Removal of Microplastics From The Environment. A Review
Removal of Microplastics From The Environment. A Review
Removal of Microplastics From The Environment. A Review
https://doi.org/10.1007/s10311-020-00983-1
REVIEW
Abstract
The production of fossil fuel-derived, synthetic plastics is continually increasing, while poor plastic waste management
has recently induced severe pollution issues. Microplastics are plastic particles smaller than 5 mm. Microplastics are ubiq-
uitous and slowly-degrading contaminants in waters and soils. Microplastics have long residence time, high stability, high
potential of being fragmented and can adsorb other contaminants. Many aquatic species contain microplastics, which are
in particular easily accumulated by planktonic and invertebrate organisms. Then, microplastics are transferred along food
chains, leading to physical damages, decrease in nutritional diet value and exposure of the living organism to pathogens.
Raw plastics contain chemical additives such as phthalates, bisphenol A and polybrominated diphenyl ethers that may induce
toxic effects after ingestion by living organisms. Furthermore, the adsorption capability of microplastics makes them prone
to carry several contaminants. Methods to remove microplastics from water and other media are actually needed. Here, we
review microplastics occurrence, transport, raw polymers and additives, toxicity and methods of removal. Removal methods
include physical sorption and filtration, biological removal and ingestion, and chemical treatments. Mechanisms, efficiency,
advantages, and drawbacks of various removal methods are discussed.
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polyethylene (PE) and polyamide (PA, nylon). Poor plastic the environment, is the secondary source of microplastics
waste management has resulted in ubiquitous microplastics (Eriksen et al. 2014). This increases plastic debris availabil-
occurrence (Gilani et al. 2019; Thompson 2015). Several ity for being ingested by a large variety of organisms and
reports show that long-term exposure to microplastics causes highlights the appearance of further environmental hazards
chronic toxicity, yet there is no evidence on their acute fatal (Thompson et al. 2009).
effects (Li et al. 2018a; Sussarellu et al. 2016). Microplas- Wastewater treatment plants are also a major source of
tic toxicity is controlled by different routes depending upon microplastics release (Browne et al. 2011; Long et al. 2019).
their chemical structure and additives used as linkage dur- Whereas large plastic particles are efficiently removed dur-
ing polymerization (Meeker et al. 2009; Sussarellu et al. ing wastewater treatment, microplastics often bypass the
2016). As an example, polystyrene microplastics are able to treatment units, thus entering and accumulating in the
be transferred in blood, causing reproductive disruption in aquatic environment (Murphy et al. 2016). Noteworthy,
marine filter feeders (Law et al. 2014). a large number of water treatment plants are located near
To our best knowledge, this is the first review on micro- the ocean and seawater, thus inducing a high microplastic
plastics removal. We discuss microplastic additives, occur- release source. For instance, in mainland China, about 1873
rence, transport and toxicity, then we review removal wastewater plants (56%), out of 3340, with 78 × 106 m3/day
methods. Removal methods include sorption and filtration, of treatment capacity, are located in coastal regions where
removal based on chemical phenomena, and biological their effluents can be directly or indirectly discharged into
ingestion treatments. Advantages, disadvantages and effi- aquatic ecosystems (Jin et al. 2014). To address this issue,
ciency of different methods are compared at the end. many researchers are investigating the fate, occurrence,
detection and removal of microplastics in the water treat-
ment plants (Beljanski 2016; Carr et al. 2016; Sun et al.
Microplastic sources, transport, polymers 2019).
and additives
Microplastic transport
Microplastic sources and occurrence
Sea and ocean are viewed as the major sinks for microplas-
Microplastics can be found worldwide in coastal regions tics, whereas freshwaters and terrestrial environments are
and aquatic ecosystems in various size fractions due to the main sources. Indeed, early research found that micro-
the transport phenomena including wind and ocean cur- plastic litter reaching oceans by rivers contains particles
rents. Primary sources are household sewage discharge found in soils (Horton et al. 2017a). This implies that
including polymeric particles from cosmetic and cleaning freshwaters and soils are also sinks of microplastics, as
products, feedstocks used to manufacture plastic products, evidenced by high concentrations of microplastics in some
and plastic pellets or powders used for air blasting (Jiang terrestrial and freshwater areas (Nizzetto et al. 2016).
2018). Progressive fragmentation of larger plastic items The long-term durability of microplastic fibers found in
under the atmospheric conditions, e.g., by mechanical deeper layers (~ 25 cm) of agricultural soils treated by
degradation and UV light exposure, thus contributing to sewage sludge as fertilizer (Zubris and Richards 2005),
the entrance of considerable amounts of microplastics to suggests a gradual transport in solid media, then further
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accumulation at depth; thus making agricultural and forest the inland freshwaters of Wuhan in China ranged between
soils more likely to retain microplastics compared to urban 1660.0 ± 639.1 and 8925 ± 1591 numbers/m3; here the major
areas (Lwanga et al. 2017). types were polyethylene terephthalate and polypropylene
As rivers carry a huge volume of plastic particles over (Wang et al. 2017). Low-density polyethylene has been also
the large distances, microplastics probably settle out along identified as the dominant type of microplastics.
with sinking sediments, particularly where flow energy Microplastics contain a large variety of chemical addi-
drops, for instance in retard-moving riverbeds. Accord- tives such as bisphenol A, phthalates and polybrominated
ingly, futher sediment deposition of microplastics in lakes diphenyl ethers, which are used during raw plastic synthesis
where water flow is the lowest and sedimentation rate is to improve plasticity (Besseling et al. 2014, Murphy 2001).
high, should induce high accumulation (Corcoran et al. These additives are endocrine disruptors, and thus may
2015). exhibit toxic effects upon release. The concentration of such
The shape diversity, small size, lightweight and low plasticizers in plastic debris of remote and urban beaches
density of microplastics contribute to their widespread is up to 35 ng/g in remote beaches and up to 700 ng/g in
transport and facile dispersal across large distances on urban beaches for bisphenol A; between 0.1 and 400 ng/g
land and within aquatic systems by storm sewers, wind and in remote beaches and up to 9900 ng/g in urban beaches for
other natural currents (Horton and Dixon 2018). Larger polybrominated diphenyl ethers; and up to 3940 ng/g for
size and higher density result in facile sinking and sedi- phthalates (Hirai et al. 2011). These plastic additives have
ment deposition of the microplastics (Horton et al. 2017b). been detected in most microplastic polymers (Jiang 2018).
