applied

sciences
Article
Efficient Removal of Heavy Metal Ions in Wastewater
by Using a Novel Alginate-EDTA Hybrid Aerogel
Min Wang 1 , Zhuqing Wang 1, * , Xiaohong Zhou 1 and Shikun Li 2, *
1 AnHui Province Key Laboratory of Optoelectronic and Magnetism Functional Materials,
College of Chemistry and Chemical Engineering, Anqing Normal University, Anqing 246133, China;
wangmin08@aqnu.edu.cn (M.W.); donnelloirgt@gmail.com (X.Z.)
2 Institute of Applied and Physical Chemistry, Faculty 2 (Chemistry/Biology), University of Bremen,
D-28359 Bremen, Germany
* Correspondence: wangzhq@aqnu.edu.cn (Z.W.); lishikun@uni-bremen.de (S.L.); Tel.: +49-0174-627-7947




Received: 5 January 2019; Accepted: 3 February 2019; Published: 6 February 2019


Abstract: In this study, we prepared a novel calcium alginate-disodium ethylenediaminetetraacetate

dihydrate hybrid aerogel (Alg-EDTA) by chemical grafting and vacuum-freeze-drying to remove
heavy metal ions from wastewater. Experimental results show that the as-prepared Alg-EDTA
adsorbent has a high affinity for heavy metal ions, such as Cd2+ , Pb2+ , Cu2+ , Cr3+ , and Co2+ , and can
adsorb >85% of metal ions from the corresponding solution. Alg-EDTA also exhibits high selectivity
toward Cd2+ , and the maximum adsorption capacity for Cd2+ reached 177.3 mg/g, which exceeds
the adsorption capacity of most reported Cd2+ -adsorbents. Adsorbent regeneration can be achieved
by a simple acid-washing process, and adsorption performance of Alg-EDTA remains stable after
repeated use. All these findings indicate that Alg-EDTA has a promising prospect in the treatment of
heavy metal ions wastewater.

Keywords: heavy metal ions; sorbent; aerogel; sodium alginate

1. Introduction
With the rapid development of industries such as mining, metallurgy, electroplating, and battery
manufacture, many heavy metal ions are released into natural waters [1]. These heavy metal ions
cannot be biodegraded and can enter and accumulate in the human body through the food chain and
drinking water, resulting in a series of irreversible physiological diseases, such as kidney damage,
nervous-system disorders, and bone necrosis. Therefore, developing new adsorbent materials for
removal of heavy metal ions from wastewater is of great significance [2,3].
Sodium alginate is a byproduct of the extraction of iodine and mannitol from kelp or brown algae
(Sargassum sp.) and is a natural polysaccharide. Sodium alginate is often used as a food thickener and
an antidote for heavy metal poisoning. In our previous research, we have used vacuum-freeze-drying
technology and chemical-grafting technology to prepare a series of calcium alginate and modified
calcium alginate aerogels [4–7]. These synthesized aerogels provide good selectivity and adsorption
capacity for Pb2+ ions. The maximum adsorption capacity of the chitosan-modified calcium alginate
aerogel for Pb2+ ion is up to 468.5 mg/g, which is higher than most of the reported Pb2+ -adsorbents [5].
Disodium ethylenediaminetetraacetate dihydrate (EDTA) is a good complexing agent with
six coordinating atoms (four O and two N atoms), which can coordinate with all metal ions at a
1:1 molar ratio. The content of coordinated metal ions can also be determined by EDTA through
complexometric titration [8]. The present study aimed to further improve the adsorption performance
and practicability of modified calcium alginate aerogels, which can adsorb various heavy metal ions
for treating wastewater containing different types of metal ions. Ethylenediamine was used as a linker

Appl. Sci. 2019, 9, 547; doi:10.3390/app9030547 www.mdpi.com/journal/applsci

Appl. Sci. 2019, 9, 547 2 of 14

to connect alginate and EDTA, and then the resulting complex was cross-linked with calcium ions in
solution. After vacuum-freeze-drying, a novel Alg-EDTA aerogel adsorbent was obtained and used
to remove heavy metal ions in wastewater. The composition of the prepared Alg-EDTA adsorbent,
as well as its adsorption performance for heavy metal ions and recyclability, were also studied.

2. Materials and Methods

2.1. Materials
Sodium alginate, EDTA salt, metal salts, N-(3-dimethylaminopropyl)-N0 -ethylcarbodiimide
hydrochloride (EDC), nitric acid (HNO3 ), 2-(N-morpholino)ethanesulfonic acid (MES), sodium
hydroxide (NaOH), and N-hydroxysuccinimide (NHS) were bought from J&K Scientific Ltd. (Beijing,
China). The pH value of the solution was adjusted with 0.05 M HNO3 or 0.1 M NaOH, and deionized
water was used to prepare solutions and wash samples.

