4.

Environmental behavior and fate of MPs and NPs

4.1 Sources
The sources of MNPs plastics are categorized into two major divisions: primary and secondary
MNPs. Primary MNPs derive in the plastics industry from consumer goods, cosmetics and
polymer raw materials such as polyethylene (PE), polystyrene (PS) and polypropylene (PP)[1].
For particular uses that require cosmetic abrasives, medicine vectors, and automotive and
aerospace applications such as air blasting, primary MNPs are purposely made. Using sewage
treatment systems, these MNPs are typically impossible to extract and will eventually
accumulate in the atmosphere until they reach waste water. Secondary MNPs derive from larger
plastics when various dynamic environmental factors such as wind, waves, temperature and UV
light are increasingly broken into smaller parts[2].
In addition, repetitive use of plastic materials can also induce fragmentation and lead to
secondary micro-nanoplastics being created. Hartline et al. (2016) found that 1471-2121
microfibers per textile were micro-fibre masses from top-load traditional home machines, which
was nearly 7 times greater than those from front-load machines. And 30,000-465,000 microfibers
per m2 (or 175-560 microfibers/g) were isolated from textile garments in a recent report. In
addition, another key cause of microplastics in the atmosphere is plastic pollution related to the
movement of cars, including tire wear and tear, braking and road markings. The global average
of microplastic emissions from road vehicle tire abrasion has been measured at 0.81 kg per capita
per year. Wear and tear emitted from airplane tires accounts for nearly 2 percent of overall tire
wear and tear emissions in the Netherlands, aside from road traffic. Furthermore, artificial turf
also plays an important part in the secondary source of microplastics, with artificial grass
emissions ranging from 760 to 4500 tonnes a year being approximately estimated. Various types
of microplastics are thus being emitted into multiple natural environments and ecosystems.[2].
Far different from ocean microplastics sources, which primarily include land-based sources
(contributing to 80%), coastal tourism, leisure, commercial fisheries (e.g. disposable fishing gear
applications, etc., contributing to 18%), marine vessels and marine industries (e.g. aquaculture,
oil rigs, etc.), microplastics enter the soil through 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. In addition, biological processes of soil species, such as feeding operations, digestion, and
excretion processes, can fragment plastic waste in the soil into microplastics. The presence of
microplastics greatly decreases the fertility of the soil, and the movement and trophic transition
of microplastics to heavily polluted soils, especially those covered by waste water and plastic
film, poses major ecological risks. (Fig. 1)[2]
 Figure 1. Sources of microplastics in land. WWTPs indicates wastewater treatment plants[2].

In terms of their bioavailability and deterioration, the scale, form, color and density of
microplastics all play a part. Usually, microplastics are known as plastics <5 mm in size or
between 1 μm and 5 mm; however, studies have identified them as <1 mm, <2 mm, 2-6 mm and
<10 mm. The most popular types of microplastics in the atmosphere include fragments, flakes,
filaments and fibres, broken edges, granules and irregularly formed microplastics. However,
owing to their pervasiveness of everyday life, synthetic fibres and microbeads are more widely
debated. Textiles, such as clothes, result in the release by ordinary use and laundering of
synthetic fibers. Nanoplastics, too small to be seen with the human eye, are similar to
microplastics in that a specific definition of scale has not been provided. However, nanoplastics
are most commonly referred to as plastic particles of <0.1 μm in dimension[3].
Microplastics may reach the atmosphere either initially or after the larger plastic has been broken
down. Microplastics, also referred to as microbeads, are processed for use in cosmetics at a
microscopic scale, such as exfoliators and toothpastes (Figure 2 (left), air blasting systems for
clearing surfaces such as rust and human medication boats and machines, acting as drug
distribution vectors. When big pieces of plastic become fragile or aged due to UV radiation,
waves and other abiotic causes, they are progressively broken down into smaller and smaller
pieces with a diameter of <5 mm.
Figure 2. Examples of microplastics from a personal care product (toothpaste on the left) and from the
breakdown of larger plastic pieces (on the right)[3].

Industrial plastic, which refers to resin pellets used as precursors in plastic processing processes,
is a third type of microplastic that is mostly kept distinct from the others (Figure 3). These pellets
are millimeter-sized and hence are quickly "lost" during manufacturing and shipment into the
environment. These missing pellets have been discovered all around the world on a number of
beaches. In different consumer goods which can shed synthetic fibers when they are cleaned,
synthetic materials are also heavily used. In areas with very basic to no waste water disposal or
due to storm water runoff from wastewater treatment plants, these fibers may reach the sea. It is
estimated that 2.4 mg of person-1 day-1 microplastic is discharged from consumer goods into the
environment[3].