Furthermore, irregularly shaped microplastics with jagged Researchers also reported the leaching of bisphenol A and
geometry and sharp ends are more likely retained under- nonylphenol from silicone and polycarbonate microplas-
water, rather than returning to the surface, whereas spheri- tics (Fasano et al. 2012). Accumulation of such chemicals
cal particles show a higher tendency to stay at the surface in human bodies through biological phenomena is also
(Ballent et al. 2012; Lagarde et al. 2016). reported (Talsness et al. 2009). The most alarming exposure
Microplastics transport pathways in the air are not fully route to microplastics for human is food, where the adverse
understood (Horton and Dixon 2018). Noteworthy, in the effects of the chemical additives and mechanism of entrance
air, there are few dispersal boundaries, compared to water to the organs are still unexplored (Wright and Kelly 2017).
systems. Nonetheless, microplastics transport within the Accordingly, many efforts must be devoted to finding effi-
atmosphere is not totally independent of aquatic and ter- cient strategies to abate the presence of microplastics in the
restrial pollutions, and here further investigations are environment. While there have been published reports on
needed to elucidate the mechanisms (Dris et al. 2016). characterizing sources, occurrence, fate, methods for detec-
As another major concern, due to their hydrophobic- tion, and environmental effects; to date, few research and
ity and high surface area/volume ratio, microplastics are review papers have discussed removal processes of micro-
highly susceptible to sorb and carry persistent organic plastics from contaminated systems.
pollutants such as polychlorinated biphenyls (PCB),
dichlorodiphenyltrichloroethane (DDT) and polyaromatic
polycyclic aromatic hydrocarbons (PAH), which can be Toxicity of microplastics
subsequently transferred to coastal regions and be des-
orbed inside living organisms (Browne et al. 2013). Conse- Toxicity from the chemical structure
quently, the concentration of organic pollutants in coastal
areas is expected to increase several orders of magnitude The potential toxicity of microplastics arises from unre-
as a result of pollutant transport by microplastics. Micro- acted monomers, oligomers and chemical additives leaked
plastic morphology and transport are thus major charac- from the plastic in the long rub (Thompson et al. 2004).
teristics controlling the other waterborne pollutants (Cole Monomers and oligomers are both able to migrate from
et al. 2011). food packaging materials (Piringer and Baner 2008). As the
concentration of the residuals reaches specific limits, they
Microplastic raw polymers and additives can be potentially absorbed by human bodies via different
pathways. For instance, the presence of polystyrene residuals
Polymeric ingredients of primary microplastics mainly in food materials is reported to cause serious health issues,
include polyethylene, polypropylene and polystyrene, while epoxy resins made of bisphenol A are absorbed by
depending upon the type of the products manufactured by the living tissues, then interfer with the rate of cell division
factory; while secondary microplastics are predominantly (Lau and Wong 2000).
made of polyester, acrylic and polyamide, forming fibers in Chemical additives are used during polymers manufac-
the environment (Jiang 2018). The microplastic number in turing for improving the products performance. Additives
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include functional additives such as plasticizers, heat stabi- former case. They explained the mechanism by interactions
lizers, flame retardants, antioxidants, colorants, e.g. soluble between the cell wall components of the marine mussels,
azo-colorants and pigments, fillers such as kaolin and clay, e.g. p-glycoprotein, involved in pollutant excretion, and
and reinforcements, e.g. carbon and glass fibers. These addi- the microplastics surface.
tives are another source of toxicity. For example, researchers Zhang et al. (2017) investigated the adverse effects of
found that the release level of some phthalates from baby microplastics on the photosynthesis of the marine microal-
bottles was in the range of 50–150 μg/kg of food content gae Skeletonema costatum. They found that the maximum
after the contact time of 120 min at 70 °C (Simoneau et al. growth inhibition ratio reached up to 39.7% after 96 h of
2012). The release level of bisphenol A from food packag- exposure to microplastics with average diameter of 1 μm.
ing items was estimated to be in the range of 100–800 ng/L, Their results show a drastic decrease in chlorophyll content
while the values were in the range of μg/L for some phtha- (20%) and photosynthetic efficiency (32%) after exposure
lates under the same conditions (Fasano et al. 2012). Most of to high concentration of microplastic (50 mg/L), leading
these additives are not chemically bound to the bulk plastic to negative effects on microalgae growth. According to
structures, implying easier release. the results of morphological studies and scanning electron
Nobre et al. (2015) studied the toxicity of raw and beach- microscopy (SEM), they proposed both adsorption and
stranded microplastics on the development of embryos of aggregation of microplastics on the outer surface of micro-
Lytechinus variegatus, simulating leaching of the chemi- algae as the most probable mechanism of toxicity.
cal additives into the water column and interstitial water by Size dependency of microplastics toxicity was also con-
assays of elutriate and pellet–water interface, respectively. firmed by Lu et al. (2016) who investigated the exposure
They found that raw microplastics induced more toxicity, effects of polystyrene microplastics to zebra fish. They stated
enhancing anomalous embryonic development by 58.1% that a 7-day exposure resulted in accumulating the micro-
and 66.5% for the former and latter evaluation method, plastics with size of 5 μm in liver, gill and gut, while those
respectively. Their results also implied that the leaching with size of 20 μm were just found in fish gill and gut. More-
of chemical compounds strongly depends upon the media over, lipid accumulation and inflammation of liver, oxidative
compartment in which microplastics accumulate, and upon stress, and adverse alterations in the metabolism profile of
the exposure pathway. Hahladakis et al. (2018) reviewed the fish liver were the main toxicity outcomes.
migration and release rate, fate, and potential toxicity effects The shape and texture of the ingested microplastics also
of additives on organisms and environment. The release of influence their toxicity and absorption capability. According
volatile compounds, e.g., benzene, toluene, ethylbenzene, to Au et al. (2015), polypropylene microplastic fibers were
styrene and methylene chloride, from plastics can also con- more toxic than polyethylene microplastic spherical particles
tribute to chronic health effects (Andrady 2017; Huff et al. to the freshwater amphipod, Hyalella azteca. They attrib-
2010; Wexler and Gad 1998). uted this to the longer residence time of the fibers in gut,
which modifies the ability of food processing, thus leading
Toxicity from physical properties to serious changes in sublethal endpoints.
