Chemical Engineering Journal 416 (2021) 129123

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Chemical Engineering Journal

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

Coagulation removal and photocatalytic degradation of microplastics in

urban waters
Qiuxiang Xu a, b, Qi-Su Huang a, Tian-Yi Luo a, Ruo-Lan Wu a, Wei Wei a, Bing-Jie Ni a, b, *
a
State Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092, PR China
b
Shanghai Institute of Pollution Control and Ecological Security, Shanghai 200092, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: The global concerns to the environmental pollution and health risks by microplastics (MPs) urgently require
Microplastics action to develop effective and sustainable processes to deal with this problem. Coagulation removal and pho­
Removal tocatalytic degradation, considered as cost- and energy-effective techniques, have attracted growing attention to
Urban waters
remove MPs from urban waters. However, its removal behavior and degradation mechanism have not been
Coagulation
Photocatalysis
systematically summarized. Therefore, the recent progress on coagulation and photocatalysis for MPs removal
Mechanisms was comprehensively reviewed in this study. Particularly, the effects of parameters (e.g., type and dosage of
coagulant, environmental conditions, characteristics of MPs and catalyst type, etc) and removal mechanisms
were commendably discussed. Moreover, the challenges of current techniques application process and the po­
tential coping strategies were also put forward. This review will not only help to deeply understand the detailed
processes and mechanisms for removing MPs by coagulation and photocatalysis but also provide constructive
information and useful data for future researches relevant to the enhanced removal of MPs from urban waters.

1. Introduction aquatic organisms can cause chronic poisoning such as reproductive

Plastic pollution in the environment, caused by large-scale improper
use of plastic products, has attracted growing concerns because of the
stable characteristics, continuous accumulation, and low biodegrad­
ability of plastics wastes [1–3]. Currently, plastic wastes have been
widely found in various environmental mediums such as water, soils and
atmosphere [4–9]. In the above environment mediums, plastic wastes
can be broken down into small fragments or particles by the effects of
sunlight, weathering, erosion, soaking, etc [10]. Those fragments or
particles with a size between 0.1 μm and 5 mm are generally known as
microplastics (MPs) [5,11,12]. Moreover, the manufactured small
plastic particles added in personal care products (PPCPs) and detergents
are also a main source of MPs [13,14].
Water, as an environmental medium with high mobility, is not only
an important carrier for the migration of MPs but also one of their main
gathering place [15,16]. The widespread presence of MPs in various
water bodies, for example oceans and urban waters (e.g., lakes, river,
wastewater and drinking water), has caused scientific and public
concern because of their adverse effect on aquatic organisms
[10,17–20]. Evidences have demonstrated that ingestion of MPs by
damage, malnutrition, internal abrasion and obstruction [10,21]. MPs
ingested by aquatic life are likely to enter the human body through the
food chain. Moreover, potentially toxic additives used to improve plastic
properties can enter the water environment in large quantities along
with the migration of MPs [22]. Although there are relatively few re­
ports on the impact of MPs on human health [23], their potential risks to
humans is a rising concern, and they are gradually recognized as
emerging pollutants such as in drinking water [24]. Urban waters are
closely related to people’s daily life and have a profound impact on
human health [25]. As such, it is imperative to remove MPs from the
urban waters.
Over the past decade, many techniques and methods like coagulation
[26], adsorption [27], filtration [28], magnetic extraction [29], sup­
porting ionic liquids [30,31], microbial degradation [32,33], and
advanced oxidation processes (AOPs) such as Fenton/Fenton-like reac­
tion and photocatalysis [34,35] have been tried to remove MPs from the
urban waters. Among them, coagulation and photocatalysis are the
research hotspots in recent years due to their simple operation, cost- and
energy- effective. Coagulation, as a widely used conventional water
treatment process at present and even in the next few decades, has been

* Corresponding author at: Shanghai Institute of Pollution Control and Ecological Security, Shanghai 200092, PR China.
E-mail address: bjni@tongji.edu.cn (B.-J. Ni).

https://doi.org/10.1016/j.cej.2021.129123

Available online 25 February 2021

1385-8947/© 2021 Elsevier B.V. All rights reserved.
Q. Xu et al.
reported to be effective in removing MPs from drinking water and
wastewater treatment plant effluent [36,37]. Compared with the widely
used coagulation technology, photocatalysis, as a low-cost and envi­
ronmentally friendly pollutant treatment technology [38], is considered
as a promising and advantageous method for the complete removal of
MPs in water because the generated strong oxidizing free radicals such
as hydroxyl radical (•OH) and superoxide radical (O•−2 ) can convert MPs
into simple non-toxic molecules (e.g., H2O and CO2) [35]. Different
removal methods have their own advantages and disadvantages.
Although a growing studies focus on the removal of MPs by coagulation
and photocatalysis, a comprehensive summary on the removal process,
the corresponding mechanism, the effects of experiment parameters and
even their potential connection is lacking.
In this review article, the environmental behaviors of MPs in urban
waters are firstly introduced with the purpose of understanding their
origin, risk as well as importance and strategy of reducing their release.
The current researches of coagulation removal and photocatalytic
degradation of MPs in urban waters are then comprehensively
concluded. Meanwhile, the corresponding removal/degradation mech­
anisms are systematically discussed. Moreover, current research gaps
and future directions in coagulation removal and photocatalytic
degradation of MPs are discussed. This study is a selective overview of
the removal of MPs using coagulation and photocatalysis techniques,
which is expected to provide useful guidance to some extent and identify
future directions for enhancing the removal of MPs for urban water
decontamination.
2. Occurrence and environmental behavior of MPs
2.1. MPs occurrences in urban waters
Urban water environment mainly consists of water supply, drainage,
wastewater treatment, involving various types of water such as surface
water (e.g., river and lake), groundwater, drinking water, wastewater,
rainwater, etc, which is related to human-related life and production
activities [24,39]. Once entering the urban water environment, MPs can
Fig. 1. Possible sources and transference processes of MPs in urban waters.
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Chemical Engineering Journal 416 (2021) 129123
be found in various types of water bodies through migration and
transformation. Fig. 1 describes possible sources and transference pro­
cesses of MPs in the above urban waters. As shown in Fig. 1, MPs
released by human-related life and production activities mainly enter
the drainage system through wastewater, rainwater, etc [40,41]. Then,
most of the MPs in the rainwater directly enter the surface water, while
those in wastewater collect in the wastewater treatment plant (WWTP)
[40]. Because most of the MPs are difficult to biodegrade in the process
of wastewater treatment, MPs are mainly removed by activated sludge
in WWTP, the remaining MPs enter the surface water with the effluent of
treated wastewater [42,43]. Those MPs that enter surface water may be
ingested by aquatic organisms, or deposited in sediments, or migrate and
transform in the water environment such as river, lake and groundwater,
or enter the water supply system along with the drinking water source
[24,44–46]. Currently, MPs cannot be completely removed in the
drinking water treatment processes, thus the released MPs finally
reenter human-related life and production activities because that
drinking water is its main water source [6]. Table 1 summarizes the
distribution of MPs in different urban waters around the world. It can be
found that although the concentration of MPs in the water bodies of
Paris, Shanghai and Wuhan are quite different, MPs have been detected
in almost all waters of the cities. In addition, although a considerable
amount of MPs has been removed in the wastewater treatment process,
their concentration in the effluent of WWTP are significantly higher than
that of the surface water, leading to a continuous increase in the con­
centration of MPs in surface water. According to Fig. 1 and Table 1, it
can be found that MPs can form an internal circulation in the urban
water environment, and human beings and aquatic organisms are
continuously exposed to them. This causes MPs to inevitably enter the
human body and other living organisms through the food chain,
resulting in potential negative effects on environment and health risks
due to their potential toxicity [10,54].
2.2. Potential environmental and health risks of MPs
The widespread presence of MPs in urban waters has long time
Q. Xu et al. Chemical Engineering Journal 416 (2021) 129123

Table 1
Distribution of MPs in different urban water environments around the world.
Location Type of water Separation method Detection method Concentration (P/L) Ref

Paris, France River Seine Plankton net (80 μm) Stereomicroscope 0.03 [47]
River Seine Manta trawl (330 mm) Stereomicroscope 3.5 × 10-4 [47]
Treated water Vacuum filtration (2.5 μm filter) FTIR 1.82 [48]
Urban wastewater Filter (1.6 μm) Stereomicroscope 260 ~ 320 [47]
Effluent of WWTP Filter (1.6 μm) Stereomicroscope 14 ~ 50 [47]

Shanghai, China Huangpu River Vacuum filtration (0.22 μm filter) Micro FTIR 26.2 ± 9.6 [40]
Seven estuaries Vacuum filtration (10 μm filter) Micro-Raman spectroscopy 13.53 ± 4.6 ~ 44.93 ± 9.41 [49]
Tap water Vacuum filtration (0.2 μm filter) Micro-Raman spectroscopy 0 [50]
Influent of WWTP Stainless-steel filter (50 μm) FTIR microscope 725 ± 25 [51]
Effluent of WWTP Stainless-steel filter (50 μm) FTIR microscope 600 ± 200 [51]

Wuhan, China 22 lakes and rivers Vacuum filtration (0.45 μm filter) FTIR 1.66 ± 0.64 ~ 8.93 ± 1.59 [44]
Tap water Vacuum filtration (0.2 μm filter) Micro-Raman spectroscopy 623 [49]
Influent of WWTP A Vacuum filtration (0.8 μm filter) Micro-Raman spectroscopy 23.3 [52]
Effluent of WWTP A Vacuum filtration (0.8 μm filter) Micro-Raman spectroscopy 7.9 [52]
Influent of WWTP B Vacuum filtration (0.8 μm filter) Micro-Raman spectroscopy 80.5 [52]
Effluent of WWTP B Vacuum filtration (0.8 μm filter) Micro-Raman spectroscopy 30.3 [52]
Rainwater Vacuum filtration (5 μm filter) Raman microscopes 2.75 ± 0.76 ~ 19.04 ± 2.96 [53]

Detection Method: FTIR: Fourier transform infrared spectroscopy; P/L: particle/L;

The source of WWTP A is mainly residential wastewater, while WWTP B is primarily urban domestic wastewater and industrial wastewater.