Figure 3. Plastic pellets from manufacturing typically found on beaches[3].

Spheres, balls, circular parts, and fibers are the most prevalent forms of microplastics detected in
the world. The most widely manufactured plastic polymer is polyethylene and this is expressed
in what is commonly found in the world. Barnacles obtained from the North Pacific, for instance,
have been found to contain 58% polyethylene, 5% polypropylene, and 1% microparticle
polystyrene. Browne (Pers. Comm.) devotes a portion to microplastic origins and pathways. He
argues for a strong distinction between "sources" and "pathways" and recommends four source
categories: greater waste, items for washing (cosmetics and air blasting), clothes (fibers),
medicines[4].
Plastic is a manmade substance which, as a consequence of inappropriate use and false waste
management strategies, has spread across land and water; it is expected to rise by 2050. Single
use disposable food packaging such as polyethylene, polypropylene, and polyethylene
terephthalate is the main cause of plastic pollutants. 8 With a broad range of uses in the
electrical, aerospace, clothing and paint sectors, micro-nano plastics have the ability for direct
discharge into river catchment areas impacting the aquatic environment. Other well-known
toxins from MNPs are from personal care products such as toothpaste, scrubs, washing materials
and cosmetics. However, current wastewater treatment facilities have demonstrated that tertiary
water treatment is not a source of micro-plastic contamination because the skimming and settling
treatment methods successfully eliminate those contaminants. Other causes include the
disintegration of synthetic fabrics through garment cleaning, commercial practices such as
polystyrene thermal cutting, agricultural activities such as the use of polyethylene, polyurethane,
polystyrene foils, films as well as soil conditioners, water-based ship-generated waste, polymer-
based nano-particles drug distribution. The current generation of secondary microplastics is a
consequence of massive plastic processing in the 1990s and earlier in the oceans around the
world. While we are attempting to reduce the disposal of pollutants in the atmosphere, advanced
knowledge is needed to eradicate MNPs[5].

Figure 3. Sources of micro-nano plastic pollutants (a) primary (b) secondary micro-nano plastics[5].
4.2 Migration of MPs and NPs
Owing to their unsystematic disposal, plastics enter the natural ecosystem and negatively impact
the marine biota. This is a significant concern in recent decades, as the marine environment has
the largest contribution to global primary productivity.
These plastic materials are weakened by different processes until they reach the atmosphere and
their structural rigidity is lost (Figure 4). Finally, significant plastic deterioration occurs in
powdery fragments and microscopic sized plastics, or microplastics. This are microparticles with
measurements that range from a few micrometers to 500 μm (0.5 mm). Nowadays, microplastics
are used by the pharmaceutical and cosmetic industries in various daily goods and contaminate
the ocean through waste water, progressively transmitted through the food chain and affecting
the marine ecosystem after touching the sea.[6].
Degradation is a chemical alteration that reduces the polymer's total molecular weight
significantly. Since plastics mechanical integrity invariably depends on their high average
molecular weight, the substance is eventually undermined by any substantial deterioration. On
treating, thoroughly deteriorated plastics become porous enough to break apart into powdery
fragments. Even these fragments, frequently not visible to the naked eye, can be further degraded
(usually by microbial-mediated biodegradation) by transforming the polymer carbon into CO2
(and incorporated into marine biomass). When this procedure is finished and all the organic
carbon in the polymer is transformed, absolute mineralization degradation is normally graded
according to the entity that induces 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.
Following entirely different processes, the fragmentation of enormous plastic issues occurs,
severally or together, such as photo oxidation by chemical reaction, ultraviolet radiation, and
mechanical shock, resulting in soil abrasion or mechanical turbulence of water or
microorganisms' biological assimilation. As exposed to ultraviolet light in soil and water
conditions, degradation of plastic pellets such as poly (lactic acid) (PLA), terephthalate (PET),
poly(ethylene) (PE), poly(styrene) (PS), and poly(propylene) (PP) takes place. Hydrolysis is one
of the first degradation mechanisms of heteroatomic polymers such as poly(urethane) (PU) and
PET. If concentrations decrease (in the case of chlorofluorocarbons (CFCs) or increase (in the
case of hydrofluorocarbons (HFCs), which are used as substitutes for CFCs in cooling and
insulation) in the global setting, the impact on the atmosphere increases. Trifluoroacetic acid, a
small atmospheric decomposition agent of some HCFCs and HFCs and fluoropolymer pyrolysis,
is spread evenly over 4000 m of seawater. Trifluoroacetate is abundant in the aqueous world; it is
found in fog, rain, rivers and streams, groundwater, and, most significantly, in sea-water[6].
