International Journal of Biological Macromolecules 172 (2021) 241–249

Contents lists available at ScienceDirect

International Journal of Biological Macromolecules

journal homepage: http://www.elsevier.com/locate/ijbiomac

A modified coagulation-ultrafiltration process for silver nanoparticles

removal and membrane fouling mitigation: The role of laminarin
Zhangjian Zou, Yingqiu Gu, Weihua Yang, Minjie Liu, Jing Han, Shuang Zhao ⁎
School of Chemistry and Materials Science, Jiangsu Normal University, Xuzhou 221116, China

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

Article history: Silver nanoparticles (AgNPs) in surface water are highly toxic to humans and difficult to remove due to their ad-
Received 3 November 2020 sorption to humic acid (HA). In this study, laminarin (LA) was used as a coagulant aid in a coagulation-
Received in revised form 4 January 2021 ultrafiltration (C-UF) system to improve AgNPs-HA removal efficiency. C-UF efficiency, membrane flux, and
Accepted 7 January 2021
flocs properties were investigated to explore the AgNPs-HA removal mechanism and membrane fouling. Results
Available online 14 January 2021
showed that when poly aluminum chloride (PAC) was dosed with LA, AgNPs-HA removal was 10–15% higher
Keywords:
than when using PAC alone. The C-UF system using only PAC improved the AgNPs-HA removal efficiency through
Laminarin increased coagulation but resulted in membrane fouling. LA application helped mitigate membrane fouling, and
Coagulant aid the highest normalized permeate flux and smallest resistance values (0.573 and 2.180 × 1010 m−1, respectively)
Coagulation-ultrafiltration were achieved when 0.1 mg/L of LA was applied with 5 mg/L of PAC. The alleviating mechanism was related to
flocs with large sizes and small fractal dimension (Df) values, generating a cake layer with porous morphology.
This cake layer was easily removed by flushing and backwashing, which resulted in minimal resistance and foul-
ing of the UF membrane.
© 2021 Elsevier B.V. All rights reserved.

1. Introduction Coagulation is regarded as an efficient technology for colloidal parti-

The rapid development of nanotechnology has led to the widespread
use of nano-silver in clothing, medical devices, food packaging and ca-
talysis [1–3]. Researchers have become concerned about the inevitable
release of silver nanoparticles (AgNPs) into aquatic environments as
AgNPs are highly bio-toxic to aquatic organisms and humans [4,5].
The predicted environmental concentration in surface water of AgNPs
is in the ng L−1 magnitude, which should be detected monthly to min-
imize risk [6,7]. However, previous studies have demonstrated that
even at a low concentration, AgNPs can penetrate organism cells, caus-
ing physiological activity disorder [8]. Even worse, the major organic
pollutant in surface water, humic acid (HA), absorbs AgNPs to form
AgNPs-HA composite colloid contaminants [7]. The adsorption process
modifies the surface charge of AgNPs and HA, therefore, it is difficult
to eliminate AgNPs and HA simultaneously. Researchers found that
nanoparticles could exist for 48 h without sedimentation in the pres-
ence of HA, which offers an opportunity for nanoparticles to enter or-
ganisms [9]. Therefore, effective technology to remove AgNPs-HA
from water should be explored to help control health risks during sur-
face water treatment.
⁎ Corresponding author.
E-mail address: zhaoshuang@jsnu.edu.cn (S. Zhao).
cle elimination [10–12], and many studies have examined AgNPs re-
moval by coagulation processes [13,14]. However, the aggregation
morphologies of AgNPs change dramatically in the presence of HA,
resulting in unstable removal efficiency. Zhang et al. found that only
20–60% of nanoparticles could be removed by alum coagulation [15].
Sun et al. reported that the elimination efficiency of AgNPs by ferric
salt was only 19% with 20 mg/L of HA [13]. By comparison, membrane
filtration processes can effectively intercept nanoparticles. Zhang et al.
found that a 0.45 μm filter could remove more than 90% of nanoparticle
mass [15]. Studies also indicate that 95% of nanoparticles could be
trapped by an ultrafiltration (UF) membrane, but the fouled membranes
are difficult to recover [16]. Considering the benefits and disadvantages
of coagulation and UF technology, it is feasible that AgNPs could be elim-
inated by coagulation-ultrafiltration (C-UF) technology with light foul-
ing of the UF membrane if pre-coagulation is applied.
The membrane fouling level depends on the characteristics of flocs
formed in the pre-coagulation unit. Generally, flocs with larger sizes
generate higher membrane flux and lower fouling degree [17,18]. Fur-
thermore, flocs formed by charge neutralization mechanisms always
generate less compressible cake layers, which results in severe mem-
brane fouling [18,19]. Therefore, to remove AgNPs-HA with light mem-
brane fouling, pre-coagulation should be optimized to generate large
and porous flocs with narrow size distribution. In this study, laminarin
(LA) was prepared from fresh kelp then applied as a novel coagulation

