4.

Environmental behavior and fate of MPs and NPs

4.1 Sources
The sources of micro-nano plastics are categorized into two major divisions: primary and
secondary MNPs. Primary micro-nano plastics originate from household products, cosmetics and
polymeric raw materials of plastic industries such as polyethylene (PE), polystyrene (PS) and
polypropylene (PE)[1].
Primary micro-nanoplastics are purposefully manufactured for specific applications, which
include cosmetic abrasives, drug vectors, and industrial and engineering applications such as air
blasting. These micro-nanoplastics are usually difficult to remove using sewage disposal
technologies and once they enter wastewater, they will ultimately accumulate in the
environment. Secondary micro-nanoplastics originate from larger plastics as they are
progressively fragmented into smaller pieces by multiple, complex environmental conditions
such as wind, waves, temperature, and UV light[2].
Furthermore, repeated use of plastic products can also cause fragmentation and result in the
formation of secondary micro-nanoplastics. Hartline et al. (2016) discovered that microfiber
masses from top-load conventional home machines were 1471–2121 microfibers per garment,
which was approximately 7 times higher than that those from front-load machines. And a recent
study reported 30,000–465,000 microfibers per m2 (or 175–560 microfibers/g) were detached
from textile garments. Besides, plastic emissions related to vehicle transport, including tire wear
and tear, brakes, road markings, are another main source of microplastics in the environment.
The global average of microplastic emissions from the abrasion of road vehicle tires was
estimated to be 0.81 kg/year per capita. Apart from road traffic, wear and tear released from
airplane tires accounts for approximately 2% of total emissions from tire wear and tear in the
Netherlands. In addition, artificial turf also plays an important role in secondary source of
microplastics, with the rough estimate of artificial turf emissions ranging from 760 to 4500
tonnes/year. Therefore, diverse types of microplastics are being emitted into various natural
habitats and ecosystems[2].
Much different from the sources of microplastics in ocean, which mainly includes land-based
sources (contributing∼80%), costal tourism, recreational, commercial fishing (e.g. plastic fishing
gear ap- plications, etc., contributing∼18%), marine vessels and marine-industries (e.g.
aquaculture, oil-rigs, etc.), microplastics enter soil via multiple sources, including landfills, soil
amendments, land application of sewage sludge, wastewater-irrigation, compost and organic
fertilizer, residues of agricultural mulching films, tire wear and tear, and atmospheric deposition,
etc. Besides, plastic waste in soil can be fragmentized into microplastics by biological processes
of soil organisms, e.g. feeding activities, digestion, and excretion process. The presence of
microplastics severely reduces soil quality, and the migration and trophic transfer of
microplastics in heavily contaminated soils, particularly those in wastewater-irrigated and
plastic-film covered areas, pose substantial risks to the ecosystem (Fig. 1)[2]
 Fig. 1. Sources of microplastics in land. WWTPs indicates wastewater treatment plants.

The size, shape, color and density of microplastics all play a role in its bioavailability and
degradation. Microplastics are typically categorized as plastics <5 mm in size or between 1 µm
to 5 mm; however, there have been studies that report them as <1 mm, <2 mm, 2–6 mm and <10
mm. Fragments, pellets, filaments and fibres, broken edges, granules and irregularly shaped
microplastics are the most common forms microplastics take in the environment. However,
synthetic fibres and microbeads are more commonly discussed due to their pervasiveness in daily
life. Textiles, such as clothing, result in the release of synthetic fibres through ordinary use and
laundering. Nanoplastics, which are too small to be seen by the naked eye, are similar to
microplastics in that they have not been given a standard size definition. However, more
frequently nanoplastics are referred to as plastic particles that are <0.1 µm in size[3].
Microplastics can either enter the environment directly or following the breakdown of larger
plastic. Microplastics, often referred to as microbeads, are manufactured at a microscopic size for
use in cosmetics, such as exfoliators and toothpastes (Figure 3 (left), air blasting technologies for
clearing surfaces like boats and machinery from rust and human medicine, serving as vectors for
drug delivery. When large plastic pieces become brittle or aged due to UV radiation, waves and
other abiotic factors, they are slowly broken down into smaller and smaller pieces that eventually
are <5 mm in diameter.
Figure 3. Examples of microplastics from a personal care product (toothpaste on the left) and from the
breakdown of larger plastic pieces (on the right).

A third category of microplastic, which is often kept separate from the others, is "industrial
plastic" which refers to resin pellets used as precursors in plastic manufacturing processes
(Figure 4). These pellets are millimeter-sized and are therefore easily “lost” into the environment
during processing and transport. Such lost pellets have been found on a range of beaches
worldwide. Synthetic materials are also heavily used in various consumer products that can shed
synthetic fibers when they are washed. These fibers can enter the sea in areas with very basic or
no wastewater treatment or due to storm water overflow from wastewater treatment plants. It is
estimated that as much as 2.4 mg person-1 day-1 of microplastic is released into the environment
from consumer products[3].

