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Science of the Total Environment 858 (2023) 159681

Contents lists available at ScienceDirect

Science of the Total Environment


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

Review

Recent approaches and advanced wastewater treatment technologies for


mitigating emerging microplastics contamination – A critical review
Radhakrishnan Yedhu Krishnan a,1, Sivasubramanian Manikandan b,1, Ramasamy Subbaiya c,
⁎ ⁎ ⁎⁎
Natchimuthu Karmegam d, , Woong Kim e, , Muthusamy Govarthanan e,f,
a
Department of Food Technology, Amal Jyothi College of Engineering, Kanjirappally, Kottayam 686 518, Kerala, India
b
Department of Biotechnology, Saveetha School of Engineering, Saveetha Institute of Medical and Technical Sciences (SIMATS), Saveetha Nagar, Thandalam, Chennai 602 105. Tamil Nadu, India
c
Department of Biological Sciences, School of Mathematics and Natural Sciences, The Copperbelt University, Riverside, Jambo Drive, P O Box 21692, Kitwe, Zambia
d
PG and Research Department of Botany, Government Arts College (Autonomous), Salem 636 007, Tamil Nadu, India
e
Department of Environmental Engineering, Kyungpook National University, Daegu, South Korea
f
Department of Biomaterials, Saveetha Dental College and Hospital, Saveetha Institute of Medical and Technical Sciences, Chennai 600077, Tamil Nadu, India

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

• Smaller microplastics (MPs) <100 μm are


not effectively separated by conventional
WWTPs.
• Granules and fragments were easier to sep-
arate than microfibers and pellet shaped
MPs.
• Blue mussels, lugworms and sea grasses are
candidate species for MPs' bioremediation.
• Rapid sand filters and membrane bioreac-
tors can remove 97 % and 99 % MPs
respectively.

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

Editor: Damià Barceló Microplastics have been identified as an emerging pollutant due to their irrefutable prevalence in air, soil, and partic-
ularly, the aquatic ecosystem. Wastewater treatment plants (WWTPs) are seen as the last line of defense which creates
Keywords: a barrier between microplastics and the environment. These microplastics are discharged in large quantities into
Microplastics aquatic bodies due to their insufficient containment during water treatment. As a result, WWTPs are regarded as
Wastewater treatment plants
point sources of microplastics release into the environment. Assessing the prevalence and behavior of microplastics
Membrane technology
Bioremediation
in WWTPs is therefore critical for their control. The removal efficiency of microplastics was 65 %, 0.2–14 %, and
Advanced techniques 0.2–2 % after the successful primary, secondary and tertiary treatment phases in WWTPs. In this review, other than
conventional treatment methods, advanced treatment methods have also been discussed. For the removal of
microplastics in the size range 20–190 μm, advanced treatment methods like membrane bioreactors, rapid sand filtra-
tion, electrocoagulation and photocatalytic degradation was found to be effective and these methods helps in increas-
ing the removal efficiency to >99 %. Bioremediation based approaches has found that sea grasses, lugworm and blue
mussels has the ability to mitigate microplastics by acting as a natural trap to the microplastics pollutants and could act
as candidate species for possible incorporation in WWTPs. Also, there is a need for controlling the use and unchecked
release of microplastics into the environment through laws and regulations.

⁎ Corresponding authors.
⁎⁎ Correspondence to: M. Govarthanan, Department of Biomaterials, Saveetha Dental College and Hospital, Saveetha Institute of Medical and Technical Sciences, Chennai 600077, Tamil Nadu, India.
E-mail addresses: kanishkarmegam@gmail.com (N. Karmegam), elshine@knu.ac.kr (W. Kim), gova.muthu@gmail.com (M. Govarthanan).
1
R. Yedhu Krishnan and S. Manikandan contributed equally to this work.

http://dx.doi.org/10.1016/j.scitotenv.2022.159681
Received 3 August 2022; Received in revised form 24 September 2022; Accepted 20 October 2022
Available online 24 October 2022
0048-9697/© 2022 Elsevier B.V. All rights reserved.
R.Y. Krishnan et al. Science of the Total Environment 858 (2023) 159681

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.1. Toxicity and health hazards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.2. Legislations for minimal microplastic pollutants in environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2. Mitigation of microplastics in wastewater treatment plants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.1. Pretreatment and primary treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.2. Secondary treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.3. Tertiary treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3. Advanced approaches in mitigation of microplastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.1. Membrane technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.1.1. Dynamic membrane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.1.2. Membrane bioreactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.1.3. Reverse osmosis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.2. Bioremediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.2.1. Eukaryotic marine plants and microalgae . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.2.2. Eukaryotic marine animals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4. Other advanced approaches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4.1. Rapid sand filtration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4.2. Electrocoagulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4.3. Photocatalytic degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4.4. Sol-gel method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
5. Future outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
6. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
CRediT authorship contribution statement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Data availability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

1. Introduction toxicity in organisms with persistent microplastics exposure (An et al.,


2021). Terrestrial microplastics that are getting generated due to various
Plastics have been vital in civilization ever since invention of the first human activities enter the wastewater treatment plants (WWTPs) before
synthetic resin at the turn of the twentieth century (Bolan et al., 2020a; getting exposed to other marine or freshwater ecosystems and their even-
Cole et al., 2011). Microplastics, which are generally described as plastics tual accumulation in the environment (Q. Wang et al., 2021; Yan et al.,
with size <5 mm, are found in a wide range of marine and terrestrial habi- 2020). Therefore, it is upmost necessity to study about the various treat-
tats and biota (Arthur et al., 2009; Bhatt et al., 2021; Bradney et al., 2020; ment techniques that are useful in WWTPs and the effectiveness of these
Schmid et al., 2021). With the evolution of time, there have been variations techniques in the removal of microplastics and thereby preventing their
in the definition of microplastics and its size range. Within the defined size entry to the natural environment.
range, microplastics has been further subclassified into large microplastics Microplastic particles have also been classified according to
(1–5 mm size) and small microplastics (< 1 mm size) (Bolan et al., 2020c; their type, which included beads, foams, pellets, fibers and fragments
Zhang et al., 2019). More recently, the size range of microplastics has (Dodson et al., 2020; Qi et al., 2020; Saborowski et al., 2019). Polymers
been redefined more conservatively by Hartmann et al. (Hartmann et al., used to manufacture microplastics include polystyrene, polyvinyl chloride,
2019). Hartmann define microplastics as synthetic polymeric matrix of par- polyethylene, polyether sulfone, low-density polyethylene, high-density
ticle size lesser than 1 mm size. The other classifications of these regular or polyethylene, polyethylene terephthalate, polypropylene, cellulose acetate,
irregularly shaped synthetic solid particles includes mesoplastics (<10 mm polyamide, polyacrylates, and polyester (Welden, 2019; Welden and
– 1 mm), nanoplastics (<1000 nm – 1 nm) and macroplastics (>1 cm) Lusher, 2020; Wong et al., 2020). Higher concentrations of microplastics
(Hartmann et al., 2019). However, it should be noted that the general ac- were commonly discharged from WWTPs due to fishing related operations
cepted definition for microplastics as reported by the bulk of available liter- and laundries. In addition to these primary sources, direct trash discharge
atures define them as synthetic particles of size <5 mm (Palansooriya et al., to surface water also played a substantial role in microplastics contamination.
2020). Furthermore, the living environment characteristics influence microplastics
Microplastics can be broadly classified into two based on their origin - discharges (Duan et al., 2021). For example, densely populated metropolitan
primary microplastics and secondary microplastics. Primary microplastics regions with greater prosperity may be greater suppliers and emitters of
are those that are specifically manufactured for household or industrial microplastics than rural regions (Eckert et al., 2018). Plastics are also widely
applications, whereas secondary microplastics are those that have been utilised in farm and agricultural related activities (Kirkham et al., 2020).
formed by the break-up of larger macroplastics due to the effects of Also, microplastics get introduced into the soil via sewage sludge, after
mechanical abrasion or UV irradiation (Jaikumar et al., 2019). Presence them being used as fertilizers in agricultural land (Nizzetto et al., 2016). It
of microplastics has been detected in freshwater (Choong et al., 2021), should be also noted that the effluent wastewater which hold higher concen-
soil (Kumar et al., 2020; Sridharan et al., 2021; Yang et al., 2021), marine trations of microplastics gets in direct contact with rivers and canal systems
ecosystem (Zhang et al., 2020), atmosphere (Chen et al., 2020), and even before eventually reaching the ocean systems (Jambeck et al., 2015).
in polar regions of the world (Mishra et al., 2021). Due to their smaller The breakdown of microplastics into their constituent oligomers,
size and higher surface area, microplastics have the ability to adsorb dimers, and monomers is one of the many stages that are involved in
other pollutants like pharmaceutical and personal care products (Atugoda the biodegradation of microplastics by microbes. Other stages in this
et al., 2021; Atugoda et al., 2020; Krishnan et al., 2021), heavy metals process include: 1) the preliminary degradation of polymeric materials
and metalloids (Liu et al., 2021; L. Wang et al., 2021), and polycyclic aro- into smaller size aggregates originating from larger polymeric structures;
matic hydrocarbons (Borges-Ramírez et al., 2021), leading to chronic 2) the breakdown of polymers into their constituent oligomers; and 3) the

