Chemical Engineering Journal 172 (2011) 361–368

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Chemical Engineering Journal

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Adsorption study of Pb(II), Cu(II) and Zn(II) from simulated acid mine drainage
using dairy manure compost
Mingliang Zhang ∗
School of Resource and Environment, University of Jinan, Jinan 250002, PR China

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

Article history: Dairy manure compost (DMC) was used to be one efficient biosorbent for the removal of heavy metals
Received 21 April 2011 from simulated acid mine drainage. Single and competitive adsorption of Pb, Cu and Zn by DMC were stud-
Received in revised form 6 June 2011 ied. The adsorption isothermal data fit the Langmuir isotherm better than the Freundlich isotherm model.
Accepted 8 June 2011
The maximum adsorption capacities calculated by applying the Langmuir isotherm were 0.460 mmol/g
for Pb, 0.428 mmol/g for Cu, and 0.237 mmol/g for Zn at pH 4.0. The single and competitive adsorption
Keywords:
studies showed that the adsorption affinity order of the three heavy metals was Pb > Cu > Zn. The rate of
Dairy manure compost
adsorption of the three metals was fast, which reached equilibrium in 60 min, and followed the pseudo-
Heavy metal
Adsorption
second-order model well. Adsorption efficiency of the heavy metals was pH dependent and the maximum
Desorption adsorption was found to occur at around 3.5 for Pb, 4.5 for Cu, 5.5 for Zn. An increase of ionic strength
Ion exchange caused a decrease in adsorption capacity for Zn and Cu, while negligible effect for Pb. The regeneration
experiments showed that the adsorbent could be regenerated and reused at least three cycles without
significant decrease in adsorption capacity. The results showed DMC could have great potential in treat-
ing heavy metals in acid mine drainage. Finally, ion exchange was found to be the primary mechanism
of adsorption.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction
Acid mine drainage (AMD) is derived from mine waste rock
piles, pit mining works, overburden and flotation reactive tailing
[1], which have resulted in severe heavy metal contamination of
surface and groundwater, as well as soil. AMD is considered as
the most serious environmental problem associated with metal
and coal mining industries in China. Heavy metals, unlike organic
pollutants, are not biodegradable and can be accumulated in liv-
ing tissues. Consequently, the removal of heavy metals from AMD
or other wastewaters has been a major concern for recent years.
Several traditional treatment processes have been used to remove
heavy metals dissolved in AMD or wastewaters, such as chemical
precipitation, ion exchange, membrane filtration, reverses osmosis
and activated carbon adsorption, etc. [2]. However, the high cost
and labor-intensive operation of these methods limit their large-
scale use for the removal of heavy metals. Considerable attention
has been paid to the development of new technologies that can
reduce heavy metal concentrations to environmentally acceptable
levels at low-cost.
∗ Tel.: +86 531 82769233; fax: +86 531 82769233.
E-mail address: stu zhangml@ujn.edu.cn
Many low-cost biosorption materials have been used in the past
few years, which have been demonstrated to be promising meth-
ods for heavy metal removal, such as tea waste [3], peanut hull
[4], grape stalk waste [5], apple waste [6], sawdust [7], sludge [8],
algae [9], peat [10], orange peel [11], mango peel waste [12], rice
husk [13], barley straw [14], rice bran [15], almond shell [16], hazel-
nut shell [17], wool fibers [18], leaf powder [19], algal biomass
[20], banana pith [21], cotton boll [22], tree bark [23], sugar beet
pulp [24], activated carbon fibers [25], coconut waste [26], chitin
[27] and many other agricultural by-products. Compared with the
traditional methods, biosorption treatment has the advantages of
low operating cost, high efficiency and minimum generation of
toxic sludge [28,29].
Although many bioadsorbents can effectively remove dissolved
heavy metals, most of them have poor adsorption effectiveness at
low pH, which has limited their use in the removal of heavy metals
from AMD. A large amount of dairy manure compost (DMC) in China
was generated, which could cause environmental pollution if not
handled properly. This kind of waste contains abundant lignin and
chitin, which has great potential for adsorption of heavy metals
[30].
Based on the research at present, the objective of this study was
to evaluate the application potential of DMC as a new, inexpen-
sive and environment-friendly adsorbent material for removal of
heavy metals in AMD. AMD contains many types of heavy metal