Figure 4. Plastic pellets from manufacturing typically found on beaches .

The most common types of microplastics found in the environment are spheres, pellets, irregular
fragments, and fibers9. Polyethylene is the most commonly produced plastic polymer and this is
reflected in what is typically found in the environment. For example, barnacles collected from
the North Pacific were found to contain 58 % polyethylene, 5 % polypropylene, and 1 %
polystyrene microparticle. Browne (Pers. Comm.) dedicates a section to sources and pathways of
microplastics. He urges for a clear separation between "sources" and "pathways" and proposes
four categories of sources: Larger debris, Cleaning products (cosmetics and air blasting),
Clothing (fibers), Medicines[4].
Plastic is a manmade product that has spread all over land and water as a result improper usage
and false waste management techniques; it is calculated to increase by 2050. The major part of
plastics contaminants comes from single-use plastics food packaging such as polyethylene,
polypropylene, and polyethylene terephthalate. 8 Micro-nano plastics used for a wide variety of
applications in electronic, automobile, textile and paint industries have a chance for direct
discharge into the river catchment areas, affecting the marine ecosystem. Other well-known
MNPs contaminants are from personal care products such as toothpaste, scrubs, cleaning
materials, and cosmetics. However, the existing wastewater treatment plants have shown that
tertiary treatment of water is not a source for micro-plastics pollution, as these pollutants are
effectively removed by the skimming and settling treatment processes. Other sources include
disintegration of synthetic fibres during washing of clothes, commercial activities like thermal
cutting of polystyrene, agricultural activities such as the use of polyethylene, polyurethane,
polystyrene foils, films as well as soil conditioners, ship-generated 9 waste in water, drug
delivery based on polymeric nano-particles. The current generation of secondary microplastics in
the oceans around the world is a result of massive plastic production in the 1990s and earlier.
Even though we are trying to reduce the contaminant disposal in the environment, specialized
expertise is needed to remove MNPs[5].

Figure 1. Sources of micro-nano plastic pollutants (a) primary (b) secondary micro-nano plastics.
4.2 Migration of MPs and NPs
Plastics are entered into the aquatic environment due to their unsystematic disposal and
adversely affect the marine biota. During the last few decades, this is an issue of major concern
as marine ecosystem has maximum contribution towards global primary productivity.
Once enters in the environment, these plastic materials are degraded by various means and lost
their structural rigidity (Fig. 2), (Browne et al. 2007). The extensive degradation of plastics
finally results into powdery fragments and microscopic-sized plastics, called microplastics
(Barnes et al. 2009). These are microparticles having dimensions ranging between few
micrometer to 500 μm (0.5 mm). Nowadays, pharmaceuticals and cosmetic industries are using
microplastics in various daily used products and contaminating the environment via wastewater,
ultimately transferred along food web and impacting marine ecosystem after reaching into the
sea[6].

Fig. 2 Environmental degradation of plastics under different conditions.

