Journal of Hazardous Materials 308 (2016) 75–83

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Journal of Hazardous Materials

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

Selective removals of heavy metals (Pb2+ , Cu2+ , and Cd2+ ) from

wastewater by gelation with alginate for effective metal recovery
Fei Wang a,b , Xingwen Lu a,c , Xiao-yan Li a,∗
a
Department of Civil Engineering, The University of Hong Kong, Pokfulam, Hong Kong
b
School of Environment and Guangzhou Key Laboratory of Environmental Exposure and Health, Jinan University, Guangzhou 510632, China
c
Research Center for Environmental Health and Pollution Control, and School of Environmental Science and Engineering, Guangdong University of
Technology, Guangzhou 510006, China

h i g h l i g h t s

• Gelation with alginate can rapidly remove heavy metal ions from wastewater.
• Pb2+ can be selectively removed by alginate when Cu2+ and Cd2+ are present.
• FTIR and XPS analyses indicate the role of OH and COO− in metal gelation.
• Calcination of the gels can obtain PbO, CuO, and CdO nanopowders for metal recovery.

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

Article history: A novel method that uses the aqueous sodium alginate solution for direct gelation with metal ions is
Received 17 August 2015 developed for effective removal and recovery of heavy metals from industrial wastewater. The experi-
Received in revised form 2 January 2016 mental study was conducted on Pb2+ , Cu2+ , and Cd2+ as the model heavy metals. The results show that
Accepted 9 January 2016
gels can be formed rapidly between the metals and alginate in less than 10 min and the gelation rates
Available online 12 January 2016
fit well with the pseudo second-order kinetic model. The optimum dosing ratio of alginate to the metal
ions was found to be between 2:1 and 3:1 for removing Pb2+ and around 4:1 for removing Cu2+ and Cd2+
Keywords:
from wastewater, and the metal removal efficiency by gelation increased as the solution pH increased.
Heavy metals
Alginate
Alginate exhibited a higher gelation affinity toward Pb2+ than Cu2+ and Cd2+ , which allowed a selective
Gelation removal of Pb2+ from the wastewater in the presence of Cu2+ and Cd2+ ions. Chemical analysis of the gels
Metal recovery suggests that the gelation mainly occurred between the metal ions and the COO− and OH groups on
Nanopowders alginate. By simple calcination of the metal-laden gels at 700 ◦ C for 1 h, the heavy metals can be well
recovered as valuable resources. The metals obtained after the thermal treatment are in the form of PbO,
CuO, and CdO nanopowders with crystal sizes of around 150, 50, and 100 nm, respectively.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction disruption of the metabolisms and biological activities of many pro-

Contamination of water and soil by heavy metals has been a
serious and long-lasting environmental problem. Lead, copper, and
cadmium are three common types of heavy metals that have been
found in industrial wastewaters, including discharges from metal
plating, mining activities, smelting, and battery manufacturing [1].
Heavy metals are not biodegradable and can be accumulative in the
ecosystems and human bodies as well [2]. Lead is toxic to humans
via interaction with the sulfhydryl group of proteins, resulting in
∗ Corresponding author. Fax: +852 25595337.
E-mail address: xlia@hkucc.hku.hk (X.-y. Li).
teins [3]. Copper can causes various types of acute and chronic
disorders in human, such as hemochromatosis and gastrointesti-
nal catarrh [4,5]. The accumulation of cadmium in human bodies
can cause itai-itai disease and renal abnormalities, including pro-
teinuria and glucosuria [6,7]. The harms of heavy metals to the
environment and public health have made the removal of such
metals a top priority in wastewater treatment. Meanwhile, these
metals are valuable resources that should be recovered as much as
possible from the wastes.
The methods commonly used for the removal of metals from
wastewater include chemical precipitation, ion exchange, mem-
brane filtration, and adsorption [8–11]. Chemical precipitation is
generally reliable and widely used; however, this process yields a

http://dx.doi.org/10.1016/j.jhazmat.2016.01.021
0304-3894/© 2016 Elsevier B.V. All rights reserved.
76 F. Wang et al. / Journal of Hazardous Materials 308 (2016) 75–83

large volume of sludge that presents little value and a great diffi-
cult for metal recovery. Ion exchange can efficiently remove heavy
metals from wastewater and it can be readily used for small-scale
industrial applications. However, ion exchange has drawbacks,
such as not suitable for high-strength wastewaters due to a rapid
saturation of the resins [12]. Membrane filtration, e.g., nanofiltra-
tion or reverse osmosis, can remove heavy metal ions with a high
efficiency, but problems such as the high cost, process complexity,
membrane fouling and low permeate flux, have hindered its appli-
cation in heavy metal removal [13]. Adsorption is considered as one
of the most effective techniques for the removal of heavy metals
from wastewater owing to its low initial cost and process sim-
plicity [14]. However, the subsequent treatment of the adsorbents
can greatly increase the treatment cost and often cause secondary
pollutions.
Besides these methods, gelation by sodium alginate has been
proposed as a novel and effective method for heavy metal removal
and recovery. Alginate is a highly promising material for biosorp-
tion of heavy metals because of (a) its low cost and wide availability
Fig. 1. The amount of the heavy metals (Pb2+ , Cu2+ , and Cd2+ ) immobilized by gel
as a major product of brown algae [15] and (b) its high affinity formation with alginate during the gelation process. The data can be well fitted with
toward heavy metals via gelation [16–20]. Studies have been con- the pseudo second-order kinetic equations (solid lines).
ducted to use alginate for the removal or recovery of heavy metals
from aquatic solutions. Jang et al. [21] reported the recovery of
Cu2+ from a synthetic aqueous solution in a loop fluidized bed Table 1
reactor with the alginate and calcium alginate spheres. Cu2+ could Rate constants of the pseudo first-order and pseudo second-order kinetic equa-
be removed by a two-step approach: direct dispensing of sodium tions fitted for the gelation process of Pb2+ , Cu2+ , and Cd2+ with the aqueous sodium
alginate. (Test condition: 200 mg/L sodium alginate with 100 mg/L metal ions at
alginate to absorb the metals from the solution followed by the pH = 4.5 ± 0.1).
addition of partially coagulated calcium alginate spheres to “polish”
the effluent. Torres et al. [22] tested the biosorption of gold and sil- Metal type Pseudo first-order Pseudo second-order