1385-8947/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2011.06.017
362 M. Zhang / Chemical Engineering Journal 172 (2011) 361–368
ions, so adsorption studies from multi-metal systems are useful
for field practice design. For each single metal, a series of batch
adsorption experiments were conducted to determine the effects
of pH, ionic strength, initial metal concentration and adsorption
time on heavy metals adsorption efficiency. Ion exchange is one
of the proposed mechanisms involved in the metal biosorption.
In order to examine ion exchange mechanism during heavy met-
als adsorption by DMC, the release of Ca2+ , Mg2+ , K+ , Na+ and
H+ while adsorbing Pb, Cu and Zn in a single metal system was
determined.
2. Materials and methods
2.1. Characterization of adsorbent and reagents
Dairy manure compost samples were obtained from one farm
in Weifang city, Shandong province, China, and the samples were
washed with distilled water, oven dried at 105 ◦ C for 24 h, ground
and passed through a 1 mm sieve and then stored in a plastic con-
tainer as the bioadsorbent in the following experiments. Standard
stock solutions of Pb, Cu and Zn (1000 mg/L, as their respective
nitrate salts, Jinan Pharmaceutical Co. Ltd. in China) were used
to prepare appropriate concentrations of each heavy metal for
the adsorption studies. The exact concentration in stock solution,
diluted solution and filtrate of Pb, Cu and Zn in the following exper-
iments were measured by ICP-OES (Perkin Elme, USA). The pH of
the working solution was adjusted to 4.0, unless otherwise stated,
using 0.5 mol/L NaOH or HCl. Fresh dilutions were used for each
adsorption study.
2.2. Major cation content of DMC
The release of alkaline and alkaline earth metals (e.g., Ca2+ , Na+ ,
K+ and Mg2+ ) from acid-washed DMC was measured as the approxi-
mate ion exchange capacity of DMC. The protonation of the material
was made to show that the exchangeable cations that were present
on the raw material could be released into the solution after the
proton uptake. 0.3 g DMC was soaked with 50 mL of 0.1 mol/L HCl,
stirred for 1 h at room temperature (25 ± 2 ◦ C) in a rotary mixer, and
then filtered through a 0.45 mm filter paper. DMC was resuspended
in the same HCl solution, and the previous treatment was repeated
three times. As control, the same procedure was carried out con-
taining 0.3 g of DMC with 50 mL of deionized water. The filtrates so
obtained were analyzed ICP-OES to determine Na+ , K+ , Mg2+ and
Ca2+ released from DMC [5].
2.3. Adsorption isotherms
Single, binary and ternary adsorption of Pb, Cu and Zn by
DMC were conducted by batch experiments at 25 ± 2 ◦ C. In sin-
gle metal ion adsorption experiments, 0.3 g DMC and 20 mL of Pb,
Cu or Zn solution (adsorbent dose, 15 g/L) were put into 50 mL
polypropylene centrifuge tubes. The pH of the solutions was main-
tained at 4.0 with HNO3 or NaOH solution. The mixtures were
agitated at 200 rpm on a shaker for 4 h, which was found to
be enough to reach adsorption equilibrium. After agitation, the
mixture was centrifuged for 30 min and then filtered through
0.45 ␮m filter paper. The adsorbed amounts of metal ions were
calculated by the difference between the initial and final con-
centrations remaining in the equilibrium filtrate after adsorption.
Meanwhile, for each sample, an experiment without adsorbent
was conducted to demonstrate negligible adsorption and pre-
cipitation of metal ions on the container walls. The adsorption
isotherm experiments were done in triplicate and the average
results were presented in this study. The adsorption efficiency of
metal ion was calculated by using the following Eq. (1), and adsorp-
tion capacity which is the amount of heavy metal ions adsorbed
per unit mass of DMC can be obtained by using the following
Eq. (2):
Co − Cf
R= × 100 (1)
Co
V (Co − Cf )
q= (2)
m
In these two equations, R represents adsorption efficiency (%), q
is the amount of metal adsorption per unit mass of the adsorbent
(mmol/g), V the volume of the solution (L), m the dry mass of the
adsorbent (g), Co and Cf initial and final concentrations (mmol/L),
respectively.
The adsorption isotherms were characterized by the Langmuir
and the Freundlich isotherm models. The Langmuir model is gen-