Degradation is a chemical change that drastically reduces the average molecular weight of the
polymer. Since the mechanical integrity of plastics invariably depends on their high average
molecular-weight, any significant extent of degradation inevitably weakens the material.
Extensively degraded plastics become brittle enough to fall apart into powdery fragments on
handling. Even these fragments, often not visible to the naked eye, can undergo further
degradation (generally via microbial-mediated biodegradation) with the carbon in polymer being
converted into CO2 (and incorporated into marine biomass). When this process goes onto
completion and all the organic carbon in the polymer is converted, it is referred to as complete
mineralization Degradation is generally classified according to the agency causing it[7].
(a) Biodegradation – action of living organisms usually microbes.
(b) Photodegradation – action of light (usually sunlight in outdoor exposure).
(c) Thermo-oxidative degradation – slow oxidative breakdown at moderate temperatures.
(d) Thermal degradation⁄ – action of high temperatures.
(e) Hydrolysis – reaction with water.
The fragmentation of huge plastic things happens following totally different mechanisms,
severally or put together, like a photo oxidation by chemical reaction, ultraviolet light, and
mechanical shock, leading to soil abrasion or mechanical turbulence in water or biological
assimilation by microorganisms. Oxidation of plastic pellets like poly (lactic acid) (PLA),
terephthalate (PET), poly(ethylene) (PE), poly(styrene) (PS), and poly(propylene) (PP) happens
when subjected to ultraviolet light in soil and water environments. Hydrolysis is one among the
first processes of degradation of heteroatom polymers like poly(urethane) (PU) and PET. The
effect on the atmosphere is increasing as concentrations fall (in the case of chlorofluorocarbons
(CFCs)) or rise (in the case of hydrofluorocarbons (HFCs), which are used as replacements for
CFCs in refrigeration and insulation) into the global set- ting. Trifluoroacetic acid, a minor
product of the atmospheric decomposition of certain HCFCs and HFCs and the pyrolysis of
fluoropolymers, is distributed uniformly in seawater of over 4000 m. In the aqueous world,
trifluoroacetate is widespread; it is present in fog, rain, rivers and lakes, groundwater, and, most
importantly, in sea- water[6].
The bond breakage of organic compound results in the chemical group formation creating the
autocatalysis, subsequently increasing the hydrolysis rate of the acidic conditions. Both
processes of photo-oxidation and degradation of the response trigger breaks split and trap to form
on the surface of items, plastic induction embrittlement. Plastic fragments are so weakened and
mechanical stress like abrasion or friction breaks into microplastic particles. The fragmentation
process relies on the environmental circumstances, the polymer substance, as well as plastic
additives that can impact the material’s physicochemical characteristics. It is therefore possible
to rapidly generate MPs of distinct sizes, forms, densities, and chemical and mechanical
properties based on environmental circumstances and plastic products. However, the mechanism
and fragmentation rate of MPs in the environment are still uncertain and desires to be studied in
order to assess the rate of MPs generated by fragmentation.
Nanoplastics formation
It is also anticipated that MPs will be fragmented into NPs as well as the formation of MPs. Even
though NPs are difficult to identify, discharge of NPs up to 30 nm in size was recorded after
being exposed to the outdoor aquatic microcosm of PP, PS, and PE pellets and thus demonstrated
by the absence of bulk material. The nanofragment’s number improved by 5 orders of magnitude
after being exposed to outdoor circumstances compared with PE mention not subjected to
weathering. The existence of NPs proves that theory of degradation of big plastic products into
MPs can be expanded to the degradation of MPs into small products like NPs. This research
proposed that the physical breakage of MPs in cosmetics during manufacturing or use could lead
to the discharge of produced NPs in water, and 2° MPs/NPs could lead to plastic pollution. As
stated previously for big fragments of plastic, the process of manufacturing has an impact on the
fragmentation of MPs because, as a consequence of their pro- duction, defects can be introduced
in particles. Primary MPs like powders, fillers and pellets are commonly generated through
comminution. In which the solid particle size reduced by effect, compression, or shear force is
intentionally. The comminution is performed generally by milling and grinding to trigger defect
like breaks on the particles that propagate into fragments until they are totally broken. In the case
of MPs ending up in water, these abnormalities would damage particle constructions and
improve the ESC owing to environmental variables including the turbulence of water, resulting
in the conversion of MPs to NPs. No experimental information was recorded demonstrating the
breakdown of MPs into NPs in water owing to the proliferation of abnormalities[6].
The vertical and horizontal distribution of microplastics in soil can be influenced by several
factors (Fig. 2), including soil biota, soil features such as soil macropores (pores > 75 μm), soil
aggregation and soil cracking, and agronomic practices such as plowing and harvesting. The
general literature on microparticle migration in soil by bioturbation suggests that plant processes
(e.g., root growth and uprooting) and inputs from various animals (e.g., larvae, earthworms,
vertebrates, etc.) can serve as preferential paths for microplastics movement. For example,
indigenous fungal mycelia may also contribute to the migration of microplastics as they can
bridge air-filled pores and efficiently translocate pollutant degrading bacteria. Microplastics can
be swallowed and subsequently excreted by earthworms, vertically transported from shallow to
deep soils by the burrows of anecic earthworms, and laterally spread across wide areas by the
movement of geophagous earthworms and mosquitoes. Mosquito larvae have been reported to
readily eat microplastics, which can persist in a mosquito's guts during metamorphosis from the
larval to adult stage. Moreover, earthworm casts, which can contain concentrated microplastics,
may be ingested by soil microarthropods. Mites and collembola have also been found to disperse
and redistribute micro- plastics by scraping or chewing microplastics, and digging mammals,
such as gophers and moles, are likely to contribute to the migration of microplastics in soil by a
similar mechanism. The distance of microplastics (100–200 μm) was much further and faster
transported by larger Folsomia candida (up to 4 cm after 5 days) than smaller Proisotoma minuta
(about 1 cm after one week), and the ability of collembola to disperse microplastics was strongly
associated with the size of organisms and microplastics as well as their type. Furthermore, Zhu et
al. (2017) found that the ability of microarthropods to transport and distribute microplastics in
soil was significantly enhanced when there exists a predator prey relationship. Thus, we can
speculate that intricate food webs in soil ecosystems which is composed of diverse and complex
species relationships will promote the migration of microplastics compared with the contribution
of single species. That is, soil cracking, pores, agronomic practices (e.g. plowing and harvesting),
root elongation of plants, the activities of ingestion and egestion of geophagous soil fauna
(notably anecic earthworms), as well as the digging behaviors of other soil animals contribute
likely to the most vertical transport of microplastics in soil; whereas the activities of hunting, life
activities of epigeic earthworms, as well as agronomic practices can facilitate the horizontal
distribution of microplastics in soil. Additionally, plastic types can also influence the migration,
because that microbeads and microfibers have been proved to show different interaction with soil
aggregation, which may exert potentially blocking effects on the transport of microplastics in
soil. Moreover, transport may be influenced by plastic surface properties and eco-corona altered
by the process of degradation. The concept diagram (Fig. 2) shows the various factors affecting
the migration of microplastics in soil[2].

