Science of the Total Environment 957 (2024) 177150

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Science of the Total Environment

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Review

Recent advances in mechanistic insights into microplastics mitigation

strategies via emerging advanced oxidation processes: Legislation,
challenges, and future direction
Arvind Kumar , Riona Indhur , Faizal Bux , Sheena Kumari *
Institute for Water and Wastewater Technology, Durban University of Technology, P.O. Box 1334, Durban 4000, South Africa

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

• Molecular mechanisms of MPs polymer

chain scission by AOPs is provided
thoroughly.
• Mechanistic insights of MPs conversion
into value-added products by AOPs
discussed.
• Photocatalytic identified as a research
hotspot for MPs degradation in water.
• Comparison and summarization of
various AOPs for MPs degradation
• Current policies and legislation for MPs
mitigation in environment are
discussed.

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

Editor: Damia Barcelo Microplastics (MPs) pollution has emerged as a global environmental concern due to its detrimental impacts on
ecosystems. Conventional wastewater/water treatment methods are inadequate for MPs removal due to their
Keywords: diminutive size ranging from micrometers to nanometers. Advanced oxidation processes (AOPs) have gained
Microplastics attention as a promising green strategy for the efficient and safe elimination of MPs from aqueous systems. In
AOPs mechanistic
recent years, various AOPs, including direct photo-degradation, photocatalytic oxidation, electrochemical
Reactive oxygen species
oxidation, sono-chemical oxidation, ozonation, as well as sulfate radicals-based AOPs (SR-AOPs), and the use of
Polymer chain cleavage
Microplastic legislations hybrid systems have all been extensively investigated for MP elimination. However, the molecular mechanisms
of MP polymer chain scission by AOPs have not been thoroughly studied so far. In this review, we have attempted
to provide a thorough overview of molecular mechanisms and highlighted recent advances in the degradation of
commonly used MP by AOPs. The characteristics and limitations of each technique are thoroughly examined.
Additionally, current policies and legislation on plastic pollution are discussed, emphasizing the need for reg-
ulatory frameworks to support effective MPs mitigation strategies. To advance the practical application of AOPs
for MPs removal, future research direction should address the transition from controlled laboratory environ-
ments to complex field conditions, assess the sustainability of AOPs in terms of catalytic material design, se-
lection of effective oxidants, power consumption, and operational costs. Given these challenges,
recommendations for future research directions are proposed based on knowledge gaps in the reported literature.

* Corresponding author.
E-mail address: sheenak1@[Link] (S. Kumari).

[Link]
Received 19 August 2024; Received in revised form 15 October 2024; Accepted 20 October 2024
Available online 16 November 2024
0048-9697/© 2024 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license ([Link]
nc-nd/4.0/).
A. Kumar et al. Science of the Total Environment 957 (2024) 177150

This review could offer a coherent summary of the molecular mechanisms involved in different MP elimination
techniques, aiding in the advancement of more dependable AOPs technology with superior removal and
degradation efficiency.

1. Introduction plastic production has surpassed 8 billion MT worldwide and is antici-

pated to continue escalating in the forthcoming decades (Ricardo et al.,
Increasing contamination of surface and groundwater with micro- 2021). In the recent study reported by Leslie et al., MP particles
plastics (MPs) around the globe poses a serious environmental risk due including PE, PP, and PET (polyethylene terephthalate) were detected in
to their multitude of sources, widespread prevalence, persistence, and human blood at a concentration of 1.6 μg/mL. Even in freshwater, MPs
adverse effects on ecosystems and human health (Yang et al., 2023). MPs particularly PE, PET, PP and PS have been commonly identified,
defined size range are typically subcategorized as plastic fragments constituting 70 % of the total MP count (Hossain et al., 2024; Nabi et al.,
ranging from 0.1 to 1000 μM (small MPs), whilst MPs in the range of 1–5 2020). Given the exponential increase in publications over the past 10
mm are regarded as large MPs (Dos Santos et al., 2023). Plastic particles years, there is an urgent need to develop advanced techniques for the
classified as nano-plastics (NPs) measure ≤0.1 μM, and are widely removal of MPs, as highlighted by the aforementioned issue. This trend
recognized as a global pollutant. The growing recognition of the wide- is depicted in Fig. 1a. However, the strategies for eliminating MP
spread occurrence and persistence of MPs, including NPs, has led to an pollution from the environment are still in their early stages. Consid-
increasing number of studies aimed at understanding their sources, ering the complexity and severity of the MP problem, it is crucial to
behavior, and impact. The major sources of MPs/NPs include plastic develop rapid and sustainable techniques for MP treatment. MPs
waste degradation, textile fibers from synthetic fabrics, tire wear, and degradation techniques should aim to break down the polymer chains
personal care products containing microbeads. Microplastics are found and simultaneously generate highly valuable intermediate products,
in various environments, including oceans, rivers, soil, and even air. posing a significant challenge on a global scale. So far, various treatment
They accumulate in marine life, drinking water, and food chains, raising strategy has been proposed, including screening, rapid sand filtration,
environmental and health concerns globally (Gao et al., 2023). These dissolved air flotation, membrane processes, membrane bioreactors,
efforts have prompted the development of detection methods and electrocoagulation, and activated sludge processes, for MPs removal
treatment strategies to mitigate their environmental and health risks. from wastewater (Elkhatib et al., 2021; Prokopova et al., 2021; Yang
The milestone timeline of research related to MP detection and treat- et al., 2022a; Zhao et al., 2022). A key limitation of each of the various
ments have been shown in Fig. 1a. The threat posed by MPs to human methods for removing MPs from WWTPs is their inability to effectively
health varies depending on their size. For example, MPs smaller than target different particle sizes and properties. Screening is primarily
110 μM can travel through the portal vein, which carries blood from the successful for removing larger plastic fragments, but less effective for
intestines, pancreas, and spleen to the liver (Gao et al., 2023). Moreover, removing particles larger than 100 μm (Dos Santos et al., 2023). Rapid
MPs smaller than 20 μM may infiltrate organs such as the liver and sand filtration is prone to clogging, leading to reduced efficiency and
kidneys, while those larger than 150 μM are not absorbed by the human frequent maintenance interruptions (Shen et al., 2022a, 2022b). Dis-
body (Uheida et al., 2021). Chronic exposure to the plastics, could create solved air flotation (DAF) faces challenges in removing hydrophobic
serious health issues in humans, including immune dysfunction, repro- MPs, which do not easily attach to air bubbles. Membrane processes and
ductive abnormalities, and neurological disorders (Gao et al., 2023). membrane bioreactors (MBRs) are both hindered by membrane fouling,
Ingestion of MPs can also transfer toxic chemicals, which adhere to the which decreases efficiency and increases operational costs due to
plastic surfaces, up the food chain, potentially reaching humans. The necessary cleaning (Shen et al., 2022a, 2022b). Electrocoagulation,
MPs inhalation, and ingestion routes accumulated by the human body, while effective, suffers from high energy consumption and can generate
and their toxic effects on human organisms are shown in Fig. 2a. secondary pollutants, such as metallic sludge, that complicate its scal-
Additionally, once in aquatic systems, MPs are ingested by various ability. Lastly, activated sludge processes are ineffective at removing
marine species, including fish, plankton, and shellfish, causing physical smaller MPs, particularly those in the nanoscale range, allowing these
damage, impaired feeding, and decreased growth and reproductive particles to pass through untreated (Ricardo et al., 2021). Additionally,
success (Yang et al., 2023). Furthermore, MPs can disrupt habitats by significant efforts have been dedicated to advancing technologies aimed
altering the physical and chemical properties of sediments, impacting at the removal of MPs, encompassing physical, chemical, and biological
the health and biodiversity of aquatic ecosystems (Ahmed et al., 2022; treatments. Despite all aforementioned advancements, these methods
Lu et al., 2023). The pervasive nature of MPs, coupled with their have shown limited effectiveness in eliminating MPs smaller than 10 μM
persistence and ability to accumulate, presents a formidable challenge to due to the size constraints of the current treatment technologies.
maintaining the health and sustainability of aquatic environments Furthermore, additional treatments are often necessary to achieve
globally (Jaiswal et al., 2022). The major sources of MPs to the envi- complete degradation, as most conventional processes merely separate
ronment are hospital, industrial, agricultural and domestic waste as MPs from the environment rather than fully breaking them down (Kim
shown in Fig. 2a. Furthermore, Fig. 2(b, c) illustrates the microbeads et al., 2022). Since their introduction in the 1980s, Advanced Oxidation
sourced from personal care products, whereas Fig. 2(c, d) depicts frag- Processes (AOPs) have been widely researched for the chemical treat-
ments that result from the breakdown of larger plastics at a wastewater ment of contaminants (Deng and Zhao, 2015). These processes generate
treatment plant (Sharma et al., 2021). Municipal wastewater treatment reactive oxygen species (ROS), or radicals, by employing techniques
plants (WWTPs) have recently garnered heightened scrutiny as possible such as light, heat, plasma, and catalysts, either individually or in
contributors to plastic pollution in surface water (Okoffo et al., 2023). combination. Due to their high redox potentials ranging from 2.5 to 3.1
These MPs however can have multiple entry points to the environment, V for sulfate radicals, 1.89–2.72 V for hydroxyl radicals, and 2.0–2.47 V
such as sewage sludge used as agricultural fertilizer and direct urban for chloride radicals these radicals are highly effective at degrading
discharges (Sharma et al., 2021). European WWTPs report MP levels various pollutants (Khan et al., 2021; Zhao et al., 2019). The benefits of
ranging from 0.25 to 15 MPs per liter across all treatment stages, with AOPs include their ability to remove persistent organic compounds,
effluent levels around 1–3 MPs per liter (Dos Santos et al., 2023). Plastic enhance biodegradability for subsequent biological treatment, and fully
production has experienced a significant escalation, reaching 288 mineralize harmful organic pollutants into non-toxic byproducts, unlike
million tons annually, and is projected to reach 33 billion tons by the physical methods that merely transfer pollutants between phases (Khan
year 2050 (Domínguez-Jaimes et al., 2021). The current cumulative et al., 2021; Zhao et al., 2019). However, limited information is

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A. Kumar et al. Science of the Total Environment 957 (2024) 177150

Fig. 1. (a): Milestone timeline of research related to microplastic, global plastic production, last 10 year publications on microplastic degradation by AOPs (Google
scholar, Microplastics degradation as keyword search made in April 2024), (b) Existing literature based on Scopus database searched by keyword “microplastic
removal” and “advanced oxidation processes”.