erally used to characterize the equilibrium between the adsorbent
and solution as a reversible chemical equilibrium between species.
A linear form for the Langmuir model is given as:
Ce 1 Ce
= + (3)
qe bqmax qmax
where qe is the amount adsorbed (mmol/g), Ce is the equilibrium
concentration of the adsorbate (mmol/L), qmax is the maximum
adsorption capacity (mmol/g), and b is the adsorption equilib-
rium constant (L/mmol), which suggests the affinity of adsorption.
The Freundlich model originally proposed as an empirical equa-
tion to describe the data for heterogeneous adsorbents such
as activated carbon. A linear form of the Freundlich model is
given as:
1
log qe = log KF + log Ce (4)
n
where KF (mmol/g) and n (g/L) are the Freundlich constants related
to adsorption capacity and adsorption intensity, respectively.
2.4. Adsorption kinetic
The adsorption kinetic of single metal ion was conducted in
1000 mL conical flasks at pH 4.0. 6 g DMC was thoroughly mixed
with 400 mL of 0.5 mmol/L metal ion solution. Samples were col-
lected at 1 mL at required time intervals, and were filtered through
0.45 ␮m filter paper. The adsorption kinetic experiments were con-
ducted in triplicate and the average results were presented in this
study.
Pseudo-second-order kinetic model was applied to simulate the
kinetic data and expressed as:
t 1 1
= + t (5)
qt kq2 qe
where qe and qt are the amounts of solute adsorbed by adsorbent
at equilibrium and at time t (mmol/g), respectively; k is the rate
constant (g/mmol min); t is the adsorption time (min). The values
of k and qe were determined using slope and intercept of regression
line. In the limit qt /t → 0, the initial adsorption rate, h (mmol/g min),
is given by h = kq2 e . The plot of t/qt against t of Eq. (5) should give
a linear relationship with a slope of 1/qe and an intercept of 1/h, or
1 = kq2 e .
2.5. Effect of pH on adsorption
In order to identify the pH effect on Pb, Cu and Zn adsorption on
DMC, the following experiments were performed: 0.3 g DMC and
20 mL of either Pb, Cu or Zn (0.5 mmol/L) solution were added into a
50 mL polypropylene centrifuge tube, respectively. The solution pH
was adjusted within the range of 1.0–8.0 by adding either HNO3 or
 M. Zhang / Chemical Engineering Journal 172 (2011) 361–368
NaOH during the experiment. After 4 h of shaking, the solution pH
was measured and then filtered through a 0.45 ␮m filter paper. The
experiments were carried out in triplicate and the average results
were presented in this study.
2.6. Effect of ionic strength
Sodium nitrate (NaNO3 ) was used to study the effects of ionic
strength on heavy metal ions adsorption. The concentration of this
salt was varied within the range of 0–1.0 mol/L. In the experiments,
initial metal concentration was 0.5 mmol/L and the pH was 4.0. The
experiments were carried out in triplicate and the average results
were presented in this study.
2.7. Desorption studies
Heavy metal-loaded DMC adsorbent (1 g) was shaken with
50 mL of 0.1 mol/L HCl as the desorbing agent in 250 mL Erlenmeyer
flasks at 200 rpm on an orbital shaker for 1 h at room temperature.
The heavy metal-loaded DMC–HCl suspension was centrifuged and
the supernatant was analyzed for heavy metal ions desorbed. The
heavy metal-desorbed DMC was reused as the adsorbent in three
repeated adsorption–desorption cycles to determine regeneration
potential of the adsorbent.
2.8. Ion exchange and energy dispersive X-ray (EDX) analysis
0.3 g DMC were contacted with 20 mL of heavy metal solution
(1 mmol/L) at pH 4.0 and agitated at 200 rpm on a shaker for 4 h,
as control, the release amount of cations after washing succes-
sively with distilled water was also measured. The amount for net
release of cations due to Pb, Cu and Zn adsorption can be calcu-
lated by subtracting the amount of heavy metal cations released
when washing with distilled water (control) to the amount of metal
cations measured in the supernatant after Pb, Cu, and Zn adsorp-
tion process. In order to further confirm of the involvement of ion
exchange process in the adsorption of heavy metals on DMC, the
surface structure of the DMC before and after heavy metals adsorp-
