Chemical Engineering Journal 424 (2021) 130282

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Chemical Engineering Journal

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

Review

A critical review on microplastics, interaction with organic and inorganic

pollutants, impacts and effectiveness of advanced oxidation processes
applied for their removal from aqueous matrices
Ivo A. Ricardo a, b, Edna A. Alberto a, e, Afonso H. Silva Júnior c,
Domingos Lusitâneo P. Macuvele c, d, Natan Padoin c, Cíntia Soares c, Humberto Gracher Riella c,
Maria Clara V.M. Starling f, Alam G. Trovó a, *
a
Institute of Chemistry, Federal University of Uberlândia, 38400-902, Uberlândia, MG, Brazil
b
Faculty of Natural and Exact Sciences, Save University, 0301-01, Chongoene, Gaza, Mozambique
c
Department of Chemical and Food Engineering, Federal University of Santa Catarina (UFSC), Florianópolis, SC, Brazil
d
Department of Science, Engineering, Technology and Mathematics, University of Rovuma, Lichinga, Niassa, Mozambique
e
District Service of Education, Youth and Technology of Bilene, 0304-02, Macia, Gaza, Mozambique
f
Universidade Federal de Minas Gerais, Departamento de Engenharia Sanitária e Ambiental, 31270-010, Belo Horizonte, MG, Brazil

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

Keywords: Microplastics have become a hot topic in the scientific community as they promote adverse effects to living
Advanced oxidative processes beings. Various analytical tools must be used simultaneously for identification and characterization of micro­
Aqueous matrices plastics and their transformation products in environmental compartments. Despite limitations associated to the
Contaminants of emerging concern
reproduction of real conditions of microplastics occurrence in environmental matrices (composition, size, con­
Heterogeneous photocatalysis
Photo-Fenton
centration), increased toxicity has been observed as a consequence of their interaction with contaminants of
emerging concern and/or heavy metals. Yet, some factors (i.e., pH, particle age and size of microplastic, among
others) may affect this phenomenon. Membrane filtration and coagulation-flocculation-settling treatments are
non-destructive, needing an additional step to degrade microplastics. Biological treatment has been demon­
strated as unsatisfactory (<15% degradation) for microplastics treatment. On the other hand, a few recent works
have pointed out advanced oxidation processes as feasible alternatives, since they present high efficiency of
microplastic degradation (≈ 30–95%). However, more studies should be conducted to evaluate the performance
of advanced oxidation processes on the degradation of microplastics in real matrices under solar irradiation.
Identification of transformation products, elucidation of degradation mechanisms, and toxicity assays using in
vivo and in vitro tests, as well as computational tools, are needed to improve the assumption of these processes as
feasible treatment alternatives. Added to this, tests in larger treatment systems are critical to promote scale up for
application in real scale.

1. Introduction properties of synthetic polymers such as: low density, resistance to

Modern society is facing serious challenges related to environmental
issues. Several of these environmental problems were originated as a
consequence of anthropogenic activities [1], especially those associated
to the use of fossil fuels [2]. Recently, attention has been directed to
waste originated from the use of synthetic polymers [3]. Discovered in
1907, bakelite was the first synthetic polymer [4]. This discovery
contributed to advances in macromolecular science due to inherent
corrosion, low electrical conductivity, among others [5]. These char­
acteristics enabled the application of polymers in a wide range of areas,
such as biomedicine [6] and environmental sciences [7], reaching
exponential growth [8]. For instance, global production of polymers
reached 360 million tons in 2018 [9].
Despite the advantages related to the application plastic in various
sectors, these materials foster a challenging environmental hazard [10].
More than 100 years are necessary for plastic biodegradation, along

* Corresponding author.
E-mail addresses: ricardoivoamildon@gmail.com (I.A. Ricardo), lusitaneom24@gmail.com (D.L.P. Macuvele), cintia.soares@ufsc.br (C. Soares), alamtrovo@ufu.
br (A.G. Trovó).

https://doi.org/10.1016/j.cej.2021.130282
Received 9 February 2021; Received in revised form 21 April 2021; Accepted 6 May 2021
Available online 12 May 2021
1385-8947/© 2021 Elsevier B.V. All rights reserved.
I.A. Ricardo et al.
these years they may threat many biological aspects of living beings
[11]. Particular interest has been recently raised on plastic debris named
microplastics (MPs) [10]. Although there is still no consensus on a
technical definition of MPs [12], the scientific community recognizes
harms associated to their occurrence in the environment.
Numerous studies have detected the occurrence of MPs in air, soil,
water, food, and other sources [13–17]. Alarmingly, these microparti­
cles were cytotoxic to living beings in all of the previously mentioned
environments [18,19]. MPs originated from polyethylene (PE) were
toxic for early-stage aquatic organisms living in freshwater ecosystems
[20]. Polystyrene (PS) MPs caused pulmonary cytotoxicity by inducing
reactive oxygen species (ROS) in in vitro assays [21]. Besides, alterations
on enzymatic patterns in soil bacteria by various MPs were detected
[22].
Furthermore, MPs interact with other chemical contaminants such as
dyes, heavy metals, and contaminants of emerging concern [23]. These
interactions allow MPs to act as vectors for the accumulation and
transportation of organic and inorganic pollutants which adhere to their
surface [23]. As a result, MPs intensify the bioaccumulation of other
contaminants in the environment and influence their pollution poten­
tial. Microparticles may adsorb and/or absorb organic contaminants,
and sorption potential is increased in aged MPs [24].
As the removal of MPs is limited in conventional sewage treatment
plants (STP) [25], many efforts have been directed to enable their
removal from environmental aqueous matrices [9,26]. Membrane
filtration, advanced oxidation processes (AOPs), biological treatment,
adsorption onto green algae, and others are among possible treatment
alternatives to remove MPs from waters [9,25]. These technologies have
been the object of many studies aiming at the removal of MPs from
aqueous matrices. Recently published reviews have compiled results
related to the degradation of MPs in aqueous matrices by distinct pro­
cesses [27–29]. A more recent review, focused on the application of
biological processes, coagulation-flocculation, flotation and others for
the removal of MPs. AOPs were also mentioned as promising strategies
[30]. However, the scope was limited to degradation performance,
without a critical analysis regarding the influence of physical features
(MP shape and size) and other operational parameters throughout the
treatment [30]. Other review articles analyzed various strategies
applied for the degradation of MPs, including AOPs, yet also without a
critical discussion regarding operational parameters and limitations
[29,31,32]. This is the first review of the current literature focusing
exclusively on the degradation of MPs via AOPs and bringing a detailed
discussion on the impact of operational parameters upon process effi­
ciency. AOPs were chosen as the main process and most promising for
the removal of AOPs in the present review considering their ability to
promote total mineralization of MPs with none or reduced generation of
waste/byproducts. Heterogeneous photocatalysis and Fenton reaction
based AOPs were selected among AOPs as there are nearly no studies
related to the removal of MPs by other AOPs.
This review brings the state of the art related to (i) the toxic effects of
MPs in the environment, (ii) the interaction between MPs and other
organic and inorganic contaminants in the environment, and (iii) the
effectiveness of heterogeneous photocatalysis and photo-Fenton applied
in distinct operational conditions aiming at the degradation of MPs in
various aqueous matrices. As effects and changes promoted by biodeg­
radation to the structure and chemical properties of MPs is fundamental
before applying AOPs, an overview of this topic is also covered in this
review.