Microplastics exert damage through the effect of a relatively Toxicity from microorganisms carried
large surface area/volume ratio. They absorb hydrophobic by microplastics
pollution from water, then carry this pollution to other habi-
tats (Setälä et al. 2014). A study of the effect of phenan- The potential of microplastics to carry pathogenic bacteria
threne-loaded low-density polyethylene glycol microplastics has been explored by Kirstein et al. (2016). They observed
on biomarker responses in juvenile African catfish revealed Vibrio parahaemolyticus bacterial strains on some polyeth-
significant tissue changes in the liver and brain of the organ- ylene, polypropylene and polystyrene marine microplas-
ism (Karami et al. 2016). tic particles gathered from North Sea. They highlighted
The ingestion of microplastics by biota is a common way the need for further consideration of health impacts of
to induce toxicological effects (Hämer et al. 2014). Polysty- microbial assemblages in microplastics. A 10-day expo-
rene microplastics enhance the bioavailability of fluoran- sure to five types of ~ 70 μm microplastics led to intesti-
thene compounds to marine mussels (Mytilus spp.) after nal damage including splitting of enterocytes and cracking
7 days of exposure under controlled experimental condi- of villi in zebrafish Danio rerio and nematode C. elegans,
tions (Paul-Pont et al. 2016). These results mean that ther as model organisms of freshwater (Lei et al. 2018). They
is a higher fluoranthene concentration in mussels exposed also demonstrated that 2-day exposure of 5.0 mg/m2 of
to fluoranthene-loaded microplastics than those exposed to microplastics considerably reduced calcium levels and sur-
pure fluoranthene. Highest levels of antioxidant markers vival rates, and inhibited body length and reproduction of
and histopathological damages were also observed for the
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C. elegans. They suggested that oxidative stress and intes- contaminants on the surface, carry them and desorb into the
tinal damages are the main toxicity effects of microplastics. new habitats (Rios et al. 2007). Their large surface area/
Prata (2018) reviewed the potential toxicity of airborne volume ratio makes adsorption of other contaminants likely.
microplastics and adverse effects of their low environmental Sundbaek et al. (2018) studied the adherence behavior
concentrations on human health. They discussed the diseases of fluorescent microplastic particles on the surface of an
aroused from airborne microplastics and pathophysiological edible marine microalgae, seaweed, named Fucus vesicu-
mechanisms of toxicity including dust overload, oxidative losus. The diameter size of the polystyrene microplastics
stress, translocation, and gene mutation. They proposed that was ~ 20 μm, while the plant cells of the sorbent contained
exposure to low atmospheric concentrations can contribute very narrow microchannels to restrict the translocation
to incidence of cardiovascular, respiratory, and interstitial of polystyrene microplastics into the tissues. The results
lung diseases. revealed a high sorption of microplastics (~ 94.5%), mainly
Overall, the toxicity of microplastics arises from near the cut surfaces of the seaweed, which is explained by
raw chemical additives, adsorption and transport of pollut- the role of released alginate compounds from cell walls in
ants and microbes, and release to life and the environment. the cut regions. Indeed, because of the gelatinous charac-
Toxicity depends physically on size and shape of microplas- teristics of this anionic polysaccharide substance, alginate
tics. Biota and humans are affected by toxic effects of micro- is able to improve the adherence of polystyrene particles
plastics via mechanisms including sorption and aggregation on the seaweed’s surface (Martins et al. 2013). This paper
in different organs, ingestion, and exertion of physical dam- and the other researches on microalgae capabilities to sorb
ages and disturbing the life systems. Research is needed to tiny plastic particles accentuate the effective role of micro-
clarify how microplastics induce tissue changes and patho- plastics’ surface charge and microalgae’s surface characters
logical disorders. (Bhattacharya et al. 2010; Nolte et al. 2017). Investigating
the adsorption of 20–500 nm polystyrene particles onto uni-
cellular green algae, Pseudokirchneriella subcapitata, Nolte
Removal of microplastics using sorption et al. (2017) concluded that positively charged polystyrene
and filtration methods microplastics are more efficiently adsorbed on the algae’s
surface than those with negative charge.
Adsorption on green algae Overall, the sorption of microplastics on algae surface
strongly depends on particles’ surface charge. Positively
The presence of microplastics in aquatic environments is charged microplastics have higher tendency to be sorbed
expected to be more critical than other pollutants due to more efficiently, which is explained by the presence of an
several harmful effects and death of organisms, e.g. fishes, anionic polysaccharide in the algal chemical structure.
mammals, marine birds and reptiles, arising from their
entanglement and bioaccumulation (Cole et al. 2011; Gra- Removal using membrane technology
ham and Thompson 2009; Gregory 2009). Their persistence
and low degradability call for removal methods. Microplas- Li et al. (2018b) reported the use of dynamic membranes
tics are generally categorized as persistent materials but for the efficient removal of microplastics from a synthetic
they degrade more of less depending upon their nature and wastewater (Fig. 2). They investigated the effect of influent
chemical structure. Microplastics with half-life times lower flux and particles concentration on the removal efficiency
than the values defined in terms of REACH criteria for per- of dynamic membranes formed on a diatomite platform
sistency (Table 1) can be considered as degradable, and with 90 μm of supporting mesh during filtration of the syn-
do not pose a threat to the environment (Verschoor 2015). thetic wastewater. Excellent filtration of microplastices was
Microplastics are prone to sorb a large variety of waterborne obtained in 20 min by decreasing the turbidity from 195
NTU for the influent to less than 1 for the effluent (Ersahin
et al. 2017; Horton and Dixon 2018). Dynamic membrane
Table 1 Persistency criteria for contaminants in different media formation is facilitated at higher influent fluxes and micro-
according to the REACH Annex XIII (Verschoor 2015) plastics concentrations.
