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Engineered Polystyrene-Based Microplastics of High Environmental

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Article in Environmental Science and Technology · July 2021

DOI: 10.1021/acs.est.1c02196

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Engineered Polystyrene-Based Microplastics of High Environmental

Relevance
Amit Kumar Sarkar,§ Andrey Ethan Rubin,§ and Ines Zucker*
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ABSTRACT: Microplastic (MP) pollutionan emerging environmental

challenge of the 21st centuryrefers to accumulation of environmentally
weathered polymer-based particles with potential environmental and health
risks. Because of technical and practical challenges when using environmental
MPs for risk assessment, most available data are generated using plastic models
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of limited environmental relevancy (i.e., with physicochemical characteristics

inherently different from those of environmental MPs). In this study, we assess
the effect of dominant weathering conditionsincluding thermal, photo-, and
mechanical degradationon surface and bulk characteristics of polystyrene
(PS)-based single-use products. Further, we augment the environmental
relevance of model-enabled risk assessment through the design of engineered
MPs. A set of optimized laboratory-based weathering conditions demonstrated
a synergetic effect on the PS-based plastic, which was fragmented into millions
of 1−3 μm MP particles in under 16 h. The physicochemical properties of
these engineered MPs were compared to those of their environmental counterpart and PS microbeads often used as MP models. The
engineered MPs exhibit high environmental relevance with rough and oxidized surfaces and a heterogeneous fragmented
morphology. Our results suggest that this top-down synthesis protocol combining major weathering mechanisms can fabricate
improved, realistic, and reproducible PS-based plastic models with high levels of control over the particles’ properties. Through
increased environmental relevancy, our plastic model bolsters the field of risk assessment, enabling more reliable estimations of risk
associated with an emerging pollutant of global concern.
KEYWORDS: degradation mechanism, fragmented morphology, environmental plastic, plastic model, particle size

■ INTRODUCTION
Since its discovery in the 19th century, plastic has become an
integral part of our modern lives. Plastics are typically
composed of polymerssuch as polyethylene (PE), poly-
propylene (PP), polystyrene (PS), and polyethylene tereph-
thalate (PET)1,2 and additives (e.g., colors and fillers)
intended to enhance polymer properties and prolong their
life.3 Associated with the plastic revolution is an increasing
growth rate of plastic waste worldwide,4 which eventually
reaches the oceans via inland waterways, wind, and tides.5
By 2050, accumulation of plastic waste in landfills and
aquatic environments is estimated to reach 33 billion tons.4
This pervasive and persistent magnitude of plastic wasteand
especially single-use plastic productsin the aquatic environ-
ment suggests plastic as a large-scale emerging environmental
pollutant.6
Rather than degrading quickly, plastics are susceptible to
slow weathering processes,7 which in the aquatic environment
include UV-driven photo-degradation (i.e., oxidation),8 wave-
driven fragmentation,9 and thermal degradation9 (Figure
1A).10 Catalytic degradation (i.e., radical propagation) was
also reported to occur under all weathering processes.9 These
combined weathering processes result in plastic decomposition
to micrometer (μm) and nanometer (nm) particles [micro-
plastics (MPs) and nanoplastics (NPs), respectively]11 along
with release of additives from the bulk plastics during
decomposition.3,12
The interactions of plastic and biological substances in the
aquatic environment influence its weathering.13 On one hand,
microbial colonization on plastic surfaces (as biofilms) may
form protective layers on the plastic surface and thus reduce
photo-degradation.14 On the other hand, colonization by
microorganisms may increase the probability of plastics being
biodegraded, depending on the composition and structure of
the microbial communities as well as the bioavailability of the
synthetic plastic.15,16 Overall, although biofilm-plastic inter-
actions are increasingly reported to have a role in the
Received: April 5, 2021
Revised: July 1, 2021
Accepted: July 1, 2021