2. Microplastics
Annually, thousands of tons of plastic are used in the most diverse
industrial processes to manufacture disposable materials [33]. The di­
versity of segments in which plastic is used as a raw material is innu­
merable (i.e., automotive, electronics, aviation, packaging, health, and
others) [34]. Since the beginning of plastics production in the 1950s, the
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Chemical Engineering Journal 424 (2021) 130282
exponential growth of unconscious consumption of this raw material has
been impressive [35]. Recent data on world plastic production reports
that 8.3 billion tons of plastic were manufactured in 65 years, yet only
9% were recycled, thus generating an inestimable accumulation of
plastic waste in the ecosystem [36]. Bui et al. [32] reported that, besides
its low recycling rate, 12% of the produced plastic is incinerated, thus
culminating in the generation of toxic gases (dioxins and furans) and air
pollution, while 79% is discharged inappropriately into the environ­
ment. These numbers are of great concern to governmental agencies and
entities that encourage sustainability. After all, numerous irreversible
consequences to fauna and flora, such as the contamination of oceans by
MPs, are caused by inappropriate disposal of plastic waste [37].
MPs are technically defined as small particles (<5 mm) derived from
raw plastic materials, such as small spheres present in beauty products,
soap, toothpaste, among others [38]. MPs represent significant risks to
human health and aquatic animals either when present solely in the
ecosystem or after interaction with other contaminants (i.e., heavy
metals, industrial dyes, etc.) generating highly hazardous compounds
[39]. Consequently, extensive research has been published on the
fundamental mechanisms of interaction between MPs and other con­
taminants in the environment [40]. Fig. 1 illustrates the increasing
number of publications related to the keyword “microplastics” in the last
10 years, thus demonstrating growing concern of the scientific com­
munity related to this contaminant.
2.1. Identification of microplastics in environmental matrices: Analytical
tools and limitations
MPs are becoming a major environmental concern. These contami­
nants have been identified in several environmental compartments. As a
new hot topic, the scientific community is currently conducting research
for comprehension of applied and fundamental aspects related to MPs.
Despite advances made with regard to other CECs, additional efforts
related to detection and characterization of MPs in environmental
matrices are critical to provide robust and reliable data about their
occurrence and fate in the environment. Data regarding MPs shape,
color, identity, size, and other characteristics, are of paramount
importance to allow for accurate determination of toxicological and
human health risks associated with these contaminants.
Various techniques have been applied to study MPs in environmental
matrices. Fourier transform infrared (FTIR) spectroscopy [41], Raman
spectroscopy [42], gas chromatography-mass spectrometry (GC–MS)
[43], matrix-assisted laser desorption/ionization time-of-flight mass
spectrometry (MALDI-TOF-MS) [44], field flow fractionation [45],
scanning electron microscopy (SEM) [46], fluorescence microscopy
[46], flow cytometry [45], dynamic light scattering (DLS) [45], nano­
particle tracking analysis [45], fluorescence spectroscopy, hyperspectral
imaging (HSI) [47], atomic force microscopy (AFM) [48], among others
[40] have all been reported as promising techniques to detect and
characterize MPs in various matrices.
Although outstanding progress achieved on this field of knowledge,
MPs are mainly found in combination with other inorganic and organic
compounds in the environment. Hence, detection and characterization
methods still need to be adapted to enable the generation of reliable
data. A comprehensive review article has recently analyzed all tech­
niques applied for separation, characterization, identification, and
detection of MPs [40]. AFM was considered an emerging technique for
this purpose [40]. Nonetheless, it should be highlighted that a combi­
nation of various techniques must be considered to gather accurate data
regarding identification, characterization and identification of MPs in
environmental matrices [40].
2.2. Microplastics in the aquatic environment
MPs are present in drinking water, wastewater, sea water as well as
other environmental matrices [49]. Effects associated to MPs are
I.A. Ricardo et al.
Fig. 1. Number of publications related to the keyword microplastic in the last 10 years (Google scholar, Microplastic as a keyword. Search made in February 2021).
extremely pronounced in the marine compartment due to direct inges­
tion and increased bioaccumulation in this environment as a conse­
quence of ecological interactions [50]. It is estimated that the ocean will
contain more plastic than fish in 2050 [51]. Zhang et al. [52] reported
that 10% of residues derived from plastic products are carried to the
oceans through storm drainage, atmospheric currents, sewers, and ships.
This compartment constitutes a sink for MPs, and the level of pollution
by MPs in the marine biome is enormous, with an estimate of 4.85
trillion MP particles resulting only from the contribution of land and STP
[53,54]. Considering that MPs bioaccumulate in the food chain, anom­
alies in fish, dolphins, whales, and marine animals will increase in the
future if no mitigating measures are taken [55]. Furthermore, necrosis
have been observed in the organs of these animals as a results of
ingestion of MPs [56].
MPs are also present in the human diet, from food to drinking water,
and in the air. However, little is known about their effects upon human
health [57]. More recently, MPs were detected in the human placenta for
the first time [13].
Plastic fragmentation is one of the main factors leading to their
propagation within different environmental compartments. For
example, agriculture is a potential source of MPs to the soil, atmosphere
and water due to intense use of plastic materials in crop fertilization,
irrigation and others [58]. Civil construction also applies plastic mate­
rials intensively including PS, polyvinyl chloride (PVC), PE, and poly­
carbonate. When handled carelessly during the construction of buildings
and houses, plastic can fragment into small pieces and flow directly into
sewers [59]. The atmospheric air is also a vector of MP dispersion as it
carries suspended particles originated from rubbers, eroded from tires or
bags, released through friction with textile fibers, and other sources
[60]. Once inhaled, MPs may go straight to the lungs and get deposited,
while some may reach the bloodstream causing unknown symptoms
[61].
It is quite challenging to identify specific sources of MPs since plastic
fragmentation may occur due to diverse factors when plastics are
exposed to humidity, sunlight, heat, friction, and others. As direct or
indirect ingestion of MPs is involuntary, it represents imminent hazard
to ecosystem integrity and health.
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Chemical Engineering Journal 424 (2021) 130282
2.3. MP structure and transformations under environmental conditions
MPs are basically debris from various plastic sources and composed
by several types of polymers, e.g., PE, PS and PVC, among others. These
materials take long periods to degrade as they present reduced de­
gradability similarly to their polymer resin. Despite that, MPs may suffer
physicochemical transformations under environmental pressures, such
as light, humidity, heat, chemicals, mechanic stress, among others,
(Fig. 2) [62,63]. As these factors act simultaneously in the natural
environment, it is fairly challenging to track all these transformation
routes as well as to reproduce them in laboratory conditions.
2.4. Toxicological aspects of microplastics
Toxicological effects caused by MPs upon living beings have been
studied by the scientific community. In these studies, MPs of different
sizes are artificially produced from PE, PS, and PVC and different con­
centrations of exposition are tested to investigate toxicological aspects
[64]. As marine biome pollution by MPs is internationally recognized
and consolidated, its toxicological aspects have been demonstrated by
countless experiments using species from all ecological environments
associated to this compartment [65]. Effects promoted by MPs upon
Ostrea edulis and macrofaunal structures concluded that MPs were
harmful to their biological systems, and influenced the abundance of
these organisms in the marine compartment [66]. After 60 days of
exposure to polylactic acid in different concentrations, Ostrea edulis
showed high levels of respiration due to stress promoted by MPs [66].
In a similar study, effects promoted by the ingestion of MPs by
mussels (Mytilus edulis) were also studied [67]. Preliminary results
showed that MPs accumulated in the intestine of mussels. Besides, a
translocation of MPs from the intestinal tract to the circulatory system in
Mytilus edulis was observed within no more than 3 days after exposition
to seawater containing MPs. Moreover, MPs persisted in the biological
system for almost 50 days [67]. The study also revealed that the
occurrence of MPs in mussel tissues is size-dependent as smaller MPs
were found in higher concentrations than larger particles. As the
occurrence of MPs in the environment is a consequence of the deterio­
ration of plastic waste disposed inadequately in environmental com­
partments, and smaller MPs are usually associated to aged particles,
I.A. Ricardo et al.