impacts on the ecological environment and human beings, the induced
potential environmental and health risks cannot be ignored. The impacts
of MPs on aquatic organisms, such as fishes, crustaceans and gastropoda,
have thoroughly been reviewed [54,55]. MPs mainly induce adverse
effects through the following mechanisms. On the one hand, when MPs
are ingested and accumulated by various organisms, it can not only
accumulate in gastrointestinal tracts of organisms, leading to blockage
of the digestive system, but also affect the structure and function of the
gastrointestinal tract to degenerate, which all would interfere with the
normal growth of organisms [56,57]. It has been demonstrated that
ingestion of polystyrene MPs could cause the weight gain rate, specific
growth rate [58,59]. On the other hand, additives used in the production
of plastics (e.g., bisphenol A and phthalates) and plastic polymer
monomers (e.g., polybrominated diphenyl and styrene monomers) can
be easily released from plastic matrices during decomposition and
degradation [10,60,61]. Evidence have confirmed that these additives
and polymer monomers have endocrine disrupting effects on organisms,
causing reduction in reproduction for some organisms [7,62]. Moreover,
MPs, as strong adsorbents due to their large specific surface area and
inherent hydrophobicity, can adsorb large amounts of environmental
contaminants such as persistent organic pollutants (POPs), heavy metals
and pathogens [63]. After ingestion of MPs, these contaminants adsor­
bed by MPs can be further desorbed inside organisms, exacerbating
contaminants bioaccumulation [64].
Evidences indicated that the ingestion of MPs by aquatic organisms
can be transferred to human body by eating aquatic products [10].
Moreover, MPs in drinking water such as tap water and bottled water
also can be ingested and accumulated in the body [24]. Ingestion is
generally considered to be the main route for MPs to enter humans
[65,66]. Although there have been sporadic studies on the interaction of
MPs with human cells, their harm to the human body has been
confirmed, causing potential risks for the health [23]. MPs may induce
oxidative stress and chronic inflammation due to their high surface area
and persist accumulation characteristics, thus generating cytotoxicity
[24,65]. Laboratory studies generally demonstrated that exposure of
cerebral and epithelial human cells to polystyrene and polyethylene
(0.05–10 mg/L) caused reactive oxygen species, leading to cytotoxicity
[67]. On the other hand, after exposure to MPs, especially those with
small particle size, they may enter peripheral tissues and circulatory
system though lymphatic aggregation, causing systemic exposure [68].
These circulating MPs may increase the risk of inflammation and pul­
monary hypertension [69]. Furthermore, although there is no direct
evidence, the toxic pollutants (such as monomers and additives)
released by MPs are considered a potential hazard to human health
[10,65,70]. Given the huge potential risks of MPs to the environment
and human health, future efforts therefore should not only reduce the
release of MPs by strengthening plastic recycling and the removal of
MPs, but also further investigate and confirm the adverse effects of MPs
on human health. Urban waters are closely related to the transport of
MPs and human health, thus the following contents mainly focuses on
the mainstream technique (e.g., coagulation) and promising technique
(e.g., photocatalysis) for removing MPs in urban waters in recent years,
guiding the development of techniques and engineering applications to
a certain extent.
3. Coagulation removal of MPs
3.1. Coagulation
Coagulation mainly uses various coagulants to alter the physical
state of dissolved and suspended solids and facilitates their removal by
sedimentation, which has been widely used in water and wastewater
treatment and is the main technology for pollutant removal in water
treatment plant [71–73]. MPs can be effectively removed through
coagulation/sedimentation process (Fig. 2). Although different co­
agulants have different removal effects on MPs [26,74], their specific
removal mechanism can still be explained by classical coagulation
removal mechanisms, such as charge neutralization, adsorption and
sweep flocculation [74,75]. The hydrolysates of metal coagulant can be
easily adsorbed on the surface of negatively charged MPs, neutralizing
the original charge on the surface of MPs and reducing the electrostatic
repulsion, accordingly making the MPs unstable [75]. The positively
charged coagulant hydrolyzed monomers can adsorb the surrounding
negatively charged MPs to form flocs [75]. As the particle size and
density of the flocs increase, strong sweep flocculation is formed during
the coagulation, leading to the amorphous precipitation [74,76].
At present, MPs in urban waters can be effectively removed in
drinking water treatment plants (DWTPs) using coagulation and its
combined methods. Pivokonsky et al. [36] studied the occurrence of
MPs in raw and treated drinking water of three water treatment plants
(WTPs) (i.e., WTP1, WTP2 and WTPs) involving coagulation/floccula­
tion in the Czech Republic. After treatment, the concentration of MPs in
the raw water remarkably decreased. The removal rates of MPs in WTP1,
WTP2 and WTPs were respectively 70%, 81% and 83%. However, the
removal performance and contribution of single coagulation/floccula­
tion and other methods such as sedimentation and filtration have not
been studied. Wang et al. [77] investigated the effect of different
treatment processes on the removal of MPs in an advanced DWTP. It was

3
Q. Xu et al. Chemical Engineering Journal 416 (2021) 129123

Fig. 2. Process of removing MPs from water via coagulation and sedimentation. Redrawn with permission from Ref. [80]. Copyright 2020, American Chemi­
cal Society.

found that 40.5–54.5% of MPs in raw water from Yangtze River was
removed by coagulation/sedimentation process, contributing the most
to the removal of MPs compared with other treatment processes
including sand filtration, ozonation and GAC filtration. Moreover, above
coagulation/sedimentation process had a preferred removal effect on
the MPs with large size (>10 μm) and fibres. Similar removal efficiency
was also observed in the study of Pivokonský et al. [78]. The coagula­
tion/sedimentation process (with alum as a coagulant) decreased the
concentration of MPs in DWTP from 1296 ± 35 MPs/L in raw water from
Úhlava River (Czech Republic) to 497 ± 44 MPs/L, achieving about 62%
of removal efficiency in all the MP categories regardless of their size or
shape, which was much higher than deep-bed filtration (20%) and
granular activated carbon filtration (6%).
In addition, the coagulation removal of MPs was also conducted in
jar tests [26,37,74,75,79,80]. Table 2 summarizes some applications of
the coagulation in removing MPs. Among the many types of MPs,
polystyrene and polyethylene MPs are the most widely studied because
they are similar in density to natural water and are more likely to enter
people’s lives and cause potential threats [75]. Ma et al. [26] first
studied the effect of Fe-based coagulant (FeCl3⋅6H2O) on the removal
performance of polyethylene MPs with different particle size (<0.5–5
mm). It was found that the removal efficiency of all sizes of polyethylene
MPs was low even in the presence of high dosage of coagulant. The
highest removal efficiency was only 13.27% ± 2.19%, which was ob­
tained in small particle-size polyethylene MPs (d < 0.5 mm) under
conditions of 2 mmol/L (112 mg/L) FeCl3⋅6H2O and pH 7. Similar
phenomenon was also found in the study of Zhou et al. [75]. Even if the
FeCl3 dosage reached 180 mg/L, the removal efficiency of polyethylene
MPs (d < 0.5 mm) was still<20%. This indicated that polyethylene MPs
were not easily adsorbed/captured by Fe-based flocs during the coagu­
lation process, which could be attributed that its low density (0.92–0.97
g/m3) caused the difficulty in settling and the average size of Fe-based
flocs formed was smaller than that of polyethylene MPs [26]. More­
over, Ma et al. [74] also compared the removal performance of
FeCl3⋅6H2O and AlCl3⋅6H2O on polyethylene MPs, and found that Al-
based salts achieved better removal performance during coagulation.

Table 2
The removal performance of MPs using coagulation.
MPs Coagulant Flocculant Reaction conditions Removal efficiency Ref

Polyethylene MPs (d < FeCl3⋅6H2O – FeCl3⋅6H2O (112 mg/L), pH 7.0, mixing (300 rpm, 1 min), mixing (100 rpm, 14 min) 13.27% ± 2.19% [26]
0.5 mm) and sedimentation (30 min)
Polyethylene MPs (d < FeCl3⋅6H2O – FeCl3⋅6H2O (28 mg/L, 280 mg/L), pH 7.0, mixing (300 rpm, 1 min), mixing (100 8.24% ± 1.22%,12.65% [74]
0.5 mm) rpm, 14 min) and sedimentation (30 min) ± 1.09%
Polyethylene MPs (d < AlCl3⋅6H2O – AlCl3⋅6H2O (13.5 mg/L and 405 mg/L), pH 7.0, mixing (300 rpm, 1 min), mixing 8.28% ± 1.06%,36.89% [74]
0.5 mm) (100 rpm, 14 min) and sedimentation (30 min) ± 3.24%
Polyethylene MPs, PAC – PAC (90 mg/L, 90 mg/L), initial pH 7.0, mixing (500 rpm, 1 min), mixing (100 rpm, 29.70%, 77.83% [75]
Polystyrene MPs 15 min) and sedimentation (30 min)
Polyethylene MPs Alum – Alum (30 mg/L), pH 7.0, mixing (200 rpm, 1 min), mixing (50 rpm, 10 min) and 70.7% [79]
sedimentation (30 min)
Polyethylene MPs (d < FeCl3⋅6H2O PAM FeCl3⋅6H2O (112 mg/L) + anionic PAM (3 mg/L)pH 7.0, mixing (300 rpm, 1 min), 89.23% ± 3.22% [26]
0.5 mm) mixing (100 rpm, 14 min) and sedimentation (30 min)
Polyethylene MPs (d < AlCl3⋅6H2O PAM AlCl3⋅6H2O (135 mg/L) + cationic PAM (15 mg/L),pH 7.0, mixing (300 rpm, 1 min), 45.34% ± 3.93% [74]
0.5 mm) mixing (100 rpm, 14 min) and sedimentation (30 min)
Polyethylene MPs (d < AlCl3⋅6H2O PAM AlCl3⋅6H2O (135 mg/L) + anionic PAM (15 mg/L),pH 7.0, mixing (300 rpm, 1 min), 61.19% ± 3.67% [74]
0.5 mm) mixing (100 rpm, 14 min) and sedimentation (30 min)
Polyethylene MPs Alum PC sand Alum (30 mg/L) + PC sand (500 mg/L), pH 7.0, mixing (200 rpm, 1 min), mixing 92.7% [79]
(50 rpm, 10 min) and sedimentation (30 min)
Polyethylene MPs Alum PAM Alum (2.73 mg/L) + PAM (0.3 mg/L), pH 7.0, coagulation (2 min), flocculation 82% [80]
(300 rpm, 2 min) and sedimentation (1 min)
polystyrene MPs Alum PAM Alum (2.73 mg/L) + PAM (0.3 mg/L), pH 7.0, coagulation (2 min), flocculation 84% [80]
(300 rpm, 2 min) and sedimentation (1 min)