© XXXX American Chemical Society https://doi.org/10.1021/acs.est.1c02196

A Environ. Sci. Technol. XXXX, XXX, XXX−XXX
Environmental Science & Technology
Figure 1. (A) Environmental degradation processes of plastic (left) and corresponding plastic product properties (right). (B) Schematic illustration
of engineered MP design, including selection of individual simulated weathering procedures (top) and top-down synthesis protocols (bottom).
formation of MPs, such interactions are rather complex,
diverse, and site-specific and not fully characterized.17
Weathered MPsoften characterized by rough, oxidized
surfaces and heterogeneous fibrous or fragmental morphol-
ogypose major environmental concerns due to their
unknown fate and transport as well as their potential toxicity
toward living organisms. Therefore, a massive research effort
has been applied in recent years to MPs’ environmental
implications throughout their life cycle, which have been found
to be highly dependent on their physicochemical character-
istics influenced by environmental weathering.18−20 For
example, sorption levels of micropollutants onto MPs’ surfaces
have been correlated with crystallinity and specific surface
areas of MPs21 as well as functional groups and hydrophobicity
of both MPs and micropollutants.22−25 The extent of overall
deposition, retention, and transport of MPs in terrestrial
systems26 was found to be dependent on MP density, shape,
and size.27 MP toxicity, on the other hand, was found to
change with MP size, specific surface area, and chemical
composition.28
Use of real environmental plastic in studies exploring their
environmental implications is difficult29 due to environmental
plastics’ complex extraction and characterization techniques,
potential contamination with non-environmental plastics
during handling,30 and heterogeneous composition and size
distribution (which hampers reproducible, statistically signifi-
cant results). Because of these restraints as well as the fact that
environmental implications of MPs are becoming a prominent
field of research, most of the available data in the field are
rapidly generated through controlled experiments using plastic
models.31,32 Because physicochemical characteristics drive the
fate, transport, and risk, such plastic models should accurately
reflect the characteristics of environmental plastics while
eliminating factors interfering with controlled risk assessment
such as the wide size and compositional distributions of plastic
particles.
Many MP models attempt to mimic environmental MPs,
albeit insufficiently. A widely used model representing
environmental MPs is commercially available polymeric
microbeads,33−39 but these commonly used spherical microbe-
ads are not accurate representations of secondary environ-
mental MPs due to the microbeads’ smooth surfaces,
homogeneous spherical shape, and pure polymeric composi-
tion.40 Another model used in literature is shredded (environ-
mental) plastic debris, but this model results in limited
reproducibility of results due to this technique’s limited control
over polymer types and the presence of contamination from
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the field.41 Prospective top-down approaches have been
suggested in literature, such as the use of commercial
weathering chambers42 or application of single degradation
mechanisms43−45 to degrade plastic products. However, the
focuses of these studies were MPs’ risk toward the environ-
ment rather than verification of the resultant plastic particles’
resemblance to their supposed environmental counterparts.45
Overall, because inappropriate or unverified MP models may
enable incorrect conclusions as to MPs’ interaction with their
environment, there is an urgent need to fundamentally develop
simulated MPs with environmentally relevant characteristics
better representing those of their real environmental samples.
In this study, we use PS-based single-use products as raw
plastic for top-down fabrication of environmentally relevant
plastic particles (Figure 1B). We screen through simple lab
procedures to simulate dominant weathering mechanisms and
degrade the PS-based plastic in a systematic and environ-
mentally relevant manner. Upon selection and optimization of
individual weathering proceduresbased on similarity of the
resultant plastic particles to environmentally degraded
plasticswe combine the most representative procedures
into several, accelerated multi-stage protocols producing
engineered plastic particles. We compare major physicochem-
ical characteristics of our simulated engineered MPs to those of
commonly used primitive models (i.e., microbeads) and semi-
environmental plastics (i.e., same PS-based product placed
under real environmental conditions). Our results suggest that
the engineered MPs have comparable surface morphology and
functionality to those of naturally weathered plastic particles,
with a defined average particle size of 1−3 μm. Overall, this
work offers a facile and reproducible method to fabricate
plastic particles of higher environmental relevance than
currently available plastic models while allowing control over
particle characteristics. In the future, this tunable MP synthesis
method could be applied to other plastic types, pushing the
entire field of plastic pollution risk assessment toward higher
reliability and real-world relevance.
■
MATERIALS AND METHODS