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A. Kumar et al. Science of the Total Environment 957 (2024) 177150

available on MPs degradation by AOPs specially, Fenton oxidation (Di that address the growing environmental threat posed by MPs. The
Luca et al., 2023), electrocoagulation process (Shen et al., 2022a), diverse nature of MPs in terms of polymer type, size, and environmental
ozonation (Hu et al., 2023a), heterogeneous catalysis, photocatalysis matrices necessitates a comprehensive evaluation of AOPs to identify
(Du et al., 2023), and sono-chemical process (Yang et al., 2024a, 2024b). the most effective approaches. Insights into various AOP mechanisms,
Insights into various AOP mechanisms, such as photocatalysis, electro- such as photocatalysis, electrochemical oxidation, and Fenton processes,
chemical oxidation, and Fenton processes, will guide the development of will guide the development of more tailored and efficient remediation
more tailored and efficient remediation strategies. This review con- strategies. This review contributes to the scientific community by
tributes to the scientific community by providing an in-depth compari- providing an in-depth comparison of AOPs, revealing gaps in current
son of AOPs, revealing gaps in current research, and highlighting research, and highlighting underexplored processes like sonochemical
underexplored processes like sonochemical oxidation and sulfate oxidation and sulfate radical-based AOPs (SR-AOPs). By identifying
radical-based AOPs (SR-AOPs). By identifying strengths, limitations, and strengths, limitations, and future research directions, this review offers a
future research directions, this review offers a valuable framework to valuable framework to optimize AOPs for large-scale, sustainable MPs
optimize AOPs for large-scale, sustainable MPs remediation, ultimately remediation, ultimately aiding efforts to protect aquatic ecosystems and
aiding efforts to protect aquatic ecosystems and public health. As of yet, public health. Additionally, this review article aims to briefly review
no review papers have provided detailed insights into the mechanism legislations aimed at minimizing MP pollutants; present the state-of-the-
and pathways by which MPs are degraded by AOPs. In addition, the art in various AOPs strategies for MPs removal; focusing on by-product
fragmentation and degradation mechanism of nano/micro-plastics by formation, degradation pathways, and discussions on detailed mecha-
AOPs remain poorly understood. Understanding the degradation of MPs nisms for cleaving MP polymer chains; and discuss the current chal-
through different AOPs is crucial for advancing remediation techniques lenges and future research priorities for MPs remediation using AOPs.

Fig. 2. (a) Potential primary sources, environmental transportation pathways of microplastics (MPs), bioaccumulation processes of microplastics/nanoplastics, and
their detrimental impacts on human health. (b, c) Microbeads extracted from personal care products, (d, e) Fragments derived from the degradation of larger plastic
items and synthetic textile fibers collected from a wastewater treatment plant. (Sharma et al., 2021); reproduced with permission from Elsevier).

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1.1. Literature search strategy adverse effects of MPs on marine ecosystems, wildlife, and human health
by promoting sustainable practices, enhancing waste management sys-
In order to achieve the aforementioned goals, we employed the tems, and fostering innovation in biodegradable alternatives. As
following methodology: We conducted a literature search on MPs using awareness grows, international cooperation and stricter enforcement
various databases, including Google Scholar, Science Direct, Web of mechanisms are crucial to address this pervasive environmental chal-
Science, and PubMed. We utilized keywords such as ‘Microplastics, lenge effectively. The third resolution of the United Nations focuses on
AOPs, photolysis, electrochemical oxidation, Fenton oxidation, sono- addressing plastic pollution through the alignment and enforcement of
catalysis, persulfate, and microplastic degradation mechanism’ both its directives with the Sustainable Development Goals (SDGs) and reg-
individually and in combination. Specifically, ‘MP’ and ‘AOPs’ were ulations pertaining to the circular economy. Its primary objectives
consistently used as the primary search criteria across all searches. The include implementing rigorous measures to curb plastic pollution and
existing literature was surveyed using the Scopus database, with promoting the adoption of sustainable material alternatives. Identified
searches conducted using the keywords “microplastic removal” and by the document UNEP/EA.4/Res.1, this resolution underscores sus-
“advanced oxidation processes,” as illustrated in Fig. 1(b), and country tainable consumption and production as indispensable elements in
covered the existing literature based on Scopus database shown in advancing sustainable development (Krishnan et al., 2023; Usman et al.,
supporting file Fig. S1(a). Apart from that each individual AOPs was also 2022).
searched as keyword. All relevant results were exported to a Mendeley In Australia, efforts to mitigate microbead pollution in the marine
reference manager database. This study includes findings up to May environment involve both industry and government actions. Microbe-
2024. ads, found in over 100 personal care products, have led to legislation
aimed at reducing plastic production and consumption to minimize
2. Legislations for MPs mitigation in the environment environmental and health risks. The US Microbead-Free Water Act
Mackuak et al., 2015, effective from July 2018, and Canada’s 2017
In recent years, legislative efforts to minimize MP pollution in the prohibition on microbead manufacture highlight similar global initia-
environment have intensified globally (Krishnan et al., 2023). The Eu- tives. The Chinese Ministry of Ecology and Environment classifies MPs
ropean Union has adopted a proactive approach by enacting measures as in cosmetics as high-risk, and further restrictions were detailed in a 2020
part of the European Green Deal to limit the use of intentionally added notice by the National Development and Reform Commission (Halfar
MPs in products like cosmetics, detergents, and fertilizers (Kentin & et al., 2021). In South Africa, legislation from 2002 aimed to reduce
Kaarto, 2018). Despite the fact that there is no comprehensive interna- plastic bag use through bans and levies but had limited success due to
tional regulation banning the production and use of MPs, especially in consumer adaptation. European countries, such as Portugal, experi-
the pharmaceutical industry and personal care product sector, some enced a notable decline in plastic bag usage following the introduction
nations have banned the production and use of microbeads, including of a plastic bag tax in Mackuak et al., 2015 (European Commission,
the United States, the United Kingdom, and Canada (Anagnosti et al., 2020). Conversely, South Africa’s government enacted legislation in
2021; Prata, 2018). The functioning of policies and regulations, along 2002 regulating disposable polythene shopping bags, which included a
with strategies on MPs employed by various international and regional complete ban on bags <30 μM thick and a levy on those exceeding 30 μM
organizations and their effective implementation over the years, is (Dikgang et al., 2012). This strategy, however, did not achieve a
illustrated in Fig. 3. Additionally, the United States has enacted the reduction in plastic bag demand. The failure was largely due to con-
Microbead-Free Waters Act, which prohibits the use of plastic sumer acceptance of the low levy, which led to a steady increase in
microbeads in rinse-off personal care products. Countries like Canada demand, indicating that plastic littering remains a significant issue in
and Australia are adopting comprehensive policies to monitor and South Africa’s litter stream. Conversely, in countries like Switzerland,
reduce MP emissions from industrial processes and consumer goods Germany, Sweden, Norway, the Netherlands, and Spain, supermarkets
(Xanthos and Walker, 2017). These legislations aim to mitigate the enforce charges for plastic bag usage. In Portugal, the introduction of a

Fig. 3. Policies and regulations with their functioning on microplastics by various international and regional organizations.

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A. Kumar et al. Science of the Total Environment 957 (2024) 177150

plastic bag tax in Mackuak et al., 2015 led to a 74 % decrease in their frameworks.
use. The public widely accepted this measure, and major retail outlets
began providing reusable plastic bag alternatives, contributing to a 3. Mechanistic approach for mitigating MPs using AOPs
significant reduction in plastic bag usage (Desalegn et al., 2022). Or-
ganizations such as Greenpeace and Beat the Microbead have been Numerous studies have demonstrated the remarkable efficacy of
instrumental in this change by pinpointing products with microbeads AOPs, achieving MP removal rates of 50 % to 99 % for persistent con-
and pushing for their prohibition. These NGOs’ efforts have influenced taminants (Hu et al., 2022; Miao et al., 2020; Nabi et al., 2020; Piazza
government policies, leading to the implementation of microbead bans et al., 2022). Several AOP technologies have been developed for con-
in numerous countries (Geyer et al., 2017). The mixed results of these taminants degradation from wastewater, including UV irradiation,
legislations highlight both achievements and areas needing improve- photocatalysts, ozone, Fenton reactions, and sono-chemical and elec-
ment, providing valuable insights for developing more effective policy trochemical oxidation processes, as shown in Fig. 4a. These

Fig. 4. (a) Representation of comprehensive diagram classification of various AOPs that may be applied to MP degradation, (b) Illustrates the generation of ROS by
different AOPs and their role in the surface degradation mechanism of MPs.