Compartment Half-life (days) Ward (2015) designed an efficient microplastic removal
tool based on polymer coatings as an elongated mesh
Marine water > 60
screen. He claimed that the tool has good durability and
Fresh or estuarine water > 40
has the advantage of being easily fabricated from com-
Marine sediment > 180
modious materials. Other tool advantages included the
Fresh or estuarine sediment > 120
absence of electrical power and mechanical devices.
Soil > 120
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Membrane bioreactors, however, exhibit higher capacitie Removal using advanced filtration technologies
than simple dynamic membranes for the removal of micro- in wastewater treatment plants
sized plastics (Lares et al. 2018; Talvitie et al. 2017a). Kno-
block et al. (1994) studied the purification capability of a Lares et al. (2018) recently studied the performance of a
coupled system, taking advantage of porous membranes in municipal wastewater treatment plant operating based on
combination with biological processes. Successful removal a pilot-scale, combined membrane bioreactor–conventional
of a large variety of complex industrial wastewaters by mem- activated sludge methodology for the removal of micro-
brane bioreactors confirms the suitability of this technol- plastics. Their study took 3 months and sampling cam-
ogy for the treatment for high-strength contaminants such paigns were every 2 weeks. The wastewater samples were
as polymeric debris and microplastics (Gurung et al. 2016). collected from a municipal water treatment plant located
Talvitie et al. (2017a) investigated the removal of various next to the city center of Mikkeli in Finland. Including an
types of microplastics from wastewater treatment plant aeration tank, for mixing the wastewater with air to activate
effluents using advanced final-stage treatment technologies microorganisms, and a sedimentation tank, where the sludge
including membrane bioreactor, disk filter, rapid sand fil- is separated from the treated wastewater, for the biologi-
tration, and dissolved air floating (Fig. 3). They concluded cal degradation and secondary purification, respectively, a
that the membrane bioreactor eliminated 99.9%, from 6.9 conventional activated sludge system is also expected to
to 0.005 microplactic particle per L (Table 2). They also improve the activity (Gurung et al. 2016). Results revealed
showed that membrane bioreactor, rapid sand filtration and a better removal of microplastics (99.4%) using a membrane
dissolved air floating removed microplastics of any size, bioreactor compared to the conventional activated sludge
even the smallest size fractions of 20–100 μm. Moreover, treatment system (98.3%). Microplastics concentration in
the removal efficiency did not depend upon the microplastics the final effluent of the former system was estimated to be
shape; particularly, textile fibers which were predominant in 0.4 ± 0.1 MP/L, which was lower in comparison with that
both influents and effluents during the treatment, were effi- evaluated for the later process (1.0 ± 0.4 MP/L). They also
ciently removed. Analysis of the samples by Fourier trans- stated that the main reason for observing a narrow range of
form infrared spectroscopy (FTIR) indicated that the mem- final microplastics concentrations is probably due to opting
brane bioreactor highly decreased the number of polymers for different processing steps and wastewater samples than
in the final effluent, too, which highlights the good sorption previous works (Leslie et al. 2017; Mintenig et al. 2017;
capacity of the setup to trap microplastics of various chemi- Murphy et al. 2016).
cal structures. 11 wastewater treatment plants in Changzhou, China,
Membrane technologies were successfully used to remove were studied for their efficiency to remove microplastics
microplastics from polluted aquatic environments. The by following the abundance, color, shape and dimensional
removal efficiency over the membranes particularly depends changes during the removal steps (Ma et al. 2019). All plants
on its durability, influent flux, size, and concentration of the that used several treatment steps such as subsequent tanks
microplastics. The combination of porous membranes with for floating and sedimentation, and filtration processes, elim-
biological processes could enhance the removal efficiency inated more than 90% of microplastics from the influents,
up to 99.9%. with a final removal efficiency reaching 97.15%. The most
important reasons that cause variation in removal efficiencies
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Table 2 Average microplastic Treatment Effluent type Before (MP/L) After (MP/L) Removal (%)
concentrations before and
after treatment with different Disk filter 10a Secondary 0.5 0.3 40.0
technologies
Disk filter 20a Secondary 2.0 0.03 98.5
Rapid sand filter Secondary 0.7 0.02 97.1
Dissolved air flotation Secondary 2.0 0.1 95.0
Membrane bioreactor Primary 6.9 0.005 99.9
might be daily processing volume, different raw water and aerated grit treatment, while the removal efficiency reached
type of treatment processes. Large-size microplastics were to 71.67% following the advance treatment processes.
less abundant in the effluents, in agreement with previous Although the overall removal efficiency in the present sew-
reports (Horton and Dixon 2018). In addition, fiber rayon age treatment plant, of 95.16%, was outstandingly less than
and polyethylene terephthalate were the main ingredients that of for membrane bioreactors, of 99.9%, it was compa-
of these microplastics, and reached the highest removals. rable to the efficiency of dissolved air flotation technolo-
The microplastics removal methodology used by munici- gies and sand filters (Talvitie et al. 2017b). Noteworthy, the
pal sewage treatment plants was studied by researchers in treatment processes currently employed at sewage treatment
Beijing, China (Yang et al. 2019). The influents were ini- plants are not necessarily designed for the removal of micro-
tially treated by a series of processes including aerated grit plastics. Regardless, these processes are able to eliminate
chamber, primary and secondary sedimentation tanks fol- a large portion of microplastics from the wastewater. The
lowing A2O treatments, e.g., anaerobic, anoxic and aerobic. researchers finally estimated that sewage treatment plants
Finally, advanced treatment processes including denitrifica- release almost 0.59 × 10 9 items of microplastic into the
tion, ultrafiltration, ozonation and ultraviolet are applied to aquatic ecosystems.