Fig. 2. The various factors affecting the migration of microplastics in soil. Vertical arrows indicate the vertical transport of
microplastics in soil. * Microplastic particles can integrate into soil aggregations and incorporate into soil clumps to varying
degrees: loosely in microbeads and fragments, while more tightly in microfibers, thus influencing the transport of microplastics
in soil.

Human survival and activities are inseparable from water, the aquatic environment may be the
largest reservoir of MPs/NPs. With water flow, MPs/NPs can be carried anywhere the water
flows. The transport of MPs/NPs in the aquatic environment has been widely concerned. This
process is not only related to the characteristics of the MPs/NPs themselves, but also depends on
the physical and chemical properties of the aquatic environment, as well as hydrodynamics,
attachment and uptake of aquatic organisms, which will directly affect the settlement, re-
suspension and transportation distance of plastic particles, and ultimately affect their
environmental fate.
Most MPs/NPs from land sources are discharged directly into rivers and lakes with the effluent
from wastewater treatment plants or through surface runoff. Generally, small and light plastic
particles are suspended on the upper water surface, while large and heavy plastic particles are
deposited at the bottom of the water. However, there are a lot of natural inorganic/organic
particles and microorganisms in the natural environment, which will aggregate (heterogeneous
aggregation) with MPs/NPs or gather together of plastic particles themselves (homogeneous
aggregation), and change the original density of plastics, then affecting the settlement and
residence time of plastic particles. Hoellein et al. (2019) studied the deposition rate of three
common microplastics (polypropylene pellets, polystyrene fragments, and acrylic fibers) in the
stream. The experiment found that the deposition rate followed the general law of density and
biofilm 'stickiness'. The deposition rate of debris was the highest, followed by fiber, and the
smallest was globular. Moreover, biofilm colonization also increased deposition rate. Therefore,
we speculate that the fibrous and spherical MPs/NPs will be further taken away by the river,
posing a threat to a wider environment. In addition, some scholars have noticed that stream
characteristics (water depth, flow and obstructions in rivers such as large weirs) can influence the
migration of microplastics in the freshwater environment, but compared with the marine, there
are few studies on freshwater environment and most of them have not paid attention to the
intrinsic relationship between hydrological characteristics of rivers and transport of MPs/NPs.
The deposited MPs/NPs will be temporarily or permanently stored in the sediment, while the
suspended plastic will continue to flow to the ocean. When the river reaches the estuary, on the
one hand, due to the sudden increase in the cross section of the estuary, the water flow speed
drops swiftly. On the other hand, the continuous influx of tidal will hinder the river water. The
seawater dissolves many strong ionizing sodium chloride, which generates lots of ions. The
above three reasons will cause a large amount of sediment to form a delta, at the same time,
some MPs/NPs are also trapped in the sediment and deposited here. For the special transition
area of river-estuary, the estuary contains a high concentration of microplastics, but the
concentration of microplastics in river sediments is much higher than that in estuaries. The
characteristics of microplastics in estuaries and rivers show a similar trend, mainly based on the
shape of thin films and fragments. This means that rivers may be more seriously polluted by
MPs/NPs than oceans. Moreover, under the tidal currents caused by buoyancy, wind, and tides,
the upper of the estuary is affected by the largest turbidity current, which contains a higher
abundance of buoyant microplastic particles, and it will form MPs hot spots in certain areas of
the estuary. Of course, plastic waste generated by human activities (such as ports, fisheries, and
tourism) is also directly discharged into coastal waters.
However, the sediment near the coast is not stable, depending on the relief of the margin. The
steep, tectonically active margins have narrow continental shelf and steep continental slope, its