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methodologies trigger the formation of highly reactive oxygen species

(ROS; SO•- •− 1 TiO2 + hv→TiO2 (e− + h+ VB ) (2)
4 , O2 , O2, OH), capable of breaking down MPs into less
• CB

harmful byproducts (Shen et al., 2022a). Common oxidizing agents used

in AOPs include hydrogen peroxide (H₂O₂), ozone (O₃), persulfate h+ VB + H2 O→• OH + H+ (3)
(S₂O₈2− ), and peroxymonosulfate (HSO₅− ). Various combinations of
e− CB + O2 →O•−2 (4)
these methods can be applied depending on the type and quantity of MP
contaminants present in the wastewater. Energy sources such as UV
O•−2 + H2 O→• OOH + OH− (5)
light, ultrasonic waves, or electrical energy can be used to initiate or
enhance the production of ROS species. Techniques like photocatalysis, 2• OOH→H2 O2 + O2 (6)
Fenton reactions, and ozonation leverage these radicals to break down
complex polymer structures. By employing AOPs, the persistence of MPs H2 O2 →2• OH (7)
in water can be significantly reduced, thereby mitigating their ecological
and health impacts (Dos Santos et al., 2023). Typically, AOPs involve The major advantage of photocatalytic degradation of MPs is that the
two key steps: firstly, the generation of potent oxidant, followed by their exposure to ultraviolet (UV) and visible light drives the reaction using
interaction with MPs in aqueous environments, as illustrated in Eq. (1). clean energy, resulting in minimal environmental impact and the pro-
duction of non-toxic byproducts. Reactive species generated can interact

MPs + AOPs SO•4- • OH →Intermediates

( / ) Mineralization
→ CO2 + H2 O + Inorganic ions (1)

with water (H₂O) or hydroxide ions (OH− ) to form ROS such as hydroxyl
radicals (•OH) and superoxide anions (O₂•− ) according to Eqs. (3)–(7).
Eq. (1) represents the general mechanism of AOPs in the degradation These ROS aggressively attack on MPs, leading to polymeric chain
of MPs. It illustrates how potent reactive oxygen species (ROS), such as rupture, branching, crosslinking, and even mineralization into carbon
hydroxyl radicals (•OH), sulfate radicals (SO•−4 ), and superoxide radicals dioxide (CO₂) and water (H₂O) (Uheida et al., 2021). Understanding
2 ), interact with MPs. These radicals, characterized by high redox
(O•− natural photolysis is essential before delving into photocatalytic pro-
potentials, attack the polymer chains of MPs, leading to the breakdown cesses, as photo-initiated degradation of plastic’s carbon‑carbon (C–C)
and fragmentation of their structures into smaller and more degradable backbone follows three main steps: initiation, propagation, and termi-
components. This process ultimately results in the partial mineralization nation, as depicted in Fig. 5a (Nabi et al., 2020). The initiation stage
of MPs into harmless end products like water (H2O) and carbon dioxide involves the breaking of the C–H bond and generation of free radicals,
(CO2) (Shen et al., 2022a). which react with oxygen in the propagation stage to produce R•, and
The primary radical species generated in these processes include ROO•, leading to autoxidation and ultimately chain scission or cross-
hydroxyl radicals (•OH), sulfate radicals (SO•- 4 ), and superoxide radicals linking. Finally, the chain reaction will end when two radicals combine
(O•−
2 ), all characterized by their significant redox potential (Dos Santos and form inert products (Hu et al., 2021). Author Li et al., explored the
et al., 2023; Kang et al., 2019). These radicals continuously engage with photocatalytic mechanism for MPs removal using novel photocatalyst Z-
MPs, leading to the breakdown and fragmentation of their polymer scheme structured BiVO4-Ag2O@g-C3N4 and activated with perox-
chains. As shown in Fig. 4b, the observable effects on MPs include ymonosulfate (PMS). The schematic mechanism of BiVO4-Ag2O@g-
reduction in size, increased brittleness, formation of cracks, and even- C3N4/PMS/visible light system generating the ROS species as shown in
tual fragmentation. The degradation manifests visibly in several ways: Fig. 5a. To augment the active sites (BiVO4/Ag2O), surface modification
the surface of the MPs becomes less smooth and more worn, indicating a becomes imperative for effective peroxymonosulfate (PMS) activation.
diminished appearance; the material itself becomes more brittle, losing Combining the photocatalysis (BiVO4-Ag2O@g-C3N4/PMS/visible light)
its flexibility and becoming prone to breaking under stress; cracks begin with PMS activation is recognized as a promising approach for elimi-
to form on the surface, further weakening the structure; and finally, the nating MPs (Li et al., 2023). Recently, a study conducted by Du et al. (Du
MPs fragment into even smaller pieces. These fragmentation is a critical et al., 2023), the photolysis of MPs under UV irradiation has been found
step in the breakdown of MPs, as it increases the surface area exposed to to notably accelerate their aging and fragmentation. This process tran-
environmental factors, potentially accelerating further degradation sitions MPs from larger particle sizes up to 40 μm sizes in the following
(Shen et al., 2022a). The eventual outcome of this process is the order of effectiveness: UV/O3 > UV/H2O2 > UV, at specific conditions i.
mineralization of MPs into H2O and CO2, facilitated by the penetration e., UV intensity 0.133 mW/cm2 and 2.0 mg/L of H2O2 or O3 concen-
and activity of these reactive oxygen species within the plastic polymer tration. Another study by (Easton et al., 2023), treated the polyester
matrix (Ebrahimbabaie et al., 2022). Each of AOPs strategies offers fiber debris (16.7 mg/L) from laundry wastewater and obtained the
unique mechanisms and efficiencies, contributing to a comprehensive maximum %wt. loss of MPs around 52.7 %, and carbon index (C.I.) 6.75,
approach to mitigating MP pollution (Ricardo et al., 2021). Different under the operating conditions i.e., 0.8 g/L H2O2 dose, 129 J/cm2 UV
strategies of MPs degradation are described in the following sections. intensity, and time 5 h. Furthermore, a sustainable green photocatalysis
strategy for the removal of polypropylene (PP) (≤5 μm size, and ~ 104
3.1. Photodegradation/photocatalytic degradation of MPs particles/L) removal in wastewater was proposed using ZnO nano-rods.
In this strategies, after two weeks of irradiation, it was observed that the
Photocatalytic degradation of MPs utilizes semiconductor photo- average volume of PP MPs decreased significantly by 65 %, and
catalysts activated by suitable light sources such as ultraviolet (UV) or achieving a carbon index of 40. This reduction occurred under specific
visible light. This process excites electrons in the photocatalyst, causing operational conditions, namely a flow rate of 300 mL/min, UV power of
them to move from the valence band to the conduction band, thereby 120 W, wavelength of 354 nm, and UV intensity of 60 mW/cm2 (Uheida
generating holes (h+) in valance band and excited electrons (e− ) in et al., 2021). Similarly, Jiang et al. successfully treated MPs by utilizing
conduction band, as illustrated in Eq. (2) (Ariza-Tarazona et al., 2019). a novel hydroxy-rich ultrathin BiOCl photocatalyst (BiOCl-X). According
to their study, photocatalysts BiOCl-X (X = 0.5, 1, 1.5, 2) showed 24

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A. Kumar et al. Science of the Total Environment 957 (2024) 177150

Fig. 5. (a) Mechanism of photocatalytic degradation of MPs and generation of ROS using a Z-Scheme BiVO4-Ag2O@g-C3N4 heterojunction photocatalyst, and (b)
Generation of ROS in sulfate radical-based advanced oxidation processes (SR-AOPs) for the scission of polymer chains.