tion was analyzed by JSM-7001F scanning electron and chemical
constituents of the adsorbents before and after heavy metals
adsorption were performed by electron dispersive X-ray analysis
(EDX).
3. Results and discussion
3.1. Major cation content of DMC
The total amount of cations released indicated a total ionic
content of 0.703 meq/g (0.415 mmol/g) dry waste in DMC, consist-
ing of 0.105, 0.022, 0.217 and 0.359 meq/g of Na+ , K+ , Mg2+ and
Ca2+ , respectively. This total ionic content can be considered as
an approximate value of the cation exchange capacity (CEC) of the
DMC.
Table 1
Isotherm parameters of Langmuir and Freundlich in single heavy metal adsorption on DMC at pH 4.0.
Adsorption system Langmuir
qmax (mmol/g) b (L/mmol)
Pb 0.460 7.869
Cu 0.428 1.328
Zn 0.237 0.506
363
3.2. Single-solute isotherm
Both Langmuir isotherm model and Freundlich isotherm model
fit the adsorption isotherms of Pb, Cu and Zn on DMC in single-
solute systems. Parameter values for the Langmuir and Freundlich
isotherm models were presented in Table 1. The Langmuir isotherm
model showed a higher regression coefficient (R2 ) than the Fre-
undlich model in general. This is in agreement with the work
of Sharma and Forster [31]. The qmax value of Pb, Cu and Zn
were 0.460 mmol/g, 0.428 mmol/g and 0.237 mmol/g respectively,
which suggested the adsorption affinity of DMC decreased in
the order of Pb > Cu > Zn. Meanwhile, the adsorption equilibrium
constants (b) corresponded to the same order (Table 1). Con-
sidering that the adsorption of heavy metals on DMC is mainly
due to ion exchanges at the surface level, it is expected that
more electronegative metals will show a higher adsorption ten-
dency [32,33]. The electronegativity (Pauling scale) of each metal
is 2.33, 1.90, and 1.65, respectively. The adsorption affinity of
heavy metal observed here is in agreement with the order of elec-
tronegativity (Pb > Cu > Zn). It is expected that metals with larger
hydrated radius will show a lower adsorption affinity. The hydrated
radius of Pb2+ , Cu2+ , Zn2+ is 4.01 Å, 4.19 Å, and 4.30 Å, respec-
tively. It could be concluded that adsorption affinity of heavy
metals on DMC was tentatively correlated with hydrated radius and
electronegativity [32,34].
3.3. Multi-solute competitive isotherm
The competitive adsorptions of Pb, Cu and Zn on the adsor-
bent followed the Langmuir isotherm model very well with the
values of R2 (0.95–0.99) (Table 2), and they also fit the Freundlich
isotherm model with the values of R2 (0.87–0.97), but not better
than the Freundlich isotherm model in general (Fig. 1). Compared
with single-solute system, the adsorption capacity (qmax ) of the
three heavy metals decreased significantly in both binary and
ternary solute systems. Furthermore, the decrease in the adsorp-
tion capacity was greater in ternary solute systems compared
to that of binary solute systems. These results indicated com-
petition existing between heavy metals for adsorption sites on
DMC.
At low initial concentration, the adsorption of Pb, Cu and Zn
increased rapidly due to the abundance of adsorption sites of DMC.
Therefore, the competitive effects were not pronounced. For exam-
ple, at the initial concentration of 0.04 mmol/L of Cu, the adsorption
capacity of Cu on DMC was 0.002 mmol/g in single and multi-solute
systems, which showed there was negligible effect of adsorptive
competition. With the increasing concentration of heavy metals,
metal cations could compete for the adsorption sites of DMC,
which would result in a decrease in the adsorption capacity. For
example, at the initial concentration of 4.75 mmol/L of Cu, the
adsorption capacity of Cu on DMC was 0.245 mmol/g in single sys-
tem, 0.205 mmol/g in the Cu–Zn system, 0.157 mmol/g in the Cu–Pb
system, 0.139 mmol/g in the Cu–Pb–Zn system, which showed sig-
nificant competition between Pb, Cu and Zn. When heavy metals
compete for the same adsorption sites on an adsorbent, metal
cations with high affinity could be bound to adsorption sites of
DMC or displace other ions with a lower affinity. Among the three
Freundlich
R2 KF (mmol/g) n (g/L) R2
0.99 1.041 1.258 0.94
0.99 0.230 1.364 0.95
0.96 0.068 1.389 0.95
364 M. Zhang / Chemical Engineering Journal 172 (2011) 361–368