4
Q. Xu et al.
The removal efficiency of small particle-size polyethylene MPs (d < 0.5
mm) increased to 36.89% ± 3.24% under conditions of 15 mmol/L (405
mg/L) AlCl3⋅6H2O compared to 2 mmol/L (112 mg/L) FeCl3⋅6H2O
under pH 7 conditions. Zhou et al. [75] also observed that poly­
aluminium chloride (PAC) performed better removal efficiency
compared with Fe-based coagulant. This may be due to the fact that the
zeta potential of Al-based flocs was higher than that of Fe, which can
better neutralize negatively charged polyethylene MPs and is more
conducive to the subsequent sweep flocculation [74]. It should also be
pointed out that the dosages of FeCl3⋅6H2O and AlCl3⋅6H2O used in the
above-mentioned jar tests were much higher than those used in actual
DWTPs (112 vs 20 mg/L as Fe and 405 mg/L vs 20 mg/L as Al). Shahi
et al. [79] showed that the removal efficiency of polyethylene MPs (d <
0.5 mm) reached 65.9% with addition of 20 mg/L alum and slightly
increased to 70.7% with increasing dosage of alum up to 30 mg/L.
However, further increasing the dosages of alum significantly reduced
the removal efficiency. The removal performance and trend reported
were significantly different from other studies, which might be the dif­
ference between the polyethylene MPs selected in the experiment and
other studies. Compared with polyethylene MPs, polystyrene MPs per­
formed better removal performance using either none coagulants or
same coagulants due to higher density. Zhou et al. [75] showed that the
removal efficiency of polyethylene MPs was only 3.19% while that of
polystyrene MPs was 50.78% without addition of coagulant. Under the
same PAC dosage (90 mg/L), the removal efficiency of polystyrene MPs
reached 77.83% while that of polyethylene MPs was only 29.7%. Similar
phenomenon was also observed in the Fe-based coagulant (FeCl3).
Flocculants have been extensively used to enhance coagulation
during water treatment [81,82]. In the studies of MPs removal, the ef­
fects of flocculants in combination with coagulants on the removal
performance of MPs have widely been investigated. Ma et al. [26] found
that the removal performance of polyethylene MPs was significantly
improved with addition the high dosage of FeCl3⋅6H2O with poly­
acrylamide (PAM) in comparison to the presence of sole FeCl3⋅6H2O.
Compared with cationic PAM, anionic PAM had better removal perfor­
mance. For example, when 2 mmol/L (112 mg/L) FeCl3⋅6H2O was
combined with 3 mg/L cationic PAM, the removal efficiency regarding
the polyethylene MPs (d < 0.5 mm) was<50%. However, when 2 mmol/
L (112 mg/L) FeCl3⋅6H2O was combined with 3 mg/L anionic PAM, the
removal efficiency of polyethylene MPs (d < 0.5 mm) significantly
increased from 13.27% ± 2.19% to 89.23% ± 3.22%. Further increase of
anionic PAM dosage to 15 mg/L did not led to a significant increase in
removal efficiency. This excellently enhanced removal of polyethylene
MPs could be attributed to stronger adsorption bridging effects in the
presence of PAM [26]. The addition of PAM could increase the particle
size and density of the flocs, making stronger sweep flocculation effect
during coagulation [83,84]. This enhanced removal induced by PAM
was also found in the Al-based coagulant and polystyrene MPs. It was
reported that the removal efficiency of polyethylene MPs (d < 0.5 mm)
increased from 25.83% ± 2.91% in presence of solo AlCl3⋅6H2O to
45.34% ± 3.93% in the presence of AlCl3⋅6H2O with PAM (15 mg/L)
[74]. However, above applied PAM dosage (15 mg/L) exceeded the
maximum allowable dosage (<1 mg/L) in DWTPs [85]. Lapointe et al.
[80] reported that polyethylene and polystyrene MPs were also effec­
tively removed with addition of allowable dosages of coagulant and
flocculant of DWTPs when using actual influent of DWTPs to conduct jar
test. When the alum and anionic PAM dosages were respectively 2.73
mg/L and 0.3 mg/L, the removal efficiencies of polyethylene and
polystyrene MPs reached 82% and 84%, respectively, which not only
indicated that polyethylene and polystyrene MPs performed similar in­
teractions with the tested coagulants and flocculants, but also indicated
that the combined use of coagulant and flocculant can reduce or even
eliminate the removal difference between the two MPs when using
single coagulant. In addition to PAM, polyamine-coated (PC) sand
combined with alum has also been reported to enhance the removal of
MPs. Shahi et al. [79] found that when the combination of 20 mg/L of
5
Chemical Engineering Journal 416 (2021) 129123
alum and 500 mg/L of PC sand was used to treat polyethylene MPs (d <
0.5 mm), the corresponding removal efficiency reached 92.7%, which
was higher than that of sole alum (65.9%). The improved removal
performance may be attributed to the addition of cationic PC sand to
strengthen the bridging effect between flocs and MPs, and ultimately to
improve the settling of suspended flocs [80].
Ultrafiltration also has a positive effect in assisting coagulation to
remove MPs. Ma et al. [26] found that the remaining polyethylene MPs
after coagulation removal was completely rejected by a membrane with
average pore diameter of 30 nm, because their particle size were much
higher than that of the membrane. However, the rejected flocs easily
formed a loose cake-like layer on the surface of the membrane, causing
membrane fouling. Moreover, the degree of membrane fouling was
positively dosage-dependent of FeCl3⋅6H2O. Similar phenomenon was
also found in the Al-based coagulant (AlCl3⋅6H2O) [74]. The greater the
dosage of AlCl3⋅6H2O is, the more severe the ultrafiltration membrane
fouling is. Severe membrane fouling will inevitably limit the large-scale
application of ultrafiltration technology in assisting coagulation for MPs
removal, and more research is needed in terms of mitigating membrane
fouling and membrane reuse.
In addition to drinking water, the removal of MPs from the effluent
matrix of the secondary wastewater treatment plant (WWTP) by coag­
ulation is also investigated. Rajala et al. [37] compared the performance
of two coagulants (i.e., FeCl3 and PAC) and one cationic polymer poly­
amine product (i.e., Kemira Superfloc® C-577) in MPs removal from
WWTP effluent samples, and found that the coagulants and polyamine
improved MPs removal at a certain dosage. The minimum MPs con­
centration after coagulation with addition of FeCl3 was lower than the
limit of detection (LOD), and the corresponding removal efficiency was
above 99.4%. With PAC, the highest removal efficiency reached 98.2%.
Although the removal performances of FeCl3 and PAC were similar, the
corresponding removal mechanism might be different. For FeCl3, the
removal mechanism may be sweep coagulation or its combination with
charge neutralization while the removal may be attributed to charge
neutralization in the case of PAC. Compared to FeCl3 and PAC, C-577
performed lower performance in MPs removal with highest removal
efficiency of 65%. Moreover, an interesting strong correlation between
the absolute value of the zeta potential and the MPs removal was also
observed, that is, as the absolute value of the zeta potential decreased,
the MPs removal efficiency increased [37], indicating that removal
mechanism was charge neutralization [86]. In addition to MPs, similar
removal differences were also observed in COD and turbidity. The
removal of turbidity and COD logically increased with the increase of
FeCl3 and PAC dosage. However, C-577 not only did not remove COD at
all dosages, but also greatly increased turbidity.
3.2. Electrocoagulation
Electrocoagulation (EC) is a novel method that combines the ad­
vantages of coagulation, flotation and electrochemistry used in water
and wastewater treatment [87]. EC refers to the complex process of the
formation of flocs from cations generated by metal electrodes under the
action of an electric field, which mainly includes the formation of
“micro-coagulants”, losing stability of suspended particles under the
action of coagulants, and the formation of flocs through the interaction
of coagulants and particles (Fig. 3) [24]. Compared to chemical coag­
ulation that requires external addition of coagulants, EC generates co­
agulants directly in situ using metal electrodes, resulting in the
coagulation process to be simple (easy automation), no chance of sec­
ondary pollution and much less sludge generation [87–89]. Therefore,
EC, considered an eco-friendly water treatment technology, has been
used to deal with stubborn pollutants in drinking water, groundwater
and refinery wastewater [24,87,90].
Perren et al. [91] investigated the removal of polyethylene MPs from
wastewater using EC in a stirred-tank batch reactor. The impacts of the
wastewater characteristics including pH, conductivity and current
Q. Xu et al.
Fig. 3. Process of removing MPs from water via electrocoagulation. Adapted with permission from Ref. [24]. Copyright Elsevier, 2020.
density on removal performance of polyethylene MPs were compre­
hensively investigated. It was found that EC effectively removed poly­
ethylene MPs from wastewater and the corresponding removal
efficiency was above 90% over a wide pH range (pH = 3–10). The
removal efficiencies under acidic (pH 3) and alkaline conditions (pH 10)
was lower than under neutral conditions, and the optimum value of
99.24% was obtained at pH 7.5, indicating that a more neutral pH is
conductive to remove polyethylene MPs because of better yield of
coagulant under neutral pH conditions, which was in accordance with
the phenomenon observed by other studies [92]. Although high water
conductivity consumed less electrical energy, it did not significantly
increase the removal efficiency of polyethylene MPs compared to low
conductivity and consumed more NaCl. The economic assessment of the
operating costs of the reactor indicated that the optimum NaCl con­
centration used is 0–2 g/L. In case of current density, the increase of
energy consumption did not increase but decrease the removal effi­
ciency of polyethylene MPs, which indicated that low current density is
more energy-efficient for polyethylene MPs [91]. Moreover, Perren et al.
[91] also compared the operating cost of using EC to treat polyethylene
MPs and other pollutants (e.g., domestic wastewater, iron and bleaching
effluent) and found that the operating cost of polyethylene MPs was
lower than other pollutants (0.05 £ per m3 [91] vs 0.86 $ per m3 [93],
0.22 $ per m3 [94] and 1.56 $ per m3 [95]), indicating that using EC
technology to remove polyethylene MPs from wastewater is feasible.
Although it shows a good removal performance and cost in wastewater,
considering the continuous cost of regular replacement of sacrificial
anode used and electricity, the application of EC technology to the
removal of MPs in other urban waters requires more pilot-scale studies
rather than only under laboratory conditions.
4. Effects of environmental conditions and characteristics of
MPs on coagulation
4.1. Solution pH