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R.Y. Krishnan et al. Science of the Total Environment 858 (2023) 159681

mineralization of microplastics by microbes (Blair Espinoza, 2019). A num- limiting development and fertility (Lahive et al., 2019; Mandal et al.,
ber of conditions must be in line for biodegradation of microplastics to be 2020; Tanaka and Takada, 2016; Yin et al., 2021). The effects of
successful; among them is the presence of potentially degrading microor- microplastic ingestion and accumulation were examined in 26 distinct
ganisms with the necessary biochemical and metabolic pathways. Further- fish species from various habitats along the Red Sea coast bordering
more, biodegradation is promoted when other supporting conditions Saudi Arabia (Baalkhuyur et al., 2018). Microplastics were discovered in
including temperature, salinity, moisture content, and pH are ideal (Gong 14.6 % of the tested fish, with Parascolopsis eriomma, a fish type that
et al., 2012). The lamellar thickness and crystal size of polymers, as well feeds on benthic organisms, having the greatest percentage of accumulated
as the percentage of crystalline and amorphous sections, all affect the enzy- microplastics. Pollutants assimilated or attached to microplastics, as well as
matic breakdown rates of microplastics. Moreover, for microorganisms to the hazardous plastic additives that gets leached are of grave consequence
attach on a polymer, the physical properties of polymer must be suitable to marine biota (X. Wang et al., 2021). Microplastics in soil, on the other
for adhesion of microorganisms to the polymer's surface (Shabbir et al., hand, have the potential to dramatically affect plant biomass, soil pH,
2020). All these factors make the biodegradation of microplastics quite microbial activity in soil, water dynamics, elemental composition of plant
challenging. tissues, and root characteristics (de Souza Machado et al., 2019).
Complete degradation of all contaminants are rarely required and often Other than ingestion, the other routes of microplastics exposure in
presents unfavorable economics. Possible alternatives include partial oxida- humans are through skin contact and respiration. Microplastics through re-
tion process of the initial molecule towards less stable intermediate com- spiratory routes are mostly derived from pulverized rubber tyres, urban
pounds, which can be further broken down in the ecosystem and pose dust, and synthetic fabrics like polyester, nylon or acrylic (Prata, 2018a).
minimal threat to human or aquatic. The nature and quantity of byproducts Wholly consumed organisms pose a larger risk to human health than
rely on the type of oxidation, the duration of treatment, and the character- disembowelled organisms (Carbery et al., 2018). Even though the human
istics of the aqueous matrix; nonetheless, in some situations, partial oxida- dermis and epidermis layer prevents direct entry of microplastics, skin
tion of contaminants can result in the synthesis of intermediates of openings such as hair follicles, skin injuries, and sweat ducts act as viable
increased toxicity (Bratovcic, 2019). For polymer biodegradation to occur entry points (Kurniawan et al., 2021; Schneider et al., 2009). Toxic effects
in an aerobic environment, the polymeric carbons must be broken down of microplastics include endothelial dysfunction (Prata et al., 2020), inflam-
into carbon dioxide, microbial biomass, and the carbon present in remnant matory lesions (Smith et al., 2018), endocrine disturbance (Amereh et al.,
monomers and polymers. For instance, there are three main stages involved 2020) and oxidative stress (Qiao et al., 2019). Numerous researches have
in the biodegradation of polyvinyl chloride: the breakdown of long polymer shown that there is a danger of neurotoxicity (Lei et al., 2018), breakdown
chains, intermediate products formation, and the complete degradation to of metabolic activities (Prata et al., 2020), and elevated risk of carcinoma in
chloride ions, carbon dioxide and water (Peng et al., 2020). Similarly, the people (Sharma et al., 2020). Table 1 describes the various classes of
degradation of polyurethanes may result in the formation of secondary microplastics and the potential health hazards caused by microplastic pol-
microplastics rich in urethane via breakdown of esters, proceeded by aggre- lutants. Particles smaller than 150 μm may translocate themselves to the
gation and attrition of oligomer chains. Also, breakdown of polyvinyl alco- lymph nodes after ingestion, although assimilation is predicted to occur
hol typically involves hydrolase and aldolase processes, which cleave the in fewer than 0.3 % of the consumed particles (Barboza et al., 2018). The
primary polymer chain. Hydroxyl fatty acid and acetic acid were the final main site of absorption of microplastics and other emerging pollutants in
products that resulted from the degradation process of polyvinyl alcohol the human body is the Peyers's patches present in the small intestine and
(Wilkes and Aristilde, 2017). the smallest of these particles penetrate the cellular membranes of various
The different techniques to remove microplastics from wastewater in- organs (Bouwmeester et al., 2015; Van Cauwenberghe and Janssen, 2014).
cludes: screening and filtration (Ding et al., 2021), rapid sand filtration The different strategies to identify, detect and characterize microplastics
(Wang et al., 2020), dissolved air flotation (Y. Wang et al., 2021), mem- include - microsphere based multiplex immunoassay (MBMIs), multispectral
brane processes (Pramanik et al., 2021), membrane bioreactor (Maliwan optoacoustic tomography, particle image velocimetry, laser printer method,
et al., 2021), electrocoagulation (Shen et al., 2022), and activated sludge dark-field hyperspectral microscopy, gas chromatography, mass spectrome-
process (Bretas Alvim et al., 2021). There are recent reviews available try, pyrolysis gas chromatography - time of flight mass spectrometry
which discusses the removal of microplastics from WWTPs. Most of these (Py-GC-TOF-MS), Fourier transform infrared (FT-IR) analysis, attenuated
reviews focusses on the shape, size and type of the microplastics that are total reflection mid-infrared spectroscopy, near infrared-hyperspectral imag-
getting removed in conventional WWTPs. There are also other literatures ing (HSI-NIR), pyrolysis-gas chromatography (GC) in combination with mass
available based on the characterization and detection methods of spectrometry (MS), infrared spectroscopy, Raman spectroscopy, solid–state
microplastics in aquatic systems. However, there have been limited focus nuclear magnetic resonance (NMR) spectroscopy, and near-infrared (NIR)
on the various novel techniques available for removal of microplastics spectroscopy (Reslova et al., 2017; Tirkey and Upadhyay, 2021; Vilakati
from wastewater. This review discusses various advanced methods based et al., 2021). The best technique possible for chemical characterization of
on membrane technology, electrocoagulation and photocatalytic degrada- microplastics are FT-IR and Raman spectroscopy (Ming-Lok Leung et al.,
tion and their effectiveness in mitigation of microplastics. In addition, 2021). FT-IR analysis can be used on particles as small as 50 μm, while
bioremediation-based approaches also have proven to be effective in Raman can be used on particles of size range 1–10 μm (Corami et al.,
microplastic containment and is one of the key focus areas in this review. 2021). FTIR and Raman are both complementary and generate information
The health hazards and the key legislations related to the control of for chemical mapping (Xu et al., 2019). NIR does not require pre-treatment
microplastics emissions are also discussed here. and can detect particles as small as 1 mm (Piarulli et al., 2020). Similarly,
quantitative NMR is a rapid, size-independent, easy to utilize approach for
1.1. Toxicity and health hazards quantifying microplastic concentration (Du and Wang, 2021).

Fish is one among the primary source of protein for humans. As a result, 1.2. Legislations for minimal microplastic pollutants in environment
people devoured a broad range of fish and other aquatic species while
also ingesting microplastics along with them. Such passive intake of Studies recommend removing purposely incorporated microplastics
microplastics is a potential risk to humans and has emerged as a growing from commodities, such as microplastics in skincare (microbeads), as it is
issue in recent decades (Bolan et al., 2020b; Bradney et al., 2019; De-la- a simpler method to execute, despite the fact that they are regarded
Torre, 2020). Microplastics not just have detrimental effects on mammals a minor concern among the bulk of other microplastic pollutants
but on other species like aquatic birds, amphibians, and reptiles by interfer- (Anagnosti et al., 2021). There is indeed a lack of serious international reg-
ing with their natural activities like as respiration, ingestion, digestion, and ulation prohibiting the production and use of microplastics, particularly in
swimming, thereby reducing their overall survival capability as well as by the field of pharmaceutical and personal care products, but certain

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R.Y. Krishnan et al. Science of the Total Environment 858 (2023) 159681

Table 1
Microplastics impact on human health.
Various classes of microplastics Health effects of microplastics References