Pretreatment of Raw-Plastic Particles. PS-based single-
use forks were crushed and milled using a mechanical grinder
(Ika Werke M20, Germany). The ground plastic particles were
sieved using a stainless steel 100 μm mesh strainer. The sieved
product (<100 μm) was used as raw plastic for all degradation
procedures conducted in this study. The average size of the
raw-plastic particles was ∼90−100 μm (Figure S1 in the
Environ. Sci. Technol. XXXX, XXX, XXX−XXX
Environmental Science & Technology
Supporting Information). Raw-plastic particles were stored in a
glass refrigerated container until use.
Accelerated Oxidation Procedure. Oxidation of raw-
plastic particles was conducted through exposure to UV and
ozone in wet conditions (both in the absence and presence of
salts) as well as in dry conditions. In wet conditions, 100 mg of
raw-plastic particles was placed in a glass Petri dish and
dispersed in 8 mL of deionized (DI) water from a Milli-Q
ultrapure water purification system (Millipore, Billerica, MA)
or salty water DI water with 33 g/L Red Sea premium salts,
Red Sea Fish, Israel). Ethanol (EtOH) was added (20%) to
allow increased dispersion of the hydrophobic raw plastic. Dry
(100 mg) and wet samples were placed in a UV-Ozone (UV-
O) chamber (ProCleaner, BioForce Nanosciences, USA) for a
predetermined period (1−4 h). The spectral distribution of the
UV irradiation is shown in Figure S2. The oxidized plastic
particles were mixed following each exposure hour. The wet
treated particles were filtered prior to analysis [other than wet
analyses such as particle size distribution (PSD) and zeta
potential] using a 0.45 μm nylon filter and washed with excess
DI water. To assure that the filter paper does not influence the
collected plastic particles (through contribution of additional
nylon particles, e.g.), a control experiment was conducted in
which only DI water was filtered (rather than degraded PS
particle suspension). The negligible presence of particles in the
retentate and filtrate confirmed that the filtration does not
interfere with analysis of the degraded PS particles (Figure S3).
The treated oxidized samples were collected using the nylon
filter paper in solid form, transferred into glass vials, and stored
in a refrigerator for further analyses.
Accelerated Mechanical Procedure. Mechanical degra-
dation of the raw-plastic particles was conducted using probe
sonication (QSonica, LLC Q 125, USA) across different
sonication times in an ice bath. First, 500 mg of raw-plastic
particles was dispersed in 50 mL of DI water with 20% EtOH
and poured into a 100 mL glass bottle. Sonication was
conducted under sequences of 7 s on (70% amplitude) and 3 s
off for 10, 20, or 30 min. The sonicated suspension was
collected, filtered (using a 0.45 μm nylon filter), and
refrigerated in glass vials for further analyses.
Accelerated Thermal Procedure. A lab oven (Carbolite,
MRC, China) was used to simulate thermal effects on the
physicochemical characteristics of PS-based plastic. Raw plastic
(100 mg) was heated in the oven at 70 °C for either 6 or 12 h
in both dry and wet (DI water with 20% EtOH) conditions. In
wet conditions, the dispersion was sealed in a 50 mL Teflon-
lined stainless steel autoclave prior to thermal treatment to
eliminate evaporative effects. The treated plastic particles were
collected, filtered (using a 0.45 μm nylon filter), and
refrigerated in glass vials until further analyses.
Design of Top-Down Synthesis Protocols Combining
Accelerated Oxidative, Mechanical, and Thermal Deg-
radation Procedures. The optimal accelerated procedures
on raw plastic (based on physicochemical similarity to
environmental samples) by means of oxidation, mechanical,
and thermal degradation were used to design multi-stage
sequenced protocols. Single-step procedures were combined
into multi-step protocols applied on raw-PS-based plastic to
achieve its cumulative degradation representing dominant
weathering processes. Treated plastics were then characterized
to elucidate the changes in physicochemical properties during
the degradation procedures and to compare their physico-
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chemical changes to those of environmentally weathered
plastics.
Semi-environmental Plastic and PS Microbeads. In
order to compare our engineered MPs to their environmental
counterparts, we generated PS-based semi-environmental
plastic particles in controlled conditions. The milled and
sieved PS-based raw plastic was dispersed in DI water, covered
by a quartz window (to avoid contamination and to allow
passage of UV irradiation to the suspension), and placed on a
rooftop at Tel Aviv University (latitude 31.11264, longitude
34.80617) for 11 months from September 2019 to August
2020. The weathered wet sample was filtered (using a 0.45 μm
nylon filter), collected in a glass vial, and refrigerated until use
as a semi-environmental plastic reference to evaluate the
environmental relevance of our engineered MPs. Non-
functionalized PS microbeads were also purchased from
Spherotech, Inc. USA for comparison to our engineered MPs
and the semi-environmental sample.
Characterization Techniques. Differential scanning
calorimetry (DSC, Q-2000) was used to determine the glass-
transition temperature (Tg) of the raw-plastic particles.
Heating and cooling were carried out in the temperature
range of 25−100 °C with a fixed heating rate (10 °C/minute)