The breakage of the bond of the organic compound results in the forming of the chemical group
producing autocatalysis, thereby increasing the hydrolysis rate of the acid conditions. Both
photo-oxidation and reaction degradation processes cause breaks to separate and trap to form
embrittlement of plastic induction on the surface of objects. Plastic fragments are so weakened as
to split into microplastic particles through mechanical stress such as abrasion or friction. The
mechanism of fragmentation depends on the environmental factors, the polymer content, as well
as plastic additives that may influence the physicochemical features of the material. Therefore,
MPs of various sizes, shapes, densities and chemical and mechanical properties can be quickly
produced based on environmental circumstances and on plastic goods. The process and
fragmentation rate of MPs in the environment, however, is still unclear and needs to be
researched in order to determine the fragmentation rate of MPs.
Nanoplastics formation
It is also predicted that MPs, as well as the creation of MPs, will be broken into NPs. While NPs
are hard to recognize, after being exposed to the outdoor aquatic microcosm of PP, PS, and PE
pellets, discharge of NPs up to 30 nm in size was reported and thus demonstrated by the absence
of bulk content. After being exposed to outdoor temperatures, the amount of nanofragment
increased by 5 orders of magnitude relative to PE note not subject to weathering. The nature of
NPs shows that it is possible to apply the principle of the degradation of large plastic products
into MPs to the degradation of MPs into small products like NPs. This study indicated that
during processing or use, the physical breakage of MPs in cosmetics could contribute to the
discharge of manufactured NPs into water and 2° MPs/NPs could lead to plastic waste. The
development process has an influence on the separation of MPs, as previously mentioned for
large plastic fragments, so defects can be inserted in particles as a consequence of their pro-
duction. Primary MPs are typically produced by comminution, such as powders, fillers and
pellets. In which the solid particle size is deliberately decreased by impact, compression, or shear
force. Comminution is normally achieved by milling and grinding to cause defects such as cracks
on particles that migrate into fragments until they are fully destroyed. In the case of MPs
winding up in water, due to environmental factors, including water turbulence, these anomalies
will damage particle structures and increase the ESC, resulting in the conversion of MPs to NPs.
No experimental evidence showing the breakdown of MPs into NPs in water due to the
proliferation of abnormalities was reported[6].
The vertical and horizontal distribution of microplastics in soil can be influenced by several
factors (Figure 5), 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 bioturbation microparticle migration in soil indicates that plant processes
(e.g. root growth and de-rooting) and inputs from different animals (e.g. larvae, earthworms,
vertebrates, etc.) can serve as preferential routes for the transportation of microplastics.
Indigenous fungal mycelia, for example, may also lead to the migration of microplastics because
they can bridge air-filled pores and translocate pollutant-degrading bacteria effectively.
Microplastics may be swallowed and eventually excreted by earthworms, transported vertically
by burrows of anecic earthworms from shallow to deep soils, and laterally dispersed across large
regions by the movement of geophagous earthworms and mosquitoes. Mosquito larvae have
been reported to consume microplastics readily, which can survive from the larval to adult stage
in the guts of a mosquito during metamorphosis. In addition, soil microarthropods may be
swallowed by earthworm casts, which may produce condensed microplastics. Mites and
collembola have also been shown to scatter and redistribute micro-plastics by scratching or
chewing microplastics, and by a related process, digging rodents, such as gophers and moles, are
likely to lead to soil movement of microplastics.
The gap between microplastics (100-200 μm) and larger Folsomia candida (up to 4 cm after 5
days) was transferred much further and faster than smaller Proisotoma minuta (about 1 cm after
one week) and the capacity of collembola to spread microplastics was closely correlated with the
size and form of species and microplastics. In addition, Zhu et al. (2017) observed that while a
predator prey relationship occurs, microarthropods' ability to move and disperse microplastics in
soil was greatly improved. It may also speculate that complicated food chains in soil
environments consisting of diverse and dynamic interactions between species would facilitate
microplastic migration relative to the contribution of single species. That is, soil breaking, pores,
agronomic practices (e.g. plowing and harvesting), plant root elongation, geophagous soil fauna
(notably anecic earthworms) ingestion and egestion operations, as well as the digging habits of
other soil animals are likely to lead to the most vertical transfer of microplastics in the soil; while
hunting activities are likely to contribute to the life activities of epigeic earth animals. In
addition, plastic forms can also impact migration, as it has been demonstrated that microbeads
and microfibers have various associations with soil accumulation, which can potentially have
blocking effects on the movement of soil microplastics. In addition, transportation may be
impaired by the properties of the plastic surface and eco-corona changed by the degradation
process. The concept diagram (Figure 5) shows the various factors affecting the migration of
microplastics in soil[2].