2.2. Apparatus
Morphology images of the adsorbent were obtained on an EVO18 scanning electron microscope
(SEM, Carl Zeiss GmbH, Dresden, Germany). Infrared (IR) spectra were recorded on a Cary660
Fourier transform IR spectrometer (FTIR, Agilent Technologies Inc., Santa Clara, CA, USA). The metal
ion concentrations were measured using an Optima 8000 inductively coupled plasma-optical
emission spectrometer (ICP-OES, Perkin-Elmer GmbH, Waltham, MA, USA). X-ray photoelectron
spectroscopy analyses were conducted on an Axis-supra X-ray photoelectron spectrometer (XPS,
Kratos Analytical Ltd., Manchester, UK).

2.3. Synthesis of the Alg-EDTA

The synthesis route of Alg-EDTA is presented in Figure 1. An appropriate amount of sodium
alginate was dissolved in 20 mL of pH 5.5 MES buffer solution, followed by 0.15 g EDC and 0.12 g NHS,
after magnetic stirring for 3 h. About 1.5 mL of ethylenediamine was added, and stirring was continued
for 6 h, before adding 0.6 g of EDTA salt. After reacting for 6 h, the mixed solution was dropped
into 500 mL of 0.2 M Ca(NO3 )2 using a 5 mL syringe (Alg-EDTA hydrogel ball formed immediately
when the mixed solution contacted with Ca2+ solution). The Alg-EDTA hydrogel was separated and
washed by ultrapure water three times, then immersed in 40 mL of deionized water, frozen in a
−60 ◦ C ultra-low temperature freezer for 4 h, and dried in a vacuum-freeze-dryer to finally obtain the
Alg-EDTA aerogel.

2.4. Adsorption–Desorption Experiments

Adsorption experiment: Approximately 100 mg of Alg-EDTA was weighed and added to 50 mL
1.5 mM of metal ion solution, magnetically stirred for 6 h and filtered. The residual metal ions in the
filtrate was measured using ICP-OES.
Desorption and circulation experiments: Cd2+ -loaded or Pb2+ -loaded Alg-EDTA was immersed
into 50 mL of 0.05 M HNO3 , magnetically stirred for 6 h, filtered, washed successively with deionized
water, calcium hydroxide (Ca(OH)2 ), deionized water, and finally dried at 50 ◦ C for 4 h, thereby
obtaining the regenerated Alg-EDTA.
Appl. Sci. 2019, 9, 547 3 of 14
Appl. Sci. 2019, 9, 547 3 of 14

Figure
Figure 1. Synthesis
1. Synthesis route
route of the
of the calciumalginate-disodium
calcium alginate-disodium ethylenediaminetetraacetate
ethylenediaminetetraacetatedihydrate
dihydrate
hybrid aerogel (Alg-EDTA).
hybrid aerogel (Alg-EDTA).

3. Results
3. Results and and Discussion
Discussion

3.1. Material
3.1. Material Characterization
Characterization
To confirm
To confirm whether
whether thethe EDTA
EDTA saltwas
salt wassuccessfully
successfully modified
modifiedtotosodium
sodium alginate, we determined
alginate, we determined
the IR spectra of sodium alginate, EDTA salt, Alg-EDTA, and Alg-EDTA loaded with Cd2+. As shown
the IR spectra of sodium alginate, EDTA salt, Alg-EDTA, and Alg-EDTA loaded with Cd2+ . As shown
in Figure 2, the absorption peaks near 2930 cm−−11 belong to the aliphatic C-H bond stretching vibration,
in Figure 2, the absorption peaks near 2930 cm belong to the−1aliphatic C-H bond stretching vibration,
and the absorption peaks at approximately 1570 and 1310 cm can be assigned to the C=O and C-O
−1 can be assigned to the C=O and
and the
bondabsorption peaks at approximately
stretching vibrations, 1570
respectively [9,10]. Theand 1310 cm
absorption peak of COO- at 1390 cm−1 in the Alg-
C-O bond
EDTAstretching vibrations,
was significantly reduced respectively
with respect[9,10].
to sodiumThealginate
absorption
owingpeak COO− at 1390
to theofcondensation cm−1 in
reaction
the Alg-EDTA was significantly
of excess amino groups with the reduced with respect
COO- groups to sodium
[11]. In addition, thealginate owing
absorption peakto the condensation
intensity of C-O
reaction
bondofand
excess
C-Namino groups with
bond increases the COO
relatively when− Alg-EDTA
groups [11]. In addition,
adsorbs the absorption
Cd2+, which peakfrom
probably results intensity
the coordination of N and O in Alg-EDTA with Cd 2+ ions. 2+
of C-O bond and C-N bond increases relatively when Alg-EDTA adsorbs Cd , which probably results
The morphology
from the coordination of and
of N Alg-EDTA has been characterized
O in Alg-EDTA and illustrated in Figure 3. Similar to one
with Cd2+ ions.
of the lunar surfaces, the surface of Alg-EDTA
The morphology of Alg-EDTA has been characterized andis rough and porous, which increases
illustrated in Figurethe3.contact area
Similar to one
of the adsorbent with the solution and provides more binding sites. In addition, the pore properties
of the lunar surfaces, the surface of Alg-EDTA is rough and porous, which increases the contact area of
of Alg-EDTA were also studied by N2 adsorption-desorption isotherm (Figure 4). The results showed
the adsorbent with the solution and provides more binding sites. In addition, the pore 2properties of
that the BET surface area, pore volume, and average pore size of Alg-EDTA are 94.63 m /g, 53.30
Alg-EDTA were also studied by N2 adsorption-desorption isotherm (Figure 4). The results showed that
the BET surface area, pore volume, and average pore size of Alg-EDTA are 94.63 m2 /g, 53.30 cm3 /g,
Appl. Sci. 2019, 9, 547 4 of 14
Appl. Sci. 2019, 9, 547 4 of 14