Table 2
Parameters of Langmuir and Freumdlich isotherms in competitive adsorption on DMC at pH 4.0.

Adsorption system Langmuir Freundlich

qmax (mmol/g) b (L/mmol) R2 qc /qs KF (mmol/g) n (g/L) R2

Pb 0.460 7.869 0.99 1.041 1.258 0.94

Pb(Pb + Zn) 0.438 6.192 0.96 0.95 0.698 1.336 0.87
Pb(Pb + Cu) 0.409 6.142 0.98 0.89 0.540 1.416 0.88
Pb(Pb + Cu + Zn) 0.407 4.905 0.99 0.88 0.493 1.377 0.92

Cu 0.428 1.328 0.99 0.230 1.364 0.95

Cu(Cu + Zn) 0.329 1.331 0.96 0.77 0.192 1.267 0.95
Cu(Cu + Pb) 0.217 1.704 0.98 0.51 0.119 1.468 0.94
Cu(Cu + Pb + Zn) 0.176 1.767 0.99 0.41 0.094 1.513 0.95

Zn 0.237 0.506 0.96 0.068 1.389 0.95

Zn(Zn + Cu) 0.130 0.523 0.95 0.55 0.038 1.250 0.95
Zn(Zn + Pb) 0.108 0.510 0.96 0.45 0.031 1.266 0.95
Zn(Zn + Pb + Cu) 0.089 0.489 0.98 0.38 0.024 1.272 0.97

5 0
4.5 a Pb -8 b -6 -4 ln(Ce) -2
-1
0 2
4 Pb(Pb+Cu)
Pb(Pb+Zn)
3.5 Pb(Pb+Cu+Zn) -2
3
-3
Ce/qe