Figure 5. 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[2].
Aquatic Life
Human life and behaviors are inseparable from water, the marine ecosystem can be the largest
source of MPs/NPs. MPs/NPs can be transported wherever there is water supply. The movement
of MPs and NPs in the aquatic environment has sparked widespread concern. This mechanism is
influenced not only by the properties of the MPs/NPs, but also by the physical and chemical
properties of the aquatic environment, as well as hydrodynamics, attachment, and uptake of
aquatic species, both of which have a significant impact on the settling, re-suspension, and
transportation distance of plastic particles, and thus on their environmental destiny. The majority
of MPs/NPs from land sources are discharged directly into rivers and lakes by wastewater
treatment plant effluent or surface runoff. Tiny and medium plastic particles are mostly floating
on the water's top, while big and hard plastic particles are collected at the bottom. However, in
the natural world, there are many natural inorganic/organic particles and microorganisms that
can aggregate (heterogeneous aggregation) of MPs/NPs or gather together with plastic particles
themselves (homogeneous aggregation), changing the original density of plastics and thereby
impacting settling and residence time. Hoellein et al. (2019) observed the rate of deposition of
three common microplastics in the stream (polypropylene pellets, polystyrene bits, and acrylic
fibers). The deposition rate was observed to obey the general law of density and biofilm
'stickiness' in the experiment. Debris had the highest rate of deposition, followed by fiber, and
globular had the lowest rate. Biofilm colonization also improved the rate of deposition. As a
result, we believe that the river will continue to take away the fibrous and spherical MPs/NPs,
posing a danger to the broader community. Furthermore, stream characteristics (water depth,
flow, and obstructions in rivers such as large weirs) can influence microplastic migration in the
freshwater environment, but there are few studies on the freshwater environment compared to the
marine, and most of them have not paid attention to the inherent relationship between
hydrological characteristics of rivers and microplastic migration. The deposited MPs/NPs will be
retained in the sediment for a short or long time, while the suspended plastic will begin to flow to
the ocean. On the one side, as the river approaches the estuary, the water flow speed rapidly
decreases owing to the abrupt rise in the cross section of the estuary. In the other side, the river
water would be hampered by the constant flow of tidal water. The heavy ionizing sodium
chloride in seawater dissolves, generating a large number of ions. Because of the three factors
mentioned above, a significant volume of sediment will create a delta, and some MPs/NPs will
be caught in the sediment and deposited here. The estuary has a high concentration of
microplastics in the special transfer region of channel-estuary, but the concentration of
microplastics in river sediments is much greater than that of estuaries. Microplastics in estuaries
and waterways have similar properties, mostly due to the form of thin films and particles. As a
result, rivers can be more severely contaminated by MPs/NPs than lakes. Furthermore, the upper
of the estuary is influenced by the highest turbidity current, which produces a greater abundance
of buoyant microplastic debris, and it can form MPs hot spots in some parts of the estuary due to
tidal waves generated by buoyancy, wind, and tides. Plastic waste created by human activities
(such as ports, fishing, and tourism) is, of course, dumped directly into coastal waters. However,
depending on the relief of the margin, the soil along the coast is not stable. The steep,
tectonically active margins have a narrow continental shelf and steep continental slope, as well
as limited onshore storage area, which reduces sediment and microplastics residence time.