cm3/g,Appl.
and Sci.22.53
2019, 9,nm,
547 respectively. The rough surface and large pore size are beneficial to4the
of 14rapid
adsorption of the target metal ions and the increase in the metal ion adsorption capacity.
and 22.53 nm, respectively. The rough surface and large pore size are beneficial to the rapid adsorption
cm3/g, and 22.53 nm, respectively. The rough surface and large pore size are beneficial to the rapid
of theadsorption
target metal ions and the increase in the metal ion adsorption capacity.
of the target metal ions and the increase in the metal ion adsorption capacity.

Figure 2.2.FTIR
Figure spectra
2. FTIR
FTIR of (a)
spectra sodium
of (a)
spectra (a) alginate,
ofsodium alginate,(b)
sodium (b) EDTA salt,
EDTA salt,
alginate, (c)
(b)(c) Alg-EDTA,
Alg-EDTA,
EDTA and
salt,and (d)
Cd2+Cd
(d)Alg-EDTA,
(c) 2+ -loaded
-loaded andAlg-
Alg- (d)
2+
EDTA. EDTA.
Cd -loaded Alg-EDTA.

Figure 3. (A) Digital photo of Alg-EDTA; (B) SEM image of Alg-EDTA; (C) partial magnification of (B).

Figure 3. (A)
Figure (A) Digital
3. Digital photo
photo of Alg-EDTA;
of Alg-EDTA; (B) (B)
SEMSEM image
image of Alg-EDTA;
of Alg-EDTA; (C)(C) partial
partial magnification
magnification ofof(B).
(B).

Figure 4. N2 adsorption-desorption isotherm of the Alg-EDTA.

3.2. Effect of Concentrations of Alginate Sodium

Figure
Figure
Sodium alginates 4.
0.5N
of 4. 2 adsorption-desorption
Nwt.%, 1.0 wt.% 1.5 wt.%, isotherm
2 adsorption-desorption 2.0 wt.%,of
isotherm of the Alg-EDTA.
the2.5
and Alg-EDTA.
wt.% have been selected to
prepare Alg-EDTA hybrid aerogel, aiming at evaluating the effect of sodium alginate concentration
3.2. Effect
3.2. on theofadsorption
Concentrations of Alginate
performance. Sodium
TheSodium
experimental results show that the mechanical properties of the
Sodium alginates
Sodium alginates of
of 0.5
0.5 wt.%,
wt.%, 1.0
1.0 wt.%
wt.% 1.5
1.5 wt.%, 2.0 wt.%,
wt.%, 2.0 wt.%, and
and 2.5
2.5 wt.%
wt.% have
have been
been selected
selected to
to
prepare Alg-EDTA hybrid aerogel, aiming at evaluating the effect of sodium alginate concentration
prepare Alg-EDTA hybrid aerogel, aiming at evaluating the effect of sodium alginate concentration
on the adsorption performance. The experimental results show that the mechanical properties of the
Appl. Sci. 2019, 9, 547 5 of 14

Appl. Sci. 2019, 9, 547 5 of 14

on the adsorption performance. The experimental results show that the mechanical properties of
the prepared
prepared Alg-EDTA
Alg-EDTA aerogel
aerogel gradually
gradually enhance
enhance withthe
with theincrease
increaseininthe
the concentration
concentration of
of sodium
sodium
alginate, and its
alginate, and its adsorption
adsorption capacity
capacity for
forheavy
heavymetal
metalions
ionsalso
alsogradually
graduallyincreases.
increases.AnAn amount
amount of
of 2.0.wt.% sodium alginate solution was used to prepare the Alg-EDTA
2.0.wt.% sodium alginate solution was used to prepare the Alg-EDTA adsorbent based adsorbent based on raw
material cost,
cost, adsorption
adsorption performance,
performance, and
and ease
ease of
of operation.
operation.