ver ions from the aqueous solutions using calcium alginate beads. k1 (min−1 ) qe (mg/g) R2 k2 (g/mg min) qe (mg/g) R2
Their results showed that the metal uptake capacities were signif- Pb2+
1.38 295.8 0.608 0.0194 304.2 0.962
icantly affected by the solution pH, and the FTIR analysis indicated Cu2+ 1.28 151.6 0.897 0.0123 152.3 0.942
that both carboxylic and hydroxylic functional groups in alginate Cd2+ 1.01 143.5 0.699 0.0085 148.0 0.887
beads were involved in the metal binding process. Papageorgiou
et al. [23] investigated the sequestration of Cu2+ and Cd2+ by means
of biosorption onto calcium alginate beads and reported that the Table 2
sorption followed a competitive mechanism in multi-metal solu- Constants of the Langmuir and Freundlich equations for gelation of Pb2+ , Cu2+ ,
tions. However, for most of the studies, the removal of heavy metals and Cd2+ with alginate (test condition: 500 mg sodium alginate in 50 mL at
was achieved mainly by adsorption onto alginate beads, which is pH = 4.5 ± 0.1).
subject to a limited surface area and a slow mass transport pro- Metal Type Langmuir constants Freundlich constants
cess. The adsorption capacity of used biosobents actually can be
KL (L/mg) qm (mg/g) R2 KF [(mg/g)(mg/L)-n)] n R2
hardly recovered by regeneration [24–26]. More importantly, the
2+
subsequent heavy metal recovery has scarcely been reported. Pb 0.046 435.3 0.977 126.0 5.22 0.902
Cu2+ 0.011 167.1 0.983 24.7 3.69 0.882
In this research work, we developed a more effective method
Cd2+ 0.018 179.0 0.990 42.9 4.85 0.908
in using alginate for both heavy metal removal and recovery from
wastewater. During the process, the aqueous alginate solution was
dosed into the wastewater, inducing its direct and rapid gelation
with the heavy metals. The metal-laden gels were then treated by Three types of heavy metals, Cu, Cd, and Pb, were selected as the
simple calcination for effective metal recovery. The experimental model metals in the experimental study. CuSO4 ·5H2 O, CdSO4 ·8H2 O,
study was conducted on Pb2+ , Cu2+ , and Cd2+ as the model heavy and Pb(NO3 )2 were purchased from BDH (Poole, Dorset, UK). Their
metals. The kinetics of metal gelation, the effects of the alginate respective stock solutions were prepared by dissolving the chemi-
dosing ratio and pH on the metal removal efficiency, and the metal cals in water to have the metal ion concentrations at 10 g/L.
products recovered after the thermal treatment were investigated.
Additionally, the metal–alginate gels were analyzed, the gelation 2.2. Gelation for the removal of heavy metals from wastewater
mechanisms were revealed, and the metal oxide nanopowders
obtained were characterized. Synthetic wastewaters were made by diluting the heavy metal
stock solutions in water to pre-determined concentrations for the
experimental study. All gelation experiments were conducted in
2. Materials and methods 50 mL polypropylene (PP) centrifuge tubes. For tests on the metal
gelation and removal kinetics, a metal concentration of 100 mg/L
2.1. Chemicals and an alginate concentration of 200 mg/L in the final solution
were adopted. For the isotherm studies, the heavy metal concentra-
Sodium alginate was purchased from Sigma–Aldrich (St. Louis, tions varied from 100 to 1000 mg/L, and the dry weight of sodium
MO). Its stock solution was prepared to have an alginate concentra- alginate in the gelation system was 500 mg in 50 mL liquid. For
tion of 10 g/L by dissolving sodium alginate in hot water (75 ◦ C) with the experiments on heavy metal removals from wastewater by
constant stirring until forming a homogeneous and clear solution. gelation, a low metal concentration of 50 mg/L and a high metal
 F. Wang et al. / Journal of Hazardous Materials 308 (2016) 75–83 77

concentration of 1000 mg/L were tested. Adjustment of pH was

made by adding 0.1 M HCl or 0.1 M NaOH. Except for the study
on the pH effect, the pH of the solutions in other studies was all
controlled at pH = 4.5 ± 0.2. After gelation, the mixtures in PP tubes
were centrifuged to separate the solids from liquid, and the heavy
metal contents remaining in the liquid phase were measured by
a flame-type atomic absorption spectrometer (AAS Model 3300,
PerkinElmer, Shelton, CT).