Mature and passive margins, on the other hand, have a broader continental shelf and a gentler
continental slope, resulting in a longer and lower relief catchment. The strength of along-shelf
currents and other oceanographic perturbations can impact sediments at this margin, and
MPs/NPs will shift and redistribute along the continental shelf. If the energy of tides decreases,
sediment movement slows down, and MPs/NPs maintain a good layered distribution based on
their own properties. Furthermore, the longer residence period encourages the fragmentation and
decay of vast parts of plastic, posing a greater danger to the area's living species. The canyon
head is likely to follow the above two marginal topography. The difference is that the former
would pour down, triggering turbid currents and bringing significant MPs/NPs of various shapes
and types directly into the deep-marine realm; however, fibers can be trapped between settling
sand-grains and eventually buried in the deposits during transportation due to their slender form;
while the latter has been slowly deposited, mainly owing to its slender form. Since entering the
deep sea, gravity will direct the MPs/NPs to begin sinking into the deeper marine realm, but
currents of all kinds complicate plastic transportation and distribution. Bottom currents can
easily have the shear force necessary to carry MPs/NPs in surface sediments, isolating plastics in
drift deposits and allowing them to travel with the currents. In general, drift deposits experience
significant ecological disruption, causing the plastic to migrate deeper into the sediment. In
contrast to bottom waves, thermohaline stratification and internal tides can prevent plastics from
settling and resuspend them in the water, where they will be transported to new locations.
Meanwhile, the organism's resuscitation is aided by its digestion and defecation. Ekman and
geostrophic flows, as well as surface Stokes drift, will impact the plastic floating on the ocean's
surface, creating MPs/NPs aggregation areas in certain areas, likely increasing the region's
ecological harm. Another critical mode of transportation in the Polar Regions that is rarely
discussed is sea ice. It uses a vertical pattern to mark polymer structure and size groups of
microplastic particles in the drift trajectories of sea area during the growth of sea ice. However,
in recent decades, global warming has accelerated the loss of sea ice, and these unquantified
microplastic sinks are re-releasing significant amounts of microplastics into the environment.
Scientists would have to reconsider the dynamics, aggregation, and possible toxicological
consequences of microplastic waste as a result of this. We have a general understanding of the
transport pattern of MPs/NPs based on studies from various areas, but the exact distribution is
still unknown. Field investigations will continue to be improved in the future, and labeled
particles can be used to model transportation and forecast plastic flow in the real world[8].
4.2.1 Physicochemical properties: from MPs to NPs
A plastic particle's size is the prevailing attribute that decides its environmental destiny (e.g.,
migration). In addition, it may be size-dependent for bioaccumulation and toxicity. Considering
that NPs derive largely from the breakup and conversion of larger plastic particles, it would be
useful for a deeper understanding of NPs to explore the downsizing processes. By means of
mechanical abrasion processes, NPs can be produced. Significant quantities of NPs are produced
by the breakdown of regular polystyrene items by household blenders. Solid plastic waste
fragmentation and MPs create NPs in the sewage system due to stream flow instability and
mechanical systems in wastewater treatment plants (WWTPs). In the sea swash region, the
natural breakup of larger plastic fragments can also be accomplished. Mechanical fragmentation
of plastic pieces of macro and micro sizes is primarily caused by crack formation. 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, Kc 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].
Another alternative mechanism for NP generation is hydrolysis (reacting with water), although it
may not be the most efficient mechanism for minimizing plastic sizes. In contrast, UV
irradiation-initiated degradation is a very successful downsizing process. The photodegradation
of plastics is primarily due to reactive species of oxygen. 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 destruction and destruction by aquatic and terrestrial species of large plastic parts and
MPs may also create environmental NPs. Zooplankton, squid, shrimps and other species have
been known to eat plastic MPs and possibly NPs in aquatic ecosystems. Fragmentation or
degradation of MPs into NPs has been recorded in polyethylene MPs (31.5 μm) exposed to
Antarctic krill (Euphausia superba) along with algal foods. NPs of 150-500 nm size that were
discovered in the digestive gland were generated after ingestion. In the common earthworm and
snails, reduction of MPs into smaller sizes was observed, while fragmentation of MPs into NPs
was not considered in these studies due to restriction of excess tools[7].
4.3 Aggregation of MPs and NPs
The environmental fate of MNPs is primarily regulated by the processes of weathering and
aggregation. The ageing of MNPs in the atmosphere is caused by different stressors
(environmental factors), such as heat, water, UV irradiation, oxidants, micro-organisms, or by a
mixture of these. As per the Arrhenius relationship, an increase in temperature will increase the
weathering of NPs. Mechanical fragmentation (physical weathering) of NPs is caused by the
shear forces of water (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. In addition,
oxygen has been added to the surface of NPs, resulting in an increased number of functional
groups including oxygen. By colonization (plastisphere) and the use of the polymer matrix as a
food supply, micro-organisms may also play essential roles in the biological weathering of NPs
(section 4.2.1)[7].