3.3.
3.3. Effect
Effect of
of pH
pH
Approximately 2+ 2+
Approximately 100 100 mg
mg of of Alg-EDTA
Alg-EDTA was was weighed
weighed and and added
addedto to5050mL
mLofof1.51.5mM
mMCd Cd2+ (Pb
(Pb2+,,
Cu 2+ Cr3+ or Co2+ ) solution of different pH values, stirred for 6 h, and filtered, and the concentration
Cu2+,, Cr 3+ or Co2+) solution of different pH values, stirred for 6 h, and filtered, and the concentration
of
of residual metal
residual metal ions
ions in
in the
the filtrate
filtrate was
was determined
determined by by ICP-OES.
ICP-OES. As As shown
shown in in Figure
Figure 5,
5, when
when thethe
solution pH is less than 1.0, Alg-EDTA can only adsorb 21.3% of Cd 2+ (19.2% of Pb2+ , 17.1% of Cu2+ ,
solution pH is less than 1.0, Alg-EDTA can only adsorb 21.3% of Cd2+ (19.2% of Pb2+, 17.1% of Cu2+,
14.4% 3+ or 13.7% of Co2+ ) probably due to the protonation of carboxyl and amino groups under
14.4% ofof Cr
Cr3+ or 13.7% of Co2+) probably due to the protonation of carboxyl and amino groups under
strongly acidic conditions,
strongly acidic conditions, therebythereby reducing
reducing the
the binding
binding sites
sites of
of Alg-
Alg- EDTA
EDTA withwith heavy
heavy metal
metal ions.
ions.
With increased solution pH, the adsorption capacity of Alg-EDTA for metal
With increased solution pH, the adsorption capacity of Alg-EDTA for metal ions increases ions increases significantly
and then stabilizes.
significantly and then The solubility
stabilizes. product
The ruleproduct
solubility suggests that
rule Pb2+ , Cd
suggests
2+ Cu2+ , Cr3+ and Co2+ in
that, Pb 2+, Cd2+, Cu2+, Cr3+ and
the
Co2+ in the solution will separately form the corresponding hydroxide precipitation the
solution will separately form the corresponding hydroxide precipitation when whensolution pH is
the solution
higher than 6.5.
pH is higher thanTherefore, the optimum
6.5. Therefore, pH liespH
the optimum in lies
the in
range of 4.0–6.5
the range for adsorption
of 4.0–6.5 of heavy
for adsorption metal
of heavy
ions by Alg-EDTA.
metal ions by Alg-EDTA.

Figure 5. Effect of solution pH on metal ion adsorption of the Alg-EDTA.

Alg-EDTA.

3.4.
3.4. Effect
Effect of
of Adsorption
Adsorption Time
Time
Approximately 2+ 2+
Approximately 100 100 mg
mg ofof Alg-EDTA
Alg-EDTA was was weighed
weighed and
and added
addedto to50
50mLmLofof1.5
1.5mM
mMCd Cd2+ (Pb
(Pb2+,,
Cu 2+ Cr3+ or Co2+ ) solution at 25 ◦ C, stirred for 2, 4, 6, 8, 10, 12, 15, 20, 30, 40, 50, 60······480 or 540 min,
Cu2+,, Cr 3+ or Co2+) solution at 25 °C, stirred for 2, 4, 6, 8, 10, 12, 15, 20, 30, 40, 50, 60······480 or 540 min,

and
and then filtered.
then filtered. The concentration of
The concentration residual metal
of residual metal ions
ions in
in the
the filtrate
filtrate was
was determined
determined by by ICP-OES.
ICP-OES.
The 2+
The experimental results are shown in Figure 6. The adsorption capacity of Alg-EDTA for Cd2+ and
experimental results are shown in Figure 6. The adsorption capacity of Alg-EDTA for Cd and
Pb 2+ increases first, and then remains constant with the increase in the adsorption time. When the
Pb2+ increases first, and then remains constant with the increase in the adsorption time. When the
adsorption
adsorption timetime isis 60
60 min, Alg-EDTA can
min, Alg-EDTA can adsorb
adsorb more
more than
than 40%
40% of heavy metal
of heavy metal ions
ions in
in the
the solution.
solution.
While the adsorption time greater than or equal to 360 min, Alg-EDTA can adsorb
While the adsorption time greater than or equal to 360 min, Alg-EDTA can adsorb more than 85% more than 85%of
of heavy
heavy metal
metal ionsions in the
in the solution.
solution. Therefore,
Therefore, an adsorption
an adsorption time
time of 360ofmin
360was
minselected
was selected
in this in this
study.
study. In addition,
In addition, the pseudo-first-order
the pseudo-first-order and pseudo-second-order
and pseudo-second-order modelsmodels were employed
were employed to fit thetokinetic
fit the
kinetic
data in data
orderintoorder
studytothestudy the adsorption
adsorption mode of mode of metal
metal ions ions by Alg-EDTA.
by Alg-EDTA. The fittingThe fitting
results showresults
that
show that the pseudo-first-order and the pseudo-second-order models are fit well with
the pseudo-first-order and the pseudo-second-order models are fit well with the kinetic data (Table the kinetic data
(Table 1), thereby
1), thereby indicating
indicating that that physisorption
physisorption andand chemisorption
chemisorption areare bothincluded
both includedininthe
the adsorption
adsorption
mechanism
mechanism [12,13].
[12,13].
Appl. Sci. 2019, 9, 547 6 of 14
Appl. Sci. 2019, 9, 547 6 of 14

Figure 6. Cont.
Appl. Sci. 2019, 9, 547 7 of 14
Appl. Sci. 2019, 9, 547 7 of 14

Figure 6.
Figure 6. Effect of adsorption
Effect of adsorption time
time on (A) Cd
on (A) Cd2+
2+, (B) Pb2+, ,(C)
, (B) Pb2+ (C)Cu , (D)
2+2+
Cu CrCr
, (D) and
3+ 3+ (E)(E)
and CoCo
2+ sorption by
2+ sorption

Alg-EDTA.
by Alg-EDTA.