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times higher MPs (1 mm size, and concentration 10 g/L) removal exposure to twenty times the irradiation dose (3600 mJcm− 2) led to
compared to pure BiOCl under 0.5 g/L photocatalyst dose, 250 W UV significant changes in surface morphology, chemical properties, and
power, λ >420 nm, pH 3 and time 5 h (Jiang et al., 2021). Furthermore, hydrophobicity. Notably, PS, PVC, and PET exhibited visible morpho-
recent research explored the photocatalytic degradation of high-density logical alterations such as cracks, wrinkles, and protuberances, whereas
polyethylene (HDPE) using a C,N-TiO2 photocatalyst, providing a PE demonstrated relative resistance to these changes (Lin et al., 2020).
comprehensive analysis of the polyethylene degradation (Ariza-Tar- In recent years, there has been significant interest in Bi-based and Ag-
azona et al., 2019; Golmohammadi et al., 2023). In addition, Golmo- based photocatalysts for their potential in visible-light photocatalysis
hammadi et al., explored the HDPE degradation pathways as due to availability of abundant source of light such as solar make it
demonstrated in Fig. 8. Photocatalytic generated hydroxyl radicals energy efficient process (Chen et al., 2019).
initiate the breakdown of weak polymer chains, leading to the formation Photocatalytic degradation of MPs presents several limitations that
of polyethylene alkyl radicals, as illustrated in Eq. (a). Subsequently, hinder its effectiveness as a large-scale solution for environmental
these alkyl radicals further oxidized to form a peroxy radical via Eq. (b) remediation. First, the efficiency of the process is highly dependent on
which then abstracts a hydrogen atom from another polyethylene chain, the photocatalyst material, with many showing limited activity under
resulting in a hydroperoxide species, as depicted in Eq. (c). Moreover, visible light, necessitating the use of UV light, which is less sustainable
hydroperoxide’s O–O bonds break, causing chain scission and gener- and cost-effective. Additionally, the degradation process can be slow
ating two free radicals, oxy and hydroxyl radicals, as described in Eq. and incomplete, leading to the formation of smaller MP fragments rather
(d). These highly reactive free radicals are essential for the ongoing than complete mineralization. The presence of natural organic matter
degradation process of polyethylene. These radicals further abstract (NOM) and other environmental factors, such as pH and ionic strength,
unstable hydrogen atoms from other polymer chains, as represented in can also interfere with the photocatalytic process, reducing its effec-
Eqs. (a) and (e). Finally, Eq. (f) shows the equilibrium ratio between tiveness. Moreover, the recovery and reuse of photocatalysts from
peroxy radicals and hydroperoxide. Similarly, authors Cao et al., syn- treated water can be challenging, and the potential release of toxic
thesized the MXene/ZnxCd1-xS photocatalysts and applied to poly- byproducts during degradation poses environmental and health risks
ethylene terephthalate (PET, 3 g/L) removal and simultaneous H2 that need to be thoroughly assessed.
production (14.17 mmol g− 1 h− 1) under visible light. The process ulti-
mately oxidizes PET bottles into organic micromolecules, including 3.1.1. Mechanistic insight of MPs conversion into value added products by
glycolate, acetate, and methanol. This research highlights an excellent photocatalytic activation
method for concurrent hydrogen production and degradation of PET A study by Qin et al. examined the detailed mechanisms involved in
MPs (Cao et al., 2022). Authors Acuna-Bedoya et al., boosted the visible- the conversion of polyvinyl chloride (PVC) MPs into value-added
light photocatalytic degradation of polystyrene (≤1 μm size, 9 mg/mL) products and suggested possible pathways for conversion of PVC.
nanoplastics with immobilized Cu2O/CuO photocatalyst by anodization. Their work focused on the catalytic conversion of PVC to acetic acid by
The maximum removal of polystyrene was observed 23 % within 50 h using CDs/Zr-MOF, as illustrated in (Fig. 7a-b) (Qin et al., 2022, 2024).
under optimum operating condition (i.e., 50 W UV power, λ 400–800 Initially, the generated •OH radicals attacked the PVC polymer and
nm, 5.3 mW/cm2 UV intensity, pH 7, temp 30 ◦ C, and 50 mL reactor broke down the polymer chain, leading to the formation of key in-
volume) (Acuña-Bedoya et al., 2021). Similarly, degradation of primary termediates, − (•CHCH2•CHCH2)n-. Under the influence of CDs/Zr-MOF
polystyrene nanoplastics (≤1 μm size, 0.9 % w/v of PS in 50 mL) by catalyst, these intermediates can further react with O2, overcoming a
photocatalysis under UV light irradiation using three different anodized low energy barrier (ΔG = − 0.13 eV), to form peroxide radicals, repre-
TiO2 structures obtained the maximum removal of PS 23.5 %, and sented as -(CH(OO•)-CH2-•CH-CH2)n-. In this process, O2 is crucial for
highest carbonyl index 0.088 under operating conditions (i.e., UV power the initial activation of PVC. Upon exposure to CDs/Zr-MOF photo-
50 W, λ 400–800 nm, UV intensity 0.021 mW/cm2, pH 7, time 50 h, and catalysis, peroxide radicals -(CH(OO•)-CH2-•CH-CH2)n- transform into
temperature 30 ◦ C) (González et al., 2020). Authors Allé et al. explored -(CH(OOH)-CH2-CH(OH)-CH2)n- via sequential hydroxylation and pro-
the degradation of polystyrene and polymethylmethacrylate (PMMA) tonation. This transformation is thermodynamically favorable, releasing
using TiO2–25/β-SiC photocatalyst under UV-A irradiation. Under the 44.9 kcal mol− 1 when compared to PVC. The produced -(CH(OOH)-CH2-
optimum operating conditions (112 W/m2 UV-A dose, 6.3 pH and 10 CH(OH)-CH2)n- acts as a reactive intermediate, promoting further C–C
mL/min of flow rate) the maximum carbon removal in PMMA was 50 %. bond cleavage, a process that has been previously documented in the
Interestingly, in their study, 140-nm polystyrene nanoparticles observed literature. Under the CDs/Zr-MOF catalysis, intermediate -(CH(OOH)-
to degrade more rapidly than 508-nm polystyrene nanoparticles (Allé CH2-CH(OH)-CH2)n- was irreversibly converted into oxygen centered
et al., 2021). Venkataramana et al., have employed photocatalytic free radical -(CH(O•)-CH2-CH(O•)-CH2)n-. This radical intermediate is
degradation of polyethylene plastics sheet (3 × 3 cm) by NiAl2O4 prone to β-scission, resulting in C–C bond cleavage. Subsequently, the
spinels-synthesis and obtained the maximum removal of PP 12.5 % with intermediates compounds –CH(O•)-CH2-CHO, (•CH2)-CHO, and O–
rate constant (k) 3.51 × 104 min− 1 under the optimum operating con- –CHOH-CH2• are formed through the C–C bond cleavage via hydrox-
ditions (i.e., UV power 350 W, λ 354 nm, UV intensity 60 mW/cm2, and ylation and protonation reactions, ultimately yielding acetic acid mol-
irradiation time 5 h) (Venkataramana et al., 2021). Another study by ecules. A streamlined process for upcycling of PVC in the CDs/Zr-MOF
(Nabi et al., 2020) investigated the photocatalytic degradation of poly- photocatalytic reaction system is illustrated in Fig. 7c. Initially, the
ethylene and polystyrene using a TiO2 nanoparticle film under the active radicals generated by CDs/Zr-MOF preferentially break the C–Cl
exposure of UV light. Their findings showed that the PE was fully bonds. This de-chlorination reaction speeds up the cleavage of the PVC
degraded within 36 h, while PS achieved a mineralization efficiency of carbon chain by reducing its stability. Subsequently, with the combined
up to 98.4 % in just 12 h. It was found that the enhanced surface hy- influence of CDs and Zr-MOF, the long-chain polymer undergoes
drophilicity improved interactions between the TiO2 films and MPs, and oxidation, forming organic fragments enriched with oxygen-containing
the nanoparticles improved the film’s texture, facilitating charge groups like CH(O), O–H, CH(OOH), O– and –C. This gradual process
transfer and separation which resulted in the rapid breakdown of the leads to the breakdown of PVC carbon chains. Ultimately, these organic
MPs (Nabi et al., 2020). The degradation process was evidenced by the fragments, (•CH2)-CHO, CH(OOH), − (CH(O•)-CH2-CHO, and O–
formation of carbonyl, hydroxyl, and hydrocarbon groups, with CO2 –CHOH-CH2•), are transformed into valuable chemicals. Similarly, au-
being the final degradation product. The surface modifications of MPs thors (Qin et al., 2022) focused on the mechanistic pathways of photo-
with sizes ranging from 150 to 300 nm, including PS, PE, PVC, and PET catalytic conversion of polyethylene glycol (PEG) as illustrated in
were assessed under the exposure of UV-C irradiation at 254 nm and Fig. 7e. The photocatalytic process of PEG involved a type-II hetero-
vacuum ultraviolet (VUV) irradiation at 185/254 nm. Extensive junction mechanism facilitated by Ag2O/Fe-MOF. When exposed to