2.5

ln(qe)
2 -4
Pb
1.5 Pb(Pb+Zn) -5
1 Pb(Pb+Cu)
0.5 Pb(Pb+Cu+Zn) -6
0
-7
0 0.5 1 1.5 2
Ce (mmol/L)

35
0
30
a Cu -6
b -4 -2 0 2
Cu(Cu+Zn) -1
Cu(Cu+Pb) Cu
25
Cu(Cu+Pb+Zn) Cu(Cu+Zn) -2
20 Cu(Cu+Pb)
Ce/qe

Cu(Cu+Pb+Zn) -3
ln(qe)

15
-4
10
-5
5
-6
0
0 1 2 3 4 5 -7
Ce (mmol/L) ln(Ce)

ln(Ce)
0
100
a -5 b -4 -3 -2 -1
-1
0 1 2
90
Zn
80 Zn(Zn+Cu) -2
Zn
70 Zn(Zn+Pb)
Zn(Zn+Pb+Cu) Zn(Zn+Cu) -3
60 Zn(Zn+Pb)
Ce/qe

50 Zn(Zn+Pb+Cu)
-4
ln(qe)

40 -5
30
-6
20
10 -7
0 -8
0 1 2 3 4 5 6
Ce (mmol/L)

Fig. 1. Linear plots of Langmuir and Freundlich isotherms of single and multi-solute adsorption of Pb, Cu and Zn on DMC at pH 4.0 ((a) for linear Langmuir isotherms, (b) for
linear Freundlich isotherms).
 M. Zhang / Chemical Engineering Journal 172 (2011) 361–368
heavy metal ions discussed above, Zn had the lowest affinity, so it
was more easily displaced by the other two heavy metal cations. Pb
cation, having the highest affinity, showed only a slight decrease in
adsorption capacity.
Mohan and Singh [35] and Qin et al. [34] investigated the com-
petitive effects of metals on their adsorption in multi-solution
systems by measuring the ratio of adsorption capacity of one
metal in multi-solute systems, qc , to that of given metal in single-
solute systems, qs . If qc /qs > 1, metals enhanced the adsorption of
each other. If qc /qs = 1, metals had no effect on each other, and if
qc /qs < 1, metals compete with other metals. As shown in Table 2,
the competitive effect of Pb, Cu, and Zn in single and muliti-
solute systems was evident according to the values of qc /qs < 1,
which further demonstrated the competitive adsorption of Pb, Cu
and Zn. Moreover, Pb, Cu and Zn had different competitive effect.
Compared to its adsorption in single-solute systems, the adsorp-
tion capacity (qmax ) of Pb on DMC decreased by 4.78% in Pb–Zn
system, 11.09% in the Pb–Cu system, 11.52% in the Pb–Zn–Cu sys-
tem. Similarly, the adsorption capacity (qmax ) of Cu on DMC was
decreased by 23.13% in the Cu–Zn system, 49.30% in the Cu–Pb
system, 58.88% in the Cu–Pb–Zn system. The adsorption capacity
(qmax ) of Zn on DMC was decreased by 45.15% in Zn–Cu sys-
tem, 54.43% in Zn–Pb, 62.45% in Zn–Pb–Cu, respectively. These
results showed that the adsorption capacity of Pb was reduced
to a lesser extent than that of Cu and Zn. The competitive abil-
ity of Pb, Cu and Zn followed the order of Pb > Cu > Zn. Differences
in competition for adsorption on DMC can be attributed to the
different affinity of co-existed ion(s) for the binding sites. Such
difference in competitive effects was also reported by Lv et al.
[36].
When multi-heavy metal ions are present together, the sum
adsorption capacity of total metal ions may increase, decrease, or
not change at al. [37]. The data in Table 2 indicated that total adsorp-
tion of Pb and Cu on DMC in the Pb–Cu multi system (0.626 mmol/g)
was higher than that of Pb (0.460 mmol/g) and Cu (0.428 mmol/g)
in their respective single solute solutions. Furthermore, in the Pb,
Cu and Zn multi-solute system, the total adsorption capacity was
(0.672 mmol/g) higher than Pb adsorption capacity (0.460 mmol/g),
Cu adsorption capacity (0.428 mmol/g) and Zn adsorption capacity
(0.237 mmol/g) in their respective single solute solutions. These
results suggest that the total adsorption capacity of heavy metals
in multi-solute systems increases, but individual metal ion adsorp-
tion will decrease due to metal ions competition for adsorption
sites. This conclusion was in agreement with the work of Hanzlík
et al. [38] and Qin et al. [34].
3.4. Kinetics
The rate of heavy metal adsorption is an important factor for
determining the reactor design and process optimization for a suc-
cessful filed application. The adsorption of Pb, Cu and Zn onto
DMC showed typical biphasic kinetics with rapid adsorption during
the first 10 min, followed by a slower one. Pb, Cu and Zn adsorp-
tion increased rapidly to 81.58%, 61.71% and 38.50%, respectively,
during the first 10 min, and then an equilibrium adsorption was
reached within 60 min that was equivalent to 96.30%, 86.77% and
Table 3
Theoretically determined parameters of pseudo-second-order kinetic model.
Metal ions Experimental qe (mmol/g)
qe (mmol/g)
Pb 0.029 0.029
Cu 0.027 0.028
Zn 0.018 0.019
365
250
200
t/Qt(min·g/mmol)
150
100
50
Pb Cu Zn
0
0 1 2 3 4 5
Time(hours)
Fig. 2. Linear plots of pseudo-second-order kinetics for the adsorptions of Pb, Cu and
Zn on DMC, (initial heavy metals concentrations, 0.5 mmol/L; DMC dosage, 15 g/L;
pH 4.0).
62.02%. Furthermore, there was no significant difference in adsorp-
tion among the obtained data for 2 h, 3 h, 4 h. The two-phase metal
adsorption process, the first being rapid and the second being
slower, has been reported in the literature [39,40]. It was observed
that 1 h contact time was chosen as an optimum time in each exper-
iment. Aringhieri et al. [41] and Lee and Yang [42] ascribed the
initial faster rate to a rapid diffusion of ions from solution to exter-
nal adsorbent surface, and the slower adsorption rate in the second
stage was probably due to the diffusion of metal ions into porous
structure of the adsorbent. The pseudo-second-order model was
used to simulate the adsorption kinetics of Pb, Cu and Zn (Fig. 2).
The parameters calculated are presented in Table 3 and indicate
that the pseudo-second-order kinetic model described the exper-
imental data well, evidenced by correlation coefficients close to
1. The initial adsorption rate h followed the descending order of
Pb > Cu > Zn, indicating that Pb was initially more rapidly adsorbed
on DMC than other two ions. Similar adsorption phenomena of Pb,
Cu and Zn on peat were also observed from single and binary solute
systems by Serrano et al. [43] and Qin et al. [34].
3.5. pH effect
It is well known that biosorption of heavy metal ions by biosor-
bents depends on the pH of the solution. The reaction of heavy
metal ions in solution with the sorbent may be described as
M n+ + AHn ↔ AM + nH + (6)
where M represents the metal, n is the charge, and A is the active
sorption site of the adsorbent. According to Eq. (6), heavy metal
ion sorption can be influenced by pH due to the competition effect
between the metal and H+ ions for active adsorption sites. At low
pH values, the H+ concentration is high, which can cause competi-
tion with heavy metal ions for surface adsorption sites and result
in a decrease in sorption of heavy metals. It was observed that the
biosorption was decreased at an initial acidic pH (Fig. 3). Biosorp-
tion of Pb, Cu and Zn increased with an increase in pH and reached a
maximum. The same trend has also been reported in the removal of
these ions by some other materials. The optimum pH of Pb, Cu and
k (g/mmol min) h (mmol/g min) R2
1134.402 0.982 0.99
455.647 0.345 0.99
630.595 0.228 0.99
366 M. Zhang / Chemical Engineering Journal 172 (2011) 361–368