Table 1.
Table Kinetic parameters
1. Kinetic parameters for
for heavy
heavy metal
metal ions
ions sorption
sorption onto
onto the
the Alg-EDTA.
Alg-EDTA.
Kinetic model Formula Parameters Cd2+ Pb2+ Cu2+ Cr3+ Co2+
Kinetic
Formula Parameters
qe (mg/g) Cd
79.932
2+ Pb
147.926
2+ Cu
44.947
2+ Cr
34.328
3+ Co
38.946
2+
model
pseudo-first-order
qt = qe (1 −
k1 (L/min) 0.009 0.008 0.008 0.007 0.007
exp(−k1 t))
qe (mg/g)
R2 79.932
0.984 147.926
0.979 44.947
0.987 34.328
0.992 38.946
0.992
pseudo-first- qt = qe(1-exp(-
qt = qe (1 − k1qe(L/min)
(mg/g) 0.009
97.141 0.008
181.306 0.008
55.578 0.007
43.500 0.007
49.693
order
pseudo-second-order k1t)) k2 (L/min) 1.006 × 10−4 4.712 × 10−5 1.530 × 10−4 1.651 × 10−4 1.365 × 10−4
1/(1 + qe k2 t)) RR22 0.984
0.991
0.979
0.989
0.987
0.992
0.992
0.993
0.992
0.993
pseudo- qe (mg/g)
qe (experiment,
97.141 181.306 55.578 43.500 49.693
- qt = qe(1-- 82.027 148.56 45.222 33.459 37.526
second- k2 (L/min)
mg/g) 1.006×10−4 4.712×10−5 1.530×10−4 1.651×10−4 1.365×10−4
1/(1+qek2t))
order R2 0.991 0.989 0.992 0.993 0.993
3.5. Effect of Environmental qe (experiment,
Temperature
- - 82.027 148.56 45.222 33.459 37.526
mg/g)
The influence of environmental temperature on the adsorption performance has also been
investigated and illustrated
3.5. Effect of Environmental in Figure 7. The adsorption performance of the Alg-EDTA is slightly
Temperature
affected by the variance in ambient temperature as shown in the figure. The adsorption rate of Cd2+
and PbThe influence
2+ by Alg-EDTA of environmental temperature
adsorbents remains between on the adsorption
90–95% performance
in a wide ambient has also
temperature been
window
investigated
from 5 ◦ C to and illustrated
40 ◦ C. Based oninthese
Figure 7. The adsorption
experimental data, theperformance
value of Gibbsof the
freeAlg-EDTA
energy (∆G) is slightly
can be
affected by the variance in ambient temperature as shown in the figure. The adsorption
calculated from Equation (1) [14,15], the enthalpy (∆H) and entropy (∆S) values can be obtained rate of from
Cd2+
andslope
the Pb2+ and
by Alg-EDTA adsorbents
intercept of linear remains
Equation between 90%–95%
(2), respectively (Figure 8).inAsa listed
wide inambient
Table 2, temperature
the negative
window
∆G at allfrom 5 °C to 40indicates
temperatures °C. Based on the
that these experimental
Alg-EDTA bind data,
to Cdthe value of Gibbs free
2+ spontaneously, energy (∆G)
the positive ∆H
can be calculated from
2+ equation (1) [14,15],
shows that the Cd adsorption process is endothermic.the enthalpy (∆H) and entropy (∆S) values can be obtained
from the slope and intercept of linear equation (2), respectively (Figure 8). As listed in Table 2, the
negative ∆G at all temperatures indicates that ∆G the
= −Alg-EDTA
RTlnKo bind to Cd2+ spontaneously, the positive (1)
∆H shows that the Cd2+ adsorption process is endothermic.
∆S ∆H
lnK o =
∆G −
= −RTlnK (2)
(1)
R RT
∆S ∆H
lnK = − 2+ (2)
Table 2. Thermodynamic parametersRfor Cd RT sorption onto Alg-EDTA.

T (K) ∆G (KJ/mol) ∆H (KJ/mol) ∆S (KJ/(mol·K)

288 −2.084 - -
293 −2.285 - -
298 −2.507 9.300 0.040
303 −2.668 - -
Appl. Sci. 2019, 9, 547 8 of 14
Appl. Sci.
Appl. Sci. 2019,
2019, 9,
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547 88 of
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Figure 7.
Figure 7. Effect of temperature
temperature on metal ion adsorption (100 mL
(100 mg of Alg-EDTA was added to 50 mL
2+ 2+
1.5 mM of Cd2+2+ (or Pb 2+
2+ ) solution at different temperatures).
(or Pb ) solution at different temperatures).

