Colloids and Surfaces A 585 (2020) 124070

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Colloids and Surfaces A

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

The role of sulfonated chitosan-based flocculant in the treatment of hematite T

wastewater containing heavy metals
⁎
Xiaomin Tanga,b, , Ting Huangb, Shixin Zhangc, Wei Wangb, Huaili Zhengc
a
School of Urban Construction and Environmental Engineering, Chongqing University, Chongqing 400045, PR China
b
Chongqing Key Laboratory of Catalysis & Functional Organic Molecules, College of Environment and Resources, Chongqing Technology and Business University,
Chongqing 400067, PR China
c
Key Laboratory of the Three Gorges Reservoir Region’s Eco-Environment, State Ministry of Education, Chongqing University, Chongqing 400045, PR China

G R A P H I C A L A B S T R A C T

A R T I C LE I N FO A B S T R A C T

Keywords: Hematite wastewater containing dissolved heavy metals is a potential threat to eco-environment and human
Chitosan-based flocculant health. Flocculation as an efficient and cost effective water treatment technology should be applied in its
Graft copolymerization treatment. A sulfonated chitosan-based flocculant (CS-g-P(AM-AMPS)) was prepared via graft copolymerization.
Synthesis mechanism Two synthesis pathways and reaction products with different molecular structure were discovered in processes.
Hematite wastewater
CS-g-P(AM-AMPS) possessed the multifarious functional groups that contributed to its excellent performance in
Flocculation mechanism
hematite wastewater treatment. Bridging, adsorption and entrapment in coagulation-flocculation were enhanced
due to CS-g-P(AM-AMPS), and the impressive floc size and high removal efficiency were represented in the
treatment as well. Dissolved heavy metals in the wastewater were removed by the chelation of sulfonate group in
CS-g-P(AM-AMPS), the adsorption of other functional groups and the co-settlement with flocs. CS-g-P(AM-
AMPS) will have the potential application in industrial wastewater treatment for its high flocculation perfor-
mance, thermal stability and solubility.

Abbreviation: AM, acrylamide; AMPS, 2-acrylamino-2-methyl-1-propanesulfonic acid; CS, chitosan; CS-g-P(AM-AMPS), a chitosan-based flocculant that grafting AM
and AMPS on CS; CAN, ceric ammonium nitrate; FT-IR, fourier transform infrared; TG/DSC, thermogravimetric/differential scanning calorimetry; XPS, X-ray
photoelectron spectroscopy; NMR, nuclear magnetic resonance; SEM, scanning electron microscope; PAFC, polyaluminium ferric chloride; AAS, atomic absorption
spectrometry
⁎
Corresponding author at: School of Urban Construction and Environmental Engineering, Chongqing University, Chongqing 400045, PR China.
E-mail address: txmno1@126.com (X. Tang).