complete the cycle and remove microplastics from waste- Overall, sorption and filtration methodologies show
water. The results of FTIR analysis revealed the presence of a good efficiency for the treatment for microplastics-con-
18 polymers in the effluent, in which polyethylene tereph- taining wastewater, mainly in combination with other pro-
thalate and polyester had the highest abundances of 42.26 cedures such as biological and sedimentation processes. To
and 19.1%, respectively. 58.84% of the microplastics popu- achieve higher removal efficiency, membrane bioreactors are
lation in influents was removed during the primary step of simultaneously used with other advanced physical–chemical
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treatments in most wastewater treatment plants all over the has better performance than Fe3+. Also, the microplas-
world, but it has still been confirmed that these plants act as tic removal efficiency was scarcely modified by the pH of
microplastics sources to aquatic environment. the solution at low concentration of Al coagulant source,
0.5 mM, whereas removal efficiency decreased by increas-
ing the pH, particularly for small-sized microplastics, of
Chemical methods to treat microplastics diameter lower than 0.5 mm. They found that polyacryla-
mide (PAM), an enhancing coagulation agent, increased
Many wastewater treatment plants worldwide use coagula- the removal efficiency for small microplastics much better
tion and agglomeration processes to form enlarged contami- than for large particles under high Al dosage of 5 mM. This
nant particles that are easier to separate (Hu et al. 2012; Lee highlights the greater growth rate of small microplastics in
et al. 2012; Shirasaki et al. 2016). These processes involve the presence of cationic polyacrylamide. The growth rate
Fe- and Al-based salts and other coagulants to bind tiny was highly enhanced when anionic polyacrylamide was
particles via uptake-complexation mechanisms initiated by used for the removal efficiency for the smaller microplas-
a ligand exchange, thus forming strong bonds between waste tics (d < 0.5 mm): here the removal was raised from 25.83%
particles (Chorghe et al. 2017). without polyacrylamide to 61.19% with 15 mg/L polyacryla-
Ariza-Tarazona et al. (2019) recently studied the removal mide, while it just increased from 4.27% to 18.34% for larger
of polyethylene microplastics using iron and aluminum microplastics, of 2–5 mm diameter.
salt coagulants and ultrafiltration (Fig. 4). The experi- Ariza-Tarazona et al. (2019) also explored the removal
ments were carried out under different concentrations of the microplastics with the same method but using
of Al3+ and F e3+ ions, and the results indicated that A l3+ FeCl3·6H2O coagulation agent (Fig. 5). They found that the
Fig. 4 Microplastic removal by coagulation, sedimentation and ultrafiltration (UF) (Ma et al. 2019). The effect of anionic polyacrylamide
(PAM), pH and the formation of Al-based flocs on the removal efficiency is well represented
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Fig. 5 Removal of polyethylene microplastics from the wastewater formation of Fe-based flocs on the removal efficiency is well repre-
using Fe3+ coagulation, sedimentation and ultrafiltration processes sented. MPs microplastics, UF ultrafiltration
(Ma et al. 2019). The effect of polyacrylamide (PAM), pH and the
removal at neutral pH enhanced as the coagulant concentra- Mn+ + nOH− → MOHn(s) (5)
(aq)
tion increased and, this trend being clearer for small micro-
plastics, of d lower than 0.5 mm. Similarly, the removal effi- The produced coagulants break up the colloids and sta-
ciency was accelerated at high pH and high concentration, bilize the suspended microparticles surface charges, which
2 mM, of the coagulant and for lower size of the micro- allows the particles to get close to each other sufficiently for
plastics. However, in this case and under high dosage of making interactions via van der Waals forces (Akbal and
the coagulation agent, 2 mM, anionic polyacrylamide acted Camcı 2011). The coagulants simultaneously form a sludge
much better than the cationic one to improve the removal blanket to trap the suspended microplastics in the wastewater
rate of polyethylene microplastics. This can be mechanisti- sample. The results show a removal efficiency higher than
cally explained based on facile formation of Fe-based flocs 90% for all experiments using proposing electrocoagula-
during the coagulation process, during which anionic poly- tion. The highest removal efficiency, 99.24%, was obtained
acrylamide makes the products dense enough to be easily with pH of 7.5 and NaCl concentration of 0–2 g/L. Further-
trapped and separated. more, the lowest tested current density of 11 A/m2, which
Researchers have also used the robust and environmen- is the best in view of energy consumption, was the most
tally compatible electrocoagulation technique (Perren et al. efficient for achieving the highest removal rate.
2018), which allows sludge minimization, energy efficiency, Herbort et al. (2018) suggested agglomeration based on
cost-effectiveness, and flexibility to automation, to remove alkoxy-silyl bond formation via sol–gel reactions as a new
the polyethylene microplastics in a stirred-tank batch reactor sustainable removal approach for treatment for the micro-
(Fig. 6). In situ formation of the metal hydroxide coagulants plastics originating from inert products of the textile and
is initiated by the reaction of metal ions such as Fe2+ and cosmetic industries. Functionalized molecular precursors
Al3+ released from sacrificial electrodes in a water stream were initially synthesized in an inert atmosphere, then used
with hydroxyl anions of the media; Eqs. 1–4 display the for bio-inspired alkoxy-silyl formation. Meanwhile, micro-
anodic and cathodic reactions, respectively: plastics adhered together to form large three-dimensional
agglomerates which can, afterward, be removed using cost-
n+
M(s) → M(aq) + ne− (1) efficient filtration methods (Fig. 7). The sol–gel formed in
this way is similar to hybrid organic–inorganic silica gels
2H2 O(l) → 4H+(aq) + O2(g) + 4e− (2) with a large variety of benefits and usages in sensors and
optical materials, medicine, and corrosion protection (Nicole
et al. 2004).