Figure8.8.(A)
Figure (A)Plots
Plotsofoflnq
lnqe /C
ee/Ce
ee versus
versus qeee at
at different
different temperatures;
temperatures; (B)
(B) plot
plot of
of lnK
lnKooo versus
versus1/T.
1/T.

3.6. Adsorption Ability

Tableand Maximum Adsorption
2. Thermodynamic Capacity
parameters for Cd2+
2+ sorption onto Alg-EDTA.

T (K) ∆𝐆
To evaluate the adsorption capability ∆𝐇 (𝐊𝐉/𝐦𝐨𝐥)
(KJ/mol)of Alg-EDTA ∆𝐒 (𝐊𝐉/(𝐦𝐨𝐥
for different heavy∙ metal
𝐊) ions, we conducted
single metal ion adsorption
288 and competitive
−2.084 adsorption
- experiments (Table
- 3). The experimental results
show that Alg-EDTA has293 good affinity for heavy metal ions, such as Cd 2+ , Pb2+ , Cu2+ , Co2+ , and Cr3+ ,
−2.285 - -
and can adsorb more than298 80% of the corresponding
−2.507 9.300heavy metal ions
0.040in the solution. In competitive
303 −2.668 - -
Appl. Sci. 2019, 9, 547 9 of 14

adsorption experiments, Alg-EDTA exhibits higher selectivity for Cd2+ , it can adsorb more than 90%
of Cd2+ in the mixed metal ion solution. This may be due to the fact that the ionic radius of Cd2+
(0.097 nm) is closer to that of Ca2+ (0.100 nm) than Pb2+ (0.132 nm) and Cu2+ (0.072 nm), and thus
has stronger ion exchange effect with Ca2+ [16]. We further conducted experiments to determine the
maximum adsorption capacity of Alg-EDTA for Cd2+ , and the experimental results are presented in
Figure 9. As the Cd2+ concentration in the solution increases from 0.1 mM to 4.0 mM, the adsorption
capacity of Alg-EDTA for Cd2+ increases rapidly, and then remains stable with further increase in
concentration. The maximum adsorption capacity of Alg-EDTA for Cd2+ is 177.3 mg/g, which is
higher than most of the reported Cd2+ -sorbents (Table 4) [17–27].

Table 3. The adsorption capacity of Alg-EDTA for heavy metal ions.

Alg-EDTA Initial concentration (mM) Adsorption (%) Adsorption capacity (mg/g)

1.5 (Cd2+ )
Appl. Sci. 2019, 9, 547 - 96.3 - 80.8 - 9 of 14
1.5 (Pb2+ ) - 95.6 - 157.0 -
1.5and 2+ )
(CuMaximum - 93.8 - 47.1 -
3.6. Adsorption Ability 2+
Adsorption Capacity
1.5 (Zn ) - 70.8 - 32.3 -
evaluate the1.5
Todeionized (Co2+ )
adsorption -
capability 84.8 for different
of Alg-EDTA - heavy37.8
metal ions, we- conducted
In 3+ )
single metal
water ion 1.5 (Cr
adsorption and -
competitive 85.5
adsorption -
experiments 33.3
(Table -
3). The experimental
1.5 (Cd2+ ) 1.5 (Co2+ ) 87.0 69.5 73.0 2+ 30.8
results show that Alg-EDTA has good affinity for heavy metal ions, such as Cd , Pb , Cu , Co2+, and
2+ 2+
1.5 (Cd2+ ) 1.5 (Zn2+ ) 85.9 60.3 72.3 29.5
Cr3+, and can adsorb 1.5 more
(Cd2+ ) than 1.5
80% (Pbof
2+ )the corresponding
90.4 heavy metal
82.5 76.0ions in the135.5
solution. In
competitive adsorption
1.5 (Cdexperiments,
2+ ) Alg-EDTA
1.5 (Cu 2+ ) exhibits higher
90.2 80.9 selectivity
75.8 for Cd , it40.5
2+ can adsorb
more than 90% of Cd in 2+
1.52+(Cd the
) mixed1.5 (Cr 3+ )
metal ion solution.
85.1 This
74.8may be due
71.3to the fact that
29.3 the ionic
radius of Cd2+ (0.0971.5
nm)(Cdis2+closer
) to that
- of Ca (0.100
2+
93.7 nm) than - Pb (0.132
2+ nm) and Cu2+ -(0.072 nm),
78.8
In tap water 2+ 2+
and thus has stronger ion )exchange
1.5 (Cd effect
1.5 (Pb ) with91.1Ca [16]. 85.5
2+ We further 76.5conducted experiments
140.5 to
determine the
In pond maximum adsorption
1.5 (Cd )2+ capacity
- of Alg-EDTA
91.2 for- Cd 2+, and the experimental results are
76.5 -
presented in Figure 1.5
9. As 2+ ) Cd2+ concentration
(Cdthe 1.5 (Pb2+ ) in90.1
the solution
84.2increases from
75.8 0.1 mM to 4.0 mM, the
138.5
water
adsorption capacity1.5
In river of(Cd
Alg-EDTA
2+ ) for -Cd2+ increases90.7 rapidly, -and then remains
76.3 stable with
- further
increasewater
in concentration.
1.5 (Cd ) The
2+ maximum 2+
1.5 (Pb ) adsorption
90.1 capacity
87.6of Alg-EDTA 75.8 for Cd 2+ is 177.3 mg/g,
144.0
which is higher than most of the reported Cd2+-sorbents (Table 4) [17–27].