100 indicated that the ionic strength of the solution influenced the
90 adsorption ability of the adsorbent. The reduction of the adsorp-
tion was greater for Zn than that of Cu and Pb. The reduction of
80
metal adsorption percentage is due to increasing concentrations
Adsorption efficiency (%)

70 of NaNO3 due to the presence of competing Na+ ions for metal

60 binding. Na+ can compete with other heavy metal ions for sur-
face adsorption sites, which can result in the decrease of metal
50
adsorption on the DMC. Thus, as NaNO3 concentration increases,
40 a decrease in heavy metal adsorption occurs. The effect of NaNO3
30
pb Cu Zn concentration on heavy metal adsorption is different for different
heavy metals due to differences in competitive adsorption abil-
20
ity. Heavy metal adsorption decreased, due to Na+ , in the order
0 1 2 3 4 5 6 7 8
pH Pb < Cu < Zn. Especially for the adsorption of Pb on DMC, the effect
of ionic strength was practically negligible. It has been reported that
Fig. 3. Effect of pH on the adsorption of Pb, Cu and Zn, (initial heavy metals concen-
strongly bound metals such as Pb are less affected by ionic strength
trations, 0.5 mmol/L; DMC dose, 15 g/L; pH 4.0).
[46].

Zn ions adsorption occurred at 3.5, 4.5 and 5.5, respectively, which 3.7. Ion exchange
was consistent with the results of Brown et al. [44]. It was also
observed that even with an acid solute, there was still a high adsorp- The existence of ion-exchange mechanism during the heavy
tion efficiency, such as Pb with the adsorption efficiency 93.13%, Cu metals adsorption by DMC was investigated in this work by follow-
77.15% and Zn 47.53% at pH 3.0. The results showed DMC could have ing the release of Ca2+ , Mg2+ , K+ and Na+ from this adsorbent after
a great potential to treat Pb, Cu and Zn in acid mine drainage, which the adsorption of Pb, Cu and Zn, respectively. For these experiments
usually has the pH of 2.0–3.0. 0.3 g DMC were mixed with 20 mL of metal solution (1 mmol/L)
The pH, at which 50% of the initial heavy metal ions were at pH 4.0. As control, the release of cations after washing succes-
adsorbed, called pH50 [45], is a measure of the relative affinity of sively with distilled water was also measured. The values for net
metal ions for the adsorbent. Lower pH50 indicates higher affin- release of cations (meq/g) due to Pb, Cu and Zn adsorption pre-
ity of metals for the adsorbent surface. The pH50 of Pb, Cu and Zn sented in Table 4, have been calculated by subtracting the amount
occurred at 1.20, 1.85 and 3.05. It was obvious that the pH50 of Pb of metal cations released when washing with deionized water (con-
is much lower than Cu and Zn, which demonstrated that the affin- trol) to the amount of metal cations measured in the supernatant
ity of Pb for DMC were higher than that of Cu and Zn. The result after Pb, Cu, and Zn adsorption process. The results show a sig-
was the same as that for the multi-solute competitive adsorption nificant release of Ca2+ , Mg2+ , K+ and H+ from DMC due to the
discussed above. adsorption of Pb, Cu and Zn. It was observed that 0.118 meq/g of
Pb, 0.106 meq/g of Cu, 0.074 meq/g of Zn was adsorbed on DMC,
3.6. Ionic strength effect meanwhile a sum of 0.113 meq/g, 0.102 meq/g, 0.071 meq/g of Ca2+ ,
Mg2+ , K+ , Na+ and H+ was released, respectively. It appeared that
The effect of NaNO3 concentration on heavy metal adsorption there was more Ca2+ released than the other cations, accounting
is shown in Fig. 4 where Pb, Cu and Zn adsorption efficiencies for 48.95% of the total cation released. The ratio of the heavy met-
at different NaNO3 concentrations are shown. The adsorption als adsorbed by the adsorbent and the alkaline and alkaline earth
efficiencies generally decreased with increasing NaNO3 concen- metals and protons released into the aqueous solution are shown
tration, however, lower concentrations (0–0.1 mol/L) caused no to be close to 1. This would mean that heavy metal ions adsorbed
significant decrease in the adsorption efficiency of Pb, Cu and from solution predominately in exchange for cations present in the
Zn, increasing ionic strength (up to 0.5 mol/L) NaNO3 resulted in adsorbent.
0.32%, 2.51% and 3.07% decrease of Pb, Cu, and Zn adsorption
respectively, and 1 mol/L NaNO3 resulted in 0.57%, 2.90%, 4.51% 3.8. Desorption studies
decrease in Pb, Cu, and Zn adsorption respectively. These results
In order to investigate the regeneration and reutilization of the
adsorbent, HCl was used as the desorbing agent for the recovery of
100 sorbed Pb, Cu and Zn from metal-loaded DMC. In the experiment,
95 1 g DMC loaded with maximum capacity of Pb (0.462 mmol/g), Cu
90
(0.426 mmol/g) and Zn (0.236 mmol/g) was mixed with the des-
orption agent (0.1 mol/L HCl) for 1 h and shaken at 200 rpm. The
Adsorption efficiency(%)

85
amount of Pb, Cu and Zn desorbed in HCl solution was then deter-
80 mined through measure the concentration of solution. Desorption
75 Pb
of Pb, Cu and Zn from the metal-loaded DMC for the first cycle
70
Cu resulted in 97.40%, 96.48% and 94.07% metal recovery, respectively.
Zn
The desorption efficiency for Pb, Cu and Zn remained high and
65
almost unchanged during the three adsorption–desorption cycles
60 (Table 5). The adsorption capacity of DMC for all three heavy met-
55 als during these repeated cycles was also shown in Table 5. In the
50
first cycle, the metal adsorption capacity of DMC was 0.462 mmol/g,
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0.426 mmol/g and 0.236 mmol/g for Pb, Cu and Zn, respectively.
Compared to the first cycle, there was a little increase in the adsorp-
Ionic strength (mol/L)
tion capacity in the second cycle, 0.485 mmol/g, 0.470 mmol/g, and
Fig. 4. Effect of ionic strength on the adsorption efficiency, (initial heavy metals 0.260 mmol/g for Pb, Cu and Zn, respectively. For the third cycle, a
concentrations, 0.5 mmol/L; DMC dose, 15 g/L; pH 4.0). non-significant decrease in the sorption capacity of DMC for three
 M. Zhang / Chemical Engineering Journal 172 (2011) 361–368 367

Table 4
Release amount of Ca, Na, K, Mg, and H due to adsorption of Pb, Cu and Zn on DMC.