Beads Micro-beads Toxicity effects of micro-beads include inflammatory lesions, (Bhutiani et al., 2017; Bolan et al., 2020d; Dong et al., 2004;
Spherical micro-beads oxidative stress, and translocation Fang et al., 2021; Nigamatzyanova and Fakhrullin, 2021;
Microspheres Reslova et al., 2017)
Foams Polystyrene and their derivatives Metabolic disorders, higher cancer risk in humans, and (Bao et al., 2021; Huang et al., 2020a; Park et al., 2021; Sarkar
Polyvinyl chloride neurotoxicity are possible, tissue inflammation and necrosis et al., 2020; Vidal and Pasquini, 2021; Vilakati et al., 2021)
Expanded polystyrene
Pellets Nibs Immune responses, physical toxicity, and cytokine production result (Bhutiani et al., 2017; Dong et al., 2004; Fang et al., 2021;
Resin in oxidative stress, inflammation, and cellular damage, hemocyte Nigamatzyanova and Fakhrullin, 2021; Reslova et al., 2017)
Pellets aggregation and respiratory failure
Urdles
Fibers Microfibre Obstruct digestive tracts, change feeding habits, and reduce the (Ali et al., 2021; Bhutiani et al., 2017; Bolan et al., 2020d)
Filaments desire to urge to eat, impact on immune system
Thread based materials
Fragments Films Higher cancer risk in humans, reduce the desire to urge to eat food, (Castelvetro et al., 2021; Löder and Gerdts, 2015;
Granules inflammatory lesions, oxidative stress, and translocation or Wijesekara et al., 2020)
Crystals increased uptake, human exposure to associated chemicals
Irregular shaped particles
Powder
Flakes
Granules
Fluff
Shavings

countries like the United States, the United Kingdom, and Canada have preliminary treatment, the cumulative abundance of microplastics was re-
prohibited the production and use of microbeads (Auta et al., 2017; Prata, duced by 6 %; after the primary treatment, it decreased by 68 %; after the
2018b). The Microbead-Free Waters Act of 2015 is a law implemented by secondary treatment, it decreased by 92 %; and after the tertiary treatment,
the 114th United States Congress that prohibits the inclusion of it decreased by 96 %. On a different note, different WWTPs utilised the
microplastics (microbeads) to manufactured goods (Xanthos and Walker, same microplastics treatment process, but achieved significantly different
2017). This legislation has been effective for industries since July 2017 levels of success in removing the microplastics. Also, in a treatment facility
and for retail outlets since July 2018. The results from these legislations in Beijing (Yang et al., 2019), it was found that the efficiency of removing
illustrate both successes and mistakes, which may be utilised to better exe- microplastics using aeration grit chambers was 58 %, while the efficiency
cute policy frameworks. Because the microplastics policies were only of using anaerobic – anoxic - oxic (A2O) was 54 %, and the efficiency of
recently implemented, there is a scarcity of scientific and quantitative utilising advanced oxidation methods was 71 %. On the other hand, in a
data to report on the results. Shanghai wastewater treatment plant (Jia et al., 2019), the microplastics
Demand from non-governmental organisations and movements de- removal efficiency for the same treatment methods declined to 49 %
manding prohibitions, such as “Beat the microbead,” prompted bodies when utilising aeration grit chambers, 26 % when using A2O, and 0.78 %
such as the United Nations to establish strategies to combat marine pollu- when using advanced oxidation processes. Hence, a comprehensive study
tion caused by microplastic particles (Anagnosti et al., 2021; EPA NSW, on the current treatment methods employed in WWTPs and their impact
2016). Other world countries like the China, New Zealand, Canada, and on removal of microplastics is critical to be analysed.
South Korea has implemented positive steps in restricting the release of
microbeads in personal care products (Anagnosti et al., 2021; Excell et al., 2. Mitigation of microplastics in wastewater treatment plants
2018). Also, countries like India and Brazil are actively considering restric-
tions on microplastics usage. On similar grounds, the European Union The majority of microplastics that reach the environment comes from
through the European Chemical Agency (ECHA) is considering a proposal sewage water and wastewater (Ajith et al., 2020; Pereao et al., 2020).
to restrict the intentional addition of microplastics to certain goods during Many research findings have confirmed the widespread presence of
its production stage (ECHA, 2019). It is estimated that with the implemen- microplastics in freshwater and marine habitats. A WWTP (serving a popu-
tation of the said proposal, the microplastic emission into the environment lation of 650,000) releases approximately 65 million microplastics into the
can be reduced by 85–95 % in the European Union. Furthermore, a pro- aquatic environment daily (Murphy et al., 2016). Over 80 % of the
posal for tackling the microplastic pollution emerging from WWTPs and microbeads released into the surface waters in China each year come
the issues related to the use of sewage sludge for agricultural purposes is from WWTPs (Cheung and Fok, 2017). The majority of microplastics
being considered by the European Parliament (European Commission, found in untreated wastewater get retained within the sludge. The concen-
2020). Such efforts could contribute actively for curtailing the release of tration of microplastics in sewage sludge varied between 1.6 × 103 and
microplastics into the environment. 56.4 × 103 particles for 1 kg of dry sludge (X. Li et al., 2018). Although
Even though the above legislations aimed at controlling the menace of wastewater / sewage treatment plants are currently not intended or opti-
microplastics were enacted, betterment of existing methods as well as de- mized for microplastics removal, certain studies indicate that enhanced
velopment of advanced treatment methods for removal of microplastics wastewater treatment technologies may improve the microplastic waste
from WWTPs are required. Waste water ought to be treated and reused if disposal (Kumar et al., 2021; Rashid and Liu, 2020; Sobczyk et al., 2021).
we are to keep up with our water needs (Velusamy et al., 2022). The term The mitigation efficiency of various microplastics by the conventional
“treatment process” refers to the procedure by which polluted water, WWTPs was determined using the difference in concentrations of
whether from domestic usage or industrial activity, is restored to a usable microplastics in both the influent and effluent. As a whole, microplastics
quality (Rathi et al., 2021). The potential presence of newly discovered or elimination efficacies were >88 % in WWTPs with no tertiary treatment
developing contaminants like microplastics in our waterways remains a protocols and >97 % in WWTPs with different tertiary treatment methods
key cause for concern for both environmental and human health (Rathi (Dris et al., 2015; Michielssen et al., 2016; Murphy et al., 2016). As a result,
and Kumar, 2021). Conventional treatment methods were unable to the percentage removal of pollutants in WWTPs is insufficient to overcome
entirely remove microplastics from wastewater, as was shown in earlier microplastics pollution and the attained effectiveness of microplastics re-
research carried out in UK (Blair et al., 2019). For instance, after the moval in each WWTP from different parts of the world varied from around

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R.Y. Krishnan et al. Science of the Total Environment 858 (2023) 159681