.
Figure 9. The maximum adsorption capacity of Alg-EDTA for Cd2+ .
Figure 9. The maximum adsorption capacity of Alg-EDTA for Cd2+.

Table 3. The adsorption capacity of Alg-EDTA for heavy metal ions.

Initial concentration Adsorption Adsorption capacity

Alg-EDTA
(mM) (%) (mg/g)
In deionized 1.5 (Cd2+) ﹣ 96.3 ﹣ 80.8 ﹣
water 1.5 (Pb2+) ﹣ 95.6 ﹣ 157.0 ﹣
1.5 (Cu2+) ﹣ 93.8 ﹣ 47.1 ﹣
1.5 (Zn )
2+ ﹣ 70.8 ﹣ 32.3 ﹣
1.5 (Co2+) ﹣ 84.8 ﹣ 37.8 ﹣
Appl. Sci. 2019, 9, 547 10 of 14

Table 4. The adsorption capacity of different heavy metal ions sorbents for Cd2+ .

Maximum adsorption
Sorbent Adsorption Time (min) Reference
capacity for Cd2+ (mg/g)
2-mercaptopyrimidine functionalized
112.5 30 [17]
Mesoporous silica
Amino functionalized MCM-41 18.3 120 [18]
Activated carbon-zeolite composite 161.8 1440 [19]
Mango peel waste 68.9 60 [20]
Nano crystallite hydroxyapatite 142 120 [21]
Natural zeolite 130.4 1440 [22]
Clinoptilolite 4.22 2880 [23]
Magnetic modified sugarcane bagasse 123.6 60 [24]
Zeolite synthesized from perlite waste 139.0 1440 [25]
Natural Egyptian bentonitic clay 8.2 60 [26]
L-cystein modified bentonite-cellulose
16.1 2880 [27]
nanocomposite
Alg-EDTA 177.3 360 This study

3.7. Adsorption Mechanism

The variation tendency of the concentration of metal ions in the solution has also been monitored
during the adsorption process in order to clarify the adsorption mechanism of the Alg-EDTA. It turns
out that the amount of Pb2+ (or Cd2+ ) in the solution gradually decreases in the progress of adsorption,
whereas the amount of Ca2+ gradually increases due to the ion exchange effect between Ca2+ in
Alg-EDTA and Pb2+ (or Cd2+ ) in solution. However, after adsorption, the amount of Ca2+ released
from Alg-EDTA (0.041 ± 0.002 mmol) is evidently smaller than the amount of adsorbed Pb2+ or
Cd2+ (0.072 ± 0.002 mmol), the ion exchange effect contributes approximately 56.9% of metal ions
adsorption. It indicates that ion exchange effect is not the only approach in which Alg-EDTA binds to
Pb2+ (or Cd2+ ) ions. Therefore, we analyzed the XPS spectra of Alg-EDTA before and after adsorption.
As shown in Figure 10A, the new Pb 4f and Pb 5 s peaks for Alg-EDTA loaded Pb2+ verify that
Alg-EDTA successfully loaded Pb2+ after equilibrated with Pb2+ -containing solution. The binding
energy of the O element of Alg-EDTA shifts from 529.86 to 529.07 eV, it might be caused by the
coordination effect between O atoms in Alg-EDTA with Pb2+ ions [28]. Based on IR, XPS, and heavy
metal ions concentration analysis of the Alg-EDTA sorbent before and after adsorption, we proposed
a possible adsorption mechanism of the Alg-EDTA combines with heavy metal ions as depicted in
Figure 11.
Appl. Sci. 2019, 9, 547 11 of 14
Appl. Sci. 2019, 9, 547 11 of 14

Figure 10. (A)

(A) XPS
XPS survey
survey of
of (a)
(a) Alg-EDTA
Alg-EDTA and (b) Alg-EDTA loaded Pb2+
loaded Pb 2+. O 1s spectra of Alg-EDTA
. O 1s spectra of Alg-EDTA
2+
(B) before and (C) after Pb adsorption.
2+ adsorption.
Appl. Sci. 2019, 9, 547 12 of 14
Appl. Sci. 2019, 9, 547 12 of 14

Figure 11. Plausible

Figure 11. Plausible adsorption
adsorption mechanism
mechanism of of Alg-EDTA combined with
Alg-EDTA combined with heavy
heavy metal
metal ions.
ions. M
M
represents heavy metal ions such as Cd2+, Pb2+
2+ 2+, Cu ,
2+2+
represents heavy metal ions such as Cd , Pb , Cu , etc. etc.