Fig. 2. Structures of some polymers, modifications under environmental conditions and interaction with other contaminants.
these results reinforce the urgency for (i) implementing effective man­
agement strategies to increase plastic recycling rates worldwide and (ii)
removing MPs from contaminated waters by applying advanced treat­
ment systems, such as AOPs.
Toxic effects promoted by MPs upon animals must be assessed not
only for hazardous effects of MPs alone, yet also to the combinations
between MPs and other pollutants. Avio et al. [68] investigated the
relationship between MPs (PE and PS) with pyrene, a polycyclic aro­
matic hydrocarbon, in mussels (Mytilus galloprovincialis). They observed
that MPs were deposited in their digestive tissues, hemolymph, and gills.
MPs altered immunological responses, damaged the lysosomal
compartment, influenced peroxisomal proliferation, and triggered
neurotoxic effects. They also revealed that pyrene adsorption upon MPs’
surface amplifies combined toxicological implications for aquatic or­
ganisms [69].
In the same way marine animals are exposed to MPs, human expo­
sure is also inevitable [11]. The retention and release of MPs from
human bodies are also intrinsically linked to the characteristics of
consumed plastic, such as shape, size, type of ingested substance, etc.
Meanwhile, the severity of symptoms depends on the nature of MPs,
time of exposure, and the susceptibility of the individual who is in
contact with the agent [11]. Several toxicological aspects related to the
impacts of MPs upon human health have been recently reported. Reports
suggest that they affect mainly humans intestinal microbiome [70].
Another study showed that MPs from PS (PS-MPs) cause pulmonary
cytotoxicity in vitro by inducing ROS [21].
Fig. 3. Effect of 24 and/or 48 h exposure to PS-MPs on cytotoxicity of BEAS-2B cells. (A) Cell viability. (B) Cell morphology. Data represent the mean ± standard
deviation of three determinations. *p < 0.05 indicates statistically significant differences from the control. Adapted from Dong et al. [21]. Copyright 2019 Elsevier.
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Chemical Engineering Journal 424 (2021) 130282
Moreover, recent reports indicate that effects upon human health are
concentration-dependent (Fig. 3) [21]. Exposure to high concentrations
of MPs, increased the risk of development of lung diseases [21]. Simi­
larly, cytotoxicity of phenol–formaldehyde MP resins upon human lung
epithelial adenocarcinoma cells (A549) (in vitro) showed increased
cytotoxicity after photoaging simulation due to increased oxidative
potential [71].
MPs were recently detected in human placenta for the first time,
rising significant of attention to the impact of these contaminants upon
human health [13]. In MPs surface were found endocrine disruptors,
compounds which cause severe human constrains in the long term [13].
In the same perspective, PE-MPs were cytotoxic and genotoxic for
human peripheral blood lymphocytes (in vitro) [72]. Cytokinesis-block
micronucleus cytome assay revealed that PE-MPs induced genetic
instability even in low concentrations. In addition, micronucleation,
nucleoplasmic bridge formation, and nuclear bud formation increased
after exposure to PE-MPs [72].
Although little is known about the ecotoxicological effects of MPs in
different organisms, it is accepted that toxicological outcomes related to
MP ingestion are diverse. MPs have a negative influence upon various
vital process, e.g., reproduction, growth, feeding, development, among
others [73]. It is broadly recognized that the intake of MPs by humans
occurs mainly from the ingestion of aquatic organisms [74], for
example, fish and seafood (Fig. 4).
Ecotoxicological studies on this matter are quite challenging, as they
require a laboratory scale scenario which is consistent with reality. This
I.A. Ricardo et al.
Fig. 4. Microplastics: source, trophic interaction, and effects upon human health [13,72,74].
requires the identification, quantification and characterization (shape,
size, etc) of each of the different types of plastic polymers present
simultaneously in environmental matrices. These factors are difficult to
analyze and to reproduce in laboratory scale, and most studies use either
low concentrations of MPs or larger sized particles than those found in
nature. Alternatively, ecotoxicological research on MPs may be con­
ducted by using computational approaches exploring the physico­
chemical properties of polymers and by in vitro tests [75]. After all,
statistical strategies in multicriteria identification using an in silico
approach enable the incorporation of numerous ecotoxicological effects,
thus promoting an optimized impact assessment which is consistent with
reality.
3. Interaction between microplastics and other pollutants
MPs can interact with other pollutants through physicochemical
mechanisms triggered by sorption [76]. Sorption is divided into two
processes, adsorption, and absorption. Adsorption involves the occur­
rence of chemical bonds between MPs and other substances which may
vary from van der Walls to covalent bonds. Meanwhile, absorption in­
volves mainly van der Walls bonds [77]. Thus, sorption transform MPs
into efficient vectors for the transportation of other chemical substances
which may be possibly carcinogenic to organisms after ingestion and/or
inhalation [78]. The interaction between MPs and pollutants is governed
by various forces and factors [79]. A recent work [77] reviewed the
significance of interactions between MPs and other persistent pollutants,
and showed that the type of hydrophobic interaction, color, pH, density,
and other properties, critically affect the sorption of other contaminants
onto MPs surface.
Interactions between MPs and other chemicals were also correlated
with toxicity [80]. An experimental study regarding the evaluation of
interactions between polypropylene (PP) MPs and polycyclic aromatic
hydrocarbons (PAHs), concluded that dark PP pellets (naturally aged)
presented higher quantities of PAHs than low colored pellets [81].
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Chemical Engineering Journal 424 (2021) 130282
Antunes et al. [82] evaluated the occurrence of plastics in the cost of
Portugal and the concentration of chemicals adsorbed onto these MPs.
Resin pellets with a diameter of 4 mm were the most abundant and
showed high proportions of PAHs. Therefore, it is critical to study the
mechanisms of interaction between MPs and other substances to develop
eco-friendly plastics. A scheme of the factors that may influence the
interaction between MPs and other pollutants is presented in Fig. 2.
3.1. Microplastics and other contaminants of emerging concern (CEC)
As there are no legal standards related to the occurrence or control of
MPs in the environment, MPs themselves are classified as CEC [83].
Illicit and licit drugs, pesticides, flame retardants, chemicals used in
personal care products and other substances are also classified as CEC,
and attention to the occurrence of CEC in the environment has been
raised in the last decades due to environmental effects associated to
these substances [68]. As stated previously, MPs may interact with other
CEC, thus increasing their accumulation and dispersion in the environ­
ment [84]. In this section, discussion will be directed to the interaction
between MPs and other CEC.
A recent study evaluated the sorption of two phthalate esters (diethyl
phthalate and dibutyl phthalate) onto MPs formed from three types of
polymers (PE, PS and PVC) [85]. A linear relationship was observed for
the isotherms related to the sorption of phthalates onto MPs, suggesting
that partition was the primary sorption mechanism. The hydrophobic
interaction governed the partition mechanism in the following order for
each type of polymer: PS > PE > PVC. Sodium chloride and calcium
chloride increased phthalate adsorption [85]. Sorption of amlodipine
and carbamazepine in colloidal MP models, natural organic matter
(NOM) and fullerene nanomaterials were also evaluated [86] and
showed that the accumulation of amlodipine is higher than that of
carbamazepine in colloidal solutions. Interestingly, results indicated a
preference for surfaces containing carboxylic groups when compared to
amine-modified surfaces. In contrast, sorption of carbamazepine
I.A. Ricardo et al.
occurred onto both modified surfaces [86]. Therefore, alterations on the
chemistry of MPs surface can affect their interactions with other con­
taminants in the environment. This is an important information to be
taken into consideration if the purpose is to explore the use of MPs as
sorption agents on the removal of CEC.
Rehse, Kloas and Zarfl [87] investigated whether the presence of
polyamide particles modified the effects of bisphenol-A in freshwater
zooplankton commonly used as test organism in toxicity assays (Daphnia
magna). Test organisms were exposed to polyamide particles and
bisphenol-A particles in different concentrations. They found that the
presence of polyamide particles alone did not trigger negative effects.