60 % to 99.9 % based on the methods implemented for water treatment primary treatment, microplastics of larger size range, generally between
(Gies et al., 2018; Liu et al., 2019). 1000 and 5000 μm get removed (Dris et al., 2015). In addition, considering
Municipal WWTPs around the globe share a fundamental architecture, the shape of microplastics, the removal efficiency of microspheres was
albeit the arrangement of this basic design varies with every facility. higher compared to fibers (Claessens et al., 2013). Similarly, in the study
Fig. 1 gives the different stages and general outline of a WWTP. The conducted by Long et al. (Long et al., 2019), it was identified that granule
common steps in a WWTP include sedimentation, flocculation, and aera- and fragment shaped particles showed a removal efficiency of 91 %,
tion. Depending on the morphological and physico-chemical features like whereas for fibers and pellets it was 79 % and 83 % respectively. The
hydrophobicity, particle size, density, and charge, the removal efficiency smooth texture of fibers and pellets meant that it was difficult for them to
of microplastics in wastewater treatment facilities may vary (Keerthana get captured by the solid flocs compared to the twisted and angular
Devi et al., 2022; Seth and Shriwastav, 2018; Ziajahromi et al., 2021). Dur- shapes of granules and fragments. Gies et al. (Gies et al., 2018) has also
ing the treatment of wastewater, the microplastics residues may be retained reported that the microfibers had better removal prospectus during primary
inside the sludge of treatment plants; occasionally, it may be processed and treatment.
used on land, an example being use for agricultural purposes (Garcés- Another approach that can be effective in removal of microplastics is
Ordóñez et al., 2021). With screen meshes of 6 mm or higher, the primary dissolved air flotation (Muniz et al., 2020). Here, the microplastics float
treatment separates larger debris particles. In secondary treatment, precip- on the surface due to the action of tiny air bubbles and the contaminants fi-
itated and other dissolved organic wastes get eliminated in massive oxida- nally get collected physically by skimming (Ødegaard, 2001; Y. Wang et al.,
tion tanks. This is followed by separation of the treated wastewater from 2021). Low density microplastics like polypropylene and polyethylene are
the processed effluent water by adopting strategies like treatment in sedi- more easily removed by using air flotation technique than when compared
mentation tanks or flocculation (Murphy et al., 2016). Following the sec- to sedimentation process which is more favorable for high density
ondary treatment, the wastewater is disinfected and then get proceeded microplastics like polyesters and polyethylene terephthalate (Liu et al.,
for sophisticated tertiary treatment protocols like activated sand filters 2019; Yang et al., 2019). In primary treatment, separation also takes
and finally gets released into nearby streams (Mahon et al., 2017). It should place by other physical methods like precipitation. Removal of highly con-
be noted that the percentage of microplastics that is getting eliminated de- centrated toxic substances from the wastewater by neutralization, oxida-
pends upon the type of treatment protocols and the nature of microplastics tion, or chemical treatments for making the water suitable for secondary
present in wastewater. treatment is an important aspect of precipitation process. Higher treatment
dosages are required for microplastics removal as they are hydrophobic in
2.1. Pretreatment and primary treatment nature than compared to non-microplastics (Bretas Alvim et al., 2020;
Hou et al., 2021). It should be also noted that in order to completely
It was found that preliminary treatment (sedimentation, screening, flo- remove microplastics, appropriate technologies must be considered in the
tation etc.) may remove between 35 % and 59 % of microplastics, and that secondary or tertiary stages of WWTPs.
primary treatment (adsorption, coagulation, ozonation, etc.) could remove
between 50 % and 98 % of microplastics (Sun et al., 2019). The bulk of the 2.2. Secondary treatment
microplastics present in wastewater could be efficiently removed during
the pretreatment and primary treatment stage. It has been observed that The secondary treatment of wastewater predominantly involves clarifi-
during a conventional primary treatment phase approximately 65 % of cation and biochemical treatment methods. During the secondary treat-
the microplastics are eliminated (Burns and Boxall, 2018), where ment, the microplastic material would settle in the secondary clarifying
microplastics with lower densities favorably get concentrated in the oil or tank after being helped along by microbial extracellular polymers or sludge
grease layer (Murphy et al., 2016), and are removed eventually (Carr flocs in the aeration tank. Various studies have reported that, as a result of
et al., 2016). Also, during the gravity settling and grit removal phase, the the secondary treatment, the microplastics percentage in wastewater gets
microplastics get entrapped within the solid flocs. In the studies conducted reduced to 0.2–14 % (Dris et al., 2015; Murphy et al., 2016; Talvitie
by Gies et al. (Gies et al., 2018) and Bayo et al. (Bayo et al., 2020b) the et al., 2017b). During secondary treatment, microplastics get trapped
microplastic removal efficiency of 92 % and 74 % was observed during within the aeration tank which consists of microbial polymers or sludge
the primary stage of wastewater treatment plant respectively. During the flocs, which then get proceeded to the clarification tank. The interaction
of microplastics with microorganisms during secondary treatment results
in the denitrification of treated water and results in NH3 accumulation in
water (Bendell et al., 2014). Generally, microorganisms associated with
nitrogen removal are more sensitive than microorganisms that aid in the ac-
PRELIMINARY TREATMENT
cumulation of phosphorous (Zheng et al., 2011). Therefore, the microbial
Sedimentation, Equalization, Screening and Aeration, Filtration, Degasiication,
Flotation, Other physical methods assisted ammonium generation and the nitrification process is getting af-
fected due to the presence of microplastics (Liu et al., 2017). However,
PRIMARY TREATMENT some of the negative effects of microplastics that affects the efficiency of
Ozonation, Coagulation, Ion-Exchange, Adsorption, Chlorination, Neutralization,
Other chemical methods.
secondary treatment processes can be subdued by increasing the contact
time of microplastics with the chemical or microbial sludge flocs
SECONDARY TREATMENT (Carr et al., 2016). Increasing the contact time results in the formation of
1) Aerobic: Lagoons, Activated sludge treatment, Oxidation ponds, Trickling a surface biofilm on the microplastics which acts as a coating that could
iltration.
2) Anaerobic : Lagoons, Septic tanks, other biological treatment methods.
greatly alter the relative densities and surface characteristics of the pollut-
ants (Rummel et al., 2017). Flocculating agents employed in secondary
TERTIARY TREATMENT treatment like ferric sulphate may have a good effect on removal of
Filtration, Membrane processes, Ion Exchange, Activated carbon treatment, microplastics by causing the dispersed particulate materials to coalesce to-
Disinfection, Oxidation, Chemically aided settling, Advanced oxidation, Softening,
Other advanced approaches.
gether and form a floc (Murphy et al., 2016). Some of the microplastics may
not be efficiently removed because they are caught in unsteady flocs and
not distributed evenly throughout the aqueous phase, where they undergo
a dynamic reorganization and ultimately evade elimination during the final
settling phase (Carr et al., 2016).
Fig. 1. Classification of different stages and general outline of a wastewater When comparing the removal efficiency of microplastics by activated
treatment plant. sludge process against A2O process, it was observed that the efficiency for

5
R.Y. Krishnan et al. Science of the Total Environment 858 (2023) 159681

microplastics removal was higher for activated sludge process. The marine sources as they deliver multifold advantages (Dalmau-Soler et al.,
microplastic removal efficiency was 66.7 % by using activated sludge pro- 2021). Some of these advantages include, operational pliability and
cess (Ziajahromi et al., 2017), whereas it was 54.4 % (Yang et al., 2019) uncomplicatedness, lesser energy utilization, ease of management and
and 28.1 % (Liu et al., 2019) by A2O process. Also, when considering the scale-up, superior stability, and the capability to handle and withstand
shape of microplastics that were getting removed during secondary treat- large quantities of water (Meng et al., 2019; Shahid et al., 2021). In this sec-
ment, fragments fared better compared to fibers. It was observed that tion, we examine the role of membranes in the elimination of microplastics
after secondary treatment, the percentage of fibers in the sludge increased from wastewater, as well as how membrane processes can be employed to
but that of fragments decreased (Talvitie et al., 2017a; Talvitie et al., control microplastics pollution.
2015). Considering the size of microplastics, particles with size >500 μm
were generally absent from the effluents after secondary treatment 3.1.1. Dynamic membrane
(Mintenig et al., 2017). Further to the secondary treatment, the wastewater Recently, dynamic membranes are being considered as an emerging
then proceeds to tertiary treatment where further removal of microplastics technology for treatment of wastewater (Hou et al., 2017). This approach
happen. is associated with the generation of a dynamic membrane or cake deposit,
which functions as a barrier or foulant formed when microplastics and
2.3. Tertiary treatment other fragments in the wastewater are initially getting filtered over a sup-
portive membrane (Isik et al., 2021). Owing to the significant differences
In tertiary treatment, the microplastics removal from wastewater is fur- in the mechanism associated with dynamic membranes when compared
ther enhanced by supplementary polishing steps. After the tertiary treat- to microfiltration or ultrafiltration processes, and because of the fact that
ment process, the microplastics in wastewater get reduced to 0.2–2 %, barriers or foulants are required to generate the dynamic membrane
and the final percentage of microplastics that are still retained depended layer, the barrier to filtration is solely caused by the cake layer (Siddiqui
upon the tertiary treatment methods adopted (Lares et al., 2018; et al., 2021). However, it should be also noted that a heavier layer of cake
Michielssen et al., 2016). The shape of microplastics reaching the tertiary deposit could significantly affect the membrane potential and operability
treatment phase varies greatly and is highly irregular due to the particle in- (Saleem et al., 2019). Fig. 2 depicts the mechanism associated with dy-
teraction with prior treatment processes. Due to the presence of such highly namic membranes. The formation of dynamic membrane was influenced
irregular shaped particles, the efficiency of filtration-based processes like by several parameters associated with the supporting membrane used,
reverse osmosis, microfiltration and ultrafiltration may get affected (Lai such as the materials and pore size associated with the membrane, the con-
et al., 2014). Even though, most WWTPs around the globe use polymer- centration and particle size distribution of the accumulated material, as
based membranes, chances are that such membranes too get worn out well as the tangential flow rate and operating pressure (Paçal et al., 2019;
due to the interaction with uneven shaped microplastics (Geise et al., Saleem et al., 2019).
2010). However, among the different tertiary treatment methods studied Dynamic membranes have been one of the widely explored strategies
by Talvitie et al. (Talvitie et al., 2017a, 2017b), membrane bioreactors for the removal of microplastics (Ersahin et al., 2012; L. Li et al., 2018). A
showed the highest removal efficiency of microplastics (99 %), followed vital step in dynamic membrane system is the identification of an adequate
by rapid sand filtration method. Also, there are reports about the reduction support material that allows the creation of a dynamic layer. The material
in concentration of microplastics after reverse osmosis and ultrafiltration must possess an acceptable permeability in order to create and maintain
process (Ziajahromi et al., 2017). Therefore, more studies on membrane- the membrane forming component on its surface, as well as be robust
based methods could provide better insights about the actual effectiveness enough to endure the requisite forces for an extended period of time
of these methods against microplastics. (Igawa et al., 1977). Through the active filtration of synthetic wastewater,
After the tertiary treatment processes, analysis of effluents has revealed dynamic membranes were allowed to be formed on a 90 μm supportive
that most of the remaining microparticles in it were fibers. The reason be- mesh and the effect of solid flux and particle concentration on the actual
hind this might be that fibers are able to pass the membranes longitudinally performance of dynamic membrane was studied (L. Li et al., 2018). After
(Yuan et al., 2021). In addition, microplastics of smaller size range 20 min of filtration, the effluent turbidness was reduced to <1 Nephelomet-
of 20–190 μm were detected in the effluents after tertiary treatment ric Turbidity Unit (NTU), demonstrating that the dynamic membranes
(Ziajahromi et al., 2017). Even though only a small percentage of could effectively remove microplastics. The transmembrane pressure dur-
microplastics are retained in the final effluent, studies have suggested ing the dynamic membrane filtering process ranged from 80 to 180 mm
that this could account to half-a-billion microplastic items that are finally of water head and was nearly 16 times lower than that of conventional ul-
getting released into the environment on a daily basis (Fortin et al., 2019; trafiltration and microfiltration, resulting in significant energy savings.
Wu et al., 2021). However, it should be noted that particles that are leaving Generally, as solid flux and particle concentration increased, so did
the tertiary treatment phase may not always enter the aquatic ecosystem as transmembrane pressure and filtration resistance. As a synergistic effect
they might get retained in the microparticle loading of the treatment plants. of the increase in resistance, there was also a quick reduction in effluent
But if these particles enter the WWTP once again, the chances for such turbidity due to the rapid development of a dynamic membrane on the
microparticles to escape the treatment phases are high (Michielssen et al., supportive mesh.
2016). Therefore, more advanced treatment methods which are particu-
larly effective against fibers and smaller sized microplastics are required. 3.1.2. Membrane bioreactor
Table 2 gives the different strategies employed and the removal efficiencies Membrane bioreactor has lately gained popularity as a treatment
of microplastics. method in WWTPs (Li et al., 2020; Xiao et al., 2019). Membrane bioreactor
technology incorporates systems wherein the catalysis process is
3. Advanced approaches in mitigation of microplastics aided by organic catalysts such as enzymes or microorganisms and is
linked to a membrane process such as ultrafiltration or microfiltration
3.1. Membrane technology (Ghoshdastidar and Tong, 2013; Xiao et al., 2019). Fig. 3 gives the sche-
matics of a membrane bioreactor. A tailored heterogeneous multiphase re-
Significant advancements for WWTPs are required to increase the effec- action system can be established using the distinct compartments generated
tiveness of microplastics containment (Zhang et al., 2018). However, only a by the membrane. The organic and water phases might be kept separate or
few of these advancements were actually reported with respect to primary disseminated in each other (Judd, 2016). Due to its favorable suspended
and secondary treatments and the majority were advanced treatment particles concentration ranging from 6 g/L to 10 g/L, the membrane biore-
methods like membrane technology (Sonune and Ghate, 2004). Membrane actor has a removal efficiency of 99 % in microplastics removal (Dvořák
processes offer a promising strategy for removing microplastics from et al., 2013; Talvitie et al., 2017a, 2017b). In the studies conducted by Lv