Mn+
(aq)
+ ne− → M(s) (3) The mechanisms of degradation of microplastics are
not fully known. Brandon et al. (2016) studied the degra-
2H2 O(l) + 2e− → H2(g) + 2OH− (4) dative changes of the chemical structure of two types of
microplastics including polypropylene and polyethylene
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Fig. 6 Bench-scale reactor setup for the removal of microplastics using electrocoagulation method in which Al3+ acts as coagulation agent (Per-
ren et al. 2018)
for 3 years under simulated realistic weather conditions. and the average size of the microplastics play a role in the
According to FTIR analysis, they found some slight nonlin- adsorption capacity and surface properties, which affect the
ear changes with time in moieties like carbonyl, hydroxyl microplastic oxidation rate significantly. Degradation of
and carbon–oxygen bonds, implying microplastics slow polyethylene microplastics in artificial seawater under dark
degradation. and UV radiation to evaluate the structural and morphologi-
The exposure of macroplastics to elements (Colom et al. cal alterations has been recently reported (Da Costa et al.
2003; Gulmine et al. 2003), microorganisms (Pathak 2017), 2018; Pathak 2017). FTIR analysis of the initial materials
catalysts (Hazrat et al. 2015), and photo-active materials (Li and products (Fig. 8) evidenced the stronger degradative
et al. 2010) has been widely reported but there are no large role of the artificial seawater compared to UV illumination.
number of publications on microplastics degradation. Liu This was confirmed by an increase of the organic content
et al. (2019) studied the long-term aging behavior of poly- of the medium. As a control experiment, the researchers
styrene and polyethylene microplastics treated by a com- exposed microplastics to UV light alone for the same period
bined heat-activated persulfate and Fenton method in the of time and did not observe significant changes in the chemi-
aquatic environment. According to their results, O/C ratio cal structure, thus showing implying that salt is needed to
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Environmental Chemistry Letters
Fig. 7 Removal of polyethylene microplastics using alkoxy-silyl- synthesis reaction in the middle exhibits the formation process of the
induced agglomeration. The microscopy images of the microplastic coagulation agent (Nicole et al. 2004)
before agglomeration (above left) and after that (above right). The
form oxidized sites. SEM images also revealed the effect of air, is the mostly common process for the breaking of poly-
salt on microplastic surface morphology, in which observ- meric chains (Yousif and Haddad 2013). Different mecha-
able crack lines were clearly detected. This strengthens the nisms were suggested for the photochemical processes in the
fact that media salinity facilitates microplastic degradation aqueous phase, in which hydroxyl radicals strongly promote
(Vasile and Pascu 2005). the degradation reactions (Li et al. 2010). Heterogeneous
Photocatalytic degradation of the organic contaminants is photocatalytic degradation of low-density polyethylene
a destructive process triggered by absorbed photons on the microplastics has been recently investigated in the aquatic
surface of a semiconducting material for generating hyperac- media over the rod-like ZnO nanoparticles (Tofa et al. 2019).
tive radicals. Depending upon the semiconductor band gap, From the optical images, morphological changes including
the energy of the incident photons and, subsequently, the the appearance of wrinkles, brittleness, cracks and spots on
suitable light source must be chosen. Photooxidation degra- photo-exposed surfaces of the microplastics were observed
dation, that is oxidation in the presence of light source and (Fig. 9). Also, the results revealed variations in elasticity
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Environmental Chemistry Letters
properties of the sample exposed to photocatalytic condi- (−CH2 − HCOO⋅ − CH2 −)n + (−CH2 − CH2 −)n
tions in comparison with nonirradiated wastewater, and → (−CH2 − HCOOH − CH2 −)n + (−CH2 − CH⋅ −)n
this directly is in correlation to the changes in the strength (8)
of chemical bonds. Accordingly, the nanorods surface area
influenced the stiffness degree of the microplastics and the (−CH2 − HCOOH − CH2 −)n → (−CH2 − HCO⋅ − CH2 −)n + OH⋅
photocatalytic performance. Liang et al. (2013) obtained (9)
FTIR data which confirmed the presence of newly formed (−CH2 − HCO − CH2 −)n → carbonyl groups (norrish type I)
⋅
functional groups such as carbonyl and vinyl during the pho- (10)
tocatalytic treatment, they proposed a mechanism for the
(−CH2 − CO − CH2 −) → (−CH2 − CO⋅ )n
mineralization of microplastics in wastewater (Eqs. 6–13):
+ (⋅ CH2 − CH2 −)n (norrish type II) (11)
(−CH2 − CH2 −)n + OH → (−CH2 − CH −)n + H2 O (6)
⋅ ⋅
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Environmental Chemistry Letters
The design and degradative capability of the T iO2-based the removal efficiency. The SEM images and FTIR spectra
micro- and nanodevices for the photocatalytic treatment have also provided good evidences to confirm the structural
for microplastics have been studied (Sekino et al. 2012). changes during the mineralization process.
Holding high potential for water purification, remediation of To conclude, coagulation and agglomeration methods
environmental pollutions and medicinal usages, photo-active have been investigated to remove microplastics in the labo-
micromotors have attracted huge attention (Eskandarloo ratory. The efficiency depends on the type of coagulant, pH,
et al. 2017; Zhang et al. 2018). Wang et al. (2019) reported the chemical composition of the media and the concentra-
the use of a Au-decorated T iO2-based micromotor for the tions. Although salinity of the media and the presence of
efficient photocatalytic removal of polystyrene microplas- illumination source are reported to affect modify the degra-
tics from wastewater under UV illumination (Fig. 10). dation of microplastic structures in the aquatic environment,
The micromotor propulsion is supplied by photochemical degradative processes have been rarely studied. Of special
reactions in water and hydrogen peroxide initiated by elec- interest are photocatalytic nanomaterials which make use of
tron–hole generation processes. Although the lack of selec- both irradiation and catalytic degradation.
tivity was the most important disadvantage of this system.
The need for low concentrations of H2O2 for promoting the
phoretic interactions, which enable the micromotor to move, Biological removal and ingestion
makes this system actually non applicable in real wastewater.