https://doi.org/10.1016/j.ijbiomac.2021.01.034
0141-8130/© 2021 Elsevier B.V. All rights reserved.
Z. Zou, Y. Gu, W. Yang et al.
aid to remove AgNPs-HA, as nanoparticles tend to generate larger flocs
under the action of algae polysaccharides [12].
Laminarin is a water-soluble anionic polymer with a linear structure,
which is easily obtained from marine brown algae. Numerous hy-
droxyls, carboxyl and ester groups are found in LA. The molecular
chain of LA ends with sulfate groups linked to the polysaccharide by
ester bonds, resulting in excellent pharmacological activity in clinical
trials [20,21]. Theoretically, the active groups in LA, AgNPs-HA and coag-
ulant hydrolysates could form network structures, which promote the
net trapping effect to form larger flocs. This property constitutes the
motivation behind this research, that is, testing if LA can be used as a po-
tential agent to obtain large flocs, which simultaneously enhances
AgNPs-HA removal and minimizes membrane fouling. More impor-
tantly, as a natural macromolecule, LA is widely used in biological appli-
cations and medicine because of its biological safety (safer than that of
chemical coagulants).
In this study, a polyaluminium chloride (PAC) coagulant was dosed
with LA to enhance AgNPs-HA removal efficiency and mitigate UF mem-
brane fouling of a C-UF system. The AgNPs-HA removal and mecha-
nisms were explored and floc properties in the pre-coagulation unit
were systematically examined to determine the mechanism of UF mem-
brane fouling.
2. Materials and methods
2.1. Coagulants and water samples
PAC was selected as the coagulant and prepared in the laboratory
using Na2CO3 and AlCl3. The preparation details are available in an ear-
lier publication [22]. Al concentration and the basicity of the synthesized
PAC stock solution were 10.0 g/L and 1.0, respectively. This product
should be kept refrigerated and used within a month. The simulated
AgNPs-HA water sample was prepared as follows: (1) AgNPs were dis-
solved thoroughly followed by ultrasonic operation for 30 min; (2) HA
and NaOH were added, followed by stirring for 2 h; (3) To prevent
Ag+ discharge from AgNPs, borate buffer was added to the sample. Con-
sidering the average concentration of AgNPs-HA in actual water and the
detection limit of the instrument, the concentration of AgNPs and HA in
simulated water samples were kept constant at 1 mg/L and 10 mg/L, re-
spectively [4,13,23–25]. The dispersion morphology of AgNPs-HA was
Fig. 1. Characterization of LA: (a) EDS spectrum; (b) FTIR spectrum; (c) XPS spectrum of C1s; (d) XPS spectrum of O1s; (e) SEM image; (f) EDS mapping of elements.
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International Journal of Biological Macromolecules 172 (2021) 241–249
examined and results are shown in Fig. S1. The uniform distributed
morphology of AgNPs powder is seen in Fig. S1(a), and its average size
was 30–60 nm. In the presence of HA, adsorption occurred between
HA and AgNPs that changed the aggregation behavior of AgNPs. This
composite contaminant shown in Fig. S1(b) improved the stability of
HA-AgNPs.
2.2. Preparation and characterization of laminarin
Laminarin was extracted from fresh kelp and used as a coagulant aid.
The specific steps are provided in the Supplementary information. Fou-
rier transform infrared spectroscopy (FTIR), scanning electron micro-
scope (SEM), energy dispersive spectrum (EDS), and X-ray
photoelectron spectroscopy (XPS) were used to explore the structure
of LA. As seen from Fig. 1, in addition to carbon and oxygen, a strong sig-
nal from sulfur also appeared in the EDS spectrum and mapping, which
indicated the existence of sulfonic acid groups. The specific functional
groups in the FTIR spectrum are listed in Table S1 of Supplementary in-
formation. The absorption bands at 1612 cm−1 and 1418 cm−1 repre-
sented stretching vibration of C_O and C\\O, respectively, which
indicated the existence of hydroxyl and carboxyl in LA [26]. XPS results
also exhibited peaks at 531.5 eV and 532.3 eV, which have been verified
as the signal of C_O and C\\O bonds, respectively [27,28]. Also, signals
at 1263 cm−1 and 883 cm−1 represent vibration of S_O and C-O-S
stretching, respectively, indicating the existence of sulfuric acid groups
[29,30]. Similarly, the signals at binding energy of 286.6 eV and
536.8 eV in the XPS images represented the C\\S and S_O bonds of sul-
fate groups, respectively, in LA [30]. All the results are consistent with
the characterizations of LA and previous studies [26].
2.3. C-UF process
Coagulation experiments were performed as a pretreatment unit.
PAC was dosed with the water sample followed by the addition of LA
30 s later, to form the PAC-LA agent. According to the results of the pre-
liminary experiment, AgNPs-HA and turbidity removal were relatively
high at a pH range of 6–8 (Fig. S2). The initial pH of our water sample