Owing to the effect on floc characteristics and hydrolysis of co­
agulants, pH is considered to have an important influence on the coag­
ulation performance [96,97]. Ma et al. [26] investigated the effect of
solution pH on the removal efficiency of polyethylene MPs and found
that the removal efficiency increased with the increase solution pH at
the high dosage of FeCl3⋅6H2O (2 mmol/L), the corresponding removal
efficiency of polyethylene MPs (d < 0.5 mm) increased from 11.56% ±
0.98% at pH 6 to 17.23% ± 1.72% at pH 8. Moreover, the size of Fe-
based flocs gradually increased from 433.8 ± 22.3 μm at pH 6 to
6
Chemical Engineering Journal 416 (2021) 129123
761.9 ± 31.7 μm at pH 8.0 while their zeta potential decreased from
1.91 mV ± 0.34 mV at pH 6.0 to − 3.43 ± 1.18 mV at pH 8.0. This
indicated that the contribution of sweep flocculation to the removal of
polyethylene MPs may be greater than that of charge neutralization with
increasing solution pH at the high dosage of FeCl3⋅6H2O. This could be
attributed to the more generation of amorphous hydroxides under high
pH conditions increased the size of Fe-based flocs [97], which was more
conducive for sweep and sedimentation. Similar phenomenon was also
found in the study of Zhou et al. [75]. The highest removal efficiency of
polyethylene and polystyrene MPs (i.e., 20.30% and 64.58%) in the
presence of FeCl3 was obtained at the initial pH 9. In addition to FeCl3,
Zhou et al. [75] also studied the effect of pH on the removal performance
of polyethylene and polystyrene MPs with addition of PAC. It was found
that the removal efficiencies of polyethylene and polystyrene MPs
changed little in the pH range of 5–8 while increased significantly at the
initial pH 9, which could be due to the fact that alkaline conditions
facilitate the hydrolysis of PAC to generate more and larger flocs [76],
benefiting the sweep and sedimentation. However, an opposite phe­
nomenon was observed in the removal of polyethylene MPs using
AlCl3⋅6H2O. Ma et al. [74] found that the removal efficiency of poly­
ethylene MPs of all sizes decreased as the solution pH increased from 6
to 8 at the high dosage of AlCl3⋅6H2O (5 mmol/L). However, the change
trend of size of flocs (i.e., from 69.3 ± 13.2 to 422.3 ± 23.1 µm) and zeta
potential (i.e., from 1.91 ± 0.34 to − 3.43 ± 1.18 mV) was consistent
with the addition of FeCl3⋅6H2O by Ma et al. [26]. This indicated that the
contribution of sweep flocculation to the removal of polyethylene MPs
may be weaker than that of charge neutralization with increasing so­
lution pH at the high dosage of AlCl3⋅6H2O. This difference in contri­
bution of sweep flocculation and charge neutralization in FeCl3⋅6H2O
and AlCl3⋅6H2O systems may be due to the fact that the size of Al-based
flocs was much smaller than Fe-based flocs at pH 8.0 (422.3 ± 23.1 vs
761.9 ± 31.7 μm).
4.2. Ions
The existence of various kinds of ions in real water may influence the
coagulation performance [98]. Zhou et al. [75] investigated the effects
of three typical ions (i.e., Cl-, SO2- 2–
4 and CO3 ) on removal performance of
polyethylene and polystyrene MPs using PAC and the FeCl3, and found
that Cl- had little effect on the removal performance of both MPs, which
was similar to the phenomenon observed by Ma et al. [26,74]. For SO2- 4,
it showed inhibition effect on the removal of both MPs. Since SO2- 4 can
remarkably reduce the positive charge of PAC hydrolysate [97], its ex­
istence is not conducive to the binding of hydrolysis products and MPs.
Q. Xu et al.
Moreover, the presence of SO2-4 impacts the destabilization with metal
coagulants [97]. Both can interfere with coagulation process, decreasing
the removal efficiency. However, the presence of CO2–3 was beneficial to
the removal of both MPs, which could be attributed to the improvement
of the hydrolysis of the coagulants by the addition of CO2–
3 induced the
alkaline conditions [75].
4.3. MPs size
Due to the existence of various characteristics of MPs (e.g., size,
shape and surface morphology) in real water, the coagulation removal
behavior of MPs becomes more complicated. The characteristics of MPs
may affect the coagulation mechanisms thereby changing the removal
performance of MPs. In terms of size, both smaller and larger sizes may
be not conducive to coagulation removal of MPs. Ma et al. [26,74]
compared the removal performance of polyethylene MPs with different
sizes (i.e., d < 0.5 mm, 0.5 < d < 1 mm, 1 < d < 2 mm and 2 < d < 5 mm)
under various dosages of FeCl3⋅6H2O and AlCl3⋅6H2O, and found that
the removal efficiency of polyethylene MPs decreased with an increase
in the size. Moreover, all removal efficiencies were low level even for
very high coagulant concentrations. For example, the highest removal
efficiency, which was obtained in smaller particle-size of polyethylene
MPs (d < 0.5 mm), was only 36.89% ± 3.24% with addition of 15 mM
AlCl3⋅6H2O (405 mg/L Al) [74]. This could be probably due to that the
particle size of the tested polyethylene MPs (0.5–5 mm) was relatively
larger than the average size of Fe-based flocs and Al-based flocs, making
it difficult to be embedded into the floc structure [26,74,80]. However,
the opposite phenomenon occurred when removing the smaller size
polyethylene MPs (10–100 μm). Shahi et al. [79] found that the larger
particle size of polyethylene MPs, the higher the removal efficiency in
the presence of higher dosage of alum (20–50 mg/L) where sweep
flocculation is dominant. Moreover, the removal efficiency of the
smaller size (10–30 μm) was also lowest in the presence of 10 mg/L alum
where charge neutralization is dominant, which was similar with the
phenomenon observed in real DWTPs by Pivokonsky et al. [36]. This
indicated that polyethylene MPs with too small particle size (10–30 μm)
might not be easy to swept or neutralized, resulting in low removal
efficiency.
4.4. MPs shape and surface morphology
Different shape and surface morphology of MPs exhibited different
coagulation removal behavior. In the study of Shahi et al. [79], the
removal efficiency of elongated MPs was higher than that of spherical
MPs in the presence of all alum dosages, which might be related to their
surface area. Under the condition of same volume, the surface area of the
elongated MPs is larger than that of spherical MPs due to the larger
Feret’s diameter, which might make MPs more easily adsorbed and
intercepted by Al(OH)s(am) particles or flocs compared with spherical
MPs. When investigating the combined effect of shape and surface
morphology of MPs, it was reported that the removal efficiencies of
spherical-rough MPs were higher than for spherical-smooth MPs in the
presence of all alum dosages. On the one hand, particles with rough
surfaces performed strong attachment compared to smooth particles
[99]. On the other hand, MPs with spherical-rough have greater asym­
metry than MPs with spherical-smooth [79]. Since the Feret’s diameter
of the MPs usually align themselves along the flow velocity’s direction,
the orientation of these nonsymmetric MPs can accelerate the agglom­
eration among nonsymmetrical particles [100]. Therefore, spherical-
rough MPs may be more conducive to sweep and sedimentation.
5. Photocatalytic degradation of MPs
Photocatalysis is considered as an advanced oxidation process that
can degrade pollutants into water and carbon dioxide using the active
species (e.g. ⋅OH, ⋅O–2, and hole (h+)) generated by photocatalysts under
7
Chemical Engineering Journal 416 (2021) 129123
light irradiation [101,102], which has been intensively researched and
applied for decades due to its good degradation performance, low cost
and eco-friendly characteristics [103,104]. Recently, some photo­
catalysts have been demonstrated to degrade MPs such as TiO2, ZnO,
and, BiOCl [105–109]. Table 3 summarizes the applications of three
metal-based catalysts in the photocatalytic degradation of MPs.
5.1. TiO2-based photocatalysis
Compared with other photocatalysts, TiO2, as a classic photocatalyst,
has received extensive attention in the degradation of MPs. Ariza-
Tarazona et al. [105] firstly reported the photocatalytic degradation of
high-density polyethylene MPs using two photocatalysts based on N-
TiO2 (i.e., protein-derived N-TiO2 and sol–gel N-TiO2). In this study, the
performance of two photocatalysts were evaluated under simulated
visible light irradiation, the protein-derived N-TiO2 showed better pro­
mote mass loss of polyethylene MPs than sol–gel N-TiO2 (6.40% vs
2.86%). Compared with low mass loss of polyethylene MPs, better
degradation performance of polystyrene MPs was observed using TiO2
under simulated UV light irradiation [35,106]. For example, Nabi et al.
[35] found that the degradation efficiency of 5 mm polystyrene MPs in
the liquid phase reached 44.66% after 12 h illumination under 254 nm
UV, which further increased to 99.99% in the solid phase under same
conditions because it avoids the adverse effect of the hydrophilicity of
polystyrene MP in the aqueous solution on the reaction. In this process,
the larger fragments of polystyrene MPs were broken into smaller pieces,
which eventually became carbon dioxide as the main end product. The
proposed photocatalysis reaction of polystyrene MPs on a solid state
mechanism was similar to the conventional TiO2 as reported [110,111],
that is specifically, the reaction was initiated by holes (h+) and reactive
oxidative species (e.g., ⋅OH and ⋅O–2) while h+ was the main contributor
in the photocatalytic degradation of polystyrene MPs. UV light stimu­
lates TiO2 to generate an electron during the conduction process (e-CB)
and form a positive hole in the valence band (h+VB) (Eq. (1)). The re­
action may be initiated in the following two ways: (i) the oxidation re­
action occurs at the valence band (Eq. (2)-(4)), (ii) the degradation
reaction occurs at the conduction band (Eq. (5)-(8)).
hvTiO2 →h+ −
VB + eCB (1)
h+
VB + MPs→CO2 + H2 O (2)
h+
VB + H2 O→∙OH + H
+
(3)
∙OH + MPs→CO2 + H2 O (4)
O2 + e−CB →O∙−
2 (5)
O∙−
2 + H2 O→∙OOH + OH
−
(6)
2∙OOH→O2 + H2 O2 (7)
H2 O2 →2∙OH (8)
Solution pH and temperature are crucial parameters for the photo­
catalysis reaction performance [103,112]. Ariza-Tarazona et al. [107]
investigated the effect of pH and temperature in the photocatalytic
degradation process of polyethylene MPs using a protein-derived C,N-
TiO2 under simulated visible light irradiation, and found that better
photocatalytic performance for degrading was obtained under low pH
(pH 3) and low temperature (0 ◦ C) conditions. The corresponding mean
mass loss of polyethylene MPs reached 71.77 ± 1.88% after 50 h of
irradiation, which was higher than that of other conditions such as pH 3
and 40 ◦ C, pH 7 and 20 ◦ C, pH 11 and 0 ◦ C, pH 11 and 40 ◦ C (12.42 ±
0.20%, 0.47 ± 0.16%, 1.55 ± 0.31% and 0.78 ± 0.17%), which could be
attributed to the incorporation of H+ ions into the reaction process by
the low pH, facilitating polyethylene MPs degradation and accordingly
Q. Xu et al. Chemical Engineering Journal 416 (2021) 129123