Recently, Ariza-Tarazona et al. (2019) reported the ability Microplastic removal by marine organisms
of a protein-based N-TiO2 photocatalyst to degrade the poly-
ethylene microplastics in solid and aqueous phases. Accord- Harrison et al. (2011) published “Interactions Between
ing to their results, photocatalytic treatment for the pollution Microorganisms and Marine Microplastics: A Call for
resulted in 1.1% of the mass loss in the solid phase with the Research” to highlight the outstanding potential of micro-
rate constant of 12.2 × 10−4/h after 20 h of treatment time. organisms, including picoeukaryotes, bacteria and archaea,
These values were reported to be 6.4% and 38.2 × 10−4/h to facilitate the biological degradation of microplastics in
in the aqueous phase. They demonstrated that surface area coastal sediments. They discuss the interactions between
of the semiconductor and interactions between the photo- synthetic microplastics and marine microorganisms. Many
catalyst surface and microplastics significantly influenced reports present the biological degradation of natural and
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Environmental Chemistry Letters
synthetic macroplastics (Ahmed et al. 2018; Bettas Ardis- the microplastics to less than 1 μm for the fragmentation
son et al. 2014). products (Fig. 11) (Dawson et al. 2018). The findings thus
Polyethylene microplastics fragmentation and size alter- provide evidence for the biologically-mediated transforma-
ation ingested by Antarctic Krill (Euphausiasuperba), a tion of microplastics to nanoplastics.
planktonic crustacean, were studied by a group of environ- The preliminary results of a four-month study on removal
mentalists in Australia (Dawson et al. 2018). The mecha- of high-density polyethylene secondary microplastics in sea-
nism of fragmentation and type of interactions between water using two types of indigenous marine communities
microplastics and zooplankton, in which biota-facilitated including Agios consortium and Souda consortium were
degradation occurs, still remains unclear but the experi- published by Cocca et al. (2017). According to the recorded
ments confirmed that smaller microplastics are much eas- weight reduction results, the Souda consortium was more
ily fragmented under environmental conditions (Ter Halle efficient. Interestingly, their results on monitoring the cell
et al. 2016). Electron microscopic evidences confirmed the content and populations suggested that microplastics acted
shrinking of polyethylene microplastics through fragmen- as a rich carbon source to feed the organisms. While the
tation, where the physical size decreased from ~ 31 μm for protein content of both communities decreased during the
Fig. 11 Fate of microplastics ingested by Antarctic krill. Microplas- cence microscopy (f). This figure typically represents the pathway of
tics on a filter paper isolated from digested krill with auto-fluorescent microplastics transformation to nanoplastics inside the organism. WB
mandible (a), digestive gland tissue (b), midgut and digestive gland whole bead, FB fragmented bead, M mandible, DG digestive gland,
tissue (c), mandible with the fragments embedded into the surface MG midgut (Dawson et al. 2018)
(d), and fecal pellet with microplastics under bright-field and fluores-
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Environmental Chemistry Letters
that microplastics adherence to the external carapace of zoo- to remove 1.7–30.6 μm polystyrene microplastics through
plankton considerably influenced the organism feeding, a uptake and ingestion inside the organism body, in which
crucial hindrance factor against normal growth conditions their intestinal tracts can hold the microplastics up to 7 days
in marine wildlife (Van Franeker et al. 2011). Although this after entrance.
work was not aimed to introduce a way for microplastics Hall et al. (2015) also reported capture and ingestion of
removal, the results reveal the high capacity of zooplankton polypropylene microplastics by scleractinian corals with a
Fig. 14 Polyethylene microplastics removal from wastewater over clams. Removal was done by retention, trapping inside the clam, and
Red Sea clams (Arossa et al. 2019). Experiments involved four con- adhesion on the surface
centrations of microplastics over two different sizes of T. Maxima
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Environmental Chemistry Letters
consumption rate of 50 μg plastic cm−2/h, and evidenced and bacterial strains, has been confirmed to be suitable to
the presence of microplastics in mesenterial tissue within remove microplastics at low concentrations. The mechanism
gut cavity of the coral for at least 24 h. However, the mecha- of interactions and fragmentation is not well understood.
nism of the affection which potentially interferes with coral Microplastics, in the most of case studies, acted as a nutri-
growth, physiology, and survival still remains unclear. This ent source for the organisms. This could not convince us
research was important since inshore coral reefs ecosystem, to consider “ingestion” as a removal strategy to treat the
the coastal areas, is easily available as touristic regions for microplastic pollutions.
long periods and many of water treatment plants also daily A comparison of treatment methods for removal of
release their effluents containing microplastics debris, as the microplastics from the environment is represented in
mentioned above, to such environments. Table 3. The table briefly summarizes the advantages, dis-
The evaluation of the capability of the Red Sea giant advantages, and the efficiency of the projects utilized for
clam, Tridacna maxima, for the removal of 53–500 μm the last few years. It is obvious that membrane-included
polyethylene microplastics from wastewater (Fig. 14) has technologies are still the most reliable techniques to remove
been reported by Arossa et al. (2019). Their results revealed microplastics in the practical applications. However, it seems
the key role of clam’s shells to remove the microplastics that finding the suitable alternatives to couple with these
by sorption on the surface, as they resulted in 66.03% of methodologies is the main goal of the ongoing projects.