In knowing the environmental fate of NPs, aggregation is a crucial challenge. Evidence has
shown that NPs in environments can form milli-sized (mm-sized) aggregates. Furthermore, the
development of heteroaggregates of inorganic colloids or organic matter contributes to NPs
being either settled or migrated. The Derjaguin-Landau-Verwey-Overbeek (DLVO) theory has
been generally adopted by numerous studies to explain the aggregation mechanism of NPs. 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 z
e

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):

√
2
2000 N A qe I
κ= [13]
ε ε 0 kT

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. For the interpretation of the
environmental variables that control the aggregation process, the DLVO theory is critical. It has
been verified by experimental findings that this principle is ideal for NP dispersion structures. In
NP aggregation, various environmental variables, including pH, ion intensity, natural minerals
and organic matter, play essential roles. 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 pH. 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 pH 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). Additionally, Yu et al. (2019) proposed that
the co-existence of natural organic matter and inorganic ions could contribute to the "bridging
effect" if the concentration of organic matter is high enough (to allow the existence of un-
adsorbed free organic matter in the system). Oxygen-containing groups in both NPs and organic
matter could be bridged by inorganic metal cations (e.g. Ca 2+), resulting in heteroaggregation. In
more complex structures, the traditional DLVO principle can be generalized to explain NP
interactions (e.g., soil). Liu et al. (2019c) adopted an expanded theory of DLVO to test the
contact energy of porous media NPs. Three forces are taken into account in Total NPs-soil
interaction energy: van der Waals force, electrostatic double layer force and hydrophobic effect
(described by the Lewis acid-base interaction). Aged NPs are likely to have higher primary
energy barriers, according to theoretical estimates, making them less likely to form aggregates.
The theoretical estimate was consistent with the experimental results that aged NPs are more
mobile 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. Steric repulsion has been introduced into the conventional DLVO
theory in order to better explain the role of EPS in aqueous media. In the solutions with EPS, the
energy barrier was larger, which was consistent with the observation that EPS prevented the
aggregation of NPs by steric effects.
It is important for the determination of the environmental destiny of NPs to consider the
collective actions of NPs. New experiments, however, rely mostly on spherical synthetic NPs,
rather than naturally aged NPs of different forms. The traditional theory of DLVO is based on
the "spherical" premise, so changes must be made when it comes to nanoplastic particles that are
not spherical[7].
The morphology of NPs is largely determined by their origin (i.e., natural weathering vs
synthetic fabrication). NPs of various roots have various forms (Figure 6). Many researchers
have followed publicly available NPs on migration, bioaccumulation and toxicity, which in most
cases exhibit ideal spherical morphology (Figure 6a, b). Metal doped nanoplastics with a
raspberry-like morphology are another type of synthetic NPs (Figure 6d). However, NPs derive
largely from the weathering and fragmentation of larger plastic particles in both terrestrial and
marine environments, rather than from regulated synthesis. The weathering of huge plastic
particles results in NPs with even rougher morphologies (Figure 6c). The forms of the resulting
NPs are hardly flat and circular due to natural forces such as mechanical water forces, UV
radiation and biological metabolism[7].
Downsizing plastic particles from the micro to the nano scale can also contribute to a change in
chemical properties, especially in the functional groups of surfaces. As seen in section 4.2.1, in
Eq. (2) - Eq. (9), during the process of photodegradation, reactive oxygen species are produced.
This can result in an in-crease in functional groups containing oxygen such as carboxyl, carbonyl
and hydroxyl on the surface of NPs. Changes in surface functional groups change NPs'
hydrophobicity and surface charges, which can influence NPs' migration, aggregation, adsorption
of toxins, bioavailability and toxicity. The weathering mechanism of plastic particles should also
be thoroughly understood. However, since it can be readily accessed, recent research primarily
concentrates on the environmental activity and toxic effects of synthetic spherical NPs. The
findings of current studies do not indicate the behavior of naturally weathered NPs under field
conditions, it is argued[7].
Figure 6. 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].
Via many physiological pathways, microplastics can be picked up by aquatic organisms and then
translocated to various tissues or organs, especially the liver, intestine, and digestive tract. The
orally absorbed PS microplastics (20 μm) for the clam Scrobicularia plana were seen to be
passed to the hemolymph and digestive tract. The ingestion by the mussel Mytilus edulis of high-
density PE microplastics (< 80 μm) is mediated by ciliary movement on the surface of the gill,
resulting in the transition of the contaminants to the digestive system (stomach and intestine) and
then to the primary and secondary digestive tubule ducts. The particles in the lysosomal system
gradually accumulate. Similarly, in the gut cavity and digestive tubules of M. Browne et al.
