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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.
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
The heavy metal ions can be rapidly removed from the wastew- following two commonly used kinetic models, pseudo first-order
ater by alginate-induced gelation. The kinetics of gelation of Pb2+ , (Eq. (1)) and pseudo second-order equations (Eq. (2)), were applied
Cu2+ , and Cd2+ by aquatic sodium alginate are shown in Fig. 1. The to fit with the kinetic data [27,28],
metal gelation is apparently a rather fast process that can be mostly
completed in less than 10 min. To describe the gelation process, the first-oder model : ln(qe − qt ) = ln qe − k1 t (1)
78 F. Wang et al. / Journal of Hazardous Materials 308 (2016) 75–83
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]:
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. 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 3.4. FTIR and XPS analysis
between these functional groups and divalent metal cations, such
as Pb2+ , Cu2+ , and Cd2+ in the present study. FTIR analysis was conducted on alginate and its gels in order to
identify the main groups involved in gelation of the metal (Pb2+ ,
3.3. Selective removal of Pb2+ from the wastewater Cu2+ , and Cd2+ ) ions. The protonated alginate was used as a con-
trol to compare the shifts of FTIR peaks after the metal gelation
Pb2+ could be removed more selectively by alginate-based gela- for identification of the functional groups participated in the metal
tion when Cu2+ or Cd2+ coexisted at a comparative concentration uptake. The stretching vibrations of functional group OH usually
level (in either mass concentration or molar concentration) in the forms a broad band region at the wavenumber of 3100–3700 cm−1 .
wastewater. As shown in Fig. 5(a) and (c) for an initial Pb2+ con- A peak shift from 3570 to 3531–3542 cm−1 can be observed after
centration of 100 mg/L, the Cu2+ or Cd2+ presence at 20 mg/L or gelation of alginate with the metal ions (Fig. 6). The decrease in
lower had little effects on Pb2+ removal by gelation at a SA/Pb2+ wavenumber of the peak may be attributed to the combination
ratio of 2:1. For a high initial Pb2+ concentration of 1000 mg/L Fig. 5 between the metal ions and the OH group [38]. When compared
(b) and (d), Pb2+ could be selectively removed over Cu2+ and Cd2+ with the protonated alginate, two obvious peaks (1028–1034 cm−1
by gelation despite their high concentrations of up to 1000 mg/L and 1606–1609 cm−1 ) can be found for the metal-laden alginates.
in the wastewater. The results showed a higher affinity of algi- As peaks at these two sites represent the alcoholic hydroxyl group
nate toward Pb2+ than the other two heavy metal ions, which is in and the carbon–oxygen double bond, respectively, these peaks sug-
agreement with the predictions by Papageorgiou et al. [36]. They gests the important role of OH and COO− in the metal gelation
suggested that the metal interactions with ligands are regulated by process. The small band at 1747 cm−1 may suggest the protona-
three parameters of the metal ions, i.e., charge, radius, and elec- tion of carboxylic groups after gelation, in consideration of pH 4.5
tronegativity. It can therefore be predicted that the strength of for the gelation system. Generally speaking, divalent cations (Pb2+ ,
covalent bonds between the metal ions and alginate would follow Cu2+ , and Cd2+ ) can be readily coordinated into the alginate macro-
the sequence of Pb2+ > Cu2+ > Cd2+ . The variation in metal binding molecules through interactions with the carboxylate groups and
strength in gelation by alginate also may be explained based on hydroxyl groups, leading to the gel formation. An in-depth study
the classification of metal ions. Based on the hard-soft-acid-base [39] on the FTIR spectra of different metal–alginate complexes sug-
(HSAB) concept [37]. Pb2+ can be classified as an intermediate acid gested a relationship between the asym (COO− ) (region at around
while Cu2+ and Cd2+ are regarded as “soft” acids [36]. According 1600 cm−1 ) and sym (COO− ) (region at around 1405 cm−1 ) bands.
to the HSAB theory, “hard” acids would prefer to bind with “hard” The metal-carboxylate coordination also has been reported [38–44]
bases while “soft” acids with “soft” bases. Thus, sodium alginate, with the bands corresponding to the coordinated modes situated
with the “hard” carboxyl base, would exhibit a higher gelation at different frequencies relative to the bands for free carboxylate
affinity toward Pb2+ than Cu2+ and Cd2+ . 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.
The peaks located at the binding energy of 287.9 eV, 286.5 eV, and Acknowledgement
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 This research was supported by grants CRF C7044-14G and
related to the bond changes after gelation. The results show that the 17204914 from the Research Grants Council (RGC) of the Govern-
quantity of the C O group was 30.1, 19.3, and 17.9 for lead alginate, ment of Hong Kong SAR. The research was also partially supported
copper alginate, cadmium alginate, respectively, in comparison to by the National Natural Science Foundation of China (Project No.
that of 14.9% for sodium alginate, and the relative content of the 41503087). The technical assistances of Mr. Keith Wong and Ms.
C O group was 45.3, 51.8, and 57.0 for lead alginate, copper algi- Vicky Fung are highly appreciated.
nate, cadmium alginate, respectively, in comparison to that of 59.6%
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