was about 7.56, Therefore, all the experiment of this study were per-
formed without pH adjustment. The coagulation-sedimentation proce-
dure and index measurement method are described in the
Z. Zou, Y. Gu, W. Yang et al.
Supplementary information. To guarantee the accuracy of data, all the
experiments were repeated three times.
Coagulation effluent without sedimentation was directly transferred
to the UF unit for ultrafiltration (C-UF system, Fig. 2) where the UF pres-
sure was constant at 0.08 ± 0.01 MPa. A polyether sulfone membrane
(EMD Millipore, USA) with a molecular weight cut-off of 100 kDa was
applied and the mass of effluent was monitored in real-time. The func-
tion of normalized specific flux J/J0 with time was calculated, where J0
represents the initial instant flux. At the beginning of the UF process, ul-
trapure water samples were filtered to obtain initial flux. A
backwashing process (0.04 MPa) by deionized water was needed after
1 L of coagulation effluent was filtrated.
2.4. Resistance analysis of membrane fouling
The resistance of the UF membrane was calculated to explore the
fouling mechanism. The total resistance in the whole UF process (Rt)
comprised the intrinsic membrane resistance (Rm), the resistance of
the cake layer (Rc), and resistance of pore-blocking (Rp), which are as
follows:
P dicated that LA addition enhanced coagulation efficiency. HA and tur-
Rm ¼ ð1Þ
μJ 0
P P
Rc ¼ − ð2Þ
μJ 1 μJ 2
P P
Rp ¼ − ð3Þ
μJ 2 μJ 0
where P and μ represents the pressure of trans-membrane (Pa) and wa-
ter viscosity (Pa·s), respectively. J represents the flux (m3/m2·h) under
different operation conditions in UF process. Initially, 300 mL deionized
water was filtrated through a clean UF membrane to obtain J0; and then
1 L coagulated effluent was filtrated to obtain J1. After backwashing,
300 mL deionized water was filtrated to obtain J2. The specific opera-
tions are listed in Fig. S3 in the Supplementary information.
2.5. Flocs properties
Flocs formed in the coagulation unit were introduced into a laser dif-
fraction apparatus (Mastersizer 3000, UK) to monitor their sizes. The co-
agulation kinetics process could be monitored in real-time as
coagulation proceeded. To explore the properties of the flocs, the
Fig. 2. Coagulation-sedimentation-ultrafiltration hybrid technology.
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procedure consisted of several stages: PAC-LA added → rapid mixing
(1 min, micro-floc formation) → slow mixing (10 min, floc
grown) → rapid mixing (3 min, floc broken) → slow mixing (5 min,
floc regrown) → settling for 20 min. Fractal dimension (Df), growth
rate (Gr), strength factor (Sf), and recovery factor (Rf) were calculated
by the formulae supplied in the Supplementary information.
3. Results and discussion
3.1. AgNPs-HA removal with LA application
3.1.1. AgNPs-HA removal efficiency
Initially, the removal efficiency of AgNPs-HA was investigated at var-
ious dosages of PAC. Fig. 3 shows that HA removal increased dramati-
cally with increasing PAC dose and then stabilized. Considering
coagulation efficiency and reagent costs, 5 mg/L was selected as the op-
timum PAC dosage.
PAC was dosed with LA (0.05–0.3 mg/L) in the pre-coagulation unit
to enhance AgNPs-HA removal. As seen from Fig. 3, HA and AgNPs re-
moval reached 92% and 90% when 0.1 mg/L of LA was dosed, which
was about 5–10% higher than levels when PAC was used alone. This in-
bidity removal were relatively low (34% and 73%) when a single UF
process was performed (results listed in Table S2). But after the C-UF
process, the removal efficiency of turbidity, HA and AgNPs reached
91%, 93% and 95%, respectively, which were much larger than that of
the single coagulation and single ultrafiltration. Therefore, the applica-
tion of LA improved AgNPs removal by coagulation, and the UF unit fur-
ther enhanced removal based on the coagulation pre-treatment.
3.1.2. AgNPs-HA removal mechanism
Fig. 3(b) shows that the zeta potential of the coagulation effluent in-
creases gradually as PAC dose increases, which indicates that negative
charges on the AgNPs-HA surface were counteracted effectively by
PAC hydrolysates. Zeta potential was ca. 0 mV at optimum dosage, but
in lower dose conditions AgNPs-HA could also be removed. This phe-
nomenon indicates that charge neutralization may not be the sole re-
moval mechanism of the PAC coagulant. Its hydrolysates, with a high
degree of polymerization, may also play a bridging role between flocs.
Zeta potential was lower after LA application but a higher coagula-
tion efficiency was obtained. This is ascribed to the special molecular
structure of LA. As shown in Fig. 4, repulsive forces between AgNPs-
HA colloids became weak due to PAC addition, and the complex formed
immediately by the reaction between the carboxylate bands of HA and
Z. Zou, Y. Gu, W. Yang et al. International Journal of Biological Macromolecules 172 (2021) 241–249