Table 3
Selected research studies on the applications of photocatalysis technologies to remove MPs in water.
Photocatalysts MPs Irradiation Reaction conditions Removal Ref
source efficiency

TiO2 Polystyrene MPs UV light [TiO2]0 = 500 mg/L, [MPs]v = 5 μm, Reaction time = 12 h, 32 W lamp (λ = 254 nm) 44.66% [35]
Protein-derived N- Polyethylene MPs Visible light [mussel-derived N-TiO2]0 = 100 mg/L, [MPs]0 = 2000 mg/L, Reaction time = 18 h, 27 6.40% [105]
TiO2 W fluorescent lamp(λ = 400–800 nm)
Sol-gel N-TiO2 Polyethylene MPs Visible light [sol–gel N-TiO2]0 = 100 mg/L, [MPs]0 = 2000 mg/L, Reaction time = 8 h, 27 W 2.86% [105]
fluorescent lamp(λ = 400–800 nm)
Au@Ni@TiO2 Polystyrene MPs UV light Reaction time = 40 s, 315 W Colibri lamp(λ = 385 nm), 1.67% H2O2 solution 67% [106]
C,N-TiO2 Polyethylene MPs Visible light [C,N-TiO2]0 = 4000 mg/L, [MPs]0 = 4000 mg/L, Reaction time = 50 h, 50 W LED lamp 71.77 ± 1.88% [107]
(λ = 400–800 nm), pH 3, 0 ◦ C
ZnO Polypropylene Visible light [TiO2] = ~60 mg, [MPs]0 = 104 particles/lite, Reaction time = 456 h, 120 W (ES- 65% [108]
MPs HALOGEN) (60 mW/cm2)
BiOCl-X Polyethene MPs Visible light [BiOCl-X]0 = 10000 mg/L, [MPs]0 = 1000 mg/L, Reaction time = 5 h, 250 W Xe lamp 5.38% [109]
(λ > 420 nm)

favouring higher interaction of the colloidal photocatalysts with the MPs
[107,113], and the fragmentation of MPs caused by low temperature,
increasing their surface area and their interaction with the photo­
catalysts [107,114].
5.2. ZnO-based photocatalysis
At present, the application of ZnO-based catalysts to degrade MPs
has also received attention owing to its excellent optical properties, high
redox potential, good electron mobility and non-toxicity [115–117].
Tofa et al. [115] studied the degradation behavior of low-density
polyethylene MPs using visible light excited heterogeneous ZnO nano­
rods (ZnO NRs). After 175 h photocatalysis reaction, the carbonyl index
of the residue increased by 30%, and its surface brittleness increased and
accompanied by a large number of wrinkles, cracks and cavities, indi­
cating that the long polymeric chains of polyethylene MPs undergo
photocatalytic oxidation to form low molecular weight compounds.
Besides, the photocatalytic activity of ZnO NRs was further improved by
depositing platinum (Pt) nanoparticles on the surface of nanorods in
another study of Tofa et al. [116]. After 175 h exposure under visible
light, 13% increase of the carbonyl index and 15% increase of the vinyl
index increase were achieved in the residue by ZnO-Pt compared to ZnO
NRs, suggesting better degradation performance of low-density poly­
ethylene MPs. Pt nanoparticles acted as electron sinks to arrest/reduce
the exciton recombination process to assist the photocatalytic reactions
[118,119], and the main contributors taking part in the photocatalytic
process were identified as ⋅OH and ⋅O–2 (Fig. 4).
Similar enhanced degradation was also observed on polypropylene
MPs in water with visible light irradiation of ZnO NRs. According to the
study [108], the reduction of the average particle volume reached 65%
by ZnO NRs after 456 h of visible light exposure compared to the raw
polypropylene MPs. Besides, they found that the degradation in­
termediates detected in water samples after photodegradation of poly­
propylene MPs were ethynyloxy/acetyl radicals, hydroxypropyl,
butyraldehyde, acetone, acrolein (propenal) and pentyl group, which
may generally be considered low toxicity to human health and aquatic
environment. The results indicated that the degradation of poly­
propylene MPs was caused by the reorganization of smaller chains
formed by the shedding of chains [108].

Fig. 4. Schematic diagram of the proposed mechanism MPs photocatalytic degradation over the ZnO-Pt under visible light irradiation. Reproduced with permission
from Ref. [116].