https://doi.org/10.1016/j.colsurfa.2019.124070
Received 5 April 2019; Received in revised form 1 October 2019; Accepted 2 October 2019
Available online 04 October 2019
0927-7757/ © 2019 Elsevier B.V. All rights reserved.
X. Tang, et al.
1. Introduction
Water pollution has aroused wide concern in developing countries,
in particular the pollution of industrial wastewater, which possesses the
potential great threat to ecological system and human health [1].
Mining industry in developing countries has the defect of high water
consumption, and wastewater containing large quantities of diverse
pollutants is produced in the processes. Hematite wastewater, as a ty-
pical mining wastewater, contains a high concentration of suspended
micron-sized colloidal particles [2]. It is required to be treated by an
efficient and cost-effective water treatment technology. Besides, the
removals of the dissolved heavy metals are rarely considered in he-
matite wastewater treatment. Their treatment should be further studied
for eliminating their threat to environment and creatures. Gravity se-
paration, magnetic separation and flotation are the common technolo-
gies in hematite wastewater treatment [3,4]. Coagulation/flocculation
is rarely applied in its treatment, and the efficient flocculants and the
role of coagulation-flocculation should be further investigated before
the application.
Coagulation/flocculation is competent and economical in water
treatment, but it is often helpless to treat the dissolved pollutants, such
as dissolved heavy metals and organic pollutants [5,6]. Inorganic coa-
gulants and organic flocculants are the key factors in coagulation/
flocculation. The novel natural flocculants, such as chitosan (CS),
starch, lignin and cellulose, are drawing wide concern for its wide
sources, low cost, non-toxic and biodegradable [7,8]. The modification
of natural flocculants via esterification, oxidization, crosslinking and
grafting might reinforce their flocculation performance [9,10]. It is
interesting to introduce the special functional groups into CS for the
treatment of special pollutants in wastewater.
In this study, a chitosan-based flocculant with anionic sulfonate
group was prepared to aim at the treatment of hematite wastewater
containing the dissolved heavy metals. It was synthesized via graft
copolymerization of CS, 2-acrylamino-2-methyl-1-propanesulfonic acid
(AMPS) and acrylamide (AM) using oxidation initiation system. The
reaction pathways and synthesis mechanisms are mainly investigated
through the analyses of structure and characteristics. It primarily fo-
cuses on coagulation-flocculation performance in hematite wastewater
treatment in terms of removal efficiency, the role of coagulation-floc-
culation in the treatment, floc characteristics and removal mechanisms
of pollutants as well.
2. Materials and methods
2.1. Materials and water characteristics
All chemical reagents used in flocculant preparation and char-
acteristic analysis were analytical grade chemicals. Deionized water
was used to make all the solution of reagents. The simulated hematite
wastewater was prepared via sieving hematite powder by a 200-mesh
sifter, mixing it with deionized water and making it uniformly disperse
in water. The sizes of colloidal particles were almost lower than 18 μm,
and the other properties of hematite wastewater were shown in
Supplementary information (Table S1).
2.2. Flocculant preparation
In the study, the modified chitosan flocculant was prepared at the
optimal condition. Chitosan powder (Sinopharm Chemical Reagent Co.,
Ltd., China) was dissolved in deionized water with the assistance of
glacial acetic acid. And then a certain amount of AM (Chengdu Cologne
Chemical Co., Ltd., China) and AMPS (Aladdin Biochemical Technology
Co., Ltd., China) were mixed with chitosan solution at the rapid stirring
until the mixture was completely dissolved. The concentration of CS
was 4%, and the mass ratio of CS, AM and AMPS (m(CS):m(AM):m
(AMPS)) was 12:25:3. Nitrogen was introduced into the reaction system
2
Colloids and Surfaces A 585 (2020) 124070
for 15 min to drive oxygen out while initiator, ceric ammonium nitrate
(CAN) with a concentration of 0.1 mol/L (Aladdin Biochemical
Technology Co., Ltd., China), was added into reactor. The concentration
of CAN in reactor was 0.37%. At last, the sealed reactor was heated in
water bath at low temperature of 40 °C for 4 h and aged at room tem-
perature for 12 h. The purified anionic chitosan-based flocculant, CS-g-
P(AM-AMPS) with sulfonate group, was obtained after it was washed by
acetone and ethyl alcohol. CS-g-P(AM-AMPS) was dried for 24 h in a
LGJ-10 vacuum freeze drier (Four-ring Science Instrument Plant Beijing
Co., Ltd., China) before characterization tests.
2.3. Characterization methods for chitosan-based flocculant
2.3.1. Intrinsic viscosity, grafting ratio and conversion rate