However, bisphenol-A combined to MPs promoted zooplankton immo­
bilization [87]. These results emphasize the urgency for measures and
legal standards related to the prevention and control of environmental
pollution by MPs, by investing on research and infrastructure that will
lead to appropriate management of plastic waste and removal of MPs
from polluted matrices in order to avoid the intensification of effects
caused by CEC. These measures will also contribute to the elimination of
other CEC from the environment as treatment technologies applied for
the removal of MPs are also effective on the elimination of other CEC.
3.2. Microplastics and heavy metals
Even though heavy metals may occur naturally in the environment
because of natural leaching from rocks and soil, these elements are
harmful in natura when in high concentrations as a consequence of
natural phenomena or mining activity. Metals may also react with other
pollutants present in the biome, such as MPs [88]. The interaction be­
tween MPs and heavy metals is affected by various factors such as pH,
type of plastic resin, age of MPs (virgin or aged pellets), and others
[24,89–91]. A study evaluated the adsorption of trace metals (Ag, Cd,
Co, Cr, Cu, Hg, Ni, Pb, and Zn) onto virgin and aged microplastic pellets
(collected in the river at pH 6.5) at room temperature [24]. Although
both types of plastic had the potential to adsorb all tested metals, the
adsorption of Ag, Cd, Co, Ni, Pb and Zn onto MPs in river water was
favored at increased pH values. Besides, adsorption rate was higher in
aged pellets compared to virgin pellets. This phenomenon was associ­
ated to chemical modifications on the surface of MPs after interaction
with organic matter and light [24] leading to higher surface area and
increased adsorptive capacity.
Similar results were obtained for the absorption of Cr, Co, Ni, Cu, Zn,
Cd, and Pb onto virgin and aged PE-MPs [90]. Brennecke et al. [91]
evaluated the adsorption of two heavy metals (Cu and Zn) onto virgin PS
spheres and aged fragments of PVC in seawater. Partition coefficients
ranged between 650 and 850 for Cu in PS and PVC, respectively. Thus,
being more significant in PVC than in PS fragments. Cu concentrations
increased in PS and PVC, while Zn concentrations increased only in PVC
[91].
3.3. Toxicological aspects of the interaction between microplastics and
other contaminants
As MPs increase the toxicity of other contaminants [92], it is relevant
to understand mechanisms associated to interactions between MPs and
other CEC to elucidate their effects upon living beings [93]. Increased
toxicity to Pomotoschistus microps was observed after exposition to PE-
MPs and chromium [94]. The association of MPs and chromium
induced mortality and changed animal behavior by decreasing its
predatory activity [94]. In the same way, isolated MPs or combined to
gold nanoparticles induced the mortality of Daphnia magna, reduced
offspring, and caused egg abortions [95]. In another study, the combi­
nation between MPs and Cd increased oxidative stress on Symphysodon
aequifasciatus [96].
Despite lack of ecotoxicological studies in terrestrial ecosystems, the
impact of MPs-PE and CECs (simazine and ibuprofen) on Caenorhabditis
elegans and Lactuca sativa was recently evaluated [97]. Negative effects
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Chemical Engineering Journal 424 (2021) 130282
upon C. elegans were observed for MPs-PE alone with greater when
combined with CECs. Leaf development and seed germination were
reduced in Lactuca sativa in the presence of MPs-PE and simazine [97].
In summary, interactions between MPs and other contaminants in­
crease adverse toxic effects. However, studies on this matter are incip­
ient and further research must be stimulated to elucidate mechanisms
related to increased toxicity promoted by the exposition to MPs associ­
ated with other contaminants. In addition, it is also important to
investigate the toxicity of transformation products generated during the
treatment of MPs associated to other contaminants to define the most
appropriate treatment alternatives for their removal from aqueous
matrices.
4. Microplastics removal/degradation in aqueous matrices
As described above, MPs are harmful to aquatic biota, either in their
original form or in combination to other CEC. Thus, it is critical to
stimulate research aiming at identifying the most appropriate methods
and technologies for their removal in aquatic environments, and to
promote effective development of scalable alternatives for the treatment
of aqueous matrices containing this type of pollutant. Filtration-
flocculation-precipitation and membrane filtration are currently used
to remove MPs from different aqueous matrices. In general, these
methods are based only on transfer-phase, and a second treatment is
necessary to degrade or mineralize MPs wastes present in solid phase.
Therefore, it is understood that these removal methods constitute a
partial solution to the problem posed by the occurrence of CEC in
aquatic environment.
As there is great concern about the destination of waste containing
high levels of MPs generated by former mentioned methods, this review
focuses on methods which enable complete degradation of MPs through
mineralization, such as AOPs. As oxidative processes may oxidize even
the most persistent compounds, this review gives special attention to
MPs degradation via AOPs.
AOPs are based on the generation of sulfate (SO•− 4 ) [98,99] or hy­
droxyl (HO•) [100] radicals which present high standard reduction
potential (+2.6 V and + 2.8 V for SO•− 4 and HO radicals, respectively),
•
thus being capable of mineralizing a wide range of organic pollutants.
However, as biological treatment systems are commonly applied as
secondary stage in STP for the removal of dissolved organic matter,
AOPs are expected to be applied as advanced treatment stages to remove
non-biodegradable pollutants which remain in the liquid phase after
biological treatment. Therefore, it is worth considering that the degra­
dation of MPs in STPs will occur as a result of an integrated process:
microbial degradation followed by physicochemical and/or AOP pro­
cesses [101]. In this context, the effect of biological treatment upon MPs
must be unraveled prior to the selection and application of AOPs. These
aspects will be covered in the following section before the specific sec­
tion on AOPs.
4.1. Biological degradation
Bacteria [102–104], fungi [105,106], consortia of bacteria
[107,108] and biofilms [109–112] have been currently investigated and
used for biological degradation of MPs. One of the main limitations of
methods which rely on biological routes is the excessively long treat­
ment time (months or weeks) required for biodegradation (Fig. 5). This
culminates in increased hydraulic retention times leading to higher
reactor volume and area necessary to reach a satisfactory degradation
level. As the availability of opened areas may be limited in urban re­
gions, the application of this type of treatment for the removal of
recalcitrant pollutants is limited.
Enzymes produced by microbes are the most potent tools for the
biodegradation of MPs. Although MPs constitute a carbon source for
microbes [28], they are less susceptible to microbial attack than other
biodegradable materials [114]. Some microbes are known for their
I.A. Ricardo et al.
ability to grow under specific stressful conditions under which they use
plastic polymers as an energy source. In this context, it is essential to
isolate and gain deep knowledge related to the metabolism and
biochemical routes explored by these during the degradation of MPs to
set the preliminary conditions needed for the development of efficient
biological treatments for the removal of MPs. From an ecological
perspective, MPs support microbial colonization and growth [28], thus
justifying the execution of reported research related to the behavior of
microbes isolated from various environmental samples containing MPs
as a carbon source.
Auta et al. (2018) [102] evaluated growth response and propylene
(0.5 g) degradation mechanism of in Bushnell Haas-BH mineral midst by
bacterium isolated from mangrove sediments. Degradation efficiency
was limited to 4.0 and 6.4% after 40 days of incubation using, respec­
tively, Bacillus sp. strain 27 and Rhodococcus sp. strain 36. Polymeric
mass decay was further confirmed using Fourier transform infrared
spectroscopy (FT-IR) analyses and scanning electron microscopy (SEM),
which revealed structural and morphological changes in propylene MPs
after microbial treatment.