8
Q. Xu et al.
5.3. BiOCl-based photocatalysis
Parallel effort has been made on photocatalytic degradation of MPs
in water by BiOCl-based catalyst under visible light irradiation. Jiang
et al. [109] synthesized a novel hydroxy-rich ultrathin BiOCl (BiOCl-X)
for degradation of high-density polyethene MPs. After 5 h of reaction,
the mass loss of polyethene MPs reached 5.38%, which was 24 times
higher than that of BiOCl under same reaction conditions. This could be
due to the more the surface hydroxyl groups in BiOCl, the more ⋅OH
could be produced under light [120]. As presented in Fig. 5, there per­
formed similar mechanisms as reported in the conventional photo­
catalysts: ⋅OH was the main contributor in the photocatalytic
degradation of MPs. The proposed degradation pathway suggested that
the starting event for this reaction was initiated by the hydroxyl radicals
generated from the BiOCl-1 attacking the C–H bond of polyethene
molecule, and these polymeric chains can continue to fracture and
eventually degrade into CO2 and H2O (Fig. 6). In addition, Jiang et al.
[109] also selected zebrafish to conduct the toxicity evaluation of the
degradation solution of polyethene MPs. Results showed that the ac­
tivity of zebrafish in the degradation solution of MPs was better than
that of the blank group (i.e., only including pure water) under dark
conditions. This may be due to some short carbon chains generated by
MPs degradation during the photocatalysis reactions [121]. Above result
suggesting that the toxicity of the polyethene MPs degradation solution
was very limited.
6. Research gap and perspective
6.1. Comprehensive exploration of coagulation removal behaviors and
mechanism in actual urban waters
In addition to the use of surface water and secondary WWTP effluent
respectively in the studies of Rajala et al. [37] and Lapointe et al. [80],
other coagulation jar tests were all conducted in synthetic water with
externally added MPs. The conditions of synthetic water and the MPs
added may inevitably be quite different from the actual DWTP influent,
drinking water, wastewater, and WWTP effluent. Moreover, the related
coagulation operating parameters are also different from actual appli­
cations. As introduced above, coagulant dosage and type, environment
conditions of water and characteristics of MPs all could affect the
coagulation removal behaviors and mechanism. Therefore, the removal
behaviors and mechanism obtained in the current jar tests may be
different from those observed in the actual urban waters, which may not
Fig. 5. Degradation mechanism of polyethylene MPs by BiOCl-X under visible light irradiation. Adapted with permission from Ref. [109]. Copyright Elsevier, 2020.
9
Chemical Engineering Journal 416 (2021) 129123
effectively guide the strengthening removal of MPs from the actual
urban waters. In addition, in the studies of Ma et al. [26] and Zhou et al.
[75], the optimum pH (i.e., pH 8 and pH 9) for removing polyethylene
and polystyrene MPs was beyond the optimal pH range reported coag­
ulation with Fe salts (5.5–6.5). Above the relevant jar tests only focus on
the removal of MPs, but many water quality indicators need to be
considered in actual urban waters. This difference in the optimal pH
value of using Fe salt coagulant to remove MPs and other substances will
inevitably affect the comprehensive removal effect of various urban
waters. Moreover, it is unknown whether the enhanced removal of MPs
by coagulation will increase additional treatment costs, resulting in
incomplete evaluation of the promotion and application of this tech­
nology for enhanced removal of MPs. Therefore, it is urgent to
comprehensively explore the coagulation removal behavior and mech­
anism of MPs in actual urban waters to provide guidance as much as
possible for the enhanced removal of MPs while ensuring that other
water quality indicators meet the standards.
6.2. Optimization of photocatalytic degradation of MPs
Although the application of photocatalysis has been widely studied
in many emerging contaminants, the research on the removal of MPs has
only recently attracted attention, thus having many research gaps to be
investigated. Most of the current studies on photocatalytic degradation
of MPs are conducted in single photocatalytic systems, which could be
limited due to the rapid recombination of electron (e− )-hole (h+),
improper band values and positions and slow surface reaction kinetic
[122,123], resulting in current unsatisfactory photocatalytic degrada­
tion performance (e.g., low degradation efficiency and long irradiation
time) and hindering further applications. Therefore, these photo­
catalysts need to be further optimized, such as preparation of composite
photocatalysts with stronger performance based on single photocatalyst.
In addition to above metal-based catalysts, metal-free-based catalysts (e.
g., g-C3N4), considered as environmentally friendly catalysts, showed
good removal performance of many emerging contaminants such as
endocrine disrupting compounds and antibiotic [124]. However, there is
no relevant research on the removal of MPs. More efforts are required to
evaluate the feasibility of degradation of MPs using metal-free-based
catalysts. Although photocatalysis is considered as a promising and
advantageous method for the complete removal of MPs in water, anal­
ysis of treatment costs is still lacking. Moreover, the reusability and
stability of the catalyst in the removal process of MPs are related to the
treatment cost and treatment effect, and are important indicators for
Q. Xu et al.
Fig. 6. Possible photocatalytic degradation process of polyethylene MPs by BiOCl-X under visible light irradiation. Adapted with permission from Ref. [109].
Copyright Elsevier, 2020.
evaluating the sustainable applicability of the catalyst, but there is
currently a lack of relevant research. At present, it is difficult to achieve
complete photocatalytic degradation of MPs, thereby generating large
number of degradation intermediates, which have been identified as
potential toxicity [108,109]. However, most of the current studies have
not covered the evaluation of the toxicity of the degradation in­
termediates (with the exception of Jiang et al. [109]). The above
research gaps inevitably lead to incomplete evaluation of the application
feasibility of MPs photocatalytic degradation. Therefore, the more
comprehensive evaluation, such as economic analysis of treatment costs,
catalyst reusability and potential ecological impact, should be carried
out to fully reveal the feasibility of its further extensive application.
6.3. Coagulation removal and photocatalytic degradation of nanoplastics
(NPs)
MPs can be further decomposed into nanoplastics (NPs) with the
particle sizes ranging from 1 to 100 nm. Moreover, NPs released from
commercial applications are also considered an important source of NPs
in the environment [10]. Therefore, NPs are abundant in urban waters.
Although studies have found that coagulation and photocatalysis tech­
niques can effectively remove MPs, few studies are available on the
removal of NPs from urban waters. It is important to assess the feasibility
of coagulation removal and photocatalytic degradation of NPs. It was
reported that the potential toxicity might increase as the particle size of
plastic shrinking [125]. Sun et al. [126] found that polystyrene NPs
induce higher toxicity on the marine bacterium Halomonas alkaliphila
compared with the polystyrene MPs. Apart from bacterium, the ingested
and accumulated NPs can enter the circulatory system of organisms by
the intestinal tissues due to smaller size, resulting in toxic effects at
cellular and molecular levels [10]. A study suggested that polystyrene
NPs can interfere with the normal gene expression and neurotransmis­
sion of mussels, reduce enzyme activity, increase oxidation state, and
cause peroxidative damage [127]. This indicated that NPs may have a
greater potential risks for the ecological environment and human health.
If NPs can be removed by coagulation and photocatalysis techniques, it
can therefore not only increase the application value of the above
technologies, but also help to alleviate the potential environmental and
health impacts of NPs, as additional benefits of the above technologies.
7. Conclusions
This review covers recent progress of MPs occurrence, fate, and
distribution and the removal methods (i.e., coagulation and
10
Chemical Engineering Journal 416 (2021) 129123
photocatalysis) in urban waters. Coagulation is mainstream technology
to remove MPs while photocatalysis is a promising technique for
degrading MPs. Since single technique cannot achieve complete removal
of MPs, the combination of coagulation and photocatalysis may be the
future development trend, resulting in a joint enhanced removal per­
formance. In the process of coagulation, potential coagulation mecha­
nisms include charge neutralization, adsorption and sweep flocculation.
Among them, charge neutralization and sweep flocculation are exten­
sively considered as the dominant coagulation mechanism. Moreover,
the coagulation removal performance of MPs is very susceptible to
environment conditions (e.g., solution pH and ions) and characteristics
of MPs (e.g., size, shape and surface morphology). In photocatalysis
system, active species (e.g. ⋅OH, ⋅O–2, and h+) play vital role in the
degradation of MPs. The degradation pathways of MPs generally refer to
the continuous cleavage of their polymer chains under the action of
active species. In addition, solution pH and temperature have been
demonstrated to significantly affect the photocatalytic degradation of
MPs. Although many efforts have been made on coagulation removal
and photocatalytic degradation of MPs recently, it should be recognized
that there are still some knowledge gaps to be studied: (i) Comprehen­
sive exploration of coagulation removal behaviors and mechanism in
actual urban waters (ii) Optimization of conventional photocatalysts (e.
g., performance, economic analysis, reusability and stability); Potential
application of metal-free-based catalysts in the degradation of MPs;
More evaluation of the toxicity of the degradation intermediates. (iii)
Further study on coagulation removal and photocatalytic degradation of
NPs.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This study was partially supported by the National Natural Science
Foundation of China (52000138 and 51978492); China Postdoctoral
Science Foundation (2019M661629); and Shanghai Postdoctoral
Excellence Program (2019273).
References
[1] K.L. Law, R.C. Thompson, Microplastics in the seas, Science 345 (2014) 144–145.
Q. Xu et al.
[2] D.K.A. Barnes, F. Galgani, R.C. Thompson, M. Barlaz, Accumulation and
fragmentation of plastic debris in global environments, Philos. Trans. R. Soc.
Lond. B Biol. Sci. 364 (2009) 1985–1998.
[3] D. Hu, M. Shen, Y. Zhang, G. Zeng, Micro(nano)plastics: an un-ignorable carbon
source? Sci. Total Environ. 657 (2019) 108–110.
[4] A. Keswani, D.M. Oliver, T. Gutierrez, R.S. Quilliam, Microbial hitchhikers on
marine plastic debris: human exposure risks at bathing waters and beach
environments, Mar. Environ. Res. 118 (2016) 10–19.
[5] P.J. Anderson, S. Warrack, V. Langen, J.K. Challis, M.L. Hanson, M.D. Rennie,
Microplastic contamination in lake winnipeg, Canada. Environ. Pollut. 225
(2017) 223–231.
[6] A.A. Koelmans, N.H.M. Nor, E. Hermsen, M. Kooi, S.M. Mintenig, J. De France,
Microplastics in freshwaters and drinking water: critical review and assessment of
data quality, Water Res. 155 (2019) 410–422.
[7] J. Sun, X. Dai, Q. Wang, M.C. van Loosdrecht, B.J. Ni, Microplastics in wastewater
treatment plants: Detection, occurrence and removal, Water Res. 152 (2019)
21–37.
[8] G.S. Zhang, Y.F. Liu, The distribution of microplastics in soil aggregate fractions
in southwestern China, Sci. Total Environ. 642 (2018) 12–20.
[9] Y. Zhang, S. Kang, S. Allen, D. Allen, T. Gao, M. Sillanpää, Atmospheric
microplastics: A review on current status and perspectives, Earth Sci. Rev. 203
(2020), 103118.