onshore storage space is small, thus shortening the residence time of sediment and microplastics.
On the contrary, mature and passive margins have wider continental shelf and gentler continental
slope, forming a longer and relatively lower relief catchment. At this margin, sediments may be
affected by the vigor of along-shelf currents and other oceanographic perturbations, MPs/NPs
will move and redistribute along the continental shelf. As the energy of currents gradually
weakens, the transport of sediments also stops slowly, and MPs/NPs retain a good layered
distribution according to their own properties. Moreover, the longer residence time also promotes
the fragmentation and degradation of large pieces of plastic, which poses a greater threat to the
living organisms in the area. The above two marginal topography are likely to meet the canyon
head. The difference is that the former dense sediment-laden water will pour down, triggering
turbid currents and bringing considerable MPs/NPs with different shapes and types directly into
deep-marine realm, however, fibers may be trapped between settling sand-grains and finally
buried in the deposits during transportation as a result of slender form; while the latter has been
slowly deposited, mainly lighter plastic particles and microplastic fibers enter the deep sea.
After entering the deep sea, gravity will guide the MPs/NPs to continue to sink into deeper
marine realm, but all sorts of currents further complicate the transportation and distribution of
plastics. Bottom currents can easily provide the shear force to transport MPs/NPs in surface
sediments, which can isolate plastics in drift deposits and move with currents. In general, there is
strong biological disturbance in drift deposits, forcing the plastic to transfer to deeper sediments.
Contrary to bottom currents, thermohaline stratification and internal tides will inhibit the
settlement of plastics, and resuspend the plastics in the ocean, which may then be carried to other
areas. Meanwhile, the ingestion and defecation of the organism also strengthen the resuspension.
The plastic floating on the surface of the ocean will be affected by Ekman and geostrophic
currents and surface Stokes drift, forming MPs/NPs accumulation areas in some regions, which
probably further increase the ecological risk of the region. In the Polar Regions, there is another
important transport mean that is rarely mentioned, and that is sea ice. During the growth of sea
ice, it uses a vertical pattern to mark polymer composition and size classes of the microplastic
particles in the drift trajectories of sea area. However, the trend of global warming in recent
decades has intensified the melting of sea ice, and these unquantified sinks of microplastics are
re-releasing substantial microplastics into the ocean. This has to make scientists re-examine the
dynamics, accumulation and potential toxicological effects of microplastic pollution. Combined
research from different regions, we have a general understanding of the transport trend of
MPs/NPs, but the specific distribution is still unclear. In the future, field investigations need to
be strengthened, and labeled particles can be used to simulate transportation to predict the
distribution of plastics in the actual environment[8]
4.2.1 Physicochemical properties: from MPs to NPs
The size of a plastic particle is the dominant characteristic determining its environmental fate
(e.g., migration). Besides, bioaccumulation and toxicity can be size-dependent. Considering that
NPs mainly originate from the fragmentation and transformation of larger plastic particles,
investigating the downsizing mechanisms will be helpful for a better understanding of NPs. NPs
can be generated through the mechanical abrasion processes The breakdown of daily-use
polystyrene products by household blender generate considerable amounts of NPs.
Fragmentation of solid plastic wastes and MPs generate NPs in sewer system due the turbulence
of water flow and mechanical devices in wastewater treatment plants (WWTPs). The natural
fragmentation of larger plastic pieces can also be achieved in the sea swash zone. The
mechanical fragmentation of macro and micro sized plastic particles are mainly caused by the
formation of cracks. The theory of crack induced solid failure can therefore be adopted to depict
this process, and the size of resulting NPs can be calculated using the following equation (Eq. 1):
 ( )
2
K √24 3
d NP= c
dε [1]
ρc 0
dt