6
Table 2
Different strategies and its effectiveness in removal of microplastics.
Treatment process Characteristics of microplastics after final treatment stage Removal efficiency of microplastics Reference
R.Y. Krishnan et al.

Primary, secondary and tertiary – rapid sand filtration Microplastics size: ≥20 μm Post-secondary treatment: 95.8 %; Rapid sand filtration: (Ben-David et al., 2021)
Microplastics shape: Fibers 97 % (post-tertiary treatment)
Microplastics type: Polyimide fibers: 63.9 %; polyethylene: 13.9 %; polyethylene
terephthalate fibers: 6.4 %; polyvinyl chloride: 5.9 %
Pretreatment, primary, secondary and tertiary Microplastics size: 200–400 μm: 24.3 %, 400–600 μm: 18.6 %; 600–800 μm: 11.4 %; Post-tertiary treatment: 64.26 %; Removal efficiency of (Bayo et al., 2021)
800–1000 μm: 12.9 % microfibers were less compared to particulate microplastics
Microplastic shape: Fibers: 79.65 %; film: 11.26 %; fragment: 9.09 %
Microplastic type: Low-density polyethylene: 63 %
Electrocoagulation Microplastic shape: Microfibers > granular Polypropylene: 98.4 %; polymethyl methacrylate: 91.7 %; (Shen et al., 2022)
Microplastic type: Polyethylene; poly methyl methacrylate; cellulose acetate; polypropylene polyethylene: 93.2 %; 98.2 % for cellulose acetate
Pretreatment, primary – membrane bioreactor and Microplastics size: >2 mm: 10 %; 1–2 mm: 31 %; 0.6–1 mm: 31 %; 0.4–0.6 mm: 24 %; Membrane bioreactor: 79.01 %; Rapid sand filtration: (Bayo et al., 2020a)
tertiary – rapid sand filtration 0.2–0.4 mm: 4 % 75.49 %
Microplastics shape: Fibers: 61 %; Films: 31 %
Microplastics type:
Low-density polyethylene: 71 %; high-density polyethylene: %
Photocatalytic degradation Microplastic type: High-density polyethylene 70 % (Ariza-Tarazona et al., 2020)
Pretreatment, primary and secondary Microplastics size: 0.4–0.6 mm: 35 %; 0.6–1 mm: 28 %; < 0.4 mm: 20 %; 1–5 mm: 17 % 90.3 % (Bayo et al., 2020b)
Microplastics shape: Fragments: 47 %; Fibers: 7 %; Films: 34 %; Beads: 12 %
Microplastics type: Low-density polyethylene: 52 %; high-density polyethylene: 9 %;
polypropylene: 9 %
Pretreatment, primary and secondary – UV treatment Microplastics size: 125–250 μm: 40 %; 40–125 μm: 21 % 76.6 % (Raju et al., 2020)
Microplastics shape: Microfibers: 58 %; micro-fragments: 25 %
Microplastics type: Polyester: 46 %; polypropylene: 24 %;
Pretreatment, primary, secondary and tertiary Microplastics size: > 500 μm: 66 %; < 500 μm: 34 % 55–97 % (Akarsu et al., 2020)

7
Microplastics shape: Microfibers: 46 %; hard and soft plastics: 33 % and 19 % respectively.
Microplastics type: Polyethylene; polypropylene; acrylic, polystyrene and cellulose
Pretreatment, primary, secondary and tertiary – Microplastics size: > 250 μm: 50 %; 63–125 μm: 29 %; 125–250 μm: 12 %; < 63 μm: 8 % Membrane bioreactor: 99.5 % (Lv et al., 2019)
membrane bioreactor Microplastics shape: Fragments: 65 %; fibers: 21 %; films: 12 %
Microplastics type: Polyethylene terephthalate: 47 %; polystyrene: 20 %; polyethylene:
18 %; polypropylene: 15 %
Primary, secondary and tertiary – rapid sand filter Microplastics size: 0.5–0.1 mm: 52 %; 0.1–0.01 mm: 27 %; 5–1 mm: 14 %; 1–0.5 mm: 7 % Rapid sand filter: 84 % (Magni et al., 2019)
Microplastics shape: Lines: 41 %; films: 38 %; fragments: 21 %
Microplastic type: Polyester: 35 %; polyamide: 17 %; polyethylene: 10 %
Pretreatment, primary, secondary – activated sludge, and Microplastics size: < 1 mm: 64 %; > 1 mm: 36 % Conventional WWTP: 98.3 % (Lares et al., 2018)
tertiary – membrane bioreactor Microplastic shape: Microfibers: 50–90 %; fragments: 10–50 % Activated sludge process: 99 %
Microplastics type: Polyester: 79 %; polyethylene: 11 % Membrane bioreactor: 99.4 %
Pretreatment, primary, secondary and tertiary – Microplastics size: 20–100 μm: 71 %; 100–300 μm: 27 %; > 300 μm: 2 % Biologically active filter: 97 % (Talvitie et al., 2017b)
biologically active filter Microplastics shape: Fragments: 62 %; fibers: 29 %; flakes: 9 %
Microplastic type: Polyester: 33 %; cotton: 44 %; linen: 11 %
Pretreatment, primary, secondary and tertiary – rapid Microplastics size: 100–300 μm: 28 %; 20–100 μm: 70 % Membrane bioreactor: 99.9 %; dissolved air flotation: (Talvitie et al., 2017a)
sand filtration, membrane bioreactor, discfilter, and Microplastics shape: Fibers: 29–100 % 95 %; discfilter: 98.5 %; rapid sand filtration: 97.1 %
dissolved air flotation Microplastic type: Polyester: 60 %; polyethylene: 14 %; polyvinylchloride: 5 %
Primary, secondary and tertiary – reverse osmosis Microplastics size: 500–25 μm Reverse osmosis: 90.4 % (Ziajahromi et al., 2017)
Microplastics shape: Microfibers; granules
Microplastics type: Polystyrene: 92–99 %
Pretreatment, primary, secondary and tertiary – Microplastics size: 300–500 μm: 27 %; 10–300 μm: 71 % 72 % (Leslie et al., 2017)
membrane bioreactor Microplastics shape: Microspheres; microfibers; foils
Pretreatment, primary, secondary and tertiary Microplastics size: 5 mm - 50 μm Primary: 58.8 % (Yang et al., 2019)
Secondary: 54.5 %
Tertiary: 71.7 %
Overall: 95.2 %
Primary, secondary and tertiary Microplastics size: 500 μm Secondary treatment: 99.3 % (Simon et al., 2018)
Primary, secondary and tertiary Microplastics size: 100 μm A2O: 98.5 % (Lee and Kim, 2018)
Science of the Total Environment 858 (2023) 159681
R.Y. Krishnan et al. Science of the Total Environment 858 (2023) 159681