Additionally, biological degradation of PE (100 mg) in a carbon-free
basal medium was examined in terms of structural and morphological
changes using SEM, atomic force microscopy (AFM), X-ray photoelec­
tron spectroscopy (XPS) and micro-attenuated total reflectance/fourier
transform infrared (micro-ATR/FTIR) imaging microscope [104].
Degradation efficiencies in the order of 6.1 ± 0.3% and 10.7 ± 0.2%
were obtained over a 60-day incubation period using suspension cul­
tures of Enterobacter asburiae YT1 and Bacillus sp. YP1 (1011 cells L− 1),
respectively, both isolated from the intestines of Indian mealmoths
(larvae of Plodia interpunctella) [104]. In contrast, isolates originated
from mixed mesophilic bacterial culture obtained from municipal
landfill sediment achieved 14.7% weight removal of PE-MPs during the
same incubation period mentioned above, thus demonstrating progress
with regard to removal rate [107].
Moreover, polyurethane was degraded by an indigenously developed
consortium of Pseudomonas and Bacillus species isolated from soil [115].
Scanning Electronic microscopy (SEM), fourier-transform infrared
spectroscopy (FT-IR), gel permeation chromatography and gas chro­
matography coupled with mass spectrometry were used to elucidate the
biodegradation mechanism of polyurethane films by bacterial strain
MZA-75 isolated from the soil [116]. Active microorganisms also used
intermediate products as carbon sources to mineralize the polymer
[116]. Another interesting aspect of the microbial treatment of aqueous
matrices containing MPs is associated to fact that higher degradation
rates are usually associated with low-molecular-weight MPs. This means
that the proportion between MP molecular mass and biodegradability
rate is inverse. Low-molecular-weight PE was not mineralized into CO2
by the bacterium Chelatococcus sp. E1 [103], and its biodegradability
decreased as molecular weight increased. FT-IR peaks attributed to the
C-O elongation appeared as a consequence of microbial action towards
mineralization of free PE from a meager molecular weight fraction
[103]. Nevertheless, a bacterial consortium isolated from the intestine of
the earthworm Lumbricus terrestris managed to significantly reduce the
7
Chemical Engineering Journal 424 (2021) 130282
Fig. 5. Weight reduction of polyethylene (PE) films.
A) Percentage of weight reduction by the different
marine consortia (A: phase I, B: phase II); B) Per­
centage of weight reduction of the different PE pieces
during phase II by both treatments. (ING- treatment
corresponded to PE pieces in seawater containing only
the indigenous microorganisms, BIOG - treatment
corresponded to seawater with the indigenous popu­
lation supplemented with Lysinibacillus sp. and Salini­
bacterium sp). Reprinted from Syranidou et al. [113].
size of low-density PE within 1 month reaching 60% decay after 21 days
in the presence of bacteria [117].
The action of fungi has also been investigated for the biodegradation
of MPs [106,118,119] and improved efficiency was obtained by using
ethanol as a co-substrate during the process. Morphological, structural,
and surface changes in low-density PE were observed after incubation
with fungi for 31 months during environmental remediation studies.
Mineralization rates were limited to 0.64% and 0.37% for Penicillium
pinophilum for samples with and without ethanol, respectively [120].
Long treatment times, generally extending until up to 9 months, were
required for most experiments aiming at biodegradation of PE
[108,113,121].
A brief analysis of the action of microorganisms on the biodegrada­
tion of MPs present in aqueous matrices indicates important discoveries
towards the improvement of process efficiency, such as: (i) the use of
bacterial pools (mixed bacterial culture); (ii) the discovery of the use of
intermediate products as a carbon source by bacteria; and (iii) the
addition of ethanol as a co-substrate to enhance the degradation process.
However, research on biological degradation of MPs is still far from
achieving desirable results since relatively long treatment times and low
degradation efficiencies prevail in most studies published on the issue.
Therefore, adopting new technologies as post-treatment in STP remains
in the dossier of efforts to prevent contamination by MPs, and eliminate
these contaminants before they are discharged onto environmental
waters.
4.2. Advanced oxidation processes (AOPs) applied for the degradation of
MPs
The absence of efficient and adequate methods for removing recal­
citrant contaminants, such as MPs, from aqueous systems makes it
essential to apply advanced treatment alternatives, which are capable to
eliminate persistent contaminants and/or significantly lower their
levels. To this end, several efforts have been made to find ways to
improve wastewater treatment technologies, such as AOPs, and enable
their application in real scale. Recent advances in the treatment of
aqueous systems point out to the use of AOPs in the degradation of MPs
in different aqueous matrices. In addition, AOPs were chosen as the
focus of this review as they are capable of mineralizing pollutants rather
than promoting a phase transfer. Another recent review [30] also covers
the effectiveness of AOPs along with other treatment technologies for
the removal of MPs. However, as this manuscript focuses mostly on this
technology, a detailed description and comparison between operational
conditions and achievements in each of the cited studies is only provided
here.
There are only a few studies on the application of AOPs aiming at the
degradation of MPs in aqueous matrices (Fig. 6). However, it is essential
to evaluate findings obtained by these few published studies to identify
limitations and advances of these technologies to pave the way for their
improvement for the treatment of wastewater and surface water con­
taining MPs. Fig. 6 shows the evolution in the number of publications
related to the application of AOPs aiming at the degradation of MPs in
I.A. Ricardo et al.
Fig. 6. Number of publications in the last 5 years related to the application of AOPs for the degradation of microplastics in aqueous matrices. (Google scholar,
Microplastic Degradation as a keyword. Search made in April 2021).
the last 5 years. Results reported in these studies suggest that the
degradation of MPs by AOPs remains a challenge to the scientific
community.
For a better understanding of the findings a brief review on Fenton
reaction based AOPs (Fenton, photo-Fenton, modified Fenton, electro-
Fenton-like, sulfate radical based AOPs) and photocatalysis is pre­
sented below. To the best of our knowledge, these are the only AOPs
assessed for the degradation of MPs so far.
4.2.1. Fenton reaction based AOPs
Fenton process is an advanced oxidation process that consists on the
generation of HO• radicals by the catalytic decomposition of H2O2 in the
presence of Fe2+ ions and in acid medium (Equation 1) [100,122–124].
The main steps of the Fenton reaction are (i) reaction between Fe2+ and
H2O2 (fast step) and (ii) regeneration of Fe2+ by H2O2 (slow step). One
way to speed up the process is to conduct this process under irradiation
(UV–Vis) (Equation 2).
Fe2+ + H2O2 → Fe3+ + OH− + HO• k = 76 L mol− 1 s− 1 (1)
Fe(OH)2+ + hv → Fe2+ + HO• (2)
UV–vis radiation combined with the Fenton reaction is known as the
photo-Fenton process. When Fe(III) aquo-complexes are irradiated
(Equation 2), an electron is promoted from an orbital centered on the
ligand to an orbital centered on the metal. This transference is called
ligand–metal charge and implies the reduction of Fe(III) to Fe(II) and
oxidation of the ligand, with formation of HO• radicals. It is well defined
that the optimal range of the pH value for Fenton reactions is between
2.5 and 3.0. Above pH 3, iron begins to precipitate as iron hydroxides,
thus limiting process efficiency. The modified photo-Fenton process has
been used as an alternative to circumvent the limitation related to the
pH of operation. This process relies on the use of organic iron complexes
in photo-Fenton reactions which lead to the stabilization of iron in a
wide pH range. Also, iron complexes increase light absorption efficiency
as they extend the absorption band to the visible region. As ferric ions
form stable and strong complexes with organic ligands (Equation 3)
unwanted interactions with other organic and inorganic species are
avoided. Besides, complexes provide a faster route for the regeneration
of ferrous ions in the presence of UV–Visible radiation [125].