where dNP is the size of NPs, K c is the stress intensity factor of the plastic material, ρ is the
density, c 0 represents the elastic wave speed, refers to the stain of plastic material, which is
dependent on the applied stress[7].
Hydrolysis (react with water) is another potential mechanism accounting for NP generation, yet
it may not be the most powerful one at reducing the sizes of plastics. In comparison, de-
gradation initiated by UV irradiation is a very efficient downsizing mechanism. The
photodegradation of plastics is mainly induced by reactive oxygen species. The decrease in
particle size may be due to the chain scission by attacks from free radicals, such as hydroxyl
(·OH), alkyl (R·), alkoxyl (RO·) and peroxyl (ROO·) radicals produced from the UV light.
Possible reaction mechanisms for free-radical induced fragmentation include three steps (Eq. 2–
9):
Step 1-initiation
RH hv R •+ H • [2]
→

Step 2-propagation
R •+O 2 → ROO • [3]

ROO •+ RH → ROOH + R • [4]

ROOH hv RO •+•OH [5]
→

2 ROOH hv ROO •+ RO •+ H 2 O [6]

→

Step 3-termination
R •+ R •→ Not free radical products [7]
R •+ ROO •→ Not free radical products [8]
ROO •+ ROO •→ Not free radical products [9]
Biological degradation and fragmentation of large plastic pieces and MPs by marine and
terrestrial animals could also generate NPs in environment. The ingestion of plastic MPs and
potentially NPs by marine organisms has been found among zooplankton, fish, shrimps and other
animals. Fragmentation or degradation of MPs into NPs has been reported in Antarctic krill
(Euphausia superba) exposed to polyethylene MPs (31.5 μm) together with algal food. After
ingestion, NPs of 150−500 nm size were formed, which were found in the digestive gland.
Reduction of MPs into smaller sizes has been observed in the common earthworm and snails,
although fragmentation of MPs into NPs was not considered in these studies due to limitation of
excess tools[7].
4.3 Aggregation of MPs and NPs
The environmental fate of MNPs is mainly governed by the weathering and the aggregation
processes. Various stressors (environmental factors), such as the heat, water, UV irradiation,
oxidants, micro- organisms, or the combination of these causes the aging of MNPs in the
environment. An elevation in temperature will accelerate the weathering of NPs as per the
Arrhenius relationship. The shear forces of the water cause the mechanical fragmentation
(physical weathering) of NPs (section 4.2.1). Artificial aging using UV and O 3 co-exposure
resulted in much rougher morphology and more oxygen-containing functional groups (e.g.,
hydroxyl, carbonyl, carboxyl) as compared with pristine NPs. During this abiotic oxidation
process, reactive oxygen species such as hydroxyl radical (O•H), singlet oxygen ( 1O2) and
superoxide radical (•O2-) induced the chain reactions, which degraded the structure of NPs.
Furthermore, oxygen was introduced to the surface of NPs, resulting in an increased number of
oxygen-containing functional groups. Micro-organisms may also play vital roles in the biological
weathering of NPs (section 4.2.1) through the colonization (plastisphere) and the utilization of
the polymer matrix as a food source[7].
Aggregation is a key issue in understanding the environmental fate of NPs. Evidence has shown
that NPs can form milli-sized (mm-sized) aggregates in ecosystems. In addition, formation of
heteroaggregates with inorganic colloids or organic matter lead to either settlement or migration
of NPs. In order to describe the aggregation process of NPs, the Derjaguin-Landau-Verwey-
Overbeek (DLVO) theory has been widely adopted by various studies. The DLVO theory
proposes that two independent forces, Van der Waals force (Eq. 11) and the electrostatic double
layer force (Eq. 12) determine the stability of suspended particles:
V T ( d ) =V vdw ( d )+ V edl (d ) [10]

V vdw ( d )=
−A
[
2a 2
+
2 a2
6 d (4 a+d ) (2 a+ d)2
+ ln
d ( 4 a+ d)
(2 a+d )2 ] [11]

( z4qkTψ ) ×e
2 2
32 πε ε 0 k T a 2 e − xd
V edl ( d)= 2 2
× tanh [12]
q ze

where, VT (d) is the total interaction energy, V vdw(d) is the Van der Waals interaction energy, and
Vedl(d) represents the electric double layer interaction energy in Eq. (10). The parameters in Eq.
(11) are defined as follows: A is the Hamaker constant for the NP dispersion system, whose
value is dependent on the types of NPs and the aqueous media; a is the radius of NPs; d is the
separation distance between NPs. As for the parameters in Eq. (12); ε is the dielectric constant of
aqueous phase; ε 0 is the dielectric constant of vacuum; k is the Boltzman constant; T is the
absolute temperature; qe is the electron charge; z is the charge number; ψ is the surface potential
of NPs (assumed to be equal to ζ-potential); κ is Debye length (Eq. 13):
κ=
√
2000 N A q2e I
ε ε 0 kT
[13]

where N A is the Avogadro constant, I is the ionic strength of the aqueous phase.