Metal ions Total metal Net amount of cations released (meq/g)

adsorbed (meq/g)
Ca Na K Mg H Sum

Pb 0.118 0.070 0.001 0.002 0.030 0.010 0.113

Cu 0.106 0.038 0.015 0.002 0.026 0.021 0.102
Zn 0.074 0.031 0.001 0.006 0.015 0.017 0.071

Table 5
Adsorption and desorption amount of Pb, Cu and Zn on DMC in adsorption–desorption cycles (mmol).

Cycle no. Pb adsorption Pb desorption Cu adsorption Cu desorption Zn adsorption Zn desorption

1 0.462 0.450 0.426 0.411 0.236 0.222

2 0.485 0.463 0.470 0.455 0.260 0.254
3 0.484 0.464 0.459 0.439 0.248 0.243

metals was observed. However, it was still a little higher than
the amount of metal adsorbed in the first cycle. The increase of
adsorption capacity in the second cycle may be attributed to the
release of remaining cations, such as Ca2+ , Mg2+ , Na+ and K+ , dur-
ing the first desorption cycle with 0.1 mmol/L HCl, which exposed
more binding sites for the sorption of heavy metal ions in the sec-
ond sorption cycle. Similar result was also reported by Iqbal et al.
[12].
3.9. EDX analysis
Further confirmation of the involvement of ion exchange pro-
cess in the adsorption of heavy metals on DMC was done by EDX
analysis. Fig. 5 shows the typical EDX patterns for DMC, before and
after the adsorption of Pb2+ and Zn2+ . The EDX pattern (Fig. 5a) for
the unloaded (native) adsorbent did not show the characteristic
signal of Pb2+ and Zn2+ , whereas for the Pb2+ and Zn2+ loaded adsor-
bent (Fig. 5b) a clear signal of the presence of Pb2+ and Zn2+ was
observed (Cu was not found, maybe hidden in the DMC). Further-
more, the presence of Ca2+ , Mg2+ and K+ , which have been shown to
be involved in the ion exchange with Pb2+ and Zn2+ (Table 4), was
indicated in the spectra of unloaded (native) adsorbent. After the
adsorption of the Pb2+ and Zn2+ onto DMC, however, these cations
were decreased or not detected in the EDX spectrum of Pb2+ and
Zn2+ loaded adsorbent. These findings on EDX analysis indicated
the involvement of ion exchange mechanism for the removal of
metal ions by DMC.
4. Conclusions
The single and competitive adsorption of Pb, Cu and Zn on DMC
was analyzed through batch experiments. The results showed the
adsorption of three heavy metals was in the order of Pb > Cu > Zn.
Heavy metals adsorption isotherm date fit Langmuir adsorp-
tion isotherm better than Freundlich isotherm. The maximum
adsorption capacities calculated by applying the Langmuir equa-
tion to single ion adsorption isotherm were 0.460 mmol/g for Pb,
0.428 mmol/g for Cu, and 0.237 mmol/g for Zn at pH 4.0. Heavy
metal adsorption is pH dependent. When the pH increased, the
adsorption rate increased and the maximum adsorption was found
to occur at around 3.5 for Pb, 4.5 for Cu, 5.5 for Zn. It was also
observed that even with an acid solute, there was still a high adsorp-
tion efficiency, which showed DMC could have a great potential to
treat Pb, Cu and Zn in acid mine drainage. Increases in ionic strength
caused decreases in metal adsorption.
In terms of adsorptive competition, the presence of mixed heavy
metal ions had little effect on Pb, followed by Cu, with Zn being most
affected. The affinity of heavy metals for adsorption onto DMC was
in the order of Pb > Cu > Zn. The desorption experiment showed that
the adsorbent could have advantage of regeneration and reutiliza-
tion concerning adsorption of Pb, Cu and Zn. Adsorption kinetics
showed that the three heavy metal ions reached equilibrium within
60 min, which indicated a rapid adsorption rate. Thus, DMC could
have a strong potential for field application. The results indicated
that adsorption via ion-exchange was the most important mecha-
nism.

Acknowledgements

This work was supported by Shandong Provincial Natural Sci-

ence Foundation, China (ZR2010DQ005), the Project of Shandong
Fig. 5. Energy dispersive X-ray (EDX) analysis of DMC, (a) before and (b) after the
Province Higher Educational Science and Technology Program
sorption of Pb and Zn. (J09LB60) and Doctoral Fundation of University of Jinan (XBS1036).
368 M. Zhang / Chemical Engineering Journal 172 (2011) 361–368
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