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A. Kumar et al. Science of the Total Environment 957 (2024) 177150

solar irradiation, electrons from Ag2O migrated to the conduction band generated ROSs in improving NPs degradation in water environments.
(CB) of Fe-MOF, contributing to the production of O•− 2 and H2. Concur- Similarly, (Elkhatib et al., 2021) conducted a study to evaluate the
rently, the holes from the valence band (VB) of Fe-MOF transferred to effectiveness of electrocoagulation methods in removing MPs from
the VB of Ag2O, which facilitated the production of •OH. The alignments synthetic solutions and wastewater samples. They optimize the oper-
of band in the photocatalyst Ag2O/Fe-MOF are illustrated in Fig. 7d. ating parameters for polyester MPs removal under the operating pa-
Moreover, the built-in electric field established at the junction between rameters included current density (1.92 to 8.07 mA/cm2), pH (2–7), MP
Ag2O and Fe-MOF enhances the efficiency of separating electron-hole size (25–1500 μm), and electrolysis duration (up to 90 min). The highest
pairs. These radicals are subsequently employed to effectively degrade removal of polyester MPs was noticed around 99 % under the pH 4, and
MPs and break down into shorter-chain organic compounds through current densities of 2.88 mA/cm2. In addition, for real wastewater
radical reactions. Due to the complex structure of plastics, the process of samples, MP removal efficiency was observed as 96.5 %, alongside
cascade photocatalysis, which includes activating C–C bonds and removal rates of 92.2 % for COD and 88.8 % for thermos tolerant coli-
modifying macromolecules. form colonies.
Electrochemical oxidation of MPs faces several limitations. The
3.2. Electrochemical oxidation of MPs process can be energy-intensive, leading to high operational costs.
Selectivity is another challenge, as it may generate harmful byproducts,
Electrochemical oxidation (EO) represents a highly promising such as toxic chlorinated compounds, depending on the water matrix.
approach for eliminating MPs from diverse environments, especially Additionally, electrode fouling, especially in complex wastewater, can
water bodies (Kiendrebeogo et al., 2022). This technique harnesses reduce the efficiency and lifespan of the electrodes. The scalability of the
electrical energy to induce oxidation reactions on an electrode’s surface, technology is still under exploration, and the long-term environmental
effectively breaking down MP pollutants. The process involves the impacts of the degradation products remain uncertain.
generation of hydroxyl radicals at the anode, continuously facilitating
the oxidative degradation of MPs into smaller fragments and their
mineralization (Kiendrebeogo et al., 2022; Shivaswamy et al., 2023). 3.3. Fenton oxidation of MPs
Recent studies have explored the electrochemical oxidation of MPs/NPs,
illustrating a typical oxidation pathway as depicted in Fig. 9a. Through The Fenton process represents an advanced oxidation technique
this mechanism, electrochemical oxidation offers a viable route to involving the catalytic decomposition of H2O2 to produce •OH radicals
degrade persistent plastic pollutants into less harmful substances, in the presence of ferrous ions (Fe2+) under acidic conditions, where
contributing to environmental remediation efforts. Fig. 9b illustrates the Fe2+/H2O2 known as Fenton reagent. According to (Hu et al., 2022), the
generation of hydroxyl radicals (•OH) through electrochemical oxida- ideal pH for the Fenton reaction is in between 2.5 and 3.0. To circum-
tion with a BDD anode. In this process, one of the main pathways for •OH vent the constraints associated with the Fenton process, particularly its
formation involves the 2-electron reduction of O2 at the cathode, where reliance on H2O2, an alternative approach utilizing electrons as the
H2O2 acts as an intermediate. Besides ROSs (SO•- 4 and OH) produced at
• primary reactant has emerged which is termed as electric-Fenton pro-
the BDD anode, OH originating from O2 reduction at the cathode and
• cess. An illustration of this process has been shown in Fig. 4a. In this
SO•-4 radical produced through direct or indirect reactions involving technique, H2O2 is produced on-site via the electrochemical reduction of
locally produced H2O2, also play a crucial role in breaking down MPs oxygen (O2) at the cathode, with continuously regenerated Fe2+ ions
and nano-plastics. The effectiveness of the electro-oxidation process being provided to facilitate the formation of •OH radicals (Eq. (8)).
depends on parameters such as current density, electrode material Another enhancement involves exposure of UV irradiation to accelerate
composition, electrolyte characteristics, and the properties specific to the Fenton process (Eq. (9)) (Ricardo et al., 2021; Shen et al., 2022a).
the MPs being treated (Chen et al., 2022). In a recent investigation
Fe2+ + H2 O2 →Fe3+ + OH− +• OH (8)
(Shivaswamy et al., 2023), the removal of MPs, specifically LDPE sheet
particles of 25 μm thickness, from rainfall runoff water (RRW)
Fe(OH)2+ + Hν→Fe2+ +• OH (9)
contaminated with MPs in agricultural areas was examined using an
innovative electrochemical coagulation (ECC) treatment method. The Authors Hu et al. developed a hydrothermal coupled Fenton system
results from their study showed that after 45 min of electrolysis, the ECC to break down the polymer chains of ultrahigh density polyethylene
technology achieved significant removal efficiencies: 98 %, 46 %, 48 %, (UHPE). This approach achieved the highest UHPE 95.9 % weight loss
and 48 %, for MPs, COD, chloride, and TDS removal, respectively. In within 16 h and 75.6 % mineralization efficiency in 12 h. The high ef-
another study on electro-coagulation (EC) conducted by (Shen et al., ficacy of this method is attributed to the synergistic effects of hydro-
2022b), the researchers thoroughly examined various wastewater thermal hydrolysis, a proton-rich environment, and the substantial
properties affecting MP removal efficiency. The results demonstrated production of hydroxyl radicals. Additionally, this system shows sig-
that aluminum anodes outperformed iron anodes in removing MPs, nificant potential for remediating various petroleum-based plastics and
consistently achieving removal rates above 80 % across all experiments. retains its effectiveness in real-world aquatic environments (Hu et al.,
Notably, MP removal rates exceeded 82 % over the pH range of 3 to 10. 2022, 2023a). Authors Miao et al., (Miao et al., 2020) developed a
Specifically, the maximum removal rate for PE, PMMA, CA and PP were heterogeneous electro-Fenton composite system comprising a TiO2 and
93.2 %, 91.7 %, 98.2 % and 98.4 %, respectively at pH 7.2, underscoring graphite cathode to effectively degrade PVC MPs in aqueous environ-
the efficacy of electrocoagulation using aluminum anode. Authors ments. Through a combined mechanism involving •OH oxidation and
(Kiendrebeogo et al., 2022) examined the electrochemical oxidation cathodic reduction, the composite system demonstrated notable per-
(EO) of nanoplastics, focusing on the roles of ROSs in both EO and formance, achieving a 56 % reduction in PVC MPs %wt. loss and a 75 %
electro-peroxidation (EO-H2O2) processes in water. They used boron- de-chlorination effect within 6 h of reaction time. The schematic illus-
doped diamond (BDD) as the anode to generate •OH, persulfates tration in Fig. 9c illustrates the proposed mechanism for PVC degrada-
(S2O2−8 ), and (H2O2) in situ, with titanium and carbon felt functioning as tion using the above process. This involves two primary degradation
cathodes in the EO and EO-H2O2 processes, respectively. The maximum pathways for PVC MPs: concurrent cathodic reduction dechlorination
degradation of NPs was noticed as 86.8 % under the optimum operating and oxidation by hydroxyl radicals. Initially, the PVC MPs receive
conditions (current density 36 mA⋅cm− 2, pH 2, reaction time 40 min, electrons directly from the TiO2/C cathode, which leads to cathodic
and 0.03 M Na2SO4). An economic assessment revealed an operating reduction under heating conditions, thereby triggering dechlorination.
cost of $2.3 per cubic meter, roughly one-tenth of the cost associated Simultaneously, oxidation by •OH radicals takes place, resulting in the
with the EO process. This study highlights the effectiveness of in situ creation of oxy-organics with oxygen functional groups such as C– –O

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A. Kumar et al. Science of the Total Environment 957 (2024) 177150

and OH. This leads to the release of organic intermediates into the so- fully degrade certain MPs, leading to partial breakdown and potential
lution. Among these intermediates, the exfoliated hydrocarbon species formation of toxic byproducts, limiting its overall effectiveness for MP
are especially prone to degradation (Kang et al., 2019). These species are removal.
subsequently oxidized by hydroxyl radicals into smaller, low molecular
weight fragments, such as alcohols, esters and carboxylic acids. Even- 3.4. Sulfate radicals based advanced oxidation process for MPs
tually, these fragments are partially mineralized into CO2 and H2O
(Miao et al., 2020). Authors Luca et al., (Di Luca et al., 2023) explored Sulfate radicals based advanced oxidation process (SR-AOPs) have
the degradation of polystyrene nanoparticles using the photo-Fenton emerged as a promising method due to their high efficiency and ability
(UV/H2O2/Fe3+) system under the exposure of broad range of UV irra- to mineralize MPs into harmless byproducts. The reaction mechanism
1
diation (250–600 nm). The complete degradation of PS nanoparticles involves generation of ROS species (SO•- 4 , O2 , O2, OH), typically
•− •