The measurement and calculation of intrinsic viscosity, grafting
ratio and conversion rate were described in previous studies [11,12].
2.3.2. Fourier transform infrared spectroscopy
Fourier transform infrared (FT-IR) spectra of CS-g-P(AM-AMPS) was
recorded by a NICOLET 5700 FT-IR spectrometer (Thermo Nicolet
Corporation Company, USA). The sample was prepared by KBr com-
pression plate method [3,13]. The infrared spectra of CS-g-P(AM-
AMPS) was measured in the range of 400 cm−1–4000 cm−1.
2.3.3. X-ray photoelectron spectroscopy
X-ray photoelectron spectroscopy (XPS) was to measure for the
analysis of the element composition and functional groups in CS-g-P
(AM-AMPS). It was performed on an ESCALAB250Xi X-ray photoelec-
tron spectrometer (Thermo Fisher Scientific Co., Ltd, USA) under the
vacuum degree of the chamber of 5∙10−10 mbar. Each analysis started
with a survey scan from 0 to 1300 eV with step of 1 eV. And the in-
dividual elements were employed with the high resolution XPS scans as
well.
2.3.4. Nuclear magnetic resonance spectroscopy
1
H NMR and 13C NMR of the graft copolymer, as another analysis
method for representing molecular structure of polymer [14], were
analyzed by using an AVANCE III HD 500 MHz nuclear magnetic re-
sonance spectrometer (Bruker Daltonics Inc., USA).
2.3.5. Thermal analysis
Thermogravimetric/differential scanning calorimetry (TG/DSC)
was to describe the thermal stability and composition of polymers [11].
The TG/DSC analysis of CS-g-P(AM-AMPS) was performed by a 204 F1
differential scanning calorimeter (Nace Instrument Manufacturing Co.,
Ltd, Germany). The graft copolymer was measured at a heating rate of
10 °C min−1 from the room temperature to 590 °C under nitrogen at-
mosphere.
2.4. Jar test procedure
The simulated hematite wastewater was treated by a compound
flocculants, polyaluminium ferric chloride (PAFC) and CS-g-P(AM-
AMPS), on a program-controlled six-paddle gang stirrer (Wuhan Meiyu
Instrument Co., Ltd, China). Coagulation-flocculation was conducted
under the fast stirring of 300 r min−1 for 2 min and the slow stirring of
40 r min-1 for 10 min in sequence. PAFC was firstly added into the he-
matite wastewater at the beginning of fast stirring, and then CS-g-P
(AM-AMPS) was dosed after fast stirring of 1 min. As a comparison,
PAFC was separately operated under the same conditions in the he-
matite wastewater treatment. The turbidity of supernatant was mea-
sured after settlement of flocs formed during coagulation-flocculation
for 30 min. Raw water and treated water were taken at a depth of 1 cm
below the surface of supernatant to determine the turbidity of waste-
water. The removal rate of turbidity is calculated by formula (1):
X. Tang, et al.
Removal rate of turbidity=(T1-T2)/T1 (1)
Where T1 and T2 are turbidity value of the original hematite wastewater
and treated water, respectively. Atomic absorption spectrometry (AAS)
was to test the concentrations of heavy metals in hematite wastewater
and treated water via the standard curve method. The hematite was-
tewater and the treated water were filtered by 0.45 μm membrane filter
before the test of a TAS-990 atomic absorption spectrophotometer
(Beijing Pushen General Instrument Co., Ltd, China).
2.5. Floc characteristics
Flocs formed during coagulation-flocculation would settle to
achieve the separation of pollutants and water. Their size played a key
role in separation efficiency [15]. Floc size was measured by a Mas-
tersizer 2000 laser particle size analyzer (Malvern Instruments Co., Ltd.,
England). A Su1510 scanning electron microscope (SEM, Hitachi High-
tech Co., Ltd, Japan) was applied to record the floc images to analyze
surface shape and structure of flocs and speculate coagulation-floccu-
lation mechanisms. Flocs were freeze-dried for 36 h before SEM test.
2.6. Zeta potential
Zeta potential, as a measure of surface charges on colloid particles
in hematite wastewater and treated water, was recorded by a Nano-
ZS90 zeta potential analyzer (Malvern Instruments Ltd., England). It is
of importance to analyze charge neutralization of flocculants [16].
3. Results and discussion
3.1. The structure and characteristics of CS-g-P(AM-AMPS)
3.1.1. FT-IR spectral analysis
FT-IR spectra of CS-g-P(AM-AMPS) presents its containing func-
tional groups that may contribute to the pollutants removal in hematite
wastewater treatment and confirms that CS-g-P(AM-AMPS) is the
grafting copolymer of CS, AM and AMPS (Fig. S1). The strong absorp-
tion peak at 3440 cm−1 results from the strong stretching vibration of
eOH and eNH, which is often found in CS and AM [17,18]. A weak
absorption at 2924 cm−1 is assigned to an asymmetrical CeH stretching
vibration of the aliphatic eCH2 group in CS [13]. The peak observed at
2370 cm−1 is from the amide group eNeC]O [19]. The characteristic
absorption peak at 1630 cm−1 is the stretching vibration peaks of eC]