[Fe3+ + L](aq) + hν → [Fe3+L]*(aq) → Fe2+(aq) + L•(aq) (3)
8
Chemical Engineering Journal 424 (2021) 130282
In 2019, Kida et al. [126] evaluated the modified Fenton process to
remove the recalcitrant plasticizer, di (2-ethylhexyl) phthalate, from the
bottom sediments of a reservoir, with an average degradation of 25%
after 24 h at pH 7.95. Sediments were distributed in 1 g samples and
contaminated with di (2-ethylhexyl) phthalate, added as an acetone
solution. Before starting the degradation process, distilled water was
added to the contaminated sediments to obtain a suspension. The
quantification of di (2-ethylhexyl) phthalate was done by capillary gas
chromatography, using a gas chromatograph coupled to a mass spec­
trometer (GC–MS). Under the same experimental conditions and in the
presence of a chelating agent (modified Fenton) treatment efficiency
was 1.7% – 3.9% higher than the efficiency obtained in the conventional
Fenton process. In summary, the degradation efficiencies obtained for di
(2-ethylhexyl) phthalate remained low and the authors suggested that
these results are due to previous desorption of contaminants from bot­
tom sediments.
Another promising perspective in the degradation of MPs is using the
heterogeneous Fenton process, which uses solid catalysts containing
active catalytic components to replace ferrous ions in the homogeneous
Fenton process [127]. Fenton’s catalytic reaction occurs at the active
site in a specific surface area of the solid catalyst, thus avoiding iron
leaching and consequent production of iron sludge, as well as enabling
process application in a wide pH range [122].
Huang et al. [128] used magnetite and ethylenediamine-N,N′ -dis­
uccinic acid (EDDS) in a heterogeneous photo-Fenton system to degrade
bisphenol-A (20 µmol L− 1 of bisphenol-A) in deionized water. It is worth
to recall that the effects of bisphenol-A combined with MPs are harmful
to aquatic biota [87]. Bisphenol-A concentration in the aqueous solution
was determined by high-performance liquid chromatography (HPLC).
After 11 h of irradiation, up to 70% degradation efficiency was obtained
at pH 6.3. Removal assessment was in agreement with the analysis of
intermediates by GC–MS [128]. It was also suggested that the photo-
Fenton reaction catalyzed by magnetite involves the formation of O•− 2
and HO• radicals at circumneutral pH. The occurrence of O•− 2 radicals at
this pH improved the generation of Fe(II) by reducing Fe(III)-EDDS to Fe
(II)-EDDS and, finally, leading to the formation of the HO• radical,
responsible for the oxidation of the target compound in the photo-
Fenton process.
I.A. Ricardo et al.
It is worth mentioning that emerging technologies based on the
electron as the primary reactant in AOPs have been developed to
circumvent the limitations pertaining to the Fenton process, such as the
electro-Fenton process. In these technologies, there is continuous in-situ
generation of H2O2 by electrochemical reduction of O2 in the cathode
combined with the supply of Fe (II) continuously regenerated in the
cathode, thus allowing for HO• radical formation [122]. A recent study
reported the degradation of MPs by AOPs that generate reactive species
by electrochemical processes [9,129].
A new technology, which is similar to the electro-Fenton process, is
based on TiO2/graphite (TiO2/C). TiO2/C was applied for the removal of
PVC-MPs in water, leading to 56% of PVC degradation and 75% of
dichlorination after 6 h of potentiostatic electrolysis at − 0.7 V vs. Ag/
AgCl and at initial pH 3.0 [129]. Dichlorination of PVC-MPs was
enhanced at elevated temperature (100 ◦ C). However, dichlorination
was limited to 29% (Fig. 7C) using only graphite as a cathode at the same
temperature. This result suggests the enhanced effect associated to the
treatment of catalyst surface with TiO2 [129].
Moreover, the dichlorination process caused morphological changes
to PVC-MPs (Fig. 7A and Fig. 7B). After the process, the smooth like
surface turned into an irregular surface [129]. Also, the degradation
mechanism of PVC was ascribed to various steps, such as electrons
capture from TiO2/C, oxidation of PVC by HO• leading to oxy organics
followed by the generation of hydrocarbons and resulting in organic
molecules with low molecular weight [129]. Furthermore, dichlorina­
tion efficiency initially increased in the presence of higher concentra­
tions of PVC (50–500 mg L− 1), yet a decrease was observed for the
highest concentration and the ideal concentration of the target MP was
100 mg L− 1 (Fig. 7D). This decrease resulted from the aggregation of
PVC-MPs when in high concentrations. These aggregates adhere to the
working electrode and consume reactive species, thus blocking active
sites in the TiO2/C catalyst [129]. In the same perspective, electro­
oxidation was applied for the first time as a strategy to degrade PS-MPs,
achieving 58 ± 21% removal in 1 h [9].
Furthermore, the highest degradation of MPs reached 89 ± 8% when
Na2SO4 − 0.03 mol L− 1 was used as supporting electrolyte (current in­
tensity of 9 A during 6 h of electrolysis) [9]. Interestingly, no organic
carbon was detected, and no size reduction of MPs was observed. This
result confirms that the PS-MPs were mineralized into gaseous inorganic
9
Chemical Engineering Journal 424 (2021) 130282
products, such as CO2 [9]. Although these advances are reported in
previous works [9,129], some drawbacks regarding the cost of the
process due to electric energy expenditure are pinpointed in the study.
Experiments were performed in batch in both works, a condition which
does not correspond to treatment mode carried out in real wastewater
treatment plants, suggesting that these processes must be tested in a
continuous system to better mimic results and electric energy con­
sumption to be required in real treatment facilities. Also, future works
should aim at the operation of solar devices.
Another recent strategy investigated to enhance the performance of
traditional HO•-based AOPs is the use of alternative oxidants such as
persulfate (S2O2−
8 ) or peroxymonosulfate (HSO5 ). These oxidants can be
−
activated by heat, UV light and ferrous ions (Equations 4 to 7), with the
generation of sulfate radical (SO•−4 ) whose standard reduction potential
(+2.60 V) is greater than that of persulfate (+2.10 V) and perox­
ymonosulfate (+1.82 V), thus allowing for the degradation of contam­
inants in trace concentrations [98].
Fe2+(aq.) + S2O2− 3+ 2−
8 (aq.) → Fe (aq.) + SO4 (aq.) + SO4 (aq.) (4)
•−
2+ 3+ 2−
Fe (aq.) + SO4 (aq.) → Fe (aq.) + SO4 (aq.) (5)
•−
Fe2+(aq.) + HSO−5 (aq.) → Fe3+(aq.) + SO•−
4 (aq.) + OH (aq.) (6)
−
Fe3+(aq.) + HSO−5 (aq.) → Fe2+(aq.) + HSO−5 (aq.) + H+(aq.) (7)
Kang et al. [130] degraded PE (5 g L− 1) in deionized water and hy­
drothermal conditions (100 to 160 ◦ C), by using nanocomposite Mn@
NCNTs (0.2 g L− 1) to activate 6.5 mmol L− 1 of peroxymonosulfate. MP
residues were collected by filtration (0.45 µm), washed with ethanol and
deionized water and then dried and weighed as the solid product. The
best mineralization rate (54 wt%) was obtained at 160 ◦ C after 8 h of
treatment. Toxicity assessment showed that intermediates formed from
the degradation of MPs pose no danger to microorganisms and serve as a
nutrient source for water-born algae.
One of the limitations of SO•−4 is the secondary pollution associated
with metal leaching and massive sludge generation. In this context, it is
worth mentioning that one of the crucial advances in the study by Kang
et al. [130], is the supply of green nanotechnology for control of MPs
since they used manganese carbide nanoparticles (Mn@NCNTs) pro­
tected by multilayered carbon spheres, which prevent corrosion and
leaching of metallic nanoparticles for the water body. A similar advance
was achieved by Huang [128] during the heterogeneous photo-Fenton
process applied for bisphenol-A degradation. Publications related to
Fig. 7. SEM images of (A) original polyvinyl chloride
(PVC) microplastics and (B) PVC residues after 6 h of
electrocatalytic treatment. (C) Comparing dichlorina­
tion efficiencies with TiO2/C cathode and graphite
cathode at different reaction temperatures and con­
ventional Fenton at room temperature. The inset in
(C) shows weight losses of polyvinyl chloride MPs
with TiO2/C cathode. (D) Effect of initial PVC con­
centration on PVC degradation. Error bars represent
the standard error of the mean. Reprinted from Miao
et al. [129]. Copyright 2020 Elsevier.