(140 nm size) was noticed under the optimum operating conditions (i.e., through the activation of persulfate or peroxymonosulfate, which then
1 mg/L Fe3+ dose, 130 mg/L H2O2 dose, pH0 3, temp 25 ◦ C, time 40 min, react with MPs, leading to the cleavage of polymer chains and subse-
and 20 mg/L PS dose). The higher efficiency of this process was largely quent degradation as detailed mechanism depicted in Fig. 5b. This
attributed to the wavelength and light intensity of the UV lamp used. process proceeds via various pathways, including oxidative scission of
Furthermore, authors Mackuak et al., (Mackuak et al., 2015) explored polymer backbones, hydroxylation of polymer chains, and formation of
the degradation of PVC using a combination of the Fenton reaction and reactive intermediates such as carbonyl groups. Furthermore, the role of
biological decomposition. In the initial phase, the Fenton reaction co-reactants and reaction conditions in enhancing the efficiency of SR-
degraded the PVC, resulting in the formation of intermediate com- AOPs is elucidated. Understanding these intricate details of the reac-
pounds such as ethylbenzene, benzene, o-xylene, cis and tans 1,2- tion mechanism is crucial for optimizing SR-AOPs and developing
dichloroethene, tri and tetra chloroethene. The resulting mixture from effective strategies for mitigating MP pollution in aquatic environments.
this process was then utilized as a substrate for anaerobic biogas pro- There is however, limited research on the SR-AOPs for the degradation
duction in the second phase. The biological degradation system ach- of MPs, so far. In a recent study by Dai et al., (Dai et al., 2024) focusing
ieved 67.3 % of COD reduction, 60 % of trans and 70 % of cis, 1,2- on the degradation efficiency and mechanism of PE degradation using
dichlorethylene and completely removed the benzene, ethylbenzene, the S-nZVI@ATP activated by persulfate oxidant. The study investigated
and o-xylene. Authors Ortiz et al., (Ortiz et al., 2022) investigated how a new catalyst, S-nZVI@ATP (sulfidized nanoscale zero-valent iron
MPs (MPs) behave when subjected to Fenton oxidation. They utilized supported on attapulgate), which are specifically designed to activate
MPs ranging in size from 150 to 250 μm, derived from five common persulfate. The results from their study noted that over a 24-h period,
polymer types (PE, PET, PP, PVC, and EPS) by cryogenically milling there was a significant reduction in the average size of PE particles from
commercial plastic products. The experiments were conducted under 64.2 μm to 28.1 μm due to persulfate oxidation of PE. This degradation
rigorous conditions: 80 ◦ C reaction temperature, pH0 3, initial [H₂O₂]0 process led to the transformation of PE into smaller molecular compo-
concentration 1000 mg/L, and initial [Fe3+]0 concentration 10 mg/L. nents such as alcohols, ketones, alkanes, alkenes, and carboxylic acids.
Despite the characteristics of the MPs, only minor weight reductions The continuous supply of Fe2+ by S-nZVI@ATP facilitated the activation
•− 1
(~10 %) were noted following Fenton oxidation. Nevertheless, smaller of persulfate, generating potent oxidants including SO•- 4 , O2 , O2, OH,
•

particle sizes exhibited notably enhanced oxidation efficiency due to with SO•-4 predominantly driving the oxidation process. Another study
their greater surface area, achieving weight losses of up to 20 % with by Liu et al., (Liu et al., 2022) explored the degradation of nylon 6 and
EPS MPs sized between 20 and 50 μm. Furthermore, it was noted that the polystyrene MPs using oxidants PMS and Fe2+ Fenton-based AOPs. The
MPs gradually diminished in size and could be entirely oxidized into research aimed to elucidate the degradation mechanisms of PA6 and PS.
CO2, as demonstrated by the oxidation of PS nanoplastics (size 140 nm), Results indicated significant mass losses after 4th treatment cycles, with
which achieved 70 % mineralization. A study by Xing et al., (Xing et al., nylon 6 and polystyrene showing reductions of 25.6 % and 22.1 %,
2023) explored the enhancement of MP degradation during sludge respectively. Analytical techniques including Raman scattering and
composting using a microbially-driven Fenton reaction. The study GC–MS analysis identified various intermediates such as low-molecular-
introduced iron-mineral-supplemented thermophilic composting weight alkanes, aldehydes, alcohols, and carboxylic acids. Similarly, a
(imTC) as a technique to enhance the breakdown of MPs in sludge by study by Luo et al., (Luo et al., 2021), assessed various AOPs for their
increasing the production of •OH radicals. The findings demonstrated efficacy in removing pigment red released from MPs. The AOPs tested
that the removal efficiency of sludge-based MPs reached about 35.93 % included persulfate-based treatments, ozonation, and Fenton reactions.
after 36 days of imTC treatment, representing a 38.99 % improvement The study also investigated changes in the nanoscale surface charac-
compared to conventional thermophilic composting (oTC). The possible teristics of MPs following these treatments. Results indicated that all
de-polymerization pathway of polystyrene MPs through a microbially three AOPs significantly degraded the released pigments from MPs at
driven Fenton reaction was proposed by (Yang et al., 2022). This rates much faster than those at which pigments leached. The dominant
pathway was deduced by analyzing data from ATR-FTIR, XPS, and ROS identified in ozone, Fenton, and heat-activated persulfate systems
GC–MS, as illustrated in Fig. 10. The breaking of normal and weak were O•−2 , OH, and SO4 , respectively. Nano infrared spectroscopy and
• •-

polymer chains resulted in the formation of terminal radicals, which imaging further revealed oxidation of -CH3 and -CH2 bonds on the sur-
then reacted with molecular oxygen to create peroxy radicals. These faces of the treated MPs. Among the treatments, the persulfate system
peroxy radicals formed stable groups on the polymer chains, such as caused the most significant oxidation, followed by ozone and then the
-OH, through hydrogen abstraction. Subsequent reactions, including Fenton system.
recombination and radical addition, transformed -OH into groups like SR-AOPs for MPs degradation faces several limitations. These
COOH and -C=O. As the reaction progressed over time and intensified, include the high cost and limited availability of efficient catalysts, which
various low-molecular weight intermediate compounds, such as 2-iso- can hinder scalability. Additionally, the process may suffer from low
propyl-5-methyl-1-heptanol and nona-hexacontanoic acid, were stability and reusability of catalysts, leading to decreased efficiency over
generated. time. The generation of sulfate radicals often requires specific condi-
Fenton oxidation, while effective in degrading many pollutants, faces tions, such as acidic environments, which might not be suitable for all
limitations in treating MPs. The process requires acidic conditions types of MPs. Furthermore, incomplete mineralization and secondary
(optimal pH around 3), which are not environmentally friendly. Addi- pollution remain concerns.
tionally, the presence of iron ions can lead to secondary pollution, and
the efficiency of Fenton oxidation decreases with complex MP struc-
tures. Furthermore, the process generates hydroxyl radicals that may not

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A. Kumar et al. Science of the Total Environment 957 (2024) 177150

Fig. 6. (a) Mechanism of sonocatalytic bubble growth and explosion for generating ROS to mitigate microplastics, and (b) Proposed pathways for DEHP (plastic
additive di(2-ethylhexyl) phthalate) degradation assisted by ultrasound irradiation (Adapted from open access (Kida et al., 2021).

3.5. Sonochemical oxidation of MPs as depicted in Fig. 6a. The collapse of these microbubbles generates
extreme temperatures (up to 5000 K) and pressures (over 1000 atm) in
Sonochemical oxidation is a promising approach for degrading MPs, their vicinity, resulting in the production of highly reactive radicals such
utilizing ultrasonic waves to create intense localized conditions that as •OH radicals and hydrogen radicals (•H) (Cai et al., 2020; Kumar
break down polymer chains (Bretas Alvim et al., 2021). This process et al., 2023). These radicals play a crucial role in the oxidative degra-
starts with the application of high-frequency sound waves, typically dation of MPs. The hydroxyl radicals, in particular, are potent oxidizing
ranging from 20 kHz to 1 MHz, to an aqueous solution containing MPs. agents that attack the polymer chains of the MPs, breaking them down
The ultrasonic waves induce alternating high and low-pressure cycles into smaller fragments. The mechanism of radical formation and sub-
within the liquid, resulting in the formation, growth, and subsequent sequent degradation involves several steps. Initially, water molecules
implosive collapse of microbubbles: a phenomenon known as cavitation, within the collapsing cavitation bubbles dissociate due to the extreme

12
A. Kumar et al. Science of the Total Environment 957 (2024) 177150

(caption on next page)

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A. Kumar et al. Science of the Total Environment 957 (2024) 177150

Fig. 7. Mechanisms of converting polyvinyl chloride (PVC) into value-added products: (a) Gibbs free energy diagram, (b) Elementary pathways for the photocatalytic
conversion of PVC to acetic acid, (c) Simplified and visualized diagram of photocatalytic upcycling of PVC using CDs/Zr-MOF (Adapted from open access (Qin et al.,
2024), (d) Proposed photocatalytic reaction mechanism on the Ag2O/Fe-MOF system for MPs conversion, (e) Potential photocatalytic conversion pathway of PEG
using the Ag2O/Fe-MOF photocatalyst, (Adapted from open access (Qin et al., 2022).