2.3. Thermal treatment for metal recovery

To obtain a sufficient amount of gels for metal recovery, large-

volume gelation experiments were conducted in 1 L beakers at the
optimum gelation ratios. After gelation, the gels were separated
naturally from the liquid by gravity. The gels on the bottom were
collected and then dried in air at room temperature. The dried
(solid) gel materials were calcined at 700 ◦ C in air for 1 h to pro-
duce solid metal oxides, i.e., PbO, CuO, and CdO. After the thermal
treatment, the metal oxides were washed with water to remove the
soluble sodium content, and the obtained dry powders were stored
in small glass bottles before material characterizations.

2.4. Material characterizations

After gelation, the as-received metal-containing gels, including

lead alginate, copper alginate, and cadmium alginate, were freeze-
dried and homogenized gently with KBr using a pestle and mortar.
Each mixture was then pressed into a pellet 13 mm in diame-
ter. The internal reflection infrared (IR) spectra of the gel samples
were obtained with a Fourier transform infrared (FTIR) spectropho-
tometer (FT-IR Spectrophotometer Spectrum One B, Perkin Elmer,
Shelton, CT) in the range from 400 to 4000 cm−1 . The samples were
further analyzed by X-ray photoelectron spectroscopy (XPS) for the
C1s regions. The XPS analysis was carried out in an ESCA Lab 250
(Thermo VG, East Grinstead, UK) using 200 W Al K␣ radiation in a
twin anode, and the distance between the sample and the X-ray gun
was approximately 1 cm. The pressure in the sample chamber was
2 × 10−7 Pa, and the pass energy constant was 20 eV for the high
resolution scans. The charging shifts of the spectra were calibrated
by placing the C 1s peak at 284.8 eV from the adventitious carbon.
The XPS results were further fitted with a nonlinear least-squares
curve fitting program (XPSPEAK41, software).
After the thermal treatment, the morphologies of as-received
metal oxide powders were examined by transmission electron
microscopy (TEM) (Philips Tecnai G220 S-TWIN, Amsterdam,
Netherlands). The solids were also grounded into fine powders with
a particle size of less than 10 ␮m for the X-ray diffraction (XRD)
analysis. The XRD data of each powder sample was obtained by
a D8 Advance Diffractometer (Bruker AXS, Karlsruhe, Germany)
equipped with a Cu K␣ X-ray tube and a LynxEye detector. The
XRD system was calibrated by Standard Reference Material 660a
(lanthanum hexaboride, LaB6), from the U.S. National Institute of
Standard and Technology, for the line positions. The diffractome-
ter was operated at 40 kV and 40 mA, and the 2 scan range was
10–80◦ with a step size of 0.02◦ and a scan speed of 0.5 s per step
for data collection.
Fig. 2. The heavy metal removal efficiency from wastewater as a function of the
3. Results and discussions dosing ratio of sodium alginate to the metal content for the metal ions at different
initial concentrations.
3.1. Metal gelation kinetics

