37%; K2O, 0.10%;
Na2O, 0.39%; Ni, 0.068%; Co, 0.014%.

Preparation of activated carbon

The carbon employed in the present study was chemically activated. For this purpose, the sludge
sample was dried at 105 C for 48 h, then crushed and sieved to pass through a 160 mesh sieve.
Measured amounts of pyrolusite were added as a fine powder to the sludge sample in a weight
ratio of 1%, the other sludge sample without pyrolusite addition being similarly prepared for
Adsorption of Pb(II) Ions by Pyrolusite-modified Activated Carbon 497

TABLE 1. Properties of Raw Sludge (wt%)


Moisture 83.40
Volatiles 66.80
Ash 31.88
Fixed carbona 1.32
Cb 35.95
H 5.42
N 6.00
a
Fixed carbon  carbon content in the solid combustible
residue remaining after pyrolysis of the adsorbent.
b
C  total carbon content of the adsorbent produced.

comparative purposes. These sludge samples were then impregnated with 6 mol/ ZnCl2 and 35
wt% H2SO4 in a volume ratio of 4:1 over a period of 24 h and dried. Subsequent pyrolysis was
performed in an electric furnace using a nitrogen atmosphere, with the samples being maintained
at 550 C for 40 min. After cooling down to room temperature, the products were washed three
times with a 1:3 aqueous HCl solution and with hot water (70 C) until the pH of the wash water
was neutral. The produced adsorbents were dried, crushed and sieved through a 200 mesh sieve
and then stored prior to further testing and application. The activated carbons with and without
pyrolusite addition are referred to as T1 and T0 below.

Adsorption experiments

The adsorption of Pb(II) ions was undertaken by batch experiments, with the effects of various
parameters being examined. For each experimental run, 50 m of a Pb(II) ion solution of a known
concentration prepared from lead nitrate [Pb(NO3)2] was added to a 150 m Erlenmeyer flask and
mixed with 0.1 g of activated carbon. The pH values of the various samples thus obtained were
adjusted by the addition of HNO3 or NaOH solutions. The resulting mixtures were agitated at a
constant rate at room temperature for a prescribed time, the aqueous phase of the sample then being
filtered off and its Pb(II) ion concentration analyzed by atomic absorption spectrophotometry (AAS).
Each adsorption experiment was carried out twice and the average value was adopted. All the
reagents used in the experiment were of A.R. reagent grade.

Analytical methods

The experimental analyses were conducted in the Analytical and Testing Center of Sichuan
University. Thus, the Pb(II) ion concentrations were determined by atomic absorption
spectrometry (Saiman GGX-6 instrument, Beijing, P. R. China), while the physical properties of
the adsorbents were determined by nitrogen adsorption at –196 C using a SSA-4200 surface area
analyzer (Beijing, P. R. China). The adsorption data was then employed to calculate the surface
area using the Brunauer, Emmett and Teller (BET) equation, while the pore-size distribution was
obtained using the Barrett, Joyner and Halenda (BJH) equation. X-Ray diffraction (XRD) patterns
of the adsorbents were obtained via an X’PertPro MPD diffractometer at 40 kV and 40 mA
employing Cu Kα radiation and step-scanning over the 2θ range 10–90.
Fourier-transform infrared (FT-IR) spectroscopic analysis was applied to the adsorbents (T0
and T1) to determine the surface functional groups, using a Nicolet-6700 spectrometer (Nicolet,
U.S.A.) and recording the spectra over the wavenumber range 400–4000 cm1.
498 Lu Fan et al./Adsorption Science & Technology Vol. 29 No. 5 2011

Adsorption isotherm and kinetics

Equilibrium relationships between an adsorbent and an adsorbate are described by adsorption


isotherms. In this study, the Pb(II) ion adsorption isotherm data were analyzed using the Langmuir
isotherm.
The linear form of the Langmuir isotherm may be written as:

1 1 1 1
= + (1)
qe Q K LQ Ce

where Ce is the equilibrium concentration of the adsorbate (mg/), qe is the amount of adsorbate
adsorbed per unit mass of adsorbent (mg/g), Q is the monolayer adsorption capacity (mg/g)
and KL is a constant related to the adsorption free energy (Langmuir adsorption constant, /mg)
(Febriantoa et al. 2009).
Kinetic studies are generally undertaken to determine the uptake rate of the adsorbate, which
controls the residual time of the whole adsorption process (Karthikeyan et al. 2005). In the present
study, three kinetic models, viz. the pseudo-first-order, pseudo-second-order and intra-particle
diffusion, were selected for a description of the adsorption process.
The pseudo-first-order rate equation can be expressed in a linear form as:

k1
log(q e − q t ) = log q e − t (2)
2.303

Similarly, the linear form of the pseudo-second-order rate equation can be written as:

t 1 1
= 2
+ t (3)
qt k 2q e qe

Finally, the intra-particle diffusion model is generally expressed as:

q t = k p t 1/ 2 (4)

where qe and qt are the amounts of Pb(II) ions adsorbed (mg/g) onto activated carbon at
equilibrium and a time t, respectively, and k1 (min1), k2 [g/(mg min)] and kp [mg/(g min1/2)] are
the adsorption rate constants for the respective models (Kula et al. 2008).

RESULTS AND DISCUSSION

Characterization of the adsorbents

On the basis of the nitrogen adsorption/desorption isotherms, it was possible to calculate the
specific surface areas, total pore volumes and pore-size distributions of the two adsorbents
studied. The corresponding values are listed in Table 2 overleaf.
It will be seen from the data listed that the specific surface area and the total pore volume of T1
with pyrolusite addition were greater than those for T0 without pyrolusite addition. Thus, the
Adsorption of Pb(II) Ions by Pyrolusite-modified Activated Carbon 499

TABLE 2. Nitrogen Adsorption Characteristics of Adsorbents


Adsorbents SBET (m2/g) Vt (cm3/g) Vmicro (cm3/g) Vmeso (cm3/g)

T0 327.67 0.5958 0.1432 0.4526


T1 364.71 0.6344 0.1617 0.4727

700

600

500

400
lodine value (mg/g)
300 MB value (mg/g)

200

100

0
T0 T1

Figure 1. Extent of iodine and MB adsorption by the laboratory-produced activated carbons.

specific surface area of T1 was 11.3% larger than that of T0. However, the activated carbon
produced had a lower specific surface area than most commercially available activated carbons,
which typically have specific surface areas in the range of ca. 400–1500 m2/g (Wang et al.
2008).This may have been due to the low level of organic matter and fairly high percentage of ash
in the sludge precursors (Liu et al. 2010). The increase in the total pore volume was mainly due
to the production of micropores and mesopores in T1, whose content were 12.9% and 4.4%,
respectively, higher than those in T0.
Iodine adsorption is considered to be a simple and quick method for evaluating the micropore
surface areas of activated carbons, while the adsorption of Methylene Blue (MB) dye is mainly
related to large micropores and mesopores (El-Sheikh 2008). The adsorption profiles of iodine and
MB onto T0 and T1 are presented in Figure 1 and shown that the iodine adsorption capacity of T1
was 16.83% higher than that of T0. In contrast, the MB adsorption capacities of T1 and T0 were
almost the same. These results are consistent with the structural data listed in Table 2.
The capacity of an activated carbon to adsorb metal ions depends not only on the quantity of
surface functional groups but also on the specific surface area. Generally, the higher the surface
area, the larger is the adsorptive capacity of the adsorbent (Rao et al. 2009). Hence, T1 with a larger
specific surface area would be expected to possess a higher adsorption capacity than T0. The
adsorption capacity is also influenced by the relationship between the diameter of the heavy metal
cation and the PSD (pore-size distribution) of the charcoal pores (Wang et al. 2008). Li et al. (2002)
found that effective adsorption usually happens when adsorbents exhibit a pore volume which is
ca. 1.3–1.8-times larger than the diameter of the target adsorbate. The ionic diameter of the Pb(II)
ion is ca. 0.224 nm and hence Pb(II) ion adsorption by a given activated carbon would largely
depend on its micropore structure. In the present study, the significant increase in the micropore
content of T1 could explain its enhanced adsorption capacity towards Pb(II) ions.
500 Lu Fan et al./Adsorption Science & Technology Vol. 29 No. 5 2011