O in AM [3]. The peak at 1415 cm−1 could be attributed to the vibra-
tion of CeH of eCH3 in AMPS. The two peaks observed at 1300 cm−1
and 1267 cm−1 are attributed to the stretching vibrations of CeN bonds
is a characteristic peak of CS [3]. The stretching vibration peak of S]O
in sulfonate group derived from AMPS appears at 1068 cm−1 [20]. And
the peak of 912 cm−1 corresponds to the stretching vibration of
eCeOe in CS [3,21]. The results are identified that sulfonate group is
grafted onto the molecular chain of CS, and CS-g-P(AM-AMPS) pos-
sesses the functional groups of eOH, eNH, eC]O, eSO3−.
3.1.2. XPS spectral analysis
XPS further represents the molecular structure and functional
groups of CS-g-P(AM-AMPS) and provides clues for active sites on CS,
which is attacked by reactive radical in synthesis. The main elements,
C, N, O and S, are found in CS-g-P(AM-AMPS) via XPS (Fig. S2), and
their atomic concentrations are described in Table S2. The C 1s spec-
trum of CS-g-P(AM-AMPS) can be divided into six peaks (Fig. 1(a)). The
peaks at 284.19 eV and 284.75 eV correspond to CeH and CeC species.
The corresponding value of 286.15 eV is attributed to the sulfonate
group, CeSO3H, originating from AMPS [22]. The peak occurred at
287.9 eV is caused by NeC=O/OeCeO in CS-g-P(AM-AMPS). Peaks at
285.63 eV and 287.38 eV are attributed to CeN and C]N. It confirms
that there are two reaction pathways and two reaction products in
3
Colloids and Surfaces A 585 (2020) 124070
grafting copolymerization among CS, AM and AMPS at least. Further
evidences are obtained from N 1s region. In the XPS spectrum of N 1s
(Fig. 1(b)), it can be differentiated into three peaks whose binding
energy (BE) are 398.69 eV, 399.26 eV and 399.74 eV, corresponding to
CeN, eCOeNHe and C]N species, respectively. The C]N and CeN in
CS-g-P(AM-AMPS) are another evidences to proves that there are two
active sites on CS, which are able to be induced to produce free radical,
then link with reactive monomer and finally generate the diversely
structural grafting copolymers. The integral area ratio of peaks origi-
nated from CeN and C]N is about 2.3:1. The two peaks of CeOeH at
532.32 eV and OeCeO at 532.84 eV in CS are observed in O 1s spec-
trum (Fig. 1(c)). The emergence of peaks valued 530.83 eV and
531.68 eV result from NeC]O and C-SO3H species, respectively
[23,24]. In the S 2p spectrum (Fig. 1(d)), the sulfonate group C-SO3H is
observed at 167.77 eV.
3.1.3. NMR spectral analysis
The similar results are found in 1H NMR spectrum and 13C NMR
spectrum. In the 1H NMR spectrum of CS-g-P(AM-AMPS) (Fig. S3(a)),
the peak of δ = 7.26 ppm corresponds to solvent. The peaks at
1.23–1.26 ppm are caused by methyl vibration in chain unit of AMPS.
The absorption peaks of protons in eCH2e and eCHe groups of AM
and AMPS are observed at 1.62 ppm and 2.09 ppm [11,14]. The char-
acteristic peaks of CS skeleton appear at 3.70–3.74 ppm (H3, H4, H5 and
H6) [25,26]. And the peaks at 5.73 ppm and 5.75 ppm result from the
proton of eNHe in the chain units of AMPS and CS in CS-g-P(AM-
AMPS), respectively [15]. The resonance peaks at 6.30 ppm and
6.33 ppm associate with two hydroxy protons eOH in CS [21].
The strong peak of δ = 77.16 ppm is attributed to solvent in 13C
NMR spectrum (Fig. S3(b)). The peak at 18.82 ppm corresponds to the
carbon of eCH3 in AMPS, and the peak of δ = 20.86 ppm is caused by
eCH2e [21]. The peak at 58.90 ppm is attributed to eCHe derived
from AM and AMPS, while the peaks of δ = 128.49 ppm and
δ = 130.28 ppm correspond to CeN and CeSO3H, respectively. In
conclusion, the functional groups originated from CS, AM and AMPS
are discovered in CS-g-P(AM-AMPS).
3.1.4. TG/DSC analysis
The thermal stability of flocculants is important for its wide appli-
cation in industrial manufacture, which is influenced by the molecular
structure and molecular weight of flocculants. The TG/DSC curves of
CS-g-P(AM-AMPS) that possesses high grafting rate and high molecular
weight are described in Fig. S4. The weight loss of CS-g-P(AM-AMPS) is
able to be divided into three stages. The first stage is in the range of
22.7–230 °C with the weightlessness rate of about 11.2% while there is
an endothermic peak at 65 °C and a large exothermic peak between 110
and 200 °C in DSC curve, mainly resulting from the evaporation of
water molecules absorbed by hydrophilic groups in CS-g-P(AM-AMPS).
In the second stage, weightlessness rate increases to about 24.5% in the
range of 230–340 °C, corresponding to two endothermic peaks at 255 °C
and 315 °C in DSC curve. It is attributed to the imidization of the amide
group and the decomposition of some functional groups, like methyl
and sulfonic acid group, which will significantly decrease the floccu-
lation efficiency of flocculants in water treatment. In the third stage, the
decomposition of copolymer backbone leads to the weightlessness rate