Without Dynamic Membrane removal when compared to other tertiary treatment methods like rapid
sand filtration, reverse osmosis, disc filters and dissolved air flotation
FLOW (Talvitie et al., 2017b; Ziajahromi et al., 2017). The employment of a
blend of several enzymes as a preceding maceration step appears to be
the most viable of the newly established techniques for microplastics re-
Microplastics moval using membrane bioreactors. The initial maceration step's goal is
to degrade all organic entities so as to generate a pure microplastic mixture
Clogged Pores
Supporting Layer for future processing (Sun et al., 2019). Several investigations have sug-
gested that phthalate esters can be completely degraded by a diverse
With Dynamic Membrane group of bacteria and actinomycetes (Gao and Wen, 2016; Gong et al.,
2018; Liang et al., 2008). At the moment, membrane bioreactor technology
FLOW in phthalate esters microbial degradation is combined with activated sludge
process from various wastewater sources including municipal and sewage
waste leachates (Boonyaroj et al., 2012; Camacho-Munoz et al., 2012). If
Dynamic Membrane Cake a membrane bioreactor was combined with an initial anaerobic digestion
and proceeded by reverse osmosis filtering, full scale microplastic break-
Supporting Layer
Microplastics down could be achieved (Balabanič et al., 2012). However, the key limita-
tions of membrane bioreactor technology for treatment of wastewater are
congestion and managing the thickness of biofilm formed, all of which de-
Fig. 2. Mechanism associated with dynamic membranes. termine the method's performance efficiency (Nicolella et al., 2000).

et al. (Lv et al., 2019), the use of membrane bioreactors aided in achieving a 3.1.3. Reverse osmosis
high removal efficacy of microplastics (99.5 %). Similarly, the removal of Reverse osmosis is indeed one of the most used and efficient water treat-
polyvinyl chloride microplastics from polluted surface water showed that ment methods (Hailemariam et al., 2020; Zhao et al., 2020). Reverse osmo-
even though there was membrane fouling as a result of the treatment, the sis works by forcing liquid across a semi-permeable membrane to eliminate
microbial community was hardly affected (Li et al., 2020). Furthermore, the impurities from the flow. In municipal wastewater treatment systems,
the technology's flexibility allows for easy assimilation with other advanced reverse osmosis is used to cleanse water by removing pollutants, salts,
processes such as reverse osmosis or pervaporation that are entirely consis- heavy metals, and other contaminants using nonporous screens with pore
tent with the principles and practices of sustainable chemistry, and thereby sizes >2 nm. Right from its inception, the reverse osmosis technology has
providing advanced opportunities in terms of quality enhancement, com- advanced significantly in terms of both synthetic procedures and materials
petitiveness and novelty (Judd, 2016; Westphalen and Abdelrasoul, 2018). used (Goh et al., 2018; Shenvi et al., 2015). Generally, reverse osmosis
Membrane bioreactors can be seen as a conglomeration of activated operates by the exertion of an increased pressure of 1 × 106 to 1 × 107
sludge method and membrane filters. The membrane bioreactor's role in Pa to a saturated solution, forcing the solution to move through the semi-
microplastics treatment is to reduce stream intricacy by decomposition of permeable membrane (Antony et al., 2011). When it comes to operability,
the organic components, resulting in microplastic extraction and subse- fouling of membranes is a significant barrier for consistent membrane func-
quent processing (S. Wang et al., 2019). In general, the cycle begins when tioning (Goh et al., 2018). Therefore, a preparatory stage like pretreatment
a treated effluent approaches the bioreactor, where degradation and bio- with coagulants, disinfectants, and oxidizing agents are often required to
transformation of organic materials takes place. The liquid stream then keep steady flux rates, limit the effects of fouling, and extend the shelf life
gets forced through a membrane filter for effective separation. As a result of the reverse osmosis unit (Jiang et al., 2017).
of the membrane process that proceeds the initial biodegradation phase, The adaptation of reverse osmosis in to WWTP for removal of
microplastics get localized in the retentate phase (Li et al., 2020; Talvitie microplastics has been reported recently (Z. Zhang et al., 2021;
et al., 2017b). It could be added that adsorption was one of the primary pro- Ziajahromi et al., 2017). The efficiency when using reverse osmosis process
cesses behind removal of microplastics by membrane bioreactors. With the for microplastics removal was low when compared to other advanced pro-
membrane pore size being another key factor, and owing to the fact that the cesses like membrane bioreactor. Only around 90 % of the polystyrene
membranes employed in membrane bioreactors had a pore size of 1 μm microplastics were removed after the four stages of primary treatment, sec-
(Li et al., 2020; Melin et al., 2006), they were perfectly suited for the ondary treatment, tertiary treatment and reverse osmosis process using 25
removal of microplastics. μm mesh screens (Ziajahromi et al., 2017). Irregular shaped microplastics
Among the different tertiary treatment strategies employed in WWTPs, in the range of approximately 1 × 107 debris per day were getting released
membrane bioreactors showed the highest percentage of microplastics along with the treated water even after the four treatment stages. In another
study conducted by Zhang et al. (Z. Zhang et al., 2021), reverse osmosis pro-
cess was conducted after ultrafiltration and nanofiltration processes. The
Membrane key observation from the study was that ultrafiltration process showed
Level Sensor Module
higher removal efficiency for microplastics in the size range of 1–5 mm
(75 %) than when compared to both reverse osmosis and nanofiltration.
Pump However, in the microplastics size range of this indicates that the removal
Bioreactor
Wastewater efficiency of reverse osmosis could be enhanced by coupling the process
+ Treated Water with membrane bioreactors which had a stand-alone microplastic removal
Microplastics efficiency of 99 % (Talvitie et al., 2017b). In another study, microplastics
were detected along the Llobregat river area and their characteristics and
removal efficiency in a drinking water treatment facility were investigated
(Dalmau-Soler et al., 2021). After the initial treatment phase of sedimenta-
tion and sand filtration, a microplastics elimination efficiency of 78 % was
Aeration Sludge
achieved. During the successive advanced treatment phase involving mem-
Microorganisms brane filtration and reverse osmosis, a microplastics removal efficiency of
54 % was achieved. In comparison, when conventional treatment methods
Fig. 3. Schematics of a membrane bioreactor. like ozonation was carried out after the initial treatment stages, a removal