Fig. 8. PE degradation mechanism using C, N-TiO2 photocatalyst involves hydroxyl radicals initiating the degradation process. The proposed mechanism progresses
through five stages, as detailed in Equations (a–f). Reproduced with permission from the referenced source (Ariza-Tarazona et al., 2019).

conditions, producing hydroxyl and hydrogen radicals via Eq. (10): vibration frequency, 3.97 W/cm2 ultrasound irradiation intensity, and
reaction time of 1 h. During the process, various intermediate com-
H2 O→• OH+• H (10)
pounds such as proto-catechic acid, mono(2-ethylhexyl) phthalate, and
These radicals then diffuse into the surrounding liquid and interact phthalic acid were identified. Based on these intermediates, the re-
with the MPs. The highly reactive •OH radicals attack the carbon‑carbon searchers proposed possible degradation pathways, as illustrated in
bonds in the polymer chains of the MPs, leading to chain scission and Fig. 6b. Zimmermann et al., (Zimmermann et al., 2021) explored the
formation of smaller, less complex molecules. This can be represented by ultrasonic degradation of polystyrene to manipulate its molecular
the reaction Eq. (11): weight and poly-dispersity. Their study focused on the effects of ultra-
sonic degradation under uniform temperature conditions using cyclo-
RH+• OH→R• + H2 O (11)
hexane and toluene as solvents, with gas atmospheres of CO2 and N2,
Here, RH represents a segment of the polymer chain, and R is a •
and varying ultrasonic amplitudes. The results indicated a significant
polymer radical that can further react with oxygen to form various change in the molecular weight and poly-dispersity of polystyrene under
oxidation products. Through continuous exposure to these sono- the N2 atmosphere, whereas the CO2 atmosphere did not produce similar
chemical conditions, MPs can be degraded into progressively smaller effects. A study by Ioannidi and team examined the sonochemical
fragments, ultimately resulting in mineralization or conversion into degradation of dexamethasone (Dex) in the presence of MPs. Using 20
carbon dioxide and water. Despite the extensive use of cavitation kHz ultrasound, 500 μg/L of Dex was efficiently removed from ultrapure
methods in wastewater treatment, their application for MP degradation water, with hydroxyl radicals driving degradation at the gas-liquid
has not been thoroughly studied. There are few case studies specifically interface. Interestingly, the presence of polyethylene and polystyrene
addressing the degradation of MPs through cavitation techniques, and microplastics slightly enhanced the degradation of Dex, though ultra-
only a limited amount of literature has been explored in this area. For sound exposure had minimal impact on the microplastics’ surfaces. This
instance, Yang et al., (Yang et al., 2024a, 2024b) recently employed a suggests a potential interaction between microplastics and sonochem-
sonocatalytic technique using ultrasound irradiation to treat MPs and ical processes that may influence pollutant breakdown, highlighting a
dye, utilizing Ti-based MOFs supported on Ti3C2 MXene. The resulting possible synergy in the treatment of contaminants in water containing
composite had a lower specific surface area compared to MIL-125(Ti) microplastics (Ioannidi et al., 2023). Another study investigated the
but retained a high porous structure. The presence of O-Ti-O species sonocatalytic degradation of MPs using Ti-based metal-organic frame-
and graphitic carbon enhanced its photosensitivity and catalytic activ- works (Ti-MOFs). The MX@MIL-125(Ti) composite showed enhanced
ity. Remarkably, the MX@MIL-125(Ti) showed excellent catalytic effi- catalytic activity due to its photosensitive properties and the presence of
ciency under ultrasound irradiation, achieving over 90 % removal of O-Ti-O species and graphitic carbon. Under ultrasound irradiation, the
Rhodamine B dye in 1 h and >75.0 % removal of micro-polyethylene composite effectively degraded over 75 % of micro PE within 4 h,
within 4 h. A study conducted by Kida et al., (Kida et al., 2021) inves- following pseudo-first-order kinetics. The sonocatalytic process was
tigated the effective degradation of plastic additive di(2-ethylhexyl) more efficient than adsorption, demonstrating the potential of Ti-MOFs
phthalate (DEHP) employing the ultrasound irradiation techniques. combined with ultrasound for the removal of MPs, providing a green and
The results indicated that the maximum average degradation efficiency sustainable approach to pollution treatment (Yang et al., 2024a, 2024b).
of DEHP was noticed 70.74 % under the operating conditions of 20 kHz Sonochemical oxidation for MP degradation faces several

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A. Kumar et al. Science of the Total Environment 957 (2024) 177150

Fig. 9. Schematic diagram of MPs/NPs degradation by (a) Electrochemical oxidation, (b) Electrooxidation-H2O2 process, using BDD anode, and (c) Illustration of the
electro-Fenton-like process for PVC MPs degradation, Reproduced with permission from Ref. (Chen et al., 2022).

limitations. The process requires specific ultrasonic frequencies and in- pollutants. Ongoing research continues to improve the efficiency and
tensities to generate sufficient hydroxyl radicals, which can be chal- feasibility of ozonation for large-scale water treatment applications. A
lenging to control and optimize. Its efficiency is often hindered by the recent study by Hu et al., (Hu et al., 2023b) explored the degradation of
low solubility of MPs in water and the potential for incomplete degra- PE MPs using ozonation combined with hydrogen peroxide (O3/H2O2).
dation. Additionally, the process may produce toxic byproducts and has The percentage of PE degradation was higher at lower concentrations,
limited scalability for large-scale applications. High energy consumption with a maximum weight loss of 32.56 % observed at a PE concentration
and cost also restrict its practical implementation. Furthermore, there is of 0.05 g/L following 8 h of ozonation. The partial mineralization of PE
very limited literature available on this technique, complicating its MPs was evident from the increase in inorganic carbon (IC) over time,
development and application. following a zero-order kinetic model in both ozonation systems.
Notably, the addition of 20 mM H2O2 significantly enhanced the
mineralization process, as indicated by a slope of IC versus ozonation
3.6. Ozonation oxidation time that was 3.25 compared to 2.20 without H2O2, confirming that
hydrogen peroxide facilitated the degradation. A recent study by Solís-
Ozonation presents a viable option for the removal of MPs from Balbín et al., (Solís-Balbín et al., 2023) employed a hybrid method that
water, leveraging its strong oxidative properties to degrade these

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A. Kumar et al. Science of the Total Environment 957 (2024) 177150

Fig. 10. The suggested degradation pathway of polystyrene microplastics (PS-MP) through the microbial Fenton reaction facilitated by the S. putrefaciens strain 200,
reproduced with permission from Ref. (Yang et al., 2022).

combined wet oxidation and ozonation to remove MPs from water ob- molecular %wt. loss of 99.9 % and mineralization efficacy of poly-
tained from a wastewater treatment plant (WWTP). The research ach- styrene 42.7 % within 240 min. In contrast, chlorination achieved much
ieved significant MP removal rates after 5 h of treatment: 86.3 ± 1.7 % lower levels of molecular weight degradation (7.1 %) and mineraliza-
through wet oxidation and 45.2 ± 1.3 % through ozonation. Addition- tion (4.3 %). The majority of molecular weight degradation occurred
ally, substituting O2 with N2 in the wet oxidation setup resulted in a rapidly within the first 30 min, with 96.3 % degradation observed for
lower MP removal efficiency of 5.5 ± 2.0 %, while replacing ozone with ozonation and 4.2 % for chlorination. Ozonation also led to surface
air yielded a removal efficiency of 43.4 ± 1.1 %. These results high- roughening and decreased particle size of the plastics, along with
lighted that most MP removal during ozonation was attributed to increased hydrophilicity might be caused of introduction of oxygen-
physical entrainment by gas bubbling in an open reactor, whereas in a containing groups on the surface. This facilitated further oxidative
closed reactor, wet oxidation mainly depended on chemical degradation degradation, yielding products like phenol, acetophenone, formic acid,
for MP removal. According to Eitzen et al. (Eitzen et al., 2019), PS un- and hydroquinone. In contrast, chlorination was less effective in altering
dergoes oxidation when exposed to O3 overnight without generating any the surface characteristics of nano-sized polystyrene plastics and pri-
byproducts. Additionally, Loh et al. (Loh et al., 2021) found that the marily caused minor destruction of C–C bonds in the main chain,
combination of O3 and H2O2 boosts the production of free radicals, such resulting in shorter chain polymers. Authors Amelia et al. (Amelia et al.,
as •OH, in natural water more efficiently than O3 by itself. Furthermore, 2021) conducted a study to assess the combined effects of ozonation and
research by Zhang et al. (Zhang et al., 2022) has shown that O3 con- H2O2 on the degradation of polyethylene MPs. The research observed
tributes to the breakdown of polymers. The ozonation process in poly- significant alterations in the MPs’ structure, particularly an increase in
mers leads to the creation of oxygen-containing functional groups and the intensity of O–H and C– –O bands. At pH 12 and a flow rate of 3 L/
shorter polymer chains. This transformation supports the potential use min, the carbonyl index reached 1.33, accompanied by a reduction in
of ozone treatment for aging and mineralization of MPs. Furthermore, C–H group intensity. These changes indicate the initiation of plastic
exposure to ozone has been shown to enhance the surface tension, hy- degradation through the formation of functional groups like hydroxyl
drophilicity, and solubility of polymers such as PE, PP, and PET, sug- (O–H) and carbonyl (C=O), along with modified C–H groups. This
gesting a modification in their environmental behavior, including chemical restructuring may offer a viable approach to accelerate the
adsorption properties post-aging. However, there remains a deficiency breakdown of MPs.
in current research regarding morphological and structural analysis of Ozonation for MP degradation faces several limitations. Its effec-
MPs, which impedes a comprehensive understanding of transformation tiveness is often diminished by the complexity and heterogeneity of MP
mechanisms during ozonation treatments (Eitzen et al., 2019). The materials, which can impede ozone’s ability to penetrate and react
research conducted by Li et al. (Li et al., 2022), investigated how nano- thoroughly. Additionally, ozonation can produce secondary contami-
scale polystyrene plastics break down when exposed to disinfection nants, and the process requires high energy inputs, making it less cost-
methods such as ozonation and chlorination. Ozonation, at recom- effective for large-scale applications. Moreover, the potential forma-
mended disinfection levels, resulted in significant degradation of tion of toxic byproducts during ozonation can pose environmental and