The heavy metal ions can be rapidly removed from the wastew-
ater by alginate-induced gelation. The kinetics of gelation of Pb2+ ,
Cu2+ , and Cd2+ by aquatic sodium alginate are shown in Fig. 1. The
metal gelation is apparently a rather fast process that can be mostly
completed in less than 10 min. To describe the gelation process, the
following two commonly used kinetic models, pseudo first-order
(Eq. (1)) and pseudo second-order equations (Eq. (2)), were applied
to fit with the kinetic data [27,28],
first-oder model : ln(qe − qt ) = ln qe − k1 t (1)
78 F. Wang et al. / Journal of Hazardous Materials 308 (2016) 75–83
Fig. 3. The isotherm study on gelation of heavy metals (Pb2+ , Cu2+ , and Cd2+ ) with
alginate. The data can be well fitted with the Langmuir equations (solid lines).
Fig. 4. The increase of the heavy metal removal efficiency with an increasing solu-
tion pH before the metal precipitations at a pH higher than 6.
t 1 t the Cd2+ removal was less than 50% at a SA/Cd2+ ratio of 5:1 for
second-order model: = + (2)
qt k2 qe 2 qe
where qt (mg/g) and qe (mg/g) are the amounts of the metals fixed in
gels by the aquatic alginate at any time (t) and equilibrium, respec-
tively, and k1 and k2 are the rate constants of the pseudo first- and
second-order models, respectively. The rate constants of the kinetic
models together with the regression coefficients (R2 ) are given in
Table 1.
The results show that the second-order model fits better than
the first-order model with the experimental data based on the R2
values. Thus, the metal gelation process followed a second-order
kinetics with respect to the availability of gelation sites on alginate
rather than the metal concentration in the bulk solution. For the
removal of heavy metals by alginate, researchers often made algi-
nate into gel beads for metal adsorption [15,16,29–31]. For such an
application using alginate beads, intra-particle transport and pore
diffusion of metal ions would become the rate limiting factor for
the biosorption and removal of heavy metals. In the present study
with the aquatic alginate solution, the reaction between the metal
ions and alginate took place in the entire volume of the mixture,
resulting in a rapid gel formation and metal removal from the liq-
uid phase. The main reaction of gelation between the metal ion
(M2+ ) and sodium alginate may be expressed as follows [32]:
M2+ + 2Na-Alginate → Alginate-M-Alginate (gel) + 2Na+ (3)
3.2. Influences of the dosing ratio and pH on heavy metal
removals by gelation
The influence of the dosing ratio of sodium alginate (SA) to
the metal ion on the metal removal efficiency from wastewater
was investigated (Fig. 2). The initial concentration of the heavy
metal (Pb2+ , Cu2+ , or Cd2+ ) was controlled at 50, 100, 200, 500,
and 1000 mg/L. For each heavy metal concentration, the sodium
alginate was dosed at a weight ratio from 1 time to 5 times of the
metal concentration. For the low initial Pb2+ concentrations of 50
and 100 mg/L, the removal efficiency of Pb2+ ions increased to about
60% as the SA/Pb2+ ratio increased from 1:1 to 2:1. However, as
the SA dosing ratio further increased, the Pb2+ removal efficiency
did not increase but greatly decreased. For higher Pb2+ concentra-
tions from 200 to 1000 mg/L, Pb2+ could be removed by more than
85% via gelation at the SA/Pb2+ ratio of 3:1. Further increase of the
SA dosing ratio resulted in a somewhat decrease in Pb2+ removal.
Alginate gelation may be considered as a fast ion exchange pro-
cess between sodium and the metal ions, which would occur as
each bivalent cation attaches to two carboxylic groups ( COO− ) of
the alginate. Thus, there might be coordination between multiple
alginic acid chains and several metal ions. The gelation capacity
of alginate with metal ions depends on the available number of
carboxylic groups for the metal ions. A higher amount of reactive
alginate sites in the system should result in a higher metal removal
efficiency. However, the test results showed that the removal effi-
ciency of Pb2+ decreased when the SA/Pb2+ ratio increased from 3:1
to 4:1 (or 5:1). It is unclear what caused the decrease of the Pb2+
removal as the SA/Pb2+ ratio increased. According to direct obser-
vations, the gelation products of Pb2+ at a lower SA/metal ratio were
flocs in the solution. However, the gelation products of Pb2+ became
gel-like when the SA/metal ratio increased to 4:1 or higher. The pos-
sible change of the gelation mechanism at different SA/Pb2+ ratios
remains to be investigated.
For Cu2+ and Cd2+ in wastewater, the removal efficiencies by
alginate-induced gelation increased clearly as the SA dosing ratio
increased. At a SA/Cu2+ ratio of 5:1, Cu2+ could be removed by about
70% from an initial concentration of 50 mg/L and by nearly 85%
from a high concentration of 1000 mg/L. For the Cd2+ wastewater,
a low initial Cd2+ concentration of 50 mg/L. At the same SA/Cd2+
ratio of 5:1, the Cd2+ removal efficiency could be as high as 80% if
the initial Cd2+ concentration was 500 mg/L or higher. The increase
of Cu2+ and Cd2+ removals with a higher SA dosing ratio became
less significant as the ratio was higher than 4:1. Moreover, a higher
SA dosage resulted in more gels formed in wastewater, increasing
the volume of gels for separation and processing. Thus, a SA dosing
ratio of 4:1 instead of 5:1 is recommended for the removal of Cu2+
and Cd2+ from wastewater.
The isotherm analysis on gelation of Pb2+ , Cu2+ , and Cd2+ with
alginate is shown in Fig. 3. The following two commonly used
isotherm models, Langmuir and Freundlich equations [33,34] (Eqs.
(4) and (5)), were adopted to fit for the experimental data, and the
fitting results are given in Table 1.
KL qm Ce
Langmuir model : qe = (4)
1 + KL Ce
Freundlichmodel : qe = KF Ce 1/n (5)
 F. Wang et al. / Journal of Hazardous Materials 308 (2016) 75–83
Fig. 5. The selective removal of Pb2+ by gelation with the presence of Cu2+ and Cd2+ in the wastewater at different initial concentrations indicated (Pb2+ = 100 mg/L = 0.48 mM,
Cu2+ = 20 mg/L = 0.31 mM, Cd2+ = 20 mg/L = 0.18 mM; Pb2+ = 1000 mg/L = 4.83 mM, Cu2+ = 1000 mg/L = 15.6 mM, Cd2+ = 1000 mg/L = 8.93 mM).
Fig. 6. FTIR spectra of the lead alginate, copper alginate and cadmium alginate