(2008) detected PS microspheres (2, 3, and 9.6 μm) Edulis within 12 h of exposure and 3 days
post-exposure in the hemolymph and hemocytes. Microplastics collect in the mussel's gonads,
mantle, adductor, viscera, and foot in addition to the gills, stomach, and intestine.
For microplastic absorption, phagocytosis and pinocytosis are two potential routes, but particle
translocation is mostly size-dependent, with simpler internalization of smaller plastic particles.
For eg, 5-μm PS microplastics were dispersed in the gills, liver, and gut in a study of the
zebrafish Danio rerio, while 20-μm PS microplastics collected only in the gills and gut. After
exposure of this rotifer, Jeong et al. (2018) confirmed the dispersion of 50-nm microplastics in
different organs of Brachionus koreanus, but 0.5- and 6-μm microplastics localized only to its
digestive tract. The distribution of microplastics in marine animals is also influenced by surface
charge. Della Torre et al. (2014) studied the deposition of microplastics in embryos of the sea
urchin Paracentrotus lividus with various surface coatings (carboxylated and amine polystyrene
microplastics) and found that while carboxylated PS microplastics were confined to its digestive
tract, amine PS microplastics were spread in the embryos[10].
A significant aspect which affects its toxicity is the accumulation of chemicals in an organism.
Chorion zebrafish has pores for the transfer of oxygen and nutrients. In the embryo process,
smaller nanoplastics can penetrate these pores (0.5-0.7 μm diameter), whereas particles greater
than pore size can bind to the chorion and be pulled inside by water flow or mistaken by larvae
as food. Growth & development, immune system, oxidative stress, glucose level, energy
metabolism and other biomarker response may adversely impact tissue accumulation of
MPs/NPs. In various fluorescent-labelled colors and sizes, MPs/NPs are now available. Live
simulation of the absorption and aggregation of fluorescent particles is due to the transparent
nature of zebrafish embryos and larvae[11].
MPs/NPs are reported to accumulate in zebrafish embryo chorion, yolk sac, endotherm, muscle
fibers, eye, spinal cord. Sites recorded for its aggregation are larvae and adult fish, mouth, gut,
head, blood, liver, heart, gills, muscle (Figure 7).
 Fig. 7. Deposition of MPs/NPs in different organs of embryo, larvae and adult zebrafish[11].

The absorption routes in fish, including oral, gill and skin absorption, are complex. Organ-
specific accumulations of MPs/NPs have been found in both larvae and adult zebrafish, with the
intestinal tract being the primary and favored pathway. Studies have shown that MPs/NPs can
accumulate rapidly in zebrafish gills and intestines rather than in other regions. Increased
accumulation of MPs in the presence of natural organic matter (NOM) was seen by the
accumulation kinetics of MPs in zebrafish, with maximal accumulation within 72 hours. During
the purification analysis, the author also reported an exponential decrease in MPs. Gills have a
large surface that causes microplastics to collect and are one of the first organs to communicate
with the marine environment. Gill accumulation may be caused by the main osmotic pressure
balance feature of the gill. The translocation of particles from the intestine to other tissues, such
as the liver and the circulatory system, is determined by the size of the particles and their
concentration in the body. Circulatory system accumulation can be caused by mouth-
gastrointestinal tract translocation and by gill/transdermal ingestion directly from peripheral
vessels. There is minimal selectivity and absorption of MPs as food particles in smaller marine
species, which can cause adverse health effects. In fish treated with PS MPs/NPs, various
histological changes such as necrosis, infiltration, and lipid droplets in hepatocytes were
reported. A recent research, however, has shown that adult zebrafish can consider MPs as
inedible materials (247.5 μm, comparatively large). Zebrafish reported a smaller (0.0-1.0
percent) percentage of accumulation (ingested particles/supplied particles) while only MPs were
supplied, although the percentage of accumulation increased to 0.5-9.4 percent under food
presence conditions, suggesting that zebrafish were required to eat MPs along with food, but they
showed spitting of MPs as they considered these particles as non-edible. The size and shape of
MPs/NPs are likely to impair their gut retention, and relatively little research is known on the
retention of these particles in the intestinal tract. To better understand its effects on organ
toxicity, a thorough analysis of the resident period of MPs/NPs in zebrafish organs is
required[11].