of about 34.1% in the range of 340–520 °C. Two endothermic peaks are
found at 385 °C and 475 °C in this range in DSC curve. The temperatures
causing the decomposition of most functional groups and molecular
chain in CS-g-P(AM-AMPS) are higher than that causing the decom-
position of other flocculants copolymerized by only monomers. It
confirms that the molecular structure of CS-g-P(AM-AMPS) with CS
groups and the intermolecular ionic bond formed by the sulfonate
group are more stable. The complete thermal decomposition of the graft
copolymer is beyond 520 °C, and the residual weight is about 30.2%.
X. Tang, et al.
Fig. 1. XPS spectra of CS-g-P(AM-AMPS): (a) C 1s spectrum, (b) N 1s spectrum, (c) O 1s spectrum and (d) S 2p spectrum.
3.2. Synthesis mechanism
Chain initiation, chain growth and chain termination are discovered
in graft copolymerization, which are similar with other studies
[3,15,21]. However, radicals in AM easier generated by induction of
CAN than that in CS and AMPS since AMPS are rarely grafted onto CS
without AM in our study. Radicals in AM play the role of trigger that
induces CS and AMPS to yield radicals and graft copolymerization, and
AM as the indispensable bridge links CS and AMPS. Besides, it is re-
ported that there might be two reaction pathways in the graft copoly-
merization of CS and AM [27]. It is confirmed in this study by the
special functional groups, CeN and C]N, in CS-g-P(AM-AMPS)
(Fig. 2), which is supported by aforementioned results of XPS and NMR.
The functional groups and long-chain molecular structure contribute to
the removal of pollutants in wastewater treatment and the excellent
thermal stability and solubility of CS-g-P(AM-AMPS).
3.3. Flocculation performance in hematite wastewater treatment
CS-g-P(AM-AMPS) and PAFC were used in hematite wastewater
treatment. The suspended hematite colloid particles and heavy metals
are removed from water via coagulation-flocculation and solid-liquid
separation. The removal efficiency of turbidity is often low in terms of
coagulant/flocculant dosage, removal rate and settling time of flocs if
PAFC or CS-g-P(AM-AMPS) separately performs in the treatment.
Although the removal rate of turbidity reaches to about 95% after in-
creasing the dosage of PAFC, the settling time of flocs made by PAFC is
always required for 30 min due to the small floc size (Fig. S5). The
settling time reduces to 5 min when CS-g-P(AM-AMPS) is dosed with
PAFC in the treatment, and the removal rate of turbidity is increased as
well (Fig. 3). The excessive PAFC and CS-g-P(AM-AMPS) will not result
in performance deterioration caused by the surface charge reversal of
hematite particles for the strong bridging of CS-g-P(AM-AMPS). Fur-
thermore, pH of wastewater is slightly changed after the treatment of
4
Colloids and Surfaces A 585 (2020) 124070
PAFC and PAFC + CS-g-P(AM-AMPS) with their different dosage (Fig.
S6).
The heavy metals in colloid particles of hematite are easily removed
with hematite through coagulation-flocculation. However, flocculants
have no effect on the removal of dissolved heavy metals in most cases
[28,29]. The dissolved heavy metals, Cu, Fe, Cr and Zn, which are
detected in hematite wastewater, are hardly treated by only PAFC.
However, the highest removal rate of one of these heavy metals
achieves about 50%, which results from the chelation of sulfonate
group in CS-g-P(AM-AMPS), the adsorption of CS-g-P(AM-AMPS) and
the co-settling with flocs (Fig. 4).
3.4. Floc size and surface characteristic
Floc characteristics are the other clues for coagulation-flocculation
performance and removal mechanism analysis. CS-g-P(AM-AMPS)
possesses the stronger bridging and adsorption than PAFC, though its
charge neutralization is weaker than the latter. It is discovered that the
floc size formed by only PAFC is about three times smaller compared
with that formed by PAFC and CS-g-P(AM-AMPS) (Figs. 5 and S7). The
size of flocs generated by PAFC is almost stable with the increase of
dosage of PAFC since the flocs are formed by the collision and ag-
gregation of colloid particles of hematite. However, floc size sig-
nificantly increases after CS-g-P(AM-AMPS) is introduced into the
treatment. CS-g-P(AM-AMPS) containing rich functional groups
bridges, adsorb and net more colloid particles than PAFC, and it leads to
the bigger and more compact flocs. It will be more obvious when the
dosage of CS-g-P(AM-AMPS) enhances.
SEM analysis was carried out to represent the size and surface
characteristic of flocs (Fig. S8). It is found that the size of flocs formed
by CS-g-P(AM-AMPS) and PAFC is larger than that of flocs formed by
PAFC. The surface of flocs yielded by only PAFC is often smooth as flocs
are mainly formed by inorganic matter, colloidal particles of hematite
and PAFC (Fig. S7(a)). But the flocs yielded by PAFC and CS-g-P(AM-
X. Tang, et al. Colloids and Surfaces A 585 (2020) 124070