formed by gelation in comparison with those of the protonated alginate and sodium
alginate.
where qe is the amount of the adsorbate on the surface of the adsor-
bent at equilibrium (mg/g), Ce is the equilibrium concentration
of the adsorbate in solution (mg/L), qm is the maximum sorption
capacity (mg/g), and KL is the Langmuir adsorption constant (L/mg),
79
while KF is the Freundlich adsorption constant [(mg/g)(mg/L)−n )],
and n represents the measure of the nonlinearity involved.
The isotherms of Pb2+ , Cu2+ , and Cd2+ gelation by alginate are
found to fit better with the Langmuir equation than the Freundlich
equation, judging from the correlation coefficients (R2 ) in Table 2.
The maximum gelation capacities (qm ) for the removal of Pb2+ , Cu2+ ,
and Cd2+ by the aqueous alginate solution were 435.3, 167.1, and
179.0 mg/g-SA (dry weight), respectively. In comparison, if biosorp-
tion of heavy metals by alginate-gel beads at the same pH (pH
4.5) is applied, the highest adsorption capacities (qm ) of the gel
beads that can be found from previous studies for removing Pb2+ ,
Cu2+ , and Cd2+ were 374.7, 113.1, and 171.5 mg/g-SA (dry weight),
respectively [35,36]. The comparisons indicate that direct gelation
of heavy metals with alginate in solution not only is more efficient
in kinetics but also has a higher capacity than biosorption of the
metals by alginate-gel beads.
For all of the three model heavy metals, their removal effi-
ciencies by gelation are greatly affected by the pH of the alginate
solution. As shown in Fig. 4, for an initial metal concentration of
100 mg/L and an optimized SA/metal ratio, the removal efficiency
increased significantly with a pH increase from 2 to 6 before the
metal precipitations. It is apparent that a low pH led to a poor gela-
tion of the heavy metals in the solution. Torres et al. [22] reported
that sodium alginate has the dissociation constants (pKa ) of its
carboxylic acids, mannuronic (M) and guluronic (G) acids, at 3.38
and 3.65, respectively. When pH is higher than pKa , the carboxylic
groups are progressively less protonated or completely deproto-
80 F. Wang et al. / Journal of Hazardous Materials 308 (2016) 75–83
Fig. 7. XPS spectra of (a) sodium alginate and the metal alginate gels formed by gelation: (b) lead alginate, (c) copper alginate, and (d) cadmium alginate.
nated, resulting in gel formation via the electrostatic interactions
between these functional groups and divalent metal cations, such
as Pb2+ , Cu2+ , and Cd2+ in the present study.
3.3. Selective removal of Pb2+ from the wastewater
Pb2+ could be removed more selectively by alginate-based gela-
tion when Cu2+ or Cd2+ coexisted at a comparative concentration
level (in either mass concentration or molar concentration) in the
wastewater. As shown in Fig. 5(a) and (c) for an initial Pb2+ con-
centration of 100 mg/L, the Cu2+ or Cd2+ presence at 20 mg/L or
lower had little effects on Pb2+ removal by gelation at a SA/Pb2+
ratio of 2:1. For a high initial Pb2+ concentration of 1000 mg/L Fig. 5
(b) and (d), Pb2+ could be selectively removed over Cu2+ and Cd2+
by gelation despite their high concentrations of up to 1000 mg/L
in the wastewater. The results showed a higher affinity of algi-
nate toward Pb2+ than the other two heavy metal ions, which is in
agreement with the predictions by Papageorgiou et al. [36]. They
suggested that the metal interactions with ligands are regulated by
three parameters of the metal ions, i.e., charge, radius, and elec-
tronegativity. It can therefore be predicted that the strength of
covalent bonds between the metal ions and alginate would follow
the sequence of Pb2+ > Cu2+ > Cd2+ . The variation in metal binding
strength in gelation by alginate also may be explained based on
the classification of metal ions. Based on the hard-soft-acid-base
(HSAB) concept [37]. Pb2+ can be classified as an intermediate acid
while Cu2+ and Cd2+ are regarded as “soft” acids [36]. According
to the HSAB theory, “hard” acids would prefer to bind with “hard”
bases while “soft” acids with “soft” bases. Thus, sodium alginate,
with the “hard” carboxyl base, would exhibit a higher gelation
affinity toward Pb2+ than Cu2+ and Cd2+ .
3.4. FTIR and XPS analysis
FTIR analysis was conducted on alginate and its gels in order to
identify the main groups involved in gelation of the metal (Pb2+ ,
Cu2+ , and Cd2+ ) ions. The protonated alginate was used as a con-
trol to compare the shifts of FTIR peaks after the metal gelation
for identification of the functional groups participated in the metal
uptake. The stretching vibrations of functional group OH usually
forms a broad band region at the wavenumber of 3100–3700 cm−1 .
A peak shift from 3570 to 3531–3542 cm−1 can be observed after
gelation of alginate with the metal ions (Fig. 6). The decrease in
wavenumber of the peak may be attributed to the combination
between the metal ions and the OH group [38]. When compared
with the protonated alginate, two obvious peaks (1028–1034 cm−1
and 1606–1609 cm−1 ) can be found for the metal-laden alginates.
As peaks at these two sites represent the alcoholic hydroxyl group
and the carbon–oxygen double bond, respectively, these peaks sug-
gests the important role of OH and COO− in the metal gelation
process. The small band at 1747 cm−1 may suggest the protona-
tion of carboxylic groups after gelation, in consideration of pH 4.5
for the gelation system. Generally speaking, divalent cations (Pb2+ ,
Cu2+ , and Cd2+ ) can be readily coordinated into the alginate macro-
molecules through interactions with the carboxylate groups and
hydroxyl groups, leading to the gel formation. An in-depth study
[39] on the FTIR spectra of different metal–alginate complexes sug-
gested a relationship between the asym (COO− ) (region at around
1600 cm−1 ) and sym (COO− ) (region at around 1405 cm−1 ) bands.
The metal-carboxylate coordination also has been reported [38–44]
with the bands corresponding to the coordinated modes situated
at different frequencies relative to the bands for free carboxylate
ions. In the FTIR results of this study, only the strong asymmetric
 F. Wang et al. / Journal of Hazardous Materials 308 (2016) 75–83 81