As shown in Eq. (12), an elevation in absolute value of ζ-potential (|ψ |) will lead to enhanced
repulsive energy (V ¿¿ edl (d))¿ and total interaction energy ( V T ( d )) , making it more difficult for
NPs to form aggregates[7].
Conversely, a reduction in |ψ | favors the aggregation process. The DLVO theory is crucial for the
comprehension of the environmental factors that affect the aggregation process. Experimental
results have confirmed that this theory is suitable for NP dispersion systems. Various
environmental factors including pH, ion strength, natural minerals and organic matter play vital
roles in NP aggregation. Liu et al. (2019a) and Mao et al. (2020) observed that the negatively
charged surfaces of polystyrene NPs possessed more negative ζ-potentials with the increase of
solution p H . This resulted in an elevation in |ψ |, making NPs more stable according to DLVO
theory. However, if the surface of NPs were positively charged at low pH conditions, an increase
in solution p H may result in the aggregation due to a decrease in |ψ | value. Inorganic ions also
affect the aggregation process through changing the ionic strength of the solution. Higher
concentrations of inorganic ions result in reduced V edl ( d ), favoring the aggregation of NPs.
Natural minerals such as clay tends to form heteroaggregates with NPs due to electrostatic
interactions. Natural organic matter protects NPs from aggregation by elevating the |ψ | value
(due to the formation of eco-corona). However, Yu et al. (2019) suggested that if the
concentration of organic matter is high enough (to enable the existence of un-adsorbed free
organic matters in the system), the co-existence of natural organic matter and inorganic ions may
lead to the “bridging effect”. Inorganic metal cations (e.g., Ca 2+) could bridge oxygen-containing
groups of both NPs and the organic matter, resulting in heteroaggregation. The conventional
DLVO theory can be adapted to describe NP interactions in more complicated systems (e.g.,
soil). Liu et al. (2019c) adopted an extended DLVO theory to assess the interaction energy of
NPs in porous media. Total NPs-soil interaction energy takes three forces into account: Van der
Waals force, electrostatic double layer force, and the hydrophobic effect (described by the Lewis
acid-base interaction). According to the theoretical calculations, aged NPs are likely to possess
higher primary energy barrier, making them less likely to form aggregates. The theoretical
calculation aligned with the experimental findings, that aged NPs have higher mobility in
saturated porous media. Mao et al. (2020) assessed the aggregation behavior of NPs in the
presence of extracellular polymeric substances (EPS) produced by microorganisms during
biofilm formation on NPs. To better understand the role of EPS in the aqueous media, steric
repulsion was incorporated in conventional DLVO theory. The energy barrier was higher in
solutions with EPS, which was consistent with the finding that EPS inhibited the aggregation of
NPs through steric effects.
Understanding the aggregation behavior of NPs is critical for the assessment of environmental
fate of NPs. However, current studies mainly focus on the spherical synthetic NPs, rather than
naturally aged NPs with diverse shapes. The conventional DLVO theory is based on the
“spherical” assumption, so modifications must be made when it comes to non-sphere nanoplastic
particles[7].
The morphology NPs are mainly determined by their origins (i.e., natural weathering vs synthetic
fabrication). NPs from different origins have diverse shapes (Fig. 2). Many studies regarding the
migration, bioaccumulation and toxicity have adopted commercially-available NPs, which
exhibit ideal spherical morphology in most cases (Fig. 2a, b). Another type of synthetic NPs is
the metal-doped nanoplastics with a raspberry-like morphology (Fig. 2d). However, in both
terrestrial and aquatic ecosystems, NPs originate mainly from the weathering and fragmentation
of larger plastic particles, rather than the controlled synthesis. NPs resulting from the weathering
of large plastic particles possess much rougher morphologies (Fig. 2c). Due to natural forces
such as mechanical forces of water, UV radiation and biological metabolism the shapes of
resulting NPs become hardly smooth and spherical[7].
Downsizing of plastic particles from micro to nano scale can also lead to a shift in chemical
properties, especially surface functional groups. As shown in Eq. (2)-Eq. (9), reactive oxygen
species are generated during the photodegradation process. This may result in an in- crease in
oxygen-containing functional groups such as carboxyl, carbonyl and hydroxyl on the surface of
NPs. The changes in surface functional groups alter the hydrophobicity and surface charges of
NPs, which may affect the migration, aggregation, contaminant adsorption, bioavailability and
toxicity of NPs. It is therefore necessary to fully understand the weathering process of plastic
particles. However, current studies mostly focus on the environmental behavior and toxic effects
of synthetic spherical NPs since they can be easily obtained. It is argued that results from current
studies may not reveal the behavior of naturally weathered NPs under field conditions[7].

Fig. 2. Morphologies of various NPs: (a) commercially available polystyrene (PS) nano-bead particles
(Lei et al., 2018); (b) commercially available polytetrafluoroethylene (PTFE) nanoparticles with diameter
of 120 nm; (c) nano-sized polystyrene (PS) particles attached on surface of polystyrene spherule, which
were fragmented from the expanded polystyrene spherules by accelerated mechanical abrasion for a
month; (d) synthetic metal-doped poly- acrylonitrile (PAN) nanoparticle with a rasp- berry-like
appearance. All images are reproduced with permission[7].