3500 (a) 1
1 --- SiO2
3000

Intensity (a.u.)
2 --- Magnesium zinc sulphide
2500
2000
1500 21
2 2
1000 1 2
1 1
500 1 21 1
11 1 1
2
1
2
1 1 1 1
12 1 211 2 1
0
20 30 40 50 60 70
2θ (degrees)

5000 (b) 1 1 --- SiO2


Intensity (a.u.)

4000 2 --- Magnesium zinc sulphide


2
3 --- MnO2
3000

2000
1
1000 3
12
2
1 1 11
3 3 1 13 2 31 3 1
33 2 3 1 3 3 2 1313 21 1312 3 1 31 1 3 1 3
3
0
20 30 40 50 60 70
2θ (degrees)

4900 1
(c) 1 --- SiO2
3600
2 --- Mn3O4
Intensity (a.u.)

2500
1
3 --- MnO2
1600
4 --- PbO
900 4
2
2 1
3 1
13 43 3 1
400 2 4 4 2 2 3 1 2 21
4 2 41 4 2 4 4 1 1 2
2 2
24
3 4 24 2 4 4 4 2 32 43 4 2 1 1 21 1
2 3 2 1 1 42 3 4 2 4 2
100
0
10 20 30 40 50 60 70 80
2θ (degrees)

Figure 2. X-Ray diffraction spectra of the initial activated carbons (a) T0 and (b) T1, and (c) that of T1 after the adsorption
of Pb(II) ions.

The chemical constitution of the samples was examined by X-ray diffraction (XRD). Figure 2
shows the XRD patterns for the initial samples T0 and T1, and of T1 after the adsorption of Pb(II)
ions. As shown in Figure 2(a), clear diffraction peaks were observed for T0 which corresponded
to quartz (SiO2) and small amounts of magnesium zinc sulphide. According to the XRD pattern
depicted in Figure 2(b), T1 also contained quartz and magnesium zinc sulphide as components.
Moreover, as a consequence of the addition of pyrolusite, higher intensity peaks were present in
the spectrum of T1, thereby indicating that the SiO2 present in T1 was of higher crystallinity. Such
crystalline SiO2 can provide a support for the formation of the activated carbon skeleton.
Diffraction peaks corresponding to manganese dioxide (MnO2), the main component of
pyrolusite, were also found in the X-ray diffraction spectrum of T1 [Figure 2(b)]. The transition
metal constituents in pyrolusite could act as catalysts promoting the decomposition and
Adsorption of Pb(II) Ions by Pyrolusite-modified Activated Carbon 501

transformation processes of some complex organic materials in the precursor. The XRD pattern of
T1 after the adsorption of Pb(II) ions is shown in Figure 2(c), which indicates the presence of
peaks due to lead oxide (PbO) in the sample obtained.
The chemical nature of the functional groups present on an adsorbent surface is vitally important
in understanding the course of a given adsorption process and the adsorption capacity of a given
adsorbent. Fourier-transform infrared (FT-IR) spectroscopy is the usual method employed for this
purpose. Application of this method allows the changes in the vibration frequencies of the
functional groups on the surfaces of activated carbons to be examined (Goel et al. 2005). In the
present study, possibly due to the detection limit of this method, the effects of the addition of
pyrolusite addition were not obvious since the FT-IR spectra of T0 and T1 were quite similar.
However, the presence of oxygen-containing functional groups such as the hydroxy group (–OH)
and carboxylic acid groups (–COOH) could still be observed in the FT-IR spectra. The abundant
production of such oxygen-containing functional groups on the surfaces of adsorbents can provide
numerous chemical adsorption sites and thus increase their ion-exchange capacities towards metal
ions such as Pb(II) (Lu et al. 2008; Pradhan and Sandle 1999).