Fig. 8. XRD profiles for the size/strain Rietveld structural refinement analysis of (a)
PbO, (b) CuO, and (c) CdO powder samples collected after the thermal treatment of
the metal gels.

stretching vibration at 1606–1612 cm−1 was observed and the peak

at 1405 cm−1 could not be clearly identified owing to the appar-
ent overlapping with a strong and wide vibration peak (for NO3 −
bands). Thus, the different binding strength and complex coordina-
tion could not be further obtained from the FTIR spectra. As for the
different FTIR profiles reported for the metal–alginate complexes,
Fig. 9. TEM images of (a) PbO, (b) CuO, and (c) CdO nanoparticles obtained from the
the discrepancy between different studies might be resulted from
thermal treatment of the metal-laden gels.
the different metal salts and sodium alginate compounds used.
XPS spectra of C1s regions of lead alginate, copper alginate, and
cadmium alginate are shown in Fig. 7. The C1s spectra can be de-
convoluted into three individual component peaks, which come
from the different groups that overlap partially with each other.
82 F. Wang et al. / Journal of Hazardous Materials 308 (2016) 75–83
The peaks located at the binding energy of 287.9 eV, 286.5 eV, and
284.5 eV can be assigned to C O, C O, and C C bonds. The relative
contents of C O, C O, and C C formed in metal alginate would be
related to the bond changes after gelation. The results show that the
quantity of the C O group was 30.1, 19.3, and 17.9 for lead alginate,
copper alginate, cadmium alginate, respectively, in comparison to
that of 14.9% for sodium alginate, and the relative content of the
C O group was 45.3, 51.8, and 57.0 for lead alginate, copper algi-
nate, cadmium alginate, respectively, in comparison to that of 59.6%
for sodium alginate. The different C O and C O abundances in dif-
ferent metal gels suggest their involvements in the metal gelation
process. The observations are consistent with the FTIR findings that
the metal atoms were directly bound with C O− in gel formation.
3.5. Thermal treatment for metal recovery
With the gelation of heavy metal ions by alginate, the metals can
be readily recovered from the gels via a simple thermal treatment.
As the immobilized metal ions are widely spaced in alginate-gels,
there was a limited opportunity to produce large crystals during the
calcination process. However, formation of metal oxide nanoparti-
cles was expected during calcination of the gels [45]. XRD patterns
of the calcination products of lead alginate, copper alginate, and
cadmium alginate are presented in Fig. 8. The results show that
PbO, CuO, and CdO crystals were the only products after the ther-
mal treatment of the respective gel samples. For CuO and CdO, only
a single crystal phase was found in the products. For PbO, there
were two types of the crystal phases, ␣-PbO and ␤-PbO, that could
be found in the final product.
A comparison is also made in Fig. 8 between the calculated and
the observed XRD patterns of the PbO, CuO, and CdO nanopowders
following a Rietveld size/strain structural refinement [45]. It shows
an excellent agreement between the experimental data and the cal-
culated XRD patterns (Rexp < 1% and Rwp < 4%). The mean crystallite
sizes calculated from the XRD Rietveld refinement are 150, 50, and
100 nm for the as-recovered PbO, CuO, and CdO, respectively, which
generally agree with the sizes of the nanoparticles measured from
their TEM images (Fig. 9). The XRD and TEM results proved that
PbO, CuO, and CdO nanoparticles can be well formed by thermal
treatment of the gels. Thus, following gelation of heavy metals in
wastewater, one-step calcination of the metal-bearing gels allows
easy and effective recovery of valuable metals from the wastes.
4. Conclusions
Gelation using sodium alginate is an effective method for the
removal and recovery of heavy metals from industrial wastewa-
ters. The experimental results showed that gels could be rapidly
formed in less than 10 min between alginate and the selected metal
ions, Pb2+ , Cu2+ , and Cd2+ , and the rate of gelation fitted well with a
pseudo second-order kinetics. Compared to biosorption of heavy
metals by alginate-gel beads, direct gelation of the metals with
alginate in solution is apparently more advantageous in terms of
both the reaction kinetics and metal fixation capacity by the gels.
The heavy metal removal by gelation increased as the solution pH
increased. Alginate exhibited a higher gelation affinity toward Pb2+
than Cu2+ and Cd2+ and hence, Pb2+ could be selectively removed