Fig. 2. Synthesis mechanisms of CS-g-P(AM-AMPS).

Fig. 4. The performance of compound flocculants, CS-g-P(AM-AMPS) and

PAFC, in the removal of heavy metals.
Fig. 3. The performance of compound flocculants, CS-g-P(AM-AMPS) and
PAFC, in hematite wastewater treatment.
3.5. Zeta potential
AMPS) are large and rough (Fig. S7(b)). It presents that the part of
Charges on the surface of hematite colloidal particles impede the
smooth colloidal particles of hematite are covered by the rough organic
collision and settlement of particles. Charge neutralization in coagula-
flocculants, CS-g-P(AM-AMPS). It confirms the effect of bridging, ad-
tion-flocculation is able to eliminate these effects. The initial zeta po-
sorption and entrapment of CS-g-P(AM-AMPS) as well.
tential of hematite wastewater was -21.8 mV since hematite, main
Fe2O3 colloid, adsorbed OH− on its surface in water. Zeta potential
dramatically increases after adding PAFC into the hematite wastewater,

5
X. Tang, et al.
Fig. 5. Size and size distribution of flocs formed by PAFC and compound
flocculants, PAFC and CS-g-P(AM-AMPS): (a) size of flocs formed by PAFC and
compound flocculants and (b) size distribution of flocs formed by compound
flocculants.
and zeta potential continues to increase with the increase of dosage of
PAFC. But the change of zeta potential is not linear dependence with
the dosage change of PAFC. Moreover, its optimal dosage of 10 mg L-1 is
not found at the zeta potential of 0 mV that is reached above the dosage
of 50 mg L-1 (Figs. 3 and 6). These results suggest that charge neu-
tralization is not the only removal mechanism of pollutants in the
treatment. Although zeta potential slightly changes and always lower
than 0 mV when CS-g-P(AM-AMPS) is introduced into hematite was-
tewater, the removal efficiency of pollutants is significantly improved
in these cases (Figs. 3 and 6). Bridging, adsorption and entrapment
conduce to the performance of CS-g-P(AM-AMPS) in hematite waste-
water treatment.
3.6. Coagulation-flocculation mechanisms
The potential removal mechanisms in hematite wastewater treat-
ment by coagulation-flocculation are discussed according to the afore-
mentioned results (Fig. 7). PAFC and CS-g-P(AM-AMPS) play the
6
Colloids and Surfaces A 585 (2020) 124070
Fig. 6. Zeta potential of hematite wastewater treated by only PAFC and the
compound flocculants of PAFC and CS-g-P(AM-AMPS).
different role in these processes. PAFC possessing strong charge neu-
tralization and weak bridging removes colloidal particles of hematite
from water with a low efficiency way in terms of long settling time and
small floc size. CS-g-P(AM-AMPS) is applied in the treatment with PAFC
to notably increase the bridging of PAFC for its long molecular chain
and a large number of functional groups, followed by the enhancement
of removal efficiency. Furthermore, the adsorption and entrapment is
improved due to the big size of flocs formed by CS-g-P(AM-AMPS)
containing the functional groups, such as sulfonate group, hydroxyl and
amido. Meanwhile, the dissolved heavy metals in the wastewater are
co-removed with colloidal particles of hematite for the chelation of
sulfonate group and the adsorption of other functional groups and flocs.
4. Conclusions
CS-g-P(AM-AMPS) was prepared via grafting AMPS with sulfonate
group onto the molecular chain of CS, which was enhanced with the
assistance of AM as the bridge between CS and AMPS. It was revealed
that CS-g-P(AM-AMPS) possessed the functional groups of eOH, eNH,
C]N, eC]O and eSO3− by the way of characterization. And it was
confirmed that there were two synthesis mechanisms and two reaction
products in the processes. The thermal stability and solubility of CS-g-P
(AM-AMPS) were improved for the introduction of sulfonate group.
PAFC had the strong charge neutralization and weak bridging, which
represented the low efficiency in removing colloidal particles of he-
matite from water. The compounded flocculants of CS-g-P(AM-AMPS)
and PAFC performed better than only PAFC in the treatment. CS-g-P
(AM-AMPS) with the rich functional groups and long molecular chain
strengthened the bridging, adsorption and entrapment in coagulation-
flocculation, which promoted floc characteristics and the removal ef-
ficiency of colloidal particles. The dissolved heavy metals in wastewater
were removed through the chelation of sulfonate group in CS-g-P(AM-
AMPS), the adsorption of other functional groups and the co-settlement
with flocs.
Declaration of Competing Interest
None.
Acknowledgements
We are grateful for the financial support provided by the National
Natural Science Foundation of China (Project No. 51608078), China
Postdoctoral Science Foundation (Project No. 2017M622970), the
Science and Technology Research Project of Chongqing Municipal
X. Tang, et al. Colloids and Surfaces A 585 (2020) 124070