Fig. 3. Effect of LA application on the efficiency of the C-UF process: (a–b) Pre-coagulation efficiency of PAC; (c–d) Pre-coagulation efficiency of PAC-LA; (e) AgNPs-HA removal after C-UF.

Al (III) species. Thirty seconds later LA was added, and cationic Al(III)
species of PAC hydrolysates could undergo bridging with carboxyl rad-
icals in guluronic acid (G) blocks of LA and then form gel networks with
an “egg-box” structure [31–33]. To verify this hypothesized inference,
flocs generated by PAC and PAC-LA were freeze-dried to conduct trans-
mission electron microscopy (TEM) characterizations. Large aggregates
with reticular morphology could be found in Fig. S4 when SA was used,
which proved the formation of “egg-box” structure. This gel network
could fully sweep the unabsorbed AgNPs. Thus, AgNPs-HA removal by
PAC-LA coagulant was higher than that by PAC alone. After the UF pro-
cess, residual AgNPs-HA could be further captured due to the minimum
aperture size of the UF membrane, which resulted in higher AgNPs-HA
removal.
Flocs formed by PAC-LA were freeze-dried then used to carry out
FTIR, EDS and X-ray diffraction (XRD) characterizations. The specific
functional groups in the FTIR spectrum are listed in the Supplementary
information (Table S3). Signals at 1622 cm−1 and 1384 cm−1 are attrib-
uted to stretching vibration of C_O [30]; the signal exhibited at
1145 cm−1 was attributed to C\\O stretching vibration, which indicated
the existence of polysaccharides in the flocs [29]. The absorption peak at
875 cm−1 represented C-O-S stretching of a sulfuric acid group [28,29].
Similarly, as typical indicator elements of LA, the sulfur element was

Fig. 4. Removal mechanism of AgNPs-HA by pre-coagulation: (a) FTIR spectrum of flocs; (b) XRD patterns of flocs; (c) EDS elements mapping of flocs; (d) Coagulation mechanism of PAC-LA.