[10] M. Shen, Y. Zhang, Y. Zhu, B. Song, G. Zeng, D. Hu, X. Wen, X. Ren, Recent
advances in toxicological research of nanoplastics in the environment: A review,
Environ. Pollut. 252 (2019) 511–521.
[11] R.C. Thompson, Y. Olsen, R.P. Mitchell, A. Davis, S.J. Rowland, A.W.G. John,
D. McGonigle, A.E. Russell, Lost at sea: where is all the plastic? Science 304
(2004) 838.
[12] P. Liu, X. Zhan, X. Wu, J. Li, H. Wang, S. Gao, Effect of weathering on
environmental behavior of microplastics: properties, sorption and potential risks,
Chemosphere 242 (2020), 125193.
[13] I.E. Napper, A. Bakir, S.J. Rowland, R.C. Thompson, Characterisation, quantity
and sorptive properties of microplastics extracted from cosmetics, Mar. Pollut.
Bull. 99 (2015) 178–185.
[14] A. Van Wezel, I. Caris, S.A.E. Kools, Release of primary microplastics from
consumer products to wastewater in The Netherlands, Environ. Toxicol. Chem. 35
(2016) 1627–1631.
[15] S. Uddin, S.W. Fowler, M. Behbehani, An assessment of microplastic inputs into
the aquatic environment from wastewater streams, Mar. Pollut. Bull. 160 (2020),
111538.
[16] E.E. Burns, A.B.A. Boxall, Microplastics in the aquatic environment: Evidence for
or against adverse impacts and major knowledge gaps, Environ. Toxicol. Chem.
37 (2018) 2776–2796.
[17] L.M.R. Mendoza, H. Karapanagioti, N.R. Alvarez, Micro(nanoplastics) in the
marine environment: current knowledge and gaps, Curr. Opin. Environ. Sci.
Health. 1 (2018) 47–51.
[18] A.A. Horton, A. Walton, D.J. Spurgeon, E. Lahive, C. Svendsen, Microplastics in
freshwater and terrestrial environments: evaluating the current understanding to
identify the knowledge gaps and future research priorities, Sci. Total Environ. 586
(2017) 127–141.
[19] W. Wei, Q. Hao, Z.J. Chen, T. Bao, B.J. Ni, Polystyrene nanoplastics reshape the
anaerobic granular sludge for recovering methane from wastewater, Water Res.
182 (2020), 116041.
[20] M. Cole, P. Lindeque, C. Halsband, T.S. Galloway, Microplastics as contaminants
in the marine environment: A review, Mar. Pollut. Bull. 62 (2011) 2588–2597.
[21] S.L. Wright, F.J. Kelly, Plastic and human health: a micro issue? Environ. Sci.
Technol. 51 (2017) 6634–6647.
[22] C.E. Talsness, A.J.M. Andrade, S.N. Kuriyama, J.A. Taylor, F.S. vom Saal,
Components of plastic: experimental studies in animals and relevance for human
health, Philos. Trans. R. Soc. 364 (2009) 2079–2096.
[23] R. Triebskorn, T. Braunbeck, T. Grummt, L. Hanslik, S. Huppertsberg, M. Jekel, T.
P. Knepper, S. Krais, Y.K. Müller, M. Pittroff, A.S. Ruhl, H. Schmieg, C. Schür,
C. Strobel, M. Wagner, N. Zumbülte, H.-R. Köhler, Relevance of nano- and
microplastics for freshwater ecosystems: a critical review, Trac. Trends Anal.
Chem. 110 (2019) 375–392.
[24] M. Shen, B. Song, Y. Zhu, G. Zeng, Y. Zhang, Y. Yang, X. Wen, M. Chen, H. Yi,
Removal of microplastics via drinking water treatment: Current knowledge and
future directions, Chemosphere 251 (2020), 126612.
[25] K. Novotna, L. Cermakova, L. Pivokonska, T. Cajthaml, M. Pivokonsky,
Microplastics in drinking water treatment - current knowledge and research
needs, Sci. Total Environ. 667 (2019) 730–740.
[26] B. Ma, W. Xue, Y. Ding, C. Hu, H. Liu, J. Qu, Removal characteristics of
microplastics by Fe-based coagulants during drinking water treatment,
J. Environ. Sci. 78 (2018) 267–275.
[27] E. Tiwari, N. Singh, N. Khandelwal, F.A. Monikh, G.K. Darbha, Application of Zn/
Al layered double hydroxides for the removal of nano-scale plastic debris from
aqueous systems, J. Hazard Mater. 397 (2020), 122769.
[28] Z. Wang, M. Sedighi, A. Lea-Langton, Filtration of microplastic spheres by
biochar: removal efficiency and immobilisation mechanisms, Water Res. 184
(2020), 116165.
[29] J. Grbic, B. Nguyen, E. Guo, J.B. You, D. Sinton, C.M. Rochman, Magnetic
extraction of microplastics from environmental samples, Environ. Sci. Technol.
Lett. 6 (2019) 68–72.
[30] A. Misra, C. Zambrzycki, G. Kloker, A. Kotyrba, M.H. Anjass, I. Franco Castillo, S.
G. Mitchell, R. Güttel, C. Streb, Water purification and microplastics removal
11
Chemical Engineering Journal 416 (2021) 129123
using magnetic polyoxometalate-supported ionic liquid phases (mag-POMSILPs),
Angew. Chem. Int. Ed. 59 (4) (2020) 1601–1605.
[31] S. Herrmann, L. De Matteis, J.M. de la Fuente, S.G. Mitchell, C. Streb, Removal of
multiple contaminants from water by polyoxometalate supported ionic liquid
phases (POM-SILPs), Angew. Chem. Int. Ed. 56 (2017) 1667–1670.
[32] J. Ru, Y. Huo, Y. Yang, Microbial degradation and valorization of plastic wastes,
Front. Microbiol. 11 (2020) 442.
[33] B.Y. Peng, Z. Chen, J. Chen, H. Yu, X. Zhou, C.S. Criddle, W.M. Wu, Y. Zhang,
Biodegradation of Polyvinyl Chloride (PVC) in Tenebrio molitor (Coleoptera:
Tenebrionidae) larvae, Environ. Int. 145 (2020), 106106.
[34] F. Miao, Y. Liu, M. Gao, X. Yu, P. Xiao, M. Wang, S. Wang, X. Wang, Degradation
of polyvinyl chloride microplastics via an electro-Fenton-like system with a TiO2/
graphite cathode, J. Hazard Mater. 399 (2020), 123023.
[35] I. Nabi, A.-U.-R. Bacha, K. Li, H. Cheng, T. Wang, Y. Liu, S. Ajmal, Y. Yang,
Y. Feng, L. Zhang, Complete photocatalytic mineralization of microplastic on
TiO2 nanoparticle film, Science 23 (2020), 101326.
[36] M. Pivokonsky, L. Cermakova, K. Novotna, P. Peer, T. Caithaml, V. Janda,
Occurrence of microplastics in raw and treated drinking water, Sci. Total Environ.
643 (2018) 1644–1651.
[37] K. Rajala, O. Grönfors, M. Hesampour, A. Mikola, Removal of microplastics from
secondary wastewater treatment plant effluent by coagulation/flocculation with
iron, aluminum and polyamine-based chemicals, Water Res. 183 (2020), 116045.
[38] A. Li, W. Zhu, C. Li, T. Wang, J. Gong, Rational design of yolk–shell
nanostructures for photocatalysis, Chem. Soc. Rev. 48 (2019) 1874–1907.
[39] Z. Yuan, G. Olsson, R. Cardell-Oliver, K. van Schagen, A. Marchi, A. Deletic,
C. Urich, W. Rauch, Y. Liu, G. Jiang, Sweating the assets–the role of
instrumentation, control and automation in urban water systems, Water Res. 155
(2019) 381–402.
[40] H. Chen, Q. Jia, X. Zhao, L. Li, Y. Nie, H. Liu, J. Ye, The occurrence of
microplastics in water bodies in urban agglomerations: Impacts of drainage
system overflow in wet weather, catchment land-uses, and environmental
management practices, Water Res. 183 (2020), 116073.
[41] S. Gündoğdu, C. Çevik, B. Ayat, B. Aydoğan, S. Karaca, How microplastics
quantities increase with flood events? An example from Mersin Bay NE Levantine
coast of Turkey, Environ. Pollut. 239 (2018) 342–350.
[42] A.M. Mahon, B. O’Connell, M.G. Healy, I. O’Connor, R. Officer, R. Nash,
L. Morrison, Microplastics in sewage sludge: Effects of treatment, Environ. Sci.
Technol. 2 (2017) 810–818.
[43] M. Bilgin, M. Yurtsever, F. Karadagli, Microplastic removal by aerated grit
chambers versus settling tanks of a municipal wastewater treatment plant,
J. Water Process Eng. 38 (2020), 101604.
[44] W. Wang, A.W. Ndungu, Z. Li, J. Wang, Microplastics pollution in inland
freshwaters of China: a case study in urban surface waters of Wuhan, China. Sci.
Total Environ. 575 (2017) 1369–1374.
[45] M. Shen, Y. Zhu, Y. Zhang, G. Zeng, X. Wen, H. Yi, S. Ye, X. Ren, B. Song, Micro
(nano)plastics: unignorable vectors for organisms, Mar. Pollut. Bull. 139 (2019)
328–331.
[46] X. Wen, C. Du, P. Xu, G. Zeng, D. Huang, L. Yin, Q. Yin, L. Hu, J. Wan, J. Zhang,
S. Tan, R. Deng, Microplastic pollution in surface sediments of urban water areas
in Changsha. China: abundance, composition, surface textures, Mar. Pollut. Bull.
136 (2018) 414–423.
[47] R. Dris, J. Gasperi, V. Rocher, M. Saad, N. Renault, B. Tassin, Microplastic
contamination in an urban area: a case study in Greater Paris, Environ. Chem. 12
(2015) 592–599.
[48] M. Kosuth, S.A. Mason, E.V. Wattenberg, Anthropogenic contamination of tap
water, beer, and sea salt, PLoS One. 13 (2018), e0194970.
[49] J. Zhang, C. Zhang, Y. Deng, R. Wang, E. Ma, J. Wang, J. Bai, J. Wu, Y. Zhou,
Microplastics in the surface water of small-scale estuaries in Shanghai, Mar.
Pollut. Bull. 149 (2019), 110569.
[50] H. Tong, Q. Jiang, X. Hu, X. Zhong, Occurrence and identification of microplastics
in tap water from China, Chemosphere 252 (2020), 126493.
[51] Z. Xu, Q. Sui, A. Li, M. Sun, L. Zhang, S. Lyu, W. Zhao, How to detect small
microplastics (20–100 μm) in freshwater, municipal wastewaters and landfill
leachates? A trial from sampling to identification, Sci. Total Environ. 733 (2020),
139218.
[52] N. Tang, X. Liu, W. Xing, Microplastics in wastewater treatment plants of Wuhan,
Central China: abundance, removal, and potential source in household
wastewater, Sci. Total Environ. 745 (2020), 141026.
[53] W. Sang, Z. Chen, L. Mei, S. Hao, C. Zhan, W.B. Zhang, M. Li, J. Liu, The
abundance and characteristics of microplastics in rainwater pipelines in Wuhan,
China, Sci. Total Environ. 755 (2020), 142606.
[54] T. Kögel, Ø. Bjorøy, B. Toto, A.M. Bienfait, M. Sanden, Micro- and nanoplastic
toxicity on aquatic life: determining factors, Sci. Total Environ. 709 (2020),
136050.
[55] W. Wang, J. Ge, X. Yu, Bioavailability and toxicity of microplastics to fish species:
A review, Environ. Toxicol. Chem. 189 (2020), 109913.
[56] A.L. Lusher, M. McHugh, R.C. Thompson, Occurrence of microplastics in the
gastrointestinal track of pelagic and demersal fish from the English Channel, Mar.
Pollut. Bull. 67 (1–2) (2013) 94–99.
[57] K. Jabeen, B. Li, Q. Chen, L. Su, C. Wu, H. Hollert, H. Shi, Effects of virgin
microplastics on goldfish (Carassiusauratus), Chemosphere 213 (2018) 323–332.
[58] L. Yin, B. Chen, B. Xia, X. Shi, K. Qu, Polystyrene microplastics alter the behavior,
energy reserve and nutritional composition of marine jacopever (Sebastes
schlegelii), J. Hazard. Mater. 360 (2018) 97–105.
[59] S. Bhargava, S.S. Chen Lee, L.S. Min Ying, M.L. Neo, S. Lay-Ming Teo,
S. Valiyaveettil, Fate of nanoplastics in marine larvae: A case study using
Q. Xu et al.
barnacles, Amphibalanus Amphitrite, ACS Sustain Chem. Eng. 6 (2018)
6932–6940.
[60] J.N. Hahladakis, C.A. Velis, R. Weber, E. Iacovidou, P. Purnell, An overview of
chemical additives present in plastics: migration, release, fate and environmental
impact during their use, disposal and recycling, J. Hazard Mater. 344 (2018)
179–199.
[61] H. Hirai, H. Takada, Y. Ogata, R. Yamashita, K. Mizukawa, M. Saha, C. Kwan,
C. Moore, H. Gray, D. Laursen, E.R. Zettler, J.W. Farrington, C.M. Reddy, E.
E. Peacock, M.W. Ward, Organic micropollutants in marine plastics debris from
the open ocean and remote and urban beaches, Mar. Pollut. Bull. 62 (2011)
1683–1692.
[62] T. Iguchi, H. Watanabe, Y. Katsu, Application of ecotoxicogenomics for studying
endocrine disruption in vertebrates and invertebrates, Environ Health Perspect.
114 (2006) 101–105.
[63] A. Bakir, S.J. Rowland, R.C. Thompson, Competitive sorption of persistent
organic pollutants onto microplastics in the marine environment, Mar. Pollut.
Bull. 64 (2012) 2782–2789.
[64] M.A. Browne, S.J. Niven, T.S. Galloway, S.J. Rowland, R.C. Thompson,
Microplastic moves pollutants and additives to worms, reducing functions linked
to health and biodiversity, Curr. Biol. 23 (2013) 2388–2392.
[65] J.C. Prata, J.P. da Costa, I. Lopes, A.C. Duarte, T. Rocha-Santos, Environmental
exposure to microplastics: an overview on possible human health effects, Sci.
Total Environ. 702 (2020), 134455.
[66] R. Lehner, C. Weder, A. Petri-Fink, B. Rothen-Rutishauser, Emergence of
nanoplastic in the environment and possible impact on human health, Environ.
Sci. Technol. 53 (2019) 1748–1765.
[67] G.F. Schirinzi, I. Pérez-Pomeda, J. Sanchís, C. Rossini, M. Farré, D. Barceló,
Cytotoxicity effects of commonly used nanomaterials and microplastics on
cerebral and epithelial human cells, Environ. Res. 159 (2017) 579–587.
[68] H. Bouwmeester, P.C. Hollman, R.J. Peters, Potential health impact of
environmentally released micro- and nanoplastics in the human food production
chain: Experiences from nanotoxicology, Environ. Sci. Technol. 49 (2015) 8932.
[69] J. Zargorski, J. Debelak, M. Gellar, J.A. Watts, J.A. Kline, Chemokines accumulate