I.A. Ricardo et al. Chemical Engineering Journal 424 (2021) 130282

Fenton reaction-based AOPs for the degradation of MPs in aqueous nanoplastics may be adsorbed by the semiconductor [144]. Even so,
matrices are summarized in Table 1. average particle size of MPs is generally larger [29,30] than the pores
present in the surface of photocatalysts [31], thus preventing their
4.2.2. Heterogeneous photocatalysis adsorption by semiconductors. Although the use of powdered photo­
The investigation of AOPs on the degradation of MPs is not limited to catalysts has been suggested as an alternative to overcome the afore­
Fenton processes, as other technologies, such as heterogeneous photo­ mentioned adsorption problems [135], it has been revealed that the
catalysis, have also been tested. Heterogeneous photocatalysis consists immobilization of photocatalysts represents a good alternative for
on the electronic excitation of a semiconductor oxide by sunlight or treatments of STP effluent, as it avoids the separation stage needed when
artificial light, generating HO• radicals responsible for the oxidation of powdered photocatalysts are used in the process [145].
organic compounds [131]. Several semiconductors can be used in het­ It is worth mentioning that elucidating the influence of the immo­
erogeneous photocatalysis, such as [132]: Fe2O3, ZnO, ZnS, CdS and bilization of a semiconductor, as well as the size and shape of the MPs on
TiO2. Although the oxidation of a wide range of pollutants is made the efficiency of photocatalytic process, represents great advances in
possible by the high standard reduction potential (+2.0 to + 3.5 V) of removing MPs from environmental monitoring studies. Recently,
the gap generated in the catalyst, the primary reaction that corresponds Brenda et al. [145] showed that the photocatalytic degradation of high-
to oxidation is due to the presence of water molecules or hydroxyl ions density PE and low-density PE MPs using an N-TiO2 coating is affected
adsorbed on the semiconductor surface, which are responsible for the by the size and shape of MPs. The authors observed that smaller MPs
generation of the HO• radicals (Equations 8 and 9) that may oxidize showed greater degradation efficiency, while film-shaped MPs led to a
organic contaminants [133]. lower degradation rate and these results are mainly due to (i) the high
h+ + H2Oads → HO• + H+ (8) surface-volume ratio of small MPs and (ii) shape target MPs, which
h+ + OH− ads → HO• (9) determine the degree of illumination and oxygenation of the reaction
The use of N – TiO2 semiconductor coatings ZnO and Pt – ZnO by medium.
direct contact achieved satisfactory degradation of high and low density Recently, promising results were reported for ZnO and TiO2 based
PE-MPs in aqueous matrices [123–125]. A larger coating surface area is photocatalysts aiming at the degradation of MPs [138,139,142]. Com­
desired for photocatalysts as it allows for greater availability of HO• plete mineralization of PS and PE MPs were described for TiO2 films
radicals, which interact with MPs due to radical diffusion and agitation. [138]. The mineralization of these MPs was observed in the solid phase,
Also, good interaction between the semiconductors and MPs allows for in which the solution containing PS (20 μL of a standard concentrated
an effective degradation of target pollutants. Unfortunately, this inter­ solution of PS spheres) (standard PS microspheres from Huge) was
action is not appropriate between catalyst and MPs present in suspen­ added to 20 mL and PE (0.001 g mL− 1) was incorporated in TiO2 film
sion in a STP effluent as they do not accumulate spontaneously on the and dried. The degradation of MPs was lower in the liquid phase when
semiconductor surface. Table 2 shows a summary of works related to the compared to the solid phase [138]. These differences were ascribed to
application heterogeneous photocatalysis on the degradation of MPs in the lower reactivity of active species with PS- and PE-MPs in the liquid
aqueous matrices. phase.
In heterogeneous photocatalysis, an adsorption equilibrium must be Furthermore, in the solid phase, direct contact between PS and the
achieved so that irradiation can be initiated, and this balance is difficult film favored the interaction between reactive species and MPs, leading
to achieve with pollutants that do not dissolve in water, as it is the case to higher degradation [138]. Another study evaluated the photocatalytic
with MPs. The size of MPs has been pointed out as a reason for low rates degradation of polymethylmethacrylate and PS nanoplastics by TiO2/
of adsorption onto the surface of the photocatalyst. However, some β-SiC alveolar foams under UV-A radiation [139]. The photocatalyst was
impregnated by dip-coating followed by thermal treatment and the
photocatalytic experiment was performed in the liquid phase in a flow-
Table 1 through photoreactor system. The degradation of nanoplastics reached
Degradation efficiency of different advanced oxidation processes related to the 50% after 7 h at an irradiance of 112 W m− 2 and at initial pH 6.3.
degradation of microplastics in aqueous matrices. Furthermore, the degradation of nanoparticles was pH-dependent, being
Process Microplastic/ Microplastic Degradation References faster at pH values between 4 and 6 [139].
Matrix concentration (%) Additionally, 140 nm PS nanoplastics degraded faster than larger
before MPs (508 nm) [139], which is in agreement with other studies regarding
treatment
the effect of the size of microplastics on its degradability
1
Electro-Fenton- Polyvinyl 100 mg L− 56 [129] [32,35,36,144,145]. A visible light source was recently applied to
like chloride
evaluate photocatalytic degradation of PP-MPs in a water flow system
(PVC)/
deionized that mimics real wastewater system [142]. The rode like shape of ZnO
water nanoparticles were immobilized onto glass fiber substrates and the
photocatalysis assays were performed in a photoreactor. After two
1
Electrooxidation Polystyrene 100 mg L− 58 ± 21 [9]
(PS)/ weeks, the PP-MPs were reduced by about 65% of the initial volume
deionized
water
compared to pristine MPs under visible light [142]. Additionally,
Sulfate radical Polyethylene 5 g L− 1
56 [130] formaldehyde, acetone, butanal and acetaldehyde were detected as
based Fenton (PE)/ transformation products by GC–MS during PP-MPs photodegradation
deionized [142], indicating that PP-MPs were not totally mineralized. Despite that,
water
1 these products obtained present low toxicity for humans and marine
Heterogeneous Bisphenol-A/ 20 µmol L− 70 [128]
photo-Fenton deionized organisms [142].
water As stated previously, a substantial advance was achieved in the
Modified Fenton Di (2- 10 and 100 30 [126] application of photocatalysis for the degradation of MPs. However,
ethylhexyl) mg kg− 1 additional studies aiming to optimize these processes are still needed.
phthalate/
Botton
The optimization could focus on simultaneous development of high-
sediments performance catalysts and in the elucidation of fundamentals aspects
Bisphenol-A/ 23 mg L− 1
greater than [127] involved in MP degradation. Multiphysics simulations have been
deionized 95 applied to improve various engineering processes, including AOPs
water
[146], showing that it is possible to optimize the system and elucidate

10
I.A. Ricardo et al.
Table 2
Efficiency of microplastics degradation in aqueous matrices via heterogeneous photocatalysis.
Microplastic Matrix
High-density polyethylene (PE) and low-density PE Deionized water
Polystyrene (PS) and PE Deionized water
Polymethylmethacrylate and PS Wastewater
High-density PE, polypropylene (PP) and Deionized water
Polyoxymethylene
PP Deionized water
PP Deionized water
Low-density PE Dimethyl
Sulfoxide
High-density PE Deionized water
Low-density PE Deionized water
Low-density PE Deionized water
theoretical details hardly attainable by experimental approaches [147].