8
R.Y. Krishnan et al. Science of the Total Environment 858 (2023) 159681

efficiency of only 18 % was achieved for microplastics. This shows the su- Monascus sp. of fungi disintegrated the polyurethane films (El-Morsy
periority of techniques like reverse osmosis compared to advanced conven- et al., 2017).
tional treatment methods. Other approaches related to synthetic biology, engineered microbes and
Although the use of membrane technology to eliminate microplastics genetic level biotechnological advancements have contributed to the degra-
has only just begun to gain traction, there has been a noticeable uptick in dation of different classes of plastics (Kumari and Chaudhary, 2020; Pratt
the number of studies conducted that combine the membrane bioreactor et al., 2020; Sharma, 2018). Theoretically, eukaryotic organisms may be
and conventional membrane processes with other already established treat- easier for bioremediation applications in WWTPs due to their larger size
ment methods to achieve a better elimination of microplastics. The removal and ability to accumulate microplastics compared to bacteria or fungi.
efficiency of microplastics was strongly dependent upon certain factors like Also, use of prokaryotic organisms pose an additional challenge due to
shape and size of membrane, membrane material, membrane surface prop- the difficulty of containment of these organisms within WWTPs and the
erties, pore size of membrane, and membrane thickness. With a removal increased chance of release of such organisms into the environment
efficiency of 99.9 % for microplastics, among the various membrane pro- (Nuzzo et al., 2020).
cesses, membrane bioreactors stand out as the most interesting among the
tertiary treatment processes. Membrane bioreactors also offer the opportu- 3.2.1. Eukaryotic marine plants and microalgae
nity to reduce the number of processing stages that are required in WWTPs Marine seagrasses has been gaining wide attention due to their ability to
(Poerio et al., 2019). grow in brackish waters and the ease of effluent treatment in sea or
seashores (Lee et al., 2019). Seagrasses also provides a large number of
3.2. Bioremediation valuable services to the environment like coastal defense, carbon sequestra-
tion, and food sources and habitat for different organisms (Luisetti et al.,
Microplastics elimination using various species such as fungi, algae and 2013; Ondiviela et al., 2014). The earliest in-situ evidence revealed
bacteria has lately been researched, and bioremediation is an exciting ap- microplastics binding to seagrasses via encrustation, to macrophyte-
proach (Shahnawaz et al., 2019; Wilkes and Aristilde, 2017). It should be associated epibionts, as well as to the mucus layer (Seng et al., 2020).
noted that use of living organisms for mitigation of microplastics is consid- Seagrasses could therefore operate as a trap or pitfall for microplastics, im-
ered difficult and more studies are required in this area to prove their actual plying that they have the prospective for sludge treatment if cultivated on
effectiveness. The most widely studied bacterial group for plastic biodegra- sludge (Huang et al., 2020b). A wide array of epibiont communities are
dation is Pseudomonas species, known for its ability to degrade different hosted by the seagrass Thalassia testudinum (Goss et al., 2018). Along with
classes of plastics (Wilkes and Aristilde, 2017). Fig. 4 gives an outline those epibionts, T. testudinum also have the ability to accumulate micropar-
about the mechanism associated with bioremediation of microplastics. In ticles and microplastics. In the sample collected close to an urban agglom-
the degradation of high density of polyethylene, Pseudomonas species was eration (Goss et al., 2018), nearly 75 % of T. testudinum blades have
observed to be the most efficient followed by the bacterial species accumulated microplastics either through attachment to the epibionts or
Arthrobacter (Balasubramanian et al., 2010). Similarly, a microbial cocktail through biofilm formation. In another study conducted on Zostera marina,
of Bacillus, Paenibacillus, Stenotrophomonas and Pseudomonas species was similar results were observed with microplastic accumulation in 94 % of
used to reduce the weight of high density polyethylene and low density Z. marina blade samples collected (Jones et al., 2020), with a total
polyethylene by 55 % and 75 % respectively after 120 days of treatment microplastic count of 280 particles (<1 μm).
(Skariyachan et al., 2017). It was observed that Pseudomonas putida, when Algae, notably microalgae, are already being evaluated for their ability
isolated from agricultural fields, has been shown to breakdown 92 % of for bioremediation in wastewater (Rempel et al., 2021). In addition, studies
polyurethane in under four days (Peng et al., 2014). Physical characteristics showed that microalgae, sometimes in combination with bacteria, can
of polyethylene can be altered and intermediate compounds such as ke- breakdown emerging micropollutants in wastewater (Pacheco et al.,
tones and aldehydes can be derived when strains of Pseudomonas putida 2020). Suspended microplastics may be retained on the membranes of sea-
and Bacillus cereus were used (Muhonja et al., 2018). Along with bacteria, weeds such as Fucus vesiculosus (Bonanno and Orlando-Bonaca, 2020;
fungi are among the most studied organism groups because of their poten- Gutow et al., 2016). Microalgae-based bioremediation is a unified idea
tial to break down polymeric contaminants. Relevant to the breakdown of that not only solves problems related to wastewater management but also
microplastics are >27 genera that belong to the phylum Ascomycota, benefits the economy by producing value-added goods. There are various
such as Fusarium and Aspergillus, as well as the phyla Zygomycota and reports of microalgae being effective in the removal of heavy metals, textile
Basidiomycota (X. Zhang et al., 2021). For instance, after 280 days wastes and wastes from rubber industry (Cheng et al., 2019; Posadas et al.,
of incubation at 37 °C, Aspergillus fumigatus lowered the weight of 2014; Sekomo et al., 2012). Therefore, their potential for removing
polyhydroxyalkanoate by 77 %, while at 25 °C, at the same moisture and microplastics from WWTPs is a promising aspect to explore and more stud-
pH, the reduction was only 59 % (Al Hosni et al., 2019). Utilising both li- ies in this dimension would produce exciting results.
pase and esterase, Aspergillus tubingensis aided in breaking down polyure-
thane sheets (Khan et al., 2017). Also, lipase, esterase and protease from 3.2.2. Eukaryotic marine animals
In the studies conducted on marine invertebrates Mytilus edulis (blue
mussel) and Arenicola marina (lugworm), possible effects of microplastics
in the cellular energy metabolism of the organisms were considered (Van
Cauwenberghe et al., 2015). Microplastics in the range of 0.2 ± 0.3
particles/g and 1.2 ± 2.8 particles/g were found in the case of M. edulis
and A. marina respectively. In addition, lugworm A. marina showed an over-
all retention rate of 240–700 microplastics over its entire lifespan with no
adverse effects on its cellular energy metabolism. This shows that the
A. marina, which has a natural habitat in brackish waters can be considered
as a possible candidate for bioremediation of microplastics in WWTPs.
Under experimental conditions, when both these marine invertebrates
were exposed to higher concentrations of polystyrene microplastics (over
110 particles g−1), the organisms did not show any adverse effects on its
overall cellular metabolism. However, more experimental studies on the
Fig. 4. Mechanism associated with bioremediation of microplastics (Model possible negative impacts of microplastics in the overall energy budget of
illustrated for styrene monomer, dimer and polymer). these organisms are required.

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R.Y. Krishnan et al. Science of the Total Environment 858 (2023) 159681

Another marine organism that is considered a possible candidate for same study, replacing synthetic solution with real wastewater samples,
bioremediation of microplastics is sea cucumber. Presence of microplastics the removal efficiency of microplastics was 96.5 %. In another study on
were observed in Apostichopus japonicus samples collected from coastal re- polyethylene microbeads removal from artificial wastewater, the highest
gions of China (Mohsen et al., 2019). A. japonicus ingested microplastics microbeads removal efficiency of 99.24 % was obtained at a pH of 7.5
in the range of 0–30 particles/intestine; and after the filtration of coelomic (Perren et al., 2018). Considering the economic aspects of the process,
fluid, microplastics in the range of 0–19 particles/animal was found. This lower current densities (11 A/m2) was found to be more energy efficient
indicated that the polymers like polyethylene terephthalate, polyesters (Perren et al., 2018). There are also reports of polyacrylamide addition fa-
and cellophane that were originally ingested by the sea cucumber got trans- voring the removal of polyethylene microplastics due to the formation of
ferred to the coelomic fluid of the organism. Based on these observations, it aluminum-based flocculants during electrocoagulation (Ma et al., 2019).
can be assumed that sea cucumbers can be a possible candidate for biore- Therefore, such enhanced methods for removal of microplastics has to be
mediation of microplastics in WWTPS. However, further studies on the studied in more detail for identifying their pros and cons.
harmful effects of microplastics on the metabolic activities of sea cucumber
is imperative for analyzing the actual potential of this strategy. It should be 4.3. Photocatalytic degradation
noted that studies have already been reported on microplastics affecting the
embryonic development of sea urchins (Murano et al., 2020; Nobre et al., Another advanced treatment method that could be operated as part of
2015). tertiary treatment of wastewaters and can be used for the removal of
microplastics is photocatalysis process (Nabi et al., 2020; Uheida et al.,
4. Other advanced approaches 2021). During photocatalytic degradation, bombardment of a semi-
conductor like TiO2 with photons results in the generation of positively
4.1. Rapid sand filtration charged holes, which on subsequent reaction with water results in the gen-
eration of OH• (Xu et al., 2021). Thus, the free radicals generated mineral-
Rapid sand filtration can be an alternative water treatment process that izes the micropollutants adsorbed on the semi-conductor surface to CO2
can be applicable in the case of both sewage water and general water treat- and H2O (Llorente-García et al., 2020). When photocatalysis was used for
ment (Brunner et al., 2019; Hidayaturrahman and Lee, 2019). However, the degradation of high-density polyethylene microplastics using porous
rapid sand filtration is more preferred as a tertiary treatment option post TiO2 semi-conductor, a mass loss of 6.4 % was observed for the
various treatment techniques like sedimentation, coagulation and floccula- microplastics after 18 h of irradiation with visible light (Ariza-Tarazona
tion (Brunner et al., 2019; Patrício Silva, 2021). An advantage of rapid sand et al., 2019). Similarly, in the visible light photocatalysis of low-density
filtration technique is their relatively low maintenance and operational polyethylene microplastics using zinc oxide nanorods (Tofa et al., 2019),
costs. In a study on artificial microplastics samples made from tyre flakes it was observed that the microplastic surface got wrinkled with large num-
and plastic bags, removal using rapid sand filtration was proved effective ber cavities and cracks opening up resulting in the increased brittleness of
(Sembiring et al., 2021). The removal efficiency of microplastics generally the low-density polyethylene microplastic. This was due to the generation
varied with the effective size of filter media. Removal efficiency of 97.7 % of compounds with low molecular weight like peroxides, hydroperoxides
and 90.6 % was achieved using an effective size of 0.39 mm pore size, and a and other unsaturated groups. Similar results were also reported by using
removal efficiency of 94.3 % and 85.2 % for 0.68 mm pore size for plastic photocatalytic TiO2 micromotors (L. Wang et al., 2019). Therefore, the
flakes and tyre flakes respectively. Also, by rapid sand filtration, use of photocatalytic degradation would provide a greener alternative for
microplastics with size >200 μm were removed (Sembiring et al., 2021). thwarting the microplastic pollution menace.
In comparison, when sand and coal filtration system was used (Mason In a photocatalytic degradation study by light in the visible region per-
et al., 2016), the removal efficiency of microplastics was 15 %. Such an ob- formed on spherical polypropylene microplastics using ZnO nanorods
servation might be due to the relative mixing of the coal and sand particles mounted upon glass fiber scaffolds, it was observed that there was around
after operation for a considerable period of time, thus resulting in the in- 65 % reduction in the mean particle volume of microplastics (Uheida
creased porosity of the filter. This shows the relative inconsistencies re- et al., 2021). Similarly, in another study on the degradation of low-
ported in microplastics removal by rapid sand filtration. density and high-density polyethylene microplastics using N-TiO2 coating,
a relationship between size of microplastics and the degradation efficiency
4.2. Electrocoagulation was reported (Llorente-García et al., 2020). Degradation was shown to be
maximum for smaller sized microplastics, and lowest for film-shaped
Electrocoagulation, like rapid sand filter, is a low cost water treatment microplastics; both trends were connected to a lack of light and oxygen in
technique for removal of microplastics (Ungureanu et al., 2020). In electro- the reaction media. It was also observed that the photocatalytic degradation
coagulation process, the sacrificial anodes are dissolved in order to release process was strongly dependent on the presence of surface hydroxyl groups
the coagulant precursors and the electrolysis proceeds at the cathode, and on microplastics (Jiang et al., 2021).
the separation of microplastics is supported by flotation process (Akarsu
and Deniz, 2021). Electrocoagulation is a complicated process in which 4.4. Sol-gel method
metal electrodes create cations in the presence of an electric field (Shen
et al., 2022). There are three phases - starting from the creation of ions to In sol-gel method, microplastic pollutants are separated from polluted
the formation of flocs such as (Perren et al., 2018): wastewater by way of agglomeration caused by the sol-gel process induced
by change in pH. The microplastic flocculates thus generated makes it eas-
(i) Electrons are created in the anode by the electric field, forming
ier for the separation of microplastics from wastewater by using detach-
“micro-coagulants,” Al3+ or Fe3+ hydroxides;
ment methods like sand traps (Collivignarelli et al., 2017). The first step
(ii) Coagulants destabilize suspended particles and colloidal contaminants
in the removal process is the development of an inclusion unit, that serves
in water; and.
as the biomolecular part of the entire molecule. The second step in the re-
(iii) Micro-coagulants and pollutant particles colloid to form micro-flocs.
moval process is the development of an acquisition unit, which is proficient
The distinct advantage of electrocoagulation process is that it could club in linking with the compound to be included via its moiety. The sol-gel
the effects of different conventional treatment techniques like flotation, method allows for the production of organized composite gels of silica,
flocculation, coagulation, and adsorption (Elkhatib et al., 2021). In the which are made possible by the ordered framework of the acquisition
studies conducted on polyesters in synthetic solution, the removal effi- unit. After that, the interplay between the acquisition unit and the
ciency of microplastics was 99 % with current densities in the range of bioinspiration of the inclusion molecule takes place. This aids in the incor-
2.88–8.07 mA/cm2 and pH values of 4–7 (Elkhatib et al., 2021). In the poration of neutral molecules, and it also makes it easy to isolate