in the lungs of rats with severe pulmonary embolism induced by polystyrene
microspheres, J. Immunol. 171 (2003) 5529–5536.
[70] M.O. Rodrigues, N. Abrantes, F.J.M. Gonçalves, H. Nogueira, J.C. Marques, A.M.
M. Gonçalves, Spatial and temporal distribution of microplastics in water and
sediments of a freshwater system (Antuã River, Portugal), Sci. Total Environ. 633
(2018) 1549–1559.
[71] K.E. Lee, N. Morad, T.T. Teng, B.T. Poh, Development, Characterization and the
application of hybrid materials in coagulation/flocculation of wastewater: A
review, Chem. Eng. J. 203 (2012) 370–386.
[72] N. Shirasaki, T. Matsushita, Y. Matsui, T. Marubayashi, Effect of aluminum
hydrolyte species on human enterovirus removal from water during the
coagulation process, Chem. Eng. J. 284 (2016) 786–793.
[73] A. Matilainen, M. Vepsäläinen, M. Sillanpää, Natural organic matter removal by
coagulation during drinking water treatment: A review, Adv. Colloid Interface
Sci. 159 (2010) 189–197.
[74] B. Ma, W. Xue, C. Hu, H. Liu, J. Qu, L. Li, Characteristics of microplastic removal
via coagulation and ultrafiltration during drinking water treatment, Chem. Eng. J.
359 (2019) 159–167.
[75] G. Zhou, Q. Wang, J. Li, Q. Li, H. Xu, Q. Ye, Y. Wang, S. Shu, J. Zhang, Removal of
polystyrene and polyethylene microplastics using PAC and FeCl3 coagulation:
Performance and mechanism, Sci. Total Environ. 752 (2021), 141837.
[76] M. Sillanpää, M.C. Ncibi, A. Matilainen, M. Vepsäläinen, Removal of natural
organic matter in drinking water treatment by coagulation: A comprehensive
review, Chemosphere 190 (2018) 54–71.
[77] Z. Wang, T. Lin, W. Chen, Occurrence and removal of microplastics in an
advanced drinking water treatment plant (ADWTP), Sci. Total Environ. 700
(2020), 134520.
[78] M. Pivokonský, L. Pivokonská, K. Novotná, L. Čermáková, M. Klimtová,
Occurrence and fate of microplastics at two different drinking water treatment
plants within a river catchment, Sci. Total Environ. 741 (2020), 140236.
[79] N.K. Shahi, M. Maeng, D. Kim, S. Dockko, Removal behavior of microplastics
using alum coagulant and its enhancement using polyamine-coated sand, Process
Saf. Environ. Prot. 141 (2020) 9–17.
[80] M. Lapointe, J.M. Farner, L.M. Hernandez, N. Tufenkji, Understanding and
improving microplastics removal during water treatment: Impact of coagulation
and flocculation, Environ. Sci. Technol. 54 (2020) 8719–8727.
[81] C.S. Lee, J. Robinson, M.F. Chong, A review on application of flocculants in
wastewater treatment, Process Saf. Environ. 92 (2014) 489–508.
[82] B. Xu, T. Ye, D.P. Li, C.H. Hu, Y.L. Lin, S.J. Xia, F.X. Tian, N.Y. Gao, Measurement
of dissolved organic nitrogen in a drinking water treatment plant: size fraction,
fate, and relation to water quality parameters, Sci. Total Environ. 409 (2011)
1116–1122.
[83] M.A. Aboulhassan, S. Souabi, A. Yaacoubi, M. Baudu, Improvement of paint
effluents coagulation using natural and synthetic coagulant aids, J. Hazard.
Mater. 138 (2006) 40–45.
[84] M.I. Aguilar, J. Sáez, A. Lloréns, A. Soler, J.F. Ortuňo, Microscopic observation of
particle reduction in slaughterhouse wastewater by coagulation-flocculation
using ferric sulphate as coagulant and different coagulant aids, Water Res. 37
(2003) 2233–2241.
[85] World Health Organization, 2003. Acrylamide in Drinking-water: Background
Document for Development of WHO Guidelines for Drinking-water Quality,
World Health Organization.
12
Chemical Engineering Journal 416 (2021) 129123
[86] L. Gillberg, B. Hansen, I. Karlsson, A. Nordström Enkel, A. Pålsson, About water
treatment, Kemira Kemwater, 171 (2003), 195-199, 72-73, 91-631-4344-5.
[87] D.T. Moussa, M.H. El-Naas, M. Nasser, M.J. Al-Marri, A comprehensive review of
electrocoagulation for water treatment: potentials and challenges, J. Environ.
Manag. 186 (2017) 24–41.
[88] S. Garcia-Segura, M.M.S.G. Eiband, J.V. de Melo, C.A. Martinez-Huitle,
Electrocoagulation and advanced electrocoagulation processes: a general review
about the fundamentals, emerging applications and its association with other
technologies, J. Electroanal. Chem. 801 (2017) 267–299.
[89] B. Zeboudji, N. Drouiche, H. Lounici, N. Mameri, N. Ghaffour, The influence of
parameters affecting boron removal by electrocoagulation process, Separ. Sci.
Technol. 48 (2013) 1280–1288.
[90] M.H. El-Naas, M.A. Alhaija, S. Al-Zuhair, Evaluation of a three-step process for
the treatment of petroleum refinery wastewater, J. Environ. Chem. Eng. 2 (2014)
56–62.
[91] W. Perren, A. Wojtasik, Q. Cai, Removal of microbeads from wastewater using
electrocoagulation, ACS Omega 3 (2018) 3357–3364.
[92] Y. Yavuz, U.B. Ogutveren, Treatment of industrial estate wastewater by the
application of electrocoagulation process using iron electrodes, J. Environ.
Manage. 207 (2018) 151–158.
[93] F. Ozyonar, B. Karagozoglu, Operating cost analysis and treatment of domestic
wastewater by electrocoagulation using aluminum electrodes, Pol. J. Environ.
Stud. 20 (2011) 173–179.
[94] K.S. Hashim, A. Shaw, R. Al Khaddar, M.O. Pedrola, D. Phipps, Iron removal,
energy consumption and operating cost of electrocoagulation of drinking water
using a new flow column reactor, J. Environ. Manage. 189 (2017) 98–108.
[95] R. Sridhar, V. Sivakumar, V.P. Immanuel, J.P. Maran, Treatment of pulp and
paper industry bleaching effluent by electrocoagulant process, J. Hazard. Mater.
186 (2011) 1495–1502.
[96] B.W. Ma, W.Z. Yu, H.J. Liu, J.H. Qu, Effect of low dosage of coagulant on the
ultrafiltration membrane performance in feedwater treatment, Water Res. 51
(2014) 277–283.
[97] J.M. Duan, J. Gregory, Coagulation by hydrolyzing metal salts, Adv. Colloid
Interface 100 (2003) 475–502.
[98] H.T. Wang, Y.Y. Ye, J. Qi, F.T. Li, Y.L. Tang, Removal of titanium dioxide
nanoparticles by coagulation: effects of coagulants, typical ions, alkalinity and
natural organic matters, Water Sci. Technol. 68 (2013) 1137–1143.
[99] B.V. Hassas, H. Caliskan, O. Guven, F. Karakas, M. Cinar, M.S. Celik, Effect of
roughness and shape factor on flotation characteristics of glass beads, Colloids
Surf. A Physicochem. Eng. Asp. 492 (2016) 88–99.
[100] Z. Jiang, Y. Guan, Flocculation morphology: effect of particulate shape and
coagulant species on flocculation, Water Sci. Technol. 53 (2006) 9–16.
[101] C. Zhou, C. Lai, P. Xu, G. Zeng, D. Huang, C. Zhang, M. Cheng, L. Hu, J. Wan,
Y. Liu, W. Xiong, Y. Deng, M. Wen, In situ grown AgI/Bi12O17Cl2 heterojunction
photocatalysts for visible light degradation of sulfamethazine: Efficiency,
pathway, and mechanism, ACS Sustain. Chem. Eng. 6 (2018) 4174–4184.
[102] Y. Pi, X. Li, Q. Xia, J. Wu, Y. Li, J. Xiao, Z. Li, Adsorptive and photocatalytic
removal of Persistent Organic Pollutants (POPs) in water by metal-organic
frameworks (MOFs), Chem. Eng. J. 337 (2018) 351–371.
[103] S. Wang, Q. Yang, F. Chen, J. Sun, K. Luo, F. Yao, X. Wang, D. Wang, X. Li,
G. Zeng, Photocatalytic degradation of perfluorooctanoic acid and
perfluorooctane sulfonate in water: A critical review, Chem. Eng. J. 328 (2017)
927–942.
[104] C. Liang, H.-Y. Niu, H. Guo, C.-G. Niu, Y.-Y. Yang, H.-Y. Liu, W.-W. Tang, H.-
P. Feng, Efficient photocatalytic nitrogen fixation to ammonia over bismuth
monoxide quantum dots-modified defective ultrathin graphitic carbon nitride,
Chem. Eng. J. 406 (2021), 126868.
[105] M.C. Ariza-Tarazona, J.F. Villarreal-Chiu, V. Barbieri, C. Siligardi, E.I. Cedillo-
González, New strategy for microplastic degradation: green photocatalysis using a
protein-based porous N-TiO2 semiconductor, Ceram. Int. 45 (2019) 9618–9624.
[106] L.L. Wang, A. Kaeppler, D. Fischer, J. Simmchen, Photocatalytic TiO2
micromotors for removal of microplastics and suspended matter, ACS Appl.
Mater. Interfaces 11 (2019) 32937–32944.
[107] M.C. Ariza-Tarazona, J.F. Villarreal-Chiu, J.M. Hernández-López, J. Rivera De la
Rosa, V. Barbieri, C. Siligardi, E.I. Cedillo-González, Microplastic pollution
reduction by a carbon and nitrogen-doped TiO2: effect of pH and temperature in
the photocatalytic degradation process, J. Hazard. Mater. 395 (2020), 122632.
[108] A. Uheida, H.G. Mejía, M. Abdel-Rehim, W. Hamd, J. Dutta, Visible light
photocatalytic degradation of polypropylene microplastics in a continuous water
flow system, J. Hazard. Mater. https://doi.org/10.1016/j.jhazmat.2020.124299.
[109] R. Jiang, G. Lu, Z. Yan, J. Liu, D. Wu, Y. Wang, Microplastic degradation by
hydroxy-rich bismuth oxychloride, J. Hazard. Mater. https://doi.org/10.1016/j.
jhazmat.2020.124247.
[110] B.A. Bhanvase, T.P. Shende, S.H. Sonawane, A review on graphene–TiO2 and
doped graphene–TiO2 nanocomposite photocatalyst for water and wastewater
treatment, Environ. Technol. Rev. 6 (2016) 1–14.
[111] N.M. Diantoro, A. Kusumaatmaja, K. Triyana, Study on photocatalytic properties
of TiO2 nanoparticle in various pH condition, IOP Conf. Series J. Phys. Conf. Ser.
1011 (2018), 012069.
[112] M.N. Chong, B. Jin, C.W. Chow, C. Saint, Recent developments in photocatalytic
water treatment technology: A review, Water Res. 44 (2010) 2997–3027.
[113] I. Kriston, Some Aspects of the Degradation and Stabilization of Phillips Type
Polyethylene. Ph.D. thesis. Laboratory of Plastics and Rubber Technology,
Budapest University of Technology and Economics, Budapest (2010).
Q. Xu et al.
[114] B. Gewert, M.M. Plassmann, M. MacLeod, Pathways for degradation of plastic
polymers floating in the marine environment, Environ. Sci. Process. Impacts. 17
(9) (2015) 1513–1521.
[115] T.S. Tofa, K.L. Kunjali, S. Paul, J. Dutta, Visible light photocatalytic degradation
of microplastic residues with zinc oxide nanorods, Environ. Chem. Lett. 17 (2019)
1341–1346.
[116] T.S. Tofa, F. Ye, K.L. Kunjali, J. Dutta, Enhanced visible light photodegradation of
microplastic fragments with plasmonic platinum/zinc oxide nanorod
photocatalysts, Catalysts 9 (2019) 819.
[117] K. Qi, B. Cheng, J. Yu, W. Ho, Review on the improvement of the photocatalytic
and antibacterial activities of ZnO, J. Alloy. Comp. 727 (2017) 792–820.
[118] J.M. Lin, H.Y. Lin, C.L. Cheng, Y.F. Chen, Giant enhancement of bandgap emission
of ZnO nanorods by platinum nanoparticles, Nanotechnology 17 (2006)
4391–4394.
[119] R. Flyunt, W. Knolle, A. Kahnt, C.E. Halbig, A. Lotnyk, T. Haupl, A. Prager,
S. Eigler, B. Abel, High quality reduced graphene oxide flakes by fast kinetically
controlled and clean indirect UV-induced radical reduction, Nanoscale 8 (2016)
7572–7579.
[120] K. Takahashi, H. Yui, Analysis of surface OH groups on TiO2 single crystal with
polarization modulation infrared external reflection spectroscopy, J. Phys. Chem.
C. 113 (2009) 20322–20327.
13
Chemical Engineering Journal 416 (2021) 129123
[121] J. Kang, L. Zhou, X. Duan, H. Sun, Z. Ao, S. Wang, Degradation of cosmetic
microplastics via functionalized carbon nanosprings, Matter 1 (2019) 745–758.
[122] Y.F. Chen, C.J. Zhang, W.X. Huang, Y. Situ, H. Huang, Multimorphologies nano-
ZnO preparing through a simple solvothermal method for photocatalytic
application, Mater. Lett. 141 (2015) 294–297.
[123] C. Martínez, M. Fernández, J. Santaballa, J. Faria, Kinetics and mechanism of
aqueous degradation of carbamazepine by heterogeneous photocatalysis using
nanocrystalline TiO2, ZnO and multi-walled carbon nanotubes–anatase
composites, Appl. Catal. B Environ. 102 (3) (2011) 563–571.
[124] S. Tian, C. Zhang, D. Huang, R. Wang, G. Zeng, M. Yan, W. Xiong, C. Zhou,
M. Cheng, W. Xue, Recent progress in sustainable technologies for adsorptive and
reactive removal of sulfonamides, Chem. Eng. J. 389 (2020), 123423.
[125] L. Miao, P. Wang, J. Hou, Y. Yao, Z. Liu, S. Liu, T. Li, Distinct community structure
and microbial functions of biofilms colonizing microplastics, Sci. Total Environ.
650 (2019) 2395–2402.
[126] X. Sun, B. Chen, Q. Li, N. Liu, B. Xia, L. Zhu, K. Qu, Toxicities of polystyrene nano-
and microplastics toward marine bacterium Halomonas alkaliphila, Sci. Total
Environ. 642 (2018) 1378–1385.
[127] Q. Chen, D.Q. Yin, Y.L. Jia, S. Schiwy, J. Legradi, S.Y. Yang, H. Hollert, Enhanced
uptake of BPA in the presence of nanoplastics can lead to neurotoxic effects in
adult zebrafish, Sci. Total Environ. 609 (2017) 1312–1321.