4.4 Deposition of MPs and NPs

In recent years, MPs and NPs have been detected in 690 species deposition of the marine
environment, throughout the food chain, including fish, crustaceans, bivalves, mammals and
plankton[9].
Microplastics can be taken up by aquatic organisms through several physiological routes and
then translocated to different tissues or organs, especially the stomach, intestine, and digestive
tract. For the clam Scrobicularia plana, orally ingested PS microplastics (20 μm) were shown to
be transferred to the hemolymph and digestive tract. The uptake of high-density PE microplastics
(< 80 μm) by the mussel Mytilus edulis is mediated by ciliary movement on the gill surface,
resulting in the transfer of the particles to the digestive system (stomach and intestine) and then
to the primary and secondary ducts of the digestive tubules. The particles finally accumulate in
the lysosomal system (von Moos et al., 2012). Similarly, Browne et al. (2008) detected PS
microspheres (2, 3, and 9.6 μm) in the gut cavity and digestive tubules of M. edulis within 12 h
of exposure and in the hemolymph and hemocytes 3 days post-exposure. In addition to the gills,
stomach, and intestine, microplastics accumulate in the mussel’s gonads, mantle, adductor,
viscera, and foot.
Phagocytosis and pinocytosis are two possible pathways for microplastic uptake but particle
translocation is largely size-dependent, with smaller plastic particles being more easily
internalized. For example, in a study of the zebrafish Danio rerio, 5-μm PS microplastics were
distributed in the gills, liver, and gut whereas 20-μm PS microplastics accumulated only in the
gills and gut. Jeong et al. (2018) reported the dispersion of 50-nm microplastics in various organs
of Brachionus koreanus after exposure of this rotifer but 0.5- and 6-μm microplastics localized
only to its digestive tract. Surface charge also influences the distribution of microplastics in
aquatic organisms. Della Torre et al. (2014) investigated the accumulation of microplastics with
different surface coatings (carboxylated and amine polystyrene microplastics) in embryos of the
sea urchin Paracentrotus lividus and found that while carboxylated PS microplastics were limited
to its digestive tract, amine PS microplastics were distributed throughout the embryos[10].
The accumulation of chemicals in an organism is an important aspect affecting its toxicity.
Zebrafish chorion has pores for the transportation of oxygen and nutrients. Smaller nanoplastics
can enter these pores (0.5–0.7 μm diameter) in the embryo phase whereas particles larger than
pore size can adhere to the chorion and brought inside by water flow or mistaken as food by
larvae. Tissue accumulation of MPs/NPs can adversely affect growth & development, immune
system, oxidative stress, glucose level, energy metabolism and other biomarker response.
MPs/NPs are now available in different fluorescent-labeled colors and sizes. Uptake and
accumulation of fluorescent particles are visualized live because of the transparent nature of
embryo and larvae of zebrafish[11].
MPs/NPs are reported to accumulate in chorion, yolk sac, endotherm, muscle fibers, eye, spinal
cord of zebrafish embryo. In the larvae and adult fish, mouth, gut, brain, blood, liver, heart, gills,
muscle are sites reported for its accumulation (Fig. 3).

Fig. 3. Deposition of MPs/NPs in different organs of embryo, larvae and adult zebrafish.

The absorption routes in fish are complex that includes oral, gill and skin absorption. Organ-
specific accumulations of MPs/NPs have been observed with the intestinal tract being the
dominant and preferred pathway in both larvae and adult zebrafish. Studies have found that
MPs/NPs can be quickly accumulated in gills and gut of zebrafish than in other parts. The
accumulation kinetics of MPs in zebrafish showed increased accumulation of MPs in presence of
natural organic matter (NOM), with the maximum accumulation reached within 72 hrs. The
author also reported exponential decrease in MPs during the depuration study. Gills are one of
the first organ to interact with the aquatic environment and have a large surface that allows
microplastic to accumulate. Accumulation in gill may be caused by the major function of gill for
osmotic pressure balance. The translocation of particles from gut to other organs such as liver,
circulatory system is governed by particle size and its concentration in the body. Accumulation
in the circulatory system may be caused by mouth-gastrointestinal tract translocation and directly
from peripheral vessels via gill/transdermal absorption. Smaller aquatic animals have limited
selectivity and ingest MPs as food particles, which can cause ad- verse health effects. Various
histological changes such as necrosis, infiltration, and lipid droplets in hepatocytes were reported
in fish treated with PS MPs/NPs. However, a recent study demonstrated that adult zebrafish can
recognize MPs (247.5 μm, relatively large) as inedible materials. Zebrafish showed lower (0.0–
1.0%) accumulation percentage (ingested particles/supplied particles)when only MPs were
supplied whereas the accumulation percentage increased to was 0.5–9.4% under food presence
conditions stating that zebrafish were compelled to ingest MPs together with food but when they
recognized these particles as nonedible, they showed spitting of MPs. Size and shape of
MPs/NPs are likely to influence its retention in the gut and there is very little information on
retention of these particles in the intestinal tract. A detailed investigation of the resident time of
MPs/NPs in zebrafish organs is required for a better understanding of its effect on organ
toxicity[11].
Microplastics (MPs) are commonly known as plastic debris 0.1–1000; whereas, plastic particles
are categorized as nanoplastics (NPs) ≤ 0.1 μm. MPs are intentionally manufactured for various
applications, like microbeads in exfoliates for personal care products. Many of the substances
contain nanoplastics like electronics, paints, drug delivery systems, and adhesives. For instance,
3D printing can emit polymer nanoparticles. This substance is emitted continuously from textile
washing ma- chines into the public wastewater containing plastic microfibers. It is characterized
by MPs as smaller or larger MPs when their size was less than or greater than 1 mm,
respectively. Whereas a further study detected particle resolution level to categorize MPs or NPs
by a 100-μm increase. They are commonly found in the ocean and aquatic areas, such as river
water, beaches, sediments, marine water, and sometimes in polar zones. The smaller size and the
highly accurate surface area of MPs or NPs allow living beings to consume and increases the
chances of adsorbing and desorbing harmful substances in tissues of organisms or in water.
Current researches have shown that NPs have enhanced negative impacts relative to MPs,
although, owing to analytical challenges in their identification, there is still a comprehension of
the existence of NPs in the water. Overall representation of the environmental fate of
microplastics is shown in Fig. 1.
Fig. 3: An overall representation of sources, transport, accumulations, and the fate of MPs in the environment

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