in the presence of Cu2+ and Cd2+ in the wastewater. The FTIR and
XPS analysis of the gels indicated that the OH and COO− groups
on alginate played a crucial role in the metal gelation process. By
simple calcination at 700 ◦ C for 1 h, the heavy metals could be well
recovered from the gels. According to the TEM and XRD character-
izations, the metals obtained after the thermal treatment were in
the form of PbO, CuO, and CdO nanopowders with crystal sizes of
around 150 nm, 50 nm, and 100 nm, respectively.
Acknowledgement
This research was supported by grants CRF C7044-14G and
17204914 from the Research Grants Council (RGC) of the Govern-
ment of Hong Kong SAR. The research was also partially supported
by the National Natural Science Foundation of China (Project No.
41503087). The technical assistances of Mr. Keith Wong and Ms.
Vicky Fung are highly appreciated.
References
[1] W.S. Wan Ngah, M.A.K.M. Hanafiah, Removal of heavy metal ions from
wastewater by chemically modified plant wastes as adsorbents: a review,
Bioresour. Technol. 99 (2008) 3935–3948.
[2] A.H. Panhwar, T.G. Kazi, H.I. Afridi, S.A. Arain, M.S. Arain, K.D. Brahaman,
Naeemullah, S.S. Arain, Correlation of cadmium and aluminum in blood
samples of kidney disorder patients with drinking water and tobacco
smoking: related health risk, Environ. Geochem. Health (2015) 1–10.
[3] H. Sone, B. Fugetsu, S. Tanaka, Selective elimination of lead(II) ions by
alginate/polyurethane composite foams, J. Hazard. Mater. 162 (2009)
423–429.
[4] M. Ajmal, R.A.K. Rao, R. Ahmad, J. Ahmad, L.A.K. Rao, Removal and recovery of
heavy metals from electroplating wastewater by using kyanite as an
adsorbent, J. Hazard. Mater. 87 (2001) 127–137.
[5] H. Jalayeri, M.M. Salarirad, M. Ziaii, Behavior and mechanism of various
components of soil in Cu(II) adsorption from aqueous solution, Desalin. Water
Treat. (2015) 1–10.
[6] K. Nogawa, E. Kobayashi, Y. Okubo, Y. Suwazono, Environmental cadmium
exposure, adverse effects and preventive measures in Japan, Biometals 17
(2004) 581–587.
[7] M. Ciarrocca, M.V. Rosati, F. Tomei, A. Pacchiarotti, P. Corbosiero, C. Di
Pastena, B. Scala, A. Capozzella, G. Tomei, T. Caciari, C. Sacco, A. Sancini,
Correlation between cadmium and blood counts in workers exposed to urban
stressor, Arch. Environ. Occup. Health 70 (2015) 70–76.
[8] T. Chen, F. Liu, C. Ling, J. Gao, C. Xu, L. Li, A. Li, Insight into highly efficient
coremoval of copper and p-nitrophenol by a newly synthesized polyamine
chelating resin from aqueous media: competition and enhancement effect
upon site recognition, Environ. Sci. Technol. 47 (2013) 13652–13660.
[9] A. Maher, M. Sadeghi, A. Moheb, Heavy metal elimination from drinking
water using nanofiltration membrane technology and process optimization
using response surface methodology, Desalination 352 (2014) 166–173.
[10] L. Guo, Y. Du, Q. Yi, D. Li, L. Cao, D. Du, Efficient removal of arsenic from dirty
acid wastewater by using a novel immersed multi-start distributor for
sulphide feeding, Sep. Purif. Technol. 142 (2015) 209–214.
[11] Y. Huang, A.A. Keller, EDTA functionalized magnetic nanoparticle sorbents for
cadmium and lead contaminated water treatment, Water Res. 80 (2015)
159–168.
[12] S. Chiarle, M. Ratto, M. Rovatti, Mercury removal from water by ion exchange
resins adsorption, Water Res. 34 (2000) 2971–2978.
[13] F. Fu, Q. Wang, Removal of heavy metal ions from wastewaters: a review, J.
Environ. Manag. 92 (2011) 407–418.
[14] S.K. Papageorgiou, F.K. Katsaros, E.P. Kouvelos, N.K. Kanellopoulos, Prediction
of binary adsorption isotherms of Cu2+ , Cd2+ and Pb2+ on calcium alginate
beads from single adsorption data, J. Hazard. Mater. 162 (2009) 1347–1354.
[15] S. Cataldo, A. Gianguzza, M. Merli, N. Muratore, D. Piazzese, M.L. Turco Liveri,
Experimental and robust modeling approach for lead(II) uptake by alginate
gel beads: influence of the ionic strength and medium composition, J. Colloid
Interface Sci. 434 (2014) 77–88.
[16] T.A. Davis, B. Volesky, A. Mucci, A review of the biochemistry of heavy metal
biosorption by brown algae, Water Res. 37 (2003) 4311–4330.
[17] L. Gottlieb, Preparation, morphology and function of biomass filled porous
epoxy beads as chelation-ion-exchange for lead ion sorption, React. Funct.
Polym. 63 (2005) 107–117.
[18] D. Şolpan, M. Torun, (Sodium alginate/acrylamide) semi-interpenetrating
polymer networks and their usability on removal of lead, cadmium, nickel
ions, J. Macromol. Sci.—Pure Appl. Chem. A 42 (2005) 1435–1449.