Fig. 7. Coagulation-flocculation mechanisms.

Education Commission of China (Project No. KJQN201900841) and removal, Sci. Total Environ. 640–641 (2018) 107–115.
Chongqing Special Postdoctoral Science Foundation (Project No. [13] K. Kavita, A. Mishra, B. Jha, Extracellular polymeric substances from two biofilm
forming Vibrio species: characterization and applications, Carbohydr. Polym. 94
Xm2017035). (2013) 882–888.
[14] Y. Sun, W. Sun, K.J. Shah, P.C. Chiang, H. Zheng, Characterization and flocculation
Appendix A. Supplementary data evaluation of a novel carboxylated chitosan modified flocculant by UV initiated
polymerization, Carbohydr. Polym. 208 (2019) 213–220.
[15] H. Zheng, J. Ma, C. Zhu, Z. Zhi, L. Liu, Y. Sun, X. Tang, Synthesis of anion poly-
Supplementary material related to this article can be found, in the acrylamide under UV initiation and its application in removing dioctyl phthalate
online version, at doi:https://doi.org/10.1016/j.colsurfa.2019.124070. from water through flocculation process, Sep. Purif. Technol. 123 (2014) 35–44.
[16] X. Tang, H. Zheng, H. Teng, Y. Sun, J. Guo, W. Xie, Q. Yang, W. Chen, Chemical
coagulation process for the removal of heavy metals from water: a review, Desalin.
References Water Treat. 57 (2016) 1733–1748.
[17] L.J. Wang, J.P. Wang, S.J. Yuan, S.J. Zhang, Y. Tang, H.Q. Yu, Gamma radiation-
induced dispersion polymerization in aqueous salts solution for manufacturing a
[1] B. Liu, X. Chen, H. Zheng, Y. Wang, Y. Sun, C. Zhao, S. Zhang, Rapid and efficient
cationic flocculant, Chem. Eng. J. 149 (2009) 118–122.
removal of heavy metal and cationic dye by carboxylate-rich magnetic chitosan
[18] K. Kavita, V.K. Singh, A. Mishra, B. Jha, Characterisation and anti-biofilm activity
flocculants: role of ionic groups, Carbohydr. Polym. 181 (2018) 327–336.
of extracellular polymeric substances from Oceanobacillus iheyensis, Carbohydr.
[2] Y. Yang, Y. Li, Y.-m. Zhang, D.-w. Liang, Applying hybrid coagulants and poly-
Polym. 101 (2014) 29–35.
acrylamide flocculants in the treatment of high-phosphorus hematite flotation
[19] S.S. Ahluwalia, D. Goyal, Removal of heavy metals by waste tea leaves from aqu-
wastewater (HHFW): optimization through response surface methodology, Sep.
eous solution, Eng. Life Sci. 5 (2010) 158–162.
Purif. Technol. 76 (2010) 72–78.
[20] L. Ji, S. Zou, M. Shen, Y. Xin, Radio frequency underwater discharge operation and
[3] D. M, B. S, Synthesis, characterization and application of acryloyl chitosan an-
its application to Congo red degradation, Plasma Sci. Technol. 14 (2012) 111–117.
chored copolymer towards algae flocculation, Carbohydr. Polym. 152 (2016)
[21] C. Zhao, H. Zheng, Y. Sun, S. Zhang, J. Liang, Y. Liu, Y. An, Evaluation of a novel
459–467.
dextran-based flocculant on treatment of dye wastewater: effect of kaolin particles,
[4] P. Juergen, T. Ulf, N. Petra, M. Peter, G. Tadeusz, Complexation-flocculation of
Sci. Total Environ. 640–641 (2018) 243–254.
organic contaminants by the application of oxyhumolite-based humic organic
[22] Z.H. Wang, Y. Zhu, M.Y. Chai, W.T. Yang, F.J. Xu, Biocleavable comb-shaped gene