244
Z. Zou, Y. Gu, W. Yang et al.
Fig. 5. Effect of LA application on UF membrane fouling: (a) Variations of J/J0; (b) Membrane resistance analysis.
discovered in the EDS mapping of flocs, indicating that LA participated
in the coagulation process and sediment in the form of flocs. Fig. 4
(b) shows peaks at 64.47°, 44.36° and 38.10°, representing the (220),
(200), and (111) crystal faces of AgNPs, respectively. Ag element was
also discovered in the EDS mapping of flocs, which confirmed our con-
clusion that AgNPs were eliminated by coprecipitation with flocs.
These results verified our hypothesized coagulation mechanism of
PAC-LA.
3.2. UF membrane fouling with LA application
3.2.1. Variations of membrane flux
Raw water, coagulation effluent from PAC and PAC-LA were filtered
under 0.08 MPa. The fouling degree of the UF membrane was analyzed
in terms of J/J0, and results are shown in Fig. 5(a). Flux curves exhibited
a sharp decline which then stabilized as filtration time increased. It is
worth noting that curves of the flux decline are not smooth and cyclical
increase (i.e. 9 min, 16 min of PAC + 0.1LA curve) was observed in Fig. 5.
It should be attributed to the re-charge of UF beaker when new water
sample was injected to continue UF operation. The cake layer was
flushed to a certain extent, which reduced the concentration
Fig. 6. Resistance analysis and fouling mechanism of the UF membrane.
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polarization effect and resulted in some cyclical rising points. After
backwashing the flux increased, but it could not be restored to the initial
flux from the first cycle due to the irreversible resistance of the UF mem-
brane. Membrane fouling originating from raw water was higher than
that from coagulation effluent. The ultimate J/J0 value of raw water
and coagulation effluent of PAC were 0.191 and 0.368, respectively. As
mentioned in Section 3.1.1, pre-coagulation removed AgNPs-HA parti-
cles effectively, while uncoagulated AgNPs-HA particles in raw water
adsorbed on the UF membrane directly or entered internal channels,
which significantly decreased the UF membrane flux. Compared with
the PAC coagulant, PAC-LA was better able to improve membrane flux.
The ultimate flux was 0.753 when PAC was dosed with 0.1 mg/L of LA.
Also, the recovery efficiency of the membrane flux after backwashing
was highest when LA was added as a coagulant aid.
3.2.2. Membrane resistance analysis
The resistance distributions of the UF membrane (including Rt, Rc
and Rp) were calculated and results are shown in Fig. 5(b). The
AgNPs-HA raw water produced the highest Rt of 6.818 × 1010 m−1.
When PAC was applied in the coagulation pretreatment, the total resis-
tance decreased to 4.032 × 1010 m−1. PAC dosed with 0.1 mg/L of LA
Z. Zou, Y. Gu, W. Yang et al.
produced the smallest Rt value (2.180 × 1010 m−1) due to the genera-
tion of loose cake layer by large flocs. The data are consistent with the
membrane flux variations of Section 3.2.1, which indicated that LA ap-
plication helped mitigate membrane fouling.
Lower Rc and Rp values were obtained with PAC coagulation
(0.907 × 1010 m−1 and 3.125× 1010 m−1, respectively) than with raw
water. As shown in Fig. 6, AgNPs-HA easily entered the pores of the UF
membrane, resulting in severe pore blocking. Also, AgNPs-HA was di-
rectly trapped on the membrane surface, which contributed to a dense
cake layer formation. The highest cake layer resistance
(1.948 × 1010 m−1) was obtained when raw water was filtered. When
LA was applied with PAC, Rc decreased (only 0.535 × 1010 m−1) since
a porous cake layer was formed. Therefore, membrane fouling was sig-
nificantly alleviated and the flux could be easily recovered by
backwashing. In addition, smaller amounts of AgNPs-HA existed in the
UF treated water due to higher pre-coagulation efficiency when LA
was applied. Subsequently, pore blocking degree was relatively low as
exhibited in Fig. 6, which resulted in lower pore blockage resistance.
3.3. Analysis of the membrane fouling mechanism
The fouling degree of the UF membrane is largely related to the char-
acteristics of flocs morphology. The rapid decline of flux in the initial
10 min can be attributed to pore blocking caused by untreated AgNPs-
HA or micro-flocs, and the subsequent gradual decline may be ascribed
the appearance of cake layer by flocs [34]. Also, the value of Rc is closely
associated with the structure of the flocs. Those with loose structure al-
ways result in relatively low cake layer resistance and high recovery flux
after backwashing [35,36]. In this section, floc properties (including size,
Fig. 7. Effect of flocs sizes on UF membrane fouling: (a) Floc growth curves; (b) Floc sedimentation curves; (c) Equilibrium time and growth rate; (d-f) SEM images of cake layer generated
by raw water, coagulant effluent of PAC and coagulant effluent of PAC-LA; (g-i) SEM images of membrane surface fouled by raw water, coagulant effluent of PAC and coagulant effluent of
PAC-LA.
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International Journal of Biological Macromolecules 172 (2021) 241–249
strength, recovery capability and structure) are thoroughly investigated
to determine the fouling mechanism of the UF membrane.
3.3.1. Floc size and membrane fouling
Floc growth and sedimentation processes with different PAC-LA dos-
ages were monitored and results are shown in Fig. 7. PAC-LA reacted
with AgNPs-HA immediately to generate micro-flocs (lag region). Then
floc sizes increased rapidly due to the effective collision (growth region)
and finally, constant sizes were obtained (steady region). The growth
rate of flocs generated by PAC-LA was significantly higher than that by
PAC with d50 and Gr being 610 μm and 94.5 μm/min, respectively, com-
pared to 452 μm and 48.5 μm/min. This is beneficial for membrane fouling
control since larger flocs generally result in higher membrane flux [18,37].
However, floc size could not be enlarged further when the LA dose was
greater than 0.1 mg/L. In these conditions, zeta potentials were relatively
low since excess LA was added. The strong repulsive force restrained the
growth of flocs and led to lower AgNPs-HA removal. Fig. 7(b) shows the