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R.Y. Krishnan et al. Science of the Total Environment 858 (2023) 159681

hydrophobic groups that have been collected (Sharma et al., 2021). It is (v) Membrane bioreactors were able to lower the concentration of
possible to perform the sol-gel process in both acidic and alkaline environ- microplastics in the primary effluent from 6 microplastics/L to 5 ×
ments. The flocculation of microplastics can be aided by sol-gel method 10−3 microplastics/L, or 99.9 % efficacy. The incorporation of
strongly dependent on pH. This means that large microplastic flocculates rapid sand filters helped in achieving a removal efficiency of 97 %
in wastewater can be more easily removed. Environmental compatibility for microplastics. In order to further increase the effectiveness of
is exemplified by the fact that heat may be reclaimed and recycled sustain- membrane bioreactors, coupling them with other membrane-based
ably from flocculate isolates (Herbort et al., 2018). Another benefit of sol- operations like reverse osmosis or microfiltration could be effective.
gel process is that agglomeration can occur regardless of the concentration, (vi) Smaller microplastics of size range 20–100 μm were found to pre-
or quantity of trace pollutants or other environmental factors like pressure dominate in majority of WWTPs. Therefore, a cutting-edge advanced
and temperature. The development of polymeric inclusion molecules is the treatment method must be employed to get rid of the microplastics
foundation for remediation of water pollution (Herbort and Schuhen, that are 100 μm or smaller in size.
2017). (vii) Although it seems that the complete removal of microplastics from
our environment is impossible due to its limited visibility and tiny
5. Future outlook size, bioremediation seems to offer a reliable solution for controlling
plastic pollution. Various microorganisms like bacteria (Pseudomonas
Considering the current state of research with respect to microplastics, and Bacillus species), fungi and algae can effectively help in the bio-
there are certain key issues that need to be addressed. The cultivation and degradation of microplastics. Along with the microorganisms, higher
management of candidate species which has the potential to retain marine organisms like sea cucumbers and lugworms too have the po-
microplastics, with special consideration to their containment in WWTPs tential to control microplastics pollution in the environment.
as well as the welfare of such candidate organisms in WWTPs should be (viii) Low-cost advanced treatment methods like electrocoagulation
assessed. Another key factor in controlling the release of microplastics and photocatalysis provide promising results with respect to
into the environment is source control. Development of household type microplastics control. So, integration of such methods into conven-
treatments for microplastics could effectively restrict the release of tional WWTPs is recommended.
microfibers from washing machine sewage. In addition, strict laws and
regulations related to the control of microplastics could pave the way for-
CRediT authorship contribution statement
effective source control. Extensive study is needed to establish the validity
of the analytical methods developed for identifying and characterizing
Radhakrishnan Yedhu Krishnan: Conceptualization, Methodology,
microplastics in WWTPs. The current research cannot be directly compared
Writing – original draft, Data curation. Sivasubramanian Manikandan:
with one another due to the discrepancies among the various units used for
Conceptualization, Methodology, Writing – original draft, Data curation.
quantitative representation of pollutant levels. Novel detection methods are
Ramasamy Subbaiya: Writing – original draft, Formal analysis, Software,
vital for controlling microplastics release into the environment. Therefore,
Validation. Natchimuthu Karmegam: Formal analysis, Writing – review &
advanced approaches for detection of pollutants using nanocomposites or
editing, Data curation, Validation. Woong Kim: Writing – review & editing,
biogenic nanoparticles and nano-sensors are promising (Boregowda et al.,
Software, Resources, Visualization. Muthusamy Govarthanan: Supervi-
2022; Mujtaba et al., 2021). Distinctive processes like enzymatic and
sion, Writing – review & editing, Data curation, Validation.
photo catalysis, interactions of surface-active sites, and electrostatic associ-
ation are observed in biofabricated nanocomposites and aid in the removal
of contaminants (Bhavya et al., 2021; Geetha et al., 2021). Data availability

No data was used for the research described in the article.


6. Conclusions

Even though current WWTPs are able to achieve a high removal effi- Declaration of competing interest
ciency of microplastics (>90 % in most cases), they are not exactly designed
to control the emission of microplastics to the environment. Therefore, a The authors declare that they have no known competing financial inter-
considerable quantity of microplastics is getting released onto the environ- ests or personal relationships that could have appeared to influence the
ment every single day not just from water discharges of WWTPs but also work reported in this paper.
from the disposed sewage sludge. Rather than conventional waste treat-
ment methods, WWTPs has to be equipped with advanced treatment Acknowledgements
methods to counter the unchecked release of microplastics to the aquatic
environment. In this study, the following key observations were made con- The authors would like to thank the Management and Department of
sidering the review of recent literatures: Food Technology, Amal Jyothi College of Engineering, Kanjirappally,
Kottayam, Kerala, India, The Management Saveetha School of Engineering
(i) After the primary treatment process microfibers showed better re- (SIMATS), Chennai, India and The Management, Vice-Chancellor, Dean of
moval characteristics and around 65 % microplastics were removed SMNS, Head of Biological Sciences, The Copperbelt University, Kitwe,
after this stage. The secondary treatment process was successful in Zambia for their constant support to complete the review article. This work
reducing the microplastics percentage to 0.2–14 % and after the was also supported by the Technology Innovation Program (Industrial Stra-
tertiary treatment process the percentage of microcontaminants get tegic Technology Development Program) (RS-2022-00155946, Develop-
reduced to 0.2–2 %. ment of methane gas conversion PHA production technology) funded By
(ii) Considering the shape of microplastics, granules and fragment the Ministry of Trade, Industry & Energy (MOTIE, Korea).
shaped particles were getting separated with much ease compared
to microfibers and pellet shaped particles. References
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