matter, Chemosphere 70 (2008) 1228–1237.
carriers from dextran backbones with bioreducible ATRP initiation sites,
[5] S. Zhang, H. Zheng, X. Tang, C. Zhao, C. Zheng, B. Gao, Sterilization by flocculants
Biomaterials 33 (2012) 1873–1883.
in drinking water treatment, Chem. Eng. J. (2019) 122961.
[23] U. Janciauskaite, V. Rakutyte, J. Miskinis, R. Makuska, Synthesis and properties of
[6] X. Tang, H. Zheng, B. Gao, C. Zhao, B. Liu, W. Chen, J. Guo, Interactions of specific
chitosan- N -dextran graft copolymers, React. Funct. Polyme. 68 (2008) 787–796.
extracellular organic matter and polyaluminum chloride and their roles in the
[24] C. Chen, T. Ma, Y. Shang, B. Gao, B. Jin, H. Dan, Q. Li, Q. Yue, Y. Li, Y. Wang, X. Xu,
algae-polluted water treatment, J. Hazard. Mater. 332 (2017) 1–9.
In-situ pyrolysis of Enteromorpha as carbocatalyst for catalytic removal of organic
[7] D. Vandamme, I. Foubert, K. Muylaert, Flocculation as a low-cost method for har-
contaminants: considering the intrinsic N/Fe in Enteromorpha and non-radical re-
vesting microalgae for bulk biomass production, Trends Biotechnol. 31 (2013)
action, Appl. Catal. B: Environ. (2019).
233–239.
[25] M.R. Kasaai, Determination of the degree of -acetylation for chitin and chitosan by
[8] Y. Xu, S. Purton, F. Baganz, Chitosan flocculation to aid the harvesting of the mi-
various NMR spectroscopy techniques: a review, Carbohydr. Polym. 79 (2010)
croalga Chlorella sorokiniana, Bioresour. Technol. 129 (2013) 296–301.
801–810.
[9] S. Lama, K. Muylaert, T.B. Karki, I. Foubert, R.K. Henderson, D. Vandamme,
[26] H. Zheng, Y. Sun, J. Guo, F. Li, Q. Guan, Characterization and evaluation of de-
Flocculation properties of several microalgae and a cyanobacterium species during
watering properties of PADB, a highly efficient cationic flocculant, Ind. Eng. Chem.
ferric chloride, chitosan and alkaline flocculation, Bioresour. Technol. 220 (2016)
Res. 53 (2014) 2572–2582.
464–470.
[27] X. Tang, J. Xue, S. Zhang, H. Zheng, X. Tan, Recent progress on graft polymerization
[10] J.P. Wang, S.J. Yuan, Y. Wang, H.Q. Yu, Synthesis, characterization and application
of natural polymer flocculants: synthesis method, mechanism and characteristic,
of a novel starch-based flocculant with high flocculation and dewatering properties,
Mini-Rev. Org. Chem. 15 (2018).
Water Res. 47 (2013) 2643–2648.
[28] N.P. Hankins, N. Lu, N. Hilal, Enhanced removal of heavy metal ions bound to
[11] X. Li, H. Zheng, Y. Wang, Y. Sun, B. Xu, C. Zhao, Fabricating an enhanced ster-
humic acid by polyelectrolyte flocculation, Sep. Purif. Technol. 51 (2006) 48–56.
ilization chitosan-based flocculants: synthesis, characterization, evaluation of ster-
[29] L.-C. Shen, X.-T. Nguyen, N.P. Hankins, Removal of heavy metal ions from dilute
ilization and flocculation, Chem. Eng. J. 319 (2017) 119–130.
aqueous solutions by polymer–surfactant aggregates: a novel effluent treatment
[12] B. Liu, H. Zheng, Y. Wang, X. Chen, C. Zhao, Y. An, X. Tang, A novel carboxyl-rich
process, Sep. Purif. Technol. 152 (2015) 101–107.
chitosan-based polymer and its application for clay flocculation and cationic dye