sedimentation curves of flocs. It took about 10 min for the flocs generated
by PAC to completely precipitate, while only 4 min was needed when LA
was used. This phenomenon is an obvious advantage since shorter times
are needed in the actual C-UF process. Also, the ratio value of flocs left in
the supernatant was small when PAC-LA was used. This means fewer re-
sidual flocs and lower turbidity of the supernatant after precipitation,
which helps to mitigate UF membrane fouling.
The UF membrane (after filtration but before backwashing) was
freeze-dried to conduct SEM characterization of the cake layer (Fig. 7).
The thickness of the cake layer followed the order of coagulated by
PAC-LA (D3) > coagulated by PAC (D2) > raw water (D1). Due to
AgNPs-HA accumulation, the cake layer formed by raw water was the
Z. Zou, Y. Gu, W. Yang et al.
most compact. This dense barrier enhanced the resistance and reduced
the flux of the UF membrane. After pre-coagulation, the cake layer be-
came thick and porous, especially when PAC-LA was used. A large pro-
portion of AgNPs-HA was coagulated and formed flocs with large sizes
(much larger than membrane pores), which reduced membrane pore
blockage. Consequently, a low level of UF membrane fouling could be
obtained by LA application. Since the sizes of AgNPs and HA are close
to the membrane pore size, membrane fouling derived from raw
water may be induced by pore blockage. Also, the cake layer was re-
moved by gentle flushing and the UF membrane surface was explored
to ascertain the fouling degree of the membrane pores. As seen from
Fig. 7(g–i), the number of holes on the fouled membrane surfaces be-
came noticeably larger when LA was dosed. The fouling of the UF mem-
brane induced by membrane pore blocking by raw water was the
highest, which is consistent with the results of the membrane resistance
values described in Section 3.2.2.
3.3.2. Floc structure and membrane fouling
The breakage of flocs was inevitable due to hydraulic instability in the
actual C-UF process, but broken flocs could re-form with new sizes and
structures, which influences the subsequent membrane flux and fouling
level. As shown in Fig. 8(a), flocs were broken into small particles by sim-
ulated shear force, and then broken flocs could regenerate when the shear-
ing forces were removed. Floc size distributions formed in the PAC and
PAC-LA coagulation system are presented in Fig. 8(c–d), and indicated
that when LA was applied as the coagulant aid, floc size distributions
after regeneration exhibited an obvious shift to the initial peak. The longer
distance of “P” means higher restoration potential of flocs generated by
PAC-LA. To quantitatively evaluate the effect of LA on anti-shearing and re-
covery abilities of flocs, Sf, and Rf were calculated (Fig. 8(e–f)).
Shen et al. highlighted that Sf and Rf had a great effect on cake layer
properties [18]. The Rf values of flocs became larger when LA was applied
with PAC, which indicated that LA addition promoted the re-association
of micro-flocs. Fragments will bond because of the special structure at-
traction, while LA exhibited effective adsorption and bridging roles.
Therefore, flocs demonstrated better restoration performance due to LA
application. Sf increased due to LA application. This is beneficial for mem-
brane fouling alleviation since flocs with low Sf values are easier to break
Fig. 8. Effect of flocs structure on UF membrane fouling: (a) Variations of flocs size; (b) Df value of flocs; (c–d) Particle size distributions of flocs formed by PAC and PAC-LA; (e–f) Sf and Rf in
three breakage and regrowth cycles.
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International Journal of Biological Macromolecules 172 (2021) 241–249
into small flocs, which always results in severe membrane pore blocking.
The Sf of flocs is closely associated with the quantity and intensity of inter-
nal bonds of flocs. Therefore, flocs with high Sf are apt to generate a po-
rous cake layer, which produces lower Rc values and higher membrane
flux. Df (representing the compact degree of flocs) has a significant impact
on membrane fouling. Flocs with high Df values generally form a dense
cake layer with a high Rc value. Fig. 8 shows the Df values of flocs formed
by PAC-LA were smaller than that of PAC alone, which indicates more
multi-hole structures of flocs.
The pore size distribution of cake layers generated by raw water,
PAC, and PAC-LA coagulation effluent were also measured and results
are shown in Fig. 9. The pore size distribution of membranes fouled by
raw water was mainly concentrated at small sizes (3.794 nm). However,
the cake layers caused by PAC-LA pre-coagulation displayed a relatively
large pore size (8.529 nm). This can be attributed to the specific coagu-
lation mechanism when LA was applied. Aluminum hydrolysis reacted
with the active groups of LA and enhanced the aggregation of AgNPs-
HA, which formed an “egg-box” structure [38]. Then, AgNPs could be
trapped in the gel network and increased the radii of suspending
AgNPs. This process bridged the primary AgNPs aggregation and then
extended outwards step by step. Thus, AgNPs-HA flocs formed by
PAC-LA exhibited a multi-branch morphology compared to those
formed by PAC alone. This morphology is beneficial for membrane per-
meability due to the loose structure of the cake layer. Aggregates pro-
duced by PAC alone were more compact and exhibited highly
uncompressible properties after their deposition on the membrane sur-
face, which resulted in an apparent increase in specific cake resistance.
SEM images showed a dense and almost non-porous cake layer when
raw water was filtered, which resulted in a dense barrier for filtration
and an obvious decline in membrane flux. Based on these results,
using 5.0 mg/L PAC with 0.1 mg/L LA, enabled effective AgNPs-HA re-
moval and reduced UF membrane fouling.
4. Conclusion
In this paper, LA was prepared and applied in a coagulation pretreat-
ment process to enhance AgNPs-HA removal and alleviate UF mem-
brane fouling. The main findings are as follows:
Z. Zou, Y. Gu, W. Yang et al. International Journal of Biological Macromolecules 172 (2021) 241–249