Microplastics (MPs) are usually referred to as 0.1-1000 plastic debris, whereas plastic particles
are known as 0.1 μm nanoplastics (NPs). For different applications, such as microbeads in
exfoliates for personal care items, MPs are purposely made. Nanoplastics, such as electronics,
paints, drug delivery devices, and adhesives are used with all of the substances. 3D printing will
emit polymer nanoparticles, for example. This material is continually discharged into municipal
waste water containing plastic microfibers from garment washing machines. MPs are
characterized as smaller or larger MPs, where their size is less than or greater than 1 mm. A
further analysis detected the degree of particle resolution in order to categorize MPs or NPs by a
rise of 100 μm. In ocean and aquatic environments, such as river water, beaches, sediments,
marine water, and even polar regions, they are usually found. The smaller scale and highly
accurate surface area of MPs or NPs helps living organisms to absorb and increases the
probability of toxic compounds being adsorbed and desorbed in organism or water tissues.
Current study has demonstrated that NPs have improved negative effects compared to MPs, but
there is still an understanding of the prevalence of NPs in the water due to methodological
difficulties in their detection[12].
References:

[1] N. Tiwari, D. Santhiya, and J. G. Sharma, “Microbial remediation of micro-nano plastics:

Current knowledge and future trends,” Environmental Pollution, vol. 265. Elsevier Ltd,
01-Oct-2020, doi: 10.1016/j.envpol.2020.115044.
[2] J. J. Guo et al., “Source, migration and toxicology of microplastics in soil,” Environ. Int.,
vol. 137, no. October 2019, p. 105263, 2020, doi: 10.1016/j.envint.2019.105263.
[3] I. Lise Nerland, C. Halsband, I. Allan, K. V Thomas, and K. Thomas Kristoffer Naes,
“Norwegian Institute for Water Research Negative environmental impact,” 2014, no. 47,
p. 55.
[4] S. Sharma and S. Chatterjee, “Microplastic pollution, a threat to marine ecosystem and
human health: a short review,” Environ. Sci. Pollut. Res., vol. 24, no. 27, pp. 21530–
21547, Sep. 2017, doi: 10.1007/s11356-017-9910-8.
[5] A. L. Andrady, “Microplastics in the marine environment,” Marine Pollution Bulletin,
vol. 62, no. 8. pp. 1596–1605, Aug-2011, doi: 10.1016/j.marpolbul.2011.05.030.
[6] S. S. Sana, L. K. Dogiparthi, L. Gangadhar, A. Chakravorty, and N. Abhishek, “Effects of
microplastics and nanoplastics on marine environment and human health,” Environ. Sci.
Pollut. Res., vol. 27, no. 36, pp. 44743–44756, Dec. 2020, doi: 10.1007/s11356-020-
10573-x.
[7] L. Wang et al., “Environmental fate, toxicity and risk management strategies of
nanoplastics in the environment: Current status and future perspectives,” J. Hazard.
Mater., vol. 401, Jan. 2021, doi: 10.1016/j.jhazmat.2020.123415.
[8] D. Huang et al., “Microplastics and nanoplastics in the environment: Macroscopic
transport and effects on creatures,” Journal of Hazardous Materials. Elsevier B.V., 2020,
doi: 10.1016/j.jhazmat.2020.124399.
[9] W. Wang, H. Gao, S. Jin, R. Li, and G. Na, “The ecotoxicological effects of microplastics
on aquatic food web, from primary producer to human: A review,” Ecotoxicol. Environ.
Saf., vol. 173, no. November 2018, pp. 110–117, 2019, doi:
10.1016/j.ecoenv.2019.01.113.
[10] S. Xu, J. Ma, R. Ji, K. Pan, and A. J. Miao, “Microplastics in aquatic environments:
Occurrence, accumulation, and biological effects,” Sci. Total Environ., vol. 703, p.
134699, 2020, doi: 10.1016/j.scitotenv.2019.134699.
[11] J. Bhagat, L. Zang, N. Nishimura, and Y. Shimada, “Zebrafish: An emerging model to
study microplastic and nanoplastic toxicity,” Sci. Total Environ., vol. 728, p. 138707,
2020, doi: 10.1016/j.scitotenv.2020.138707.
[12] M. Shen, G. Zeng, Y. Zhang, X. Wen, B. Song, and W. Tang, “Can biotechnology
strategies effectively manage environmental (micro)plastics?,” Science of the Total
Environment, vol. 697. Elsevier B.V., 20-Dec-2019, doi:
10.1016/j.scitotenv.2019.134200.