Adsorption studies of Pb(II) ions

Effect of contact time

The effect of contact time on the adsorption of Pb(II) ions by the activated carbons produced is
demonstrated by the data depicted in Figure 3. The corresponding studies were undertaken
employing an initial Pb(II) ion concentration of 200 mg/ together with an initial pH of 5.4 (which
was not adjusted during the studies) and an adsorbent dosage of 2 g/. It can be seen from Figure
3 that the adsorption of Pb(II) ions by T0 and T1 increased with increasing contact time. After
allowing the adsorption process to proceed for 4 h, the corresponding adsorption capacities of T0
and T1 towards Pb(II) ions were 58.20 mg/g and 67.33mg/g, respectively. This result indicates
that the adsorption capacity of T1 was 15.69% greater than that of T0.

70

65
Adsorption capacity (mg/g)

60

55

50

45
T0
40 T1

35
0 50 100 150 200 250 300
Contact time (min)

Figure 3. Effect of contact time on Pb(II) ion adsorption by the laboratory-produced activated carbons. Experimental
conditions employed: initial Pb(II) ion conc.  200 mg/; pH  5.4; adsorbent dosage  2 g/.
502 Lu Fan et al./Adsorption Science & Technology Vol. 29 No. 5 2011

80

70

Adsorption capacity (mg/g)


60

50

40

30

20 T0

T1
10

0
0 2 4 6
pH

Figure 4. Effect of pH on Pb(II) ion adsorption by the laboratory-produced activated carbons. Experimental conditions
employed: initial Pb(II) ion conc.  200 mg/; contact time  5 h; adsorbent dosage  2 g/.

Effect of pH

Since the surface charge on an adsorbent can be modified by changing the pH of the solution with
which it is in contact, it follows that pH is one of the most important parameters affecting the
adsorption processes of metal ions (Uyanik and Aygün 2006). Figure 4 shows the effect of pH on
the adsorption of Pb(II) ions by T0 and T1. The data depicted in the figure were obtained by
conducting experiments in which the initial pH was varied from 1 to 6, employing an initial Pb(II)
ion concentration of 200 mg/, a contact time of 5 h and an adsorbent dosage of 2 g/. Basically,
the adsorption capacity increased with increasing pH for both adsorbents. Since the pH value at
which Pb(II) ions precipitate is ca. 7–8 (Kadirvelu et al. 2000), studies of the adsorption of Pb(II)
ions were not conducted above a pH value of 7 in the tests employed in this study, thereby
ensuring that the mechanism for Pb(II) ion removal only depended on adsorption. In such studies,
the surface of the adsorbent was surrounded by H ions present in the contacting aqueous phase.
These ions could compete with Pb(II) ions for surface adsorption sites, thereby preventing the
Pb(II) ions from approaching the binding sites on the adsorbent. This led to lower Pb(II) ion
adsorption at low pH values. With increasing pH, competition between H and Pb(II) ions for
surface adsorption sites decreased. At the same time, the negative charge density on the activated
carbon surface increased due to deprotonation of the H ion-containing binding sites, thereby
improving the adsorption capacity towards Pb(II) ions.
The maximum adsorption capacity of T1 (77.01 mg/g) occurred at a pH value of 5.0, while that
of T0 (60.98 mg/g) occurred at a pH value of 5.0. Goel et al. (2004) used coconut shell-based
activated carbon for the adsorption of Pb(II) ions and showed that maximum adsorption occurred
in the pH range 4.0–5.0 in this case. According to Goel et al. (2004), partial hydrolysis of the
metal ions may result in the formation of hydrolyzed species capable of greater adsorption onto
the non-polar carbon surface. At the initial pH value of the solution (5.4), the adsorption capacities
of T1 and T0 towards Pb(II) ions were 69.87 mg/g and 65.38 mg/g, respectively, indicating that
the adsorbents in this experiment could perform well in the removal of Pb(II) ions without any
initial pH adjustment.
Adsorption of Pb(II) Ions by Pyrolusite-modified Activated Carbon 503