Fig. 9. Morphology and pore size distribution of cake layers fouled by (a) Raw water; (b) Coagulant effluent by PAC; (c) Coagulant effluent by PAC-LA.

(1) AgNPs-HA could be removed effectively when LA was applied as Declaration of competing interest
the coagulant aid of PAC due to the formation of gel networks.
The removal efficiency of the UF system was improved with co- The authors declare that they have no known competing financial
agulation pre-treatment. interests or personal relationships that could have appeared to
(2) Coagulation pre-treatment was necessary and effective for UF influence the work reported in this paper.
membrane fouling control. The highest membrane flux was
achieved with the lowest resistance when an appropriate Acknowledgements
amount of LA was dosed. Also, UF membrane flux exhibited bet-
ter recovery ability after backwashing when LA was applied. This work was supported by National Natural Science Foundation of
(3) The alleviating mechanism of membrane fouling was related to China (No. 51908256). The valuable suggestions from the anonymous
floc properties. Flocs with large sizes and Sf values were obtained reviewers are highly appreciated.
with LA addition, which reduced membrane pore blockage. More-
over, flocs formed by PAC-LA have lower Df values than those Appendix A. Supplementary data
formed by PAC alone, which generated a porous cake layer. The
lower cake layer resistance and higher membrane flux obtained Supplementary data to this article can be found online at https://doi.
by LA addition significantly reduced membrane fouling. org/10.1016/j.ijbiomac.2021.01.034.

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Z. Zou, Y. Gu, W. Yang et al.
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