3.8. Regeneration Performance

H protons can exchange metal ions attached to the carboxyl group and the amino group by
protonation under
under acidic
acidicconditions.
conditions.Therefore,
Therefore, weweuseuse
0.050.05 M HNO
M HNO 3 as 3anaseluent
an eluent
to eluteto elute
the Cdthe
2+-
2+
Cd -loaded Alg-EDTA to achieve regeneration of the adsorbent.
loaded Alg-EDTA to achieve regeneration of the adsorbent. AsAs shown
shown ininFigure
Figure12,12,the
the adsorption
adsorption
rate of Alg-EDTA to Cd 2+2+still lies in the range of 92.0–95.0% after nine adsorption–desorption cycles,
of Alg-EDTA to Cd still lies in the range of 92.0%–95.0% after nine adsorption–desorption
although
cycles, the morphology
although of Alg-EDTA
the morphology changedchanged
of Alg-EDTA slightly slightly
(from spherical to flat). We
(from spherical propose
to flat). that the
We propose
as-prepared
that Alg-EDTA
the as-prepared has stablehas
Alg-EDTA adsorption performance
stable adsorption after the repetition
performance after the of the usage
repetition ofacting as a
the usage
potential
acting as low-cost and
a potential highly-efficient
low-cost heavy metalheavy
and highly-efficient ion adsorbent.
metal ionMoreover,
adsorbent. weMoreover,
further analyzed the
we further
chemical composition
analyzed the chemical of the Alg-EDTA
composition using
of the an elemental
Alg-EDTA analyzer.
using an Elemental
elemental analyzer. analysis
Elementalresult shows
analysis
that the
result C%, N%
shows that and H% N%
the C%, of initial
and H% Alg-EDTA is Alg-EDTA
of initial 35.27%, 15.21% and 3.84%,
is 35.27%, 15.21%respectively. The C%, N%
and 3.84%, respectively.
and H%
The C%,ofN%Alg-EDTA
and H%after nine adsorption-desorption
of Alg-EDTA cycles is 34.36%, 14.47%
after nine adsorption-desorption cycles and 4.05%, respectively.
is 34.36%, 14.47% and
The chemical
4.05%, composition
respectively. of Alg-EDTA
The chemical after repeated
composition use isafter
of Alg-EDTA consistent
repeatedwith that
use before adsorption.
is consistent with that
before adsorption.
Appl. Sci. 2019, 9, 547 13 of 14
Appl. Sci. 2019, 9, 547 13 of 14

Figure 12. Adsorption

Figure performance
12. Adsorption of of
performance thetheAlg-EDTA innine
Alg-EDTA in nineadsorption–desorption
adsorption–desorptioncycles.cycles.

4. Conclusions
4. Conclusions

In this study, a novel

In this study, heavy
a novel metal
heavy ions
metal ionsadsorbent (Alg-EDTA)
adsorbent (Alg-EDTA) was
was successfully
successfully prepared
prepared by by
grafting grafting EDTA
EDTA salt salt sodium
onto onto sodium alginate.
alginate. Owingto
Owing to the
the strong
strongcoordination ability
coordination of EDTA
ability and ionand ion
of EDTA
exchange effect 2+
exchange effect of Ca of with
Ca2+ with heavy metal ions, the as-prepared Alg-EDTA shows high affinity for
heavy metal ions, the as-prepared Alg-EDTA shows high affinity for
heavy metal ions such as2+Cd2+, Pb2+ , ,Cu
2+ Cu2+, Cr3+, and Co2+. The maximum adsorption capacity of Alg-
2+ , Cr3+ , and Co2+ . The maximum adsorption capacity of
heavy metal ions such as Cd , Pb
EDTA for Cd2+ is up to 177.3 mg/g, which is higher than most of the reported Cd2+-sorbents. Alg-
Alg-EDTA forhas 2+ is up to 177.3 mg/g, which is higher than most of the reported Cd2+ -sorbents.
Cdshown
EDTA potential applications in the treatment of heavy metal ion wastewater by virtue of
Alg-EDTA thehas shown
low-cost rawpotential
materials, applications
simple synthesis in and
the regeneration
treatment ofprocesses,
heavy metal ion wastewater by virtue
and recyclability.
of the low-cost
Author Contributions: Conceptualization, Z.W.; formal analysis, X.Z.; investigation, M.W.; recyclability.
raw materials, simple synthesis and regeneration processes, and writing—original
draft preparation, Z.W. and M.W.; writing—review and editing, Z.W. and S.L.
Author Contributions: Conceptualization, Z.W.; formal analysis, X.Z.; investigation, M.W.; writing—original
Funding: This work was supported by the natural science foundation of Anhui province grant number [No.
draft preparation, Z.W. and M.W.; writing—review and editing, Z.W. and S.L.
KJ2017A345].
Funding: This work was supported by the natural science foundation of Anhui province grant number
Conflicts of Interest: The authors declare no conflict of interest.
[No. KJ2017A345].
of Interest: The authors declare no conflict of interest.
ConflictsReferences

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