100

80

% Removal
60

40 T0

T1

20
0 2 4 6 8 10

Adsorbent dosage (g/ℓ)

Figure 5. Effect of adsorbent dosage on Pb(II) ion adsorption by the laboratory-produced activated carbons. Experimental
conditions employed: initial Pb(II) ion conc.  200 mg/; contact time  5 h; pH  5.4.

Effect of adsorbent dosage

The effect of adsorbent dosage on Pb(II) ion adsorption was studied employing a contact time of
5 h, an initial Pb(II) ion concentration of 200 mg/ and an initial solution pH value of 5.4. As
shown by the data depicted in Figure 5, the percentage removal of Pb(II) ions by both adsorbents
increased initially with increasing adsorbent dosage and then became constant. Increasing the
amount of adsorbent employed led to an increase in the amount of surface accessible for
adsorption, thereby causing an increasing in the extent of Pb(II) ion removal (Kapica et al. 2002).
In the present studies, an adsorbent dosage of 9 g/ was sufficient to achieve 95.8% removal of
Pb(II) ions by T1 and 93.77% removal by T0.

Adsorption capacity

As listed in Table 3 overleaf, the activated carbons prepared from various materials employed for the
removal of Pb(II) ions from aqueous media have exhibited quite different adsorption capacities.
However, from the data given in the table, it can be seen that activated carbon T1 generated in our
studies showed a comparable adsorption capacity to the other adsorbents listed and exhibited a
relatively high Pb(II) ion adsorption capacity. This demonstrates that pyrolusite-modified sewage
sludge-based activated carbon is suitable for removing Pb(II) ions from aqueous solutions.
Indeed, on comparison with the behaviour of T1, those activated carbon prepared from other
materials, such as Ceiba pentandra hulls and apricot stone, showed lower Pb(II) ion adsorption
capacities even though they possessed relatively high surface areas. Pyrolusite-modified
adsorbents also exhibit a good performance relative to other sewage sludge-based activated
carbons (Rozada et al. 2008), despite the latter having higher surface areas due to the higher
carbon content of their precursors. This was probably due to other factors capable of influencing
the adsorption capacity besides the surface area, e.g. the quantity of surface functional groups, as
well as the relationship between the diameter of the heavy metal cation and the PSD (particle-size
504 Lu Fan et al./Adsorption Science & Technology Vol. 29 No. 5 2011

TABLE 3. Adsorption Capacities of Activated Carbons Prepared from Various Materials Towards Pb(II) Ions

Adsorbents Adsorption capacity SBET Reference


(mg/g) (m2/g)

Euphorbia rigida carbon 279.72 741.21 Gerçel and Gerçel (2007)


Tamarind wood carbon 134.22 612.00 Singh et al. (2008)
Rice straw carbon 121.30 128.10 Qiu et al. (2008)
Sewage sludge activated carbon 64.10 472.00 Rozada et al. (2008)
Coconut shell carbon 26.50 265.96 Sekar et al. (2004)
Ceiba pentandra hulls carbon 25.50 521.00 Rao et al. (2008)
Apricot stone carbon 22.85 566.00 Kobya et al. (2005)
Eichhornia carbon 16.61 265.96 Shekinah et al. (2002)
Pyrolusite-modified sewage sludge carbon 69.87 364.71 Present study

distribution) of the charcoal pore, etc. The good adsorption capacities of the activated carbons
produced in our study could have resulted from the high percentage of micropores generated and
the improvement in the surface chemical characteristics induced by pyrolusite modification of T1.