16
A. Kumar et al. Science of the Total Environment 957 (2024) 177150

health risks, complicating the treatment process and its overall efficacy. the existing challenges in detecting, characterizing, and quantifying
nanoparticles and MFs. Moreover, investigations into the degrada-
4. Challenges and future research directions in MPs remediation tion of MFs by AOPs are urgently needed.
by AOPs • There has been limited research on microplastic degradation using
sonocatalytic processes. Future studies should prioritize optimizing
While the review highlights photocatalytic degradation as the most ultrasound frequency and intensity parameters. Additionally,
studied and effective method for MP degradation, it also reveals the coupling sonochemistry with other AOPs could enhance degradation
underutilization of other AOPs such as electrochemical oxidation, rates. Ongoing research is focused on cavitation phenomena and
ozonation, and Fenton oxidation, alongside a notable gap in research on their effects on microplastic fragmentation and chemical reactions.
sonochemical oxidation and heterogeneous SR-AOPs. These findings set • There is currently no standardized understanding of how AOPs affect
the stage for addressing the challenges in optimizing AOP efficiency and the physicochemical properties of MPs and their interactions with
scalability, which remain critical for advancing MP remediation tech- other pollutants. Research using real-world aquatic matrices and
niques. MPs pollution presents a multifaceted environmental challenge continuous flow systems is a significant knowledge gap that warrants
that necessitates a critical evaluation of current remediation strategies, further exploration.
particularly those utilizing AOPs. Although significant advancements • Most AOP experiments have been conducted in batch mode, which
have been made, several challenges must be addressed to optimize AOP does not reflect typical conditions used in wastewater and drinking
efficiency and efficacy in MP degradation. The following are significant water treatment facilities. Additionally, the environmental footprint
challenges based on recent progress: of MP degradation must be considered, especially in terms of energy
consumption. Technologies that reduce energy usage, such as those
• Despite the promising potential of photocatalytic degradation for the utilizing solar irradiation in photolysis systems, present a viable
removal of MPs, photocatalysts with high activity and selectivity alternative.
should be prepared to selectively degrade MPs into useful and non-
toxic products through regulating the breaking of chemical bonds In summary, while photocatalytic degradation is the most researched
in MPs. Ensuring the long-term stability and reusability of these and effective advanced oxidation process (AOP) for MP removal, there is
catalysts is essential for sustainable applications, as durable catalysts a pressing need to investigate other methods such as electrochemical
that retain their efficiency over multiple cycles are crucial for large- oxidation, ozonation, and Fenton processes. Optimizing reaction con-
scale adoption. ditions and enhancing the efficiency of these AOPs in real-world sce-
• Heterogeneous photo-Fenton and photocatalysis processes can narios are essential for improving their scalability and practicality.
reduce the size of certain MPs, such as PVC and PP, by up to 96 %. Future research should aim to understand how AOPs affect MP frag-
However, the long reaction times required (5 to 400 h) limit their mentation and their interactions with other pollutants. Additionally,
practicality for large-scale applications. developing energy-efficient and continuous treatment systems will be
• Many AOPs degrade microplastics only partially, resulting in smaller vital for ensuring the sustainability of MP remediation efforts.
microplastics or microplastic fragments, which may still pose envi- Addressing these technical and environmental barriers will be crucial for
ronmental risks. However, during degradation, harmful by-products, advancing AOP applications.
such as toxic organic compounds and persistent radicals, can form,
complicating the overall environmental impact assessment (Dos 5. Concluding remarks
Santos et al., 2023).
• Some AOPs, such as ozonation and SR-AOP processes, may generate MPs pose a significant and persistent threat to environmental and
harmful secondary products during the degradation of microplastics. human health, underscoring the urgent need for effective remediation
These by products could be more toxic than the parent material and strategies. This review highlights the potential of AOPs as a promising
complicate post-treatment. solution for MPs degradation, offering valuable insights into their
• Photocatalytic, electrochemical, and sono-chemical oxidation often mechanisms and efficacy. While photocatalysis remains the most
require significant energy input, which can make them less sustain- extensively studied AOP for MP degradation, other processes such as
able for large-scale applications. electrochemical oxidation, Fenton reactions, and ozonation remain
• Most AOP research for microplastic degradation is still in laboratory underexplored. These processes present unique opportunities for
settings. There is a lack of real-world studies that address variability enhancing remediation efforts, especially when combined with
in environmental conditions (e.g., pH, temperature, presence of emerging AOPs like sonochemical and sulfate radical-based approaches.
natural organic matter) that could affect the process efficiency. However, challenges such as optimizing operational conditions,
• In photocatalytic and electrochemical oxidation, catalysts (e.g., TiO₂, addressing size-dependent degradation, minimizing secondary pollut-
metal oxides) may undergo fouling or deactivation due to the ants, and improving scalability hinder the widespread adoption of AOPs
deposition of polymer byproducts or other contaminants, reducing for large-scale applications. This review provides the scientific com-
their efficiency over time. munity with a comprehensive understanding of the strengths, limita-
• Focus on developing novel catalysts and reagents that generate sul- tions, and future directions for AOP-based MPs remediation. The
fate radicals more efficiently, such as persulfate or perox- mechanistic insights and identification of research gaps outlined here
ymonosulfate activation methods. Combination of SR-AOPs with aim to catalysed advancements in catalyst development, energy-
photocatalysis or electrochemical systems that could offer enhanced efficient processes, and real-world applicability, making AOPs a
radical generation. viable, scalable, and sustainable option for addressing the global issue of
• Future directions in advanced oxidation processes (AOPs) for MP pollution. Additional novelty is attributed to mechanistic insight of
microplastic degradation focus on hybrid AOP systems to enhancing MPs conversion into value added products by photocatalytic activation.
efficiency, scalability, and sustainability. Combining AOPs like By accumulating current knowledge and identifying critical areas for
photocatalytic oxidation with electrochemical or ozonation systems future research, this review offers a roadmap for the development of
can improve degradation efficiency by leveraging synergies between more efficient, environmentally friendly, and cost-effective AOP tech-
processes. Integration with membrane technologies or biofiltration nologies. The integration of AOPs with conventional treatment methods
could enhance treatment performance. and the development of novel catalytic systems will be essential in
• Future research should prioritize the study of MP fragmentation and overcoming existing barriers, ensuring that AOPs can be deployed
the formation of smaller particles after oxidative treatments, despite effectively in real-world water treatment systems. Continued research in

17
A. Kumar et al. Science of the Total Environment 957 (2024) 177150

this domain will contribute to the broader goal of mitigating the Dos Santos, N. de O., Busquets, R., Campos, L.C., 2023. Insights into the removal of
microplastics and microfibres by advanced oxidation processes. Sci. Total Environ.
ecological and health impacts of MP pollution.
861, 160665.
Supplementary data to this article can be found online at [Link] Du, Z., Li, G., Ding, S., Song, W., Zhang, M., Jia, R., Chu, W., 2023. Effects of UV-based
org/10.1016/[Link].2024.177150. oxidation processes on the degradation of microplastic: fragmentation, organic
matter release, toxicity and disinfection byproduct formation. Water Res. 237,
119983.
CRediT authorship contribution statement Easton, T., Koutsos, V., Chatzisymeon, E., 2023. Removal of polyester fibre microplastics
from wastewater using a UV/H2O2 oxidation process. J. Environ. Chem. Eng. 11,
109057.
Arvind Kumar: Writing – review & editing, Writing – original draft, Ebrahimbabaie, P., Yousefi, K., Pichtel, J., 2022. Photocatalytic and biological
Software, Methodology, Investigation, Conceptualization. Riona technologies for elimination of microplastics in water: current status. Sci. Total
Indhur: Writing – original draft, Software, Methodology, Investigation, Environ. 806, 150603.
Eitzen, L., Paul, S., Braun, U., Altmann, K., Jekel, M., Ruhl, A.S., 2019. The challenge in
Conceptualization. Faizal Bux: Supervision. Sheena Kumari: Writing – preparing particle suspensions for aquatic microplastic research. Environ. Res. 168,
review & editing, Validation, Supervision, Resources, Data curation. 490–495.
Elkhatib, D., Oyanedel-Craver, V., Carissimi, E., 2021. Electrocoagulation applied for the
removal of microplastics from wastewater treatment facilities. Sep. Purif. Technol.
276, 118877.
Declaration of competing interest Gao, Z., Chen, L., Cizdziel, J., Huang, Y., 2023. Research progress on microplastics in
wastewater treatment plants: a holistic review. J. Environ. Manag. 325, 116411.
The authors declare that they have no known competing financial Geyer, R., Jambeck, J.R., Law, K.L., 2017. Production, use, and fate of all plastics ever
made. Sci. Adv. 3, 25–29.
interests or personal relationships that could have appeared to influence
Golmohammadi, M., Fatemeh Musavi, S., Habibi, M., Razmjou, A., 2023. Molecular
the work reported in this paper. This work was supported by the Water mechanisms of microplastics degradation: a review. Sep. Purif. Technol. 309,
Research Commission of South Africa (2022/2023-00886). 122906.
González, T., Dominguez, J.R., Cuerda-Correa, E.M., Correia, S.E., Donoso, G., 2020.
Selecting and improving activated homogeneous catalytic processes for pollutant
Data availability removal. Kinetics, mineralization and optimization. J. Environ. Manag. 256, 109972.
Halfar, J., Brožová, K., Čabanová, K., Heviánková, S., Kašpárková, A., Olšovská, E., 2021.
Data will be made available on request. Disparities in methods used to determine microplastics in the aquatic environment: a
review of legislation, sampling process and instrumental analysis. Int. J. Environ.
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