removal from the wastewater. The authors suggested that this
marine biota can be used for rapid removal of the anthro-
pogenic microplastics debris from aquatic surfaces in the Conclusion
regions with low concentration of microplastics, a fact
partly demonstrated by previous researchers (Martí et al. After short surveying on sources, occurrence, and transport
2017). The effect of microplastics initial concentration and pathways of microplastics, recent studies on three major
clam’s size on the removal rates through active, microplas- approaches including chemical, biological, and physical
tics retention inside the body, and/or passive, trapping by methods to remove them from the environments have been
the shells, pathways was investigated. The results indicated summarized. Sorption and filtration processes coupled with
that big clams tend to retain bigger microplastics inside their membrane bioreactors lead to removing a high percentage of
bodies, while small clams did not show any sharp preference microplastics in the influents entering into the water treatment
for them. Moreover, at any concentration, the microplastics plants but these systems acted themselves as daily microplas-
easily penetrated into the digestive system of all clams used tic sources since the effluents are directly released to aquatic
in this experiment. According to their measurements, the environments. Conventional activated sludge strategy is also
passive route of removal accounts averagely for 35.95% of used to treat wastewaters in water treatment plants but shows
the microplastics, leading to a significant increase in the den- lower efficiency than membrane bioreactor technologies
sity of microplastics attached to clam’s shells and normally, which makes it a less popular methodology. Electrocoagula-
the larger clams adsorb higher concentrations of the micro- tion and agglomeration have also become reliable techniques
plastics. As a whole, this research opened a new window for easy separation of microplastics but are needed to be cou-
for environmental pollution management making use of the pled with eminent extra filtration stages. Photocatalytic degra-
marine biota possessing complex surface and structure. But, dation using T iO2 and ZnO semiconductors is experimentally
finding the mechanism of interactions between the micro- revealed to be a suitable method among the aforementioned
plastics and organisms needs to be explored. Accordingly, strategies. FTIR and electron microscopy analyses are widely
we will be able to opt the type of sorbent biota and opera- served to elucidate any structural alterations during the degra-
tional conditions for achieving the highest microplastics dation process. Biological degradation has been investigated
removal efficiency. over the bacterial strains and marine organisms. Appearance
In brief, microplastics can provide a platform to grow of hydroperoxide and hydroxyl groups, carbonyl groups, and
a variety of microbial assemblages. Biological degrada- double-bond characteristic bands in the FTIR patterns of the
tion using microorganisms, e.g., zooplankton, marine fungi treated microplastics suggests the oxidative mechanism for
13
Table 3 Comparison of different methods for the removal of microplastics from the environment
Method Efficiency% Advantages Drawbacks References
13
Adsorption on green microalgae 94.5 High affinity of the cut surfaces to sorb Nonrecyclable method, chemical adher- Lagarde et al. (2016) and Zhang et al.
tiny microplastic particles, selectivity ence of the microplastics to the surface (2017)
based on microplastics surface charge and poisoning it
Dynamic membranes > 90 Low filtration resistance, low trans- much cleaning to avoid excessive mem- Li et al. (2018b)
membrane pressure, easy operation, brane fouling, energy demand, sludge
nonchemical treatment accumulation due to its flat structure
Membrane bioreactors > 99 Using combined advanced treatment Shape dependency of the removal per- Lares et al. (2018)
methods with porous membranes, centage, membrane fouling
Conventional activated sludge 98 Robust, cost-effective, flexible, treating a long retention times in the tank, the large Gurung et al. (2016)
wide range of influent concentrations, sedimentation surface, the high cost of
applicable for large-scale treatments energy and the processing and disposal
of sludge
Wastewater treatment plants > 95 Efficient mix of sorption-biological treat- Act as secondary microplastic sources, Leslie et al. (2017), Long et al. (2019) and
ment processes, low maintenance costs, disability to treat small-sized micro- Mintenig et al. (2017)
simple operation plastics, sludge aggregation, large
mechanical devices
Classic coagulation and 61 Suitable to remove small microparticles, Addition of chemicals to media, nonus- Herbort et al. (2018) and Ma et al. (2019)
agglomeration methods controllable operational conditions, able for large microplastics,
simple mechanical devices
Electrocoagulation > 90 No chance of secondary pollution, Repeated need of replacing the sacrificial Perren et al. (2018)
suitable for the removal of smallest anode, cathode passivation, nonusable
particles, sludge minimization, energy in areas without electricity
efficiency, cost-effectiveness, flexibility
to automation
Photocatalytic degradation No need to add other chemicals, extend- Lack of selectivity, lower efficiency com- Sekino et al. (2012), Tofa et al. (2019),
able applications to solar light as a pared to the other methods, difficult to Wang et al. (2019) and Ariza-Tarazona
renewable and pollution-free energy scale up, generation of secondary-type et al. (2019)
source, efficient mineralization, envi- organic pollutants, huge photoreactors
ronmentally friendly remediation setup, energy consuming, photocatalyst
recovery
Biological degradation Depends on type of Simplicity and safety for large-scale use, Aggregation of the microbial assem- Arossa et al. (2019), Auta et al. (2017),
microbial community, low operating costs, practically applica- blages on the surface, environmental Cole et al. (2013), Dawson et al. (2018),
mostly > 20 ble in different environments, flexibility conditions cannot be easily controlled, Hall et al. (2015) and Paço et al. (2017)
to handle a wide range of wastewater difficulties to analysis of the products in
characteristics and flows large scale, lack of reproducibility, find-
ing the suitable microbial community
Environmental Chemistry Letters
Environmental Chemistry Letters
biological removal. Ingestion by organisms has still not con- Boudart M, Djéga-Mariadassou G (2014) Kinetics of heterogeneous
sidered as a removal strategy but Red Sea giant clam exhibits catalytic reactions. Princeton University Press, Princeton. https
://doi.org/10.1007/978-3-662-05981-4_13
good potential for microplastics sorption on the shells besides Brandon J, Goldstein M, Ohman MD (2016) Long-term aging and deg-
its degradation in digestive system. radation of microplastic particles: comparing in situ oceanic and
experimental weathering patterns. Mar Pollut Bull 110(1):299–
Acknowledgements This work is financially supported by SAFEA of 308. https://doi.org/10.1016/j.marpolbul.2016.06.048
China (High-End Foreign Expert Project # G20190241013) and the Browne MA, Crump P, Niven SJ, Teuten E, Tonkin A, Galloway T,
scientific research startup fund of Shaanxi University of Science and Thompson R (2011) Accumulation of microplastic on shorelines
Technology. worldwide: sources and sinks. Environ Sci Technol 45(21):9175–
9179. https://doi.org/10.1021/es201811s
Browne MA, Niven SJ, Galloway TS, Rowland SJ, Thompson RC
(2013) Microplastic moves pollutants and additives to worms,
reducing functions linked to health and biodiversity. Curr Biol
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