Adsorption kinetics and isotherms

Equilibrium adsorption isotherms provide most useful data for understanding the mechanism of a
given adsorption process (Gerçel and Gerçel 2007). In the present study, adsorption isotherm
experiments were conducted at room temperature, employing an initial Pb(II) ion concentration
of 150 mg/, a pH value of 5.4 and a contact time of 300 min. The equilibrium adsorption
isotherms of Pb(II) ions onto T0 and T1 are depicted in Figure 6. The data depicted in the figure
could be fitted by the Langmuir isotherm model with high values of the corresponding correlation
coefficients, i.e. 0.9785 for T0 and 0.9577 for T1 (both r2  0.95). The Langmuir constants Q and
KL calculated using equation (1) were 64.10 mg/g and 0.0479 /mg for T0, and 72.46 mg/g and
0.0493 /mg for T1, respectively.

60

50

40
qe (mg/g)

30

20
T0
10
T1
0
0 10 20 30 40 50 60
Ce (mg/ℓ)

Figure 6. Adsorption isotherms for Pb(II) ions onto T0 and T1.


Adsorption of Pb(II) Ions by Pyrolusite-modified Activated Carbon 505

TABLE 4. Kinetic Parameters for the Adsorption of Pb(II) Ions onto Adsorbents Examined in this Study
Adsorbent Pseudo-first-order Pseudo-second-order Intra-particle diffusion

k1 (min1) r2 k2 [g/(mg min)] r2 kp [mg/(g min0.5)] r2

T0 0.1310 0.8102 0.0171 0.9926 1.2847 0.9251


T1 0.0109 0.8883 0.0148 0.9955 1.3680 0.9464

In order to understand the adsorption kinetics of Pb(II) ions, the kinetic data obtained in the
present work (Figure 3) were examined employing the pseudo-first-order, pseudo-second-order
and intra-particle diffusion models, respectively.The calculated parameters for all the kinetic
models obtained using equations (2)–(4) are listed in Table 4.
According to Table 4, the highest correlation coefficients were obtained from the application of
the pseudo-second-order kinetic model, thereby demonstrating that this model provided the best
explanation and fit for the data obtained with both T0 and T1. This indicates that the
concentrations of both Pb(II) ions and adsorbent employed in the sorption process were involved
in the rate-determining step, which might involve a single chemical sorption or a succession of
chemisorptions (Rao et al. 2008).

CONCLUSIONS

Activated carbons were prepared from sewage sludge with and without the addition of pyrolusite
using ZnCl2 as the chemical activating agent. The experimental results showed that activated
carbons modified by the addition of 1% pyrolusite possessed higher BET surface areas and larger
pore volumes than the sample without pyrolusite addition. X-Ray diffraction data showed that
MnO2, the main constituent of pyrolusite, was loaded onto the activated carbon surface produced.
Adsorption was effective for an initial pH value of 5.4 for the Pb(II) ion solution, the
corresponding adsorption capacity of the activated carbons examined being ca. 70 mg/. The
Pb(II) ion adsorption capacity also increased with increasing contact time and adsorbent dosage.
The pyrolusite-modified activated carbon exhibited a relatively high Pb(II) ion adsorption
capacity in comparison to other activated carbons prepared from various materials. This
demonstrates that the adsorbent produced in this study was suitable for the removal of Pb(II) ions
from aqueous solutions. The data arising from the corresponding adsorption kinetic experiments
were examined by various isotherm models in order to study the adsorption characteristics. The
results showed that the equilibrium and kinetic adsorption data for Pb(II) ions onto the adsorbents
were well fitted by both the Langmuir isotherm and the pseudo-second-order kinetic model.

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