However, multiphysics simulations have not yet been applied for MPs
degradation via AOPs. Therefore, contributions aiming at optimization
of MPs degradation in aqueous matrices via photocatalysis should focus
on these aspects. High entropy alloys have recently attracted attention
due to their excellent (photo)catalytic capacity [148]. However, no
works explore these materials alone or in combination with TiO2 to
improve photocatalytic degradation of MPs.
4.2.3. Mechanisms involved in the degradation of microplastics via AOPs
The elucidation of mechanisms involved in the degradation of pol­
lutants by AOPs is challenging as MPs, unlike other contaminants, are
not soluble in water. Furthermore, the application of AOPs for MPs
degradation is an emerging topic and there are only few works in the
literature proposing degradation mechanisms [136,138,140,142]. The
photocatalytic degradation of PS in the solid state was initiated by holes
and reactive oxidative species, such as HO• and O•− 2 [138]. UV light
stimulates TiO2 to produce an electron in the conduction band (e− CB)
and the formation of a positive hole in the valence band (h+VB) [138].
Two degradation routes have been considered. The first route assumes
that reaction occurs in the valence band. h+VB is able to oxidize organic
compounds resulting in mineralization and/or generation of HO• radi­
cals. Due to their electrophilic nature, these radicals are non-selective
and able to oxidize all electron-rich organic compounds eventually
promoting their mineralization. The second route involves the conduc­
tion band, where the e− CB reacts with oxygen, forming a superoxide
radical whose reaction with water produces HO•2, thus generating H2O2
[138]. Finally, H2O2 turns into HO•, which attacks the MP leading to
degradation. The degradation mechanism and transformation products
(TPs) were studied by in situ diffuse reflectance infrared Fourier trans­
form spectroscopy and high-pressure photon ionization, showing the
generation of hydroxyl, carbonyl, and carbon-hydrogen groups during
the photodegradation of PS [138]. Numerous characteristic ion frag­
ments originated from the cleavage of PS spheres and its three main
transformation products (styrene, benzene and toluene) have been
identified [138]. In addition, TiO2/PS IR spectra showed the formation
of OH and carbonyl groups, which were attributed to aromatic and
aliphatic ketones of acetophenone and OH groups in the PS chain [138].
These two bands can result from chain splitting, competitive cross-
linking or oxidation of the benzene ring [138].
A similar mechanism was observed during the photocatalytic
degradation of the low-density PE film, where the HO• and O•− 2 radicals
generated from ZnO initiated the degradation in weak sites of the
polymeric chains to generate alkyl radicals, followed by chain breaking,
branching, crosslinking and oxidation of the target compound [136].
Subsequently, oxygen was incorporated into the alkyl radical and
abstraction of hydrogen atoms from the polymer chains took place to
form hydroperoxide groups. The dissociation of these groups undergoes
successive reactions and generates species containing carbonyl and vinyl
Chemical Engineering Journal 424 (2021) 130282
Microplastic concentration/size before Degradation (%) References
treatment
0.4% w/v 1.38 ± 0.13 (HDPE) and 4.65 ± 0.35 [137]
(LDPE)
400 nm 98.4 [138]
1
5% w/v (12 mg L− TOC) 50 (TOC conversion) [139]
10 g L− 1/100 mL 5.4 [140]
25 mm2 L− 1 38 [141]
104 particles L− 1
65 [142]
3 cm × 3 cm 12.5 [143]
200 mg/100 mL 6.4 [135]
50 µm (1 cm × 1 cm) 30% (increase of the carbonyl index) [136]
1 cm × 1 cm 13% (increase of the carbonyl index) [134]
groups, which, in turn, lead to the cleavage [136]. The two former steps
are based on the Norrish mechanism, in which the reaction between
polymeric chain with carbonyl groups generate two radicals (Norrish
type I), or forms CO2 and H2O in a two-step process (Norrish Type II)
[136]. A possible pathway for the degradation of high-density PE mi­
crospheres (PE-S) [140] and PP [142] involving the aforementioned
mechanisms [136] has also been proposed. This radical mechanism is
recognized as one of the main mechanisms contributing to the degra­
dation of other classes of CEC during AOPs [100,149]. So far, published
literature on the subject indicates that mechanisms involved in photo­
catalysis of MPs and CECs are similar (Fig. 8).
In summary, the degradation of MPs by AOPs involves a radical
mechanism with some particularities depending on the type of polymer,
size, surface electronic charge, molecular weight, and other aspects. As
it occurs with other CECs, it is likely that matrix composition probably
affects MP degradation via AOPs, as organic matter and ions may act as
scavengers of oxidative radicals [150].
5. Concluding remarks and future trends
Although many advances have been made regarding environmental
contamination by MPs, some aspects remain as challenges to the sci­
entific community. Among these challenges is the search for effective
treatment alternatives to prevent the contamination of aqueous matrices
by MPs through wastewater discharge, thus conserving ecosystem
quality and integrity. The toxicity of MPs towards aquatic organisms is a
consensus in the scientific literature, yet more studies are still needed to
elucidate the toxic mechanisms and its variants. Regarding human
health, in vitro studies showed that some MPs are cytotoxic and geno­
toxic for certain cells. In addition, MPs were detected for the first time in
human placenta in combination with endocrine disruptors. MPs interact
with other pollutants increasing their toxicity and accumulation. These
interactions vary depending on the physicochemical properties and age
of MPs, as well as on matrix composition and environmental conditions.
A limited number of studies have reported the application of AOPs
for the removal of MPs, and current results are auspicious. While other
advanced treatment technologies only promote phase transfer from the
liquid to the solid state, thus generating hazardous waste, complete
mineralization of microplastics was achieved in some studies applying
AOPs in solid phase and under UV light. Furthermore, studies performed
in liquid phase achieved a maximum degradation of 65% without
complete mineralization. However, drawbacks, such as the low perfor­
mance of AOPs to degrade large MPs particles was also reported.
More studies aiming to improve the degradation of MPs by AOPs
should focus on:
(i) the investigation of AOP efficiency aiming at the degradation of
MPs in real matrices (surface water and STP effluent) and under
11
I.A. Ricardo et al.
Fig. 8. Structures proposed for PE-S TPs and possible fragmentation mechanisms. Reprinted from Jiang et al. [140]. Copyright 2020 Elsevier.
solar irradiation to pave the way for process application in real
treatment facilities while reducing expenses with electricity;
(ii) the synthesis of novel catalysts to improve degradation and
mineralization efficiencies of target MPs;
(iii) in-depth studies on the solubility of target MPs to ensure greater
solubilization prior to the application of AOPs without enhancing
environmental hazard;
(iv) the synthesis of photocatalysts with higher textural characteris­
tics, thus enabling adsorption of large MPs;
(v) the application of Multiphysics simulation and other modeling
systems to achieve a higher degradation yield for MPs;
(vi) the elucidation of oxidative mechanisms taking place during the
degradation of MPs in environmental matrices as well as the
impact of matrix composition on process efficiency, and
(vii) the elucidation of mechanisms related to the toxic effect pro­
moted by MPs and transformation products formed during AOP
treatment in aqueous matrices by bioassays and computational
tools used to assess ecotoxicity.
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
Authors thank Conselho Nacional de Desenvolvimento Científico e
Tecnológico - CNPq (Project 405043/2018-0 and the Research Fellow­
ship 305215/2018-3), Fundação de Amparo à Pesquisa do Estado de
Minas Gerais - FAPEMIG (PPM-00509-18), Coordenação de Aperfei­
çoamento de Pessoal de Nível Superior - CAPES (001), and CAPES-Print
(Project 88887.310560/2018-00).
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