[19] R. Lagoa, J.R. Rodrigues, Kinetic analysis of metal uptake by dry and gel
alginate particles, Biochem. Eng. J. 46 (2009) 320–326.
[20] A. Nussinovitch, O. Dagan, Hydrocolloid liquid-core capsules for the removal
of heavy-metal cations from water, J. Hazard. Mater. 299 (2015) 122–131.
[21] L.K. Jang, S.L. Lopez, S.L. Eastman, P. Pryfogle, Recovery of copper and cobalt
by biopolymer gels, Biotechnol. Bioeng. 37 (1991) 266–273.
[22] E. Torres, Y.N. Mata, M.L. Blázquezy, J.A. Muñoz, F. González, A. Ballester, Gold
and silver uptake and nanoprecipitation on calcium alginate beads, Langmuir
21 (2005) 7951–7958.
[23] S.K. Papageorgiou, E.P. Kouvelos, F.K. Katsaros, Calcium alginate beads from
Laminaria digitata for the removal of Cu+2 and Cd+2 from dilute aqueous metal
solutions, Desalination 224 (2008) 293–306.
[24] I. Aldor, E. Fourest, B. Volesky, Desorption of cadmium from algal biosorbent,
Can. J. Chem. Eng. 73 (1995) 516–522.
[25] I.P. Suhasini, G. Sriram, S.R. Asolekar, G.K. Sureshkumar, Biosorptive removal
and recovery of cobalt from aqueous systems, Process Biochem. 34 (1999)
239–247.
 F. Wang et al. / Journal of Hazardous Materials 308 (2016) 75–83
[26] J. Yang, Biosorption of Uranium, Cadmium on Sargassum Seawed Biomass.
Ph.D. Thesis, Department of Chemical Engineering, McGill University,
Montreal, Canada, 1999.
[27] Y.S. Ho, G. McKay, Pseudo-second order model for sorption processes, Process
Biochem. 34 (1999) 451–465.
[28] M.S. Chiou, H.Y. Li, Adsorption behavior of reactive dye in aqueous solution on
chemical cross-linked chitosan beads, Chemosphere 50 (2003) 1095–1105.
[29] B. An, H. Lee, S. Lee, S.H. Lee, J.W. Choi, Determining the selectivity of divalent
metal cations for the carboxyl group of alginate hydrogel beads during
competitive sorption, J. Hazard. Mater. 298 (2015) 11–18.
[30] L.E. de-Bashan, Y. Bashan, Immobilized microalgae for removing pollutants:
review of practical aspects, Bioresour. Technol. 101 (2010) 1611–1627.
[31] J. He, J.P. Chen, A comprehensive review on biosorption of heavy metals by
algal biomass: materials, performances, chemistry, and modeling simulation
tools, Bioresour. Technol. 160 (2014) 67–78.
[32] G. Ciofani, V. Raffa, T. Pizzorusso, A. Menciassi, P. Dario, Characterization of an
alginate-based drug delivery system for neurological applications, Med. Eng.
Phys. 30 (2008) 848–855.
[33] I. Langmuir, The adsorption of gases on plane surfaces of glass, mica and
platinum, J. Am. Chem. Soc. 40 (1918) 1361–1403.
[34] H. Freundlich, Colloid and Capillary Chemistry, E.P. Dutton and Company,
New York, 1922 (translated from German by Hatfield H.S.).
[35] E.G. Deze, S.K. Papageorgiou, E.P. Favvas, F.K. Katsaros, Porous alginate aerogel
beads for effective and rapid heavy metal sorption from aqueous solutions:
effect of porosity in Cu2+ and Cd2+ ion sorption, Chem. Eng. J. 209 (2012)
537–546.
83
[36] S.K. Papageorgiou, F.K. Katsaros, E.P. Kouvelos, J.W. Nolan, H. Le Deit, N.K.
Kanellopoulos, Heavy metal sorption by calcium alginate beads from
Laminaria digitata, J. Hazard. Mater. 137 (2006) 1765–1772.
[37] R.G. Pearson, Hard and soft acids and bases, HSAB, part I: fundamental
principles, J. Chem. Educ. 45 (1968) 581–587.
[38] S.F. Lim, Y.M. Zheng, S.W. Zou, J.P. Chen, Characterization of copper
adsorption onto an alginate encapsulated magnetic sorbent by a combined
FT-IR, XPS, and mathematical modeling study, Environ. Sci. Technol. 42 (2008)
2551–2556.
[39] S.K. Papageorgiou, E.P. Kouvelos, E.P. Favvas, A.A. Sapalidis, G.E. Romanos, F.K.
Katsaros, Metal–carboxylate interactions in metal–alginate complexes
studied with FTIR spectroscopy, Carbohydr. Res. 345 (2010) 469–473.
[40] E. Fourest, B. Volesky, Contribution of sulfonate groups and alginate to heavy
metal biosorption by the dry biomass of Sargassum fluitans, Environ. Sci.
Technol. 30 (1996) 277–282.
[41] J.E. Tackett, FT-IR characterization of metal acetates in aqueous solution, Appl.
Spectrosc. 43 (1989) 483–489.
[42] R.D. Mounts, T. Ogura, Q. Fernando, Crystal structure of copper(II) acetate,
Inorg. Chem. 13 (1974) 802–805.
[43] N.W. Alcock, V.M. Tracy, T.C. Waddington, Acetates and acetato-complexes.
Part 2. Spectroscopic studies, J. Chem. Soc., Dalton Trans. (1976) 2243–2246.
[44] W. Harrison, J. Trotter, Crystal and molecular structure of cadmium diacetate
dihydrate, J. Chem. Soc., Dalton Trans. (1972) 956–960.
[45] Z. Wang, G.M. Kale, Q. Yuan, M. Ghadiri, X-Ray micro-tomography of freeze
dried nickel alginate beads and transformation into NiO nanopowders, RSC
Adv. 2 (2012) 9993–9997.