under an inert nitrogen atmosphere. The raw plastic and
treated plastic with individual simulated weathering proce-
dures, surface chemistry, surface morphology and composition,
and PSD were characterized by attenuated total reflection
(ATR)-equipped Fourier transform infrared spectrometry
(FT-IR), high-resolution scanning electron microscopy (HR-
SEM) coupled with energy-dispersive X-ray spectroscopy
(EDX), and micro-flow imaging technique, respectively.
FT-IR (Tensor 27, Bruker, USA) spectra were recorded in
the range of 400−4000 cm−1 at a spectral resolution of 4 cm−1
with 16 scans. For each spectrum, approximately 10 mg of the
dry sample was placed and compressed on the ATR and the
spectrum was normalized to the background spectrum. The
surface morphologies of raw plastic and treated plastic were
examined using HR-SEM (ZEISS, Gemini SEM 300,
Germany) in high vacuum mode and an acceleration voltage
of 3 kV. All samples were sputter-coated (Quorum-150TS
plus; UK) with Chromium for 5 min before HR-SEM imaging.
EDX was used for elemental analysis of probe-sonicated
plastics using a silicon drift detector-x-act from Quanta 200
FEG Environmental SEM. Particle sizes and concentrations
were quantified by micro-flow imaging (PSD-MFI5200, CL,
USA), wherein a digital camera with an illumination and
magnification system captured in situ images of suspended
particles in a flowing sample. Upon injection of the plastic
particle suspension into the flow cell, the plastic particles are
illuminated by a light-emitting diode (475 nm) and imaged
using a digital camera. Each image was processed to determine
the equivalent circular diameter of particles in the range of 1−
100 μm.
Surface charges, surface crystallinities, and specific surface
areas were also determined for the final engineered MPs, semi-
environmental MPs, and PS microbeads. The zeta potentials
(determining surface charge) of each sample were measured
twice at 25 °C using a Zeta-Sizer system (Malvern Instru-
ments, UK).46 The X-ray diffraction (XRD) patterns
(determining crystallinity) of each sample were measured
using an X’PERT system with Cu Kα radiation between 10°
and 90° at a scan rate of 2° per min. Specific surface area
(SSA) measurements were obtained using Brunauer−Emmet−
Environ. Sci. Technol. XXXX, XXX, XXX−XXX
Environmental Science & Technology
Figure 2. Characteristics of PS-based plastic particles following simulated photo-degradation procedures under a UV-O instrument for 3 h in dry
and wet conditions (DI water and salty water at pH 8.5 and conductivity of 66.07 μS/cm). (A) FT-IR spectra, (B) representative HR-SEM images,
and (C) PSD in the range of 1−10 μm. In wet experiments, 100 mg of raw-plastic particles was dispersed in 10 mL of aqueous solution containing
20% EtOH.
Teller (BET) measurements on a Quantachrome Autosorb
LX4, Austria, with krypton (Kr) as the analysis adsorptive. All
samples were degassed under vacuum at 50 °C for 16 h before
analysis to ensure moisture-free samples.
■ RESULTS AND DISCUSSION
Effect of Individual Accelerated Degradation Proce-
dures on the Properties of PS-Based Plastic. Top-down
fabrication of environmentally relevant MPs in lab conditions
should simulate the major weathering processes driving the
degradation of bulk plastics in the environment. To ensure that
the selected lab-based simulated procedures best represent
natural weathering processes, changes in the physicochemical
properties of the degraded plastics were compared to those
observed in naturally weathered plastics.
Photo-degradation. To mimic environmental photo-
degradation, we exposed raw plastics to a UV-O instrument,
which facilitated UV irradiation and oxidation via ozone and
radical reactions. FT-IR spectra of the UV-O-treated plastics in
all experimental conditions showed new peaks at approx-
imately 1700 and 2300 cm−1, which were not observed in the
spectra of raw PS-plastic (Figures 2A and S4). Whereas the
peak at 2300 cm−1 is associated with CO247 from measuring
conditions, this new peak at ∼1700 cm−1 was due to the
formation of carbonyl functional groups during UV-O
treatment.48 Photo-degradation processes typically result in
chain scission and cross-linking reactions, facilitating the
formation of MPs49 with ketones.48 Such observations were
reported for environmentally weathered PS-based plastics.50−54
It should be noted that the insertion of carbonyl functional
groups was also reported following biodegradation.14,15 Thus,
although biodegradation is excluded from our accelerated
procedures, its associated surface functionalization is expressed
in our degraded MPs. Irradiation time of 3 h was selected
because of its highest relative peak intensity at ∼1700 cm−1
(which was similar to the relative peak intensity at 4 h of
irradiation) in all tested conditions, including both wet
(presence and absence of salt) and dry conditions (Figure S4).
HR-SEM images of large plastic particles were compared
before and after photo-degradation (Figure 2B). Oxidized
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plastics in dry and wet conditions (in the presence and absence
of salts) exhibited similar surface morphology to that of raw
plastic, most likely because the long polymer chain responsible
for structural integrity was unaltered in the tested conditions
and the general morphology was therefore maintained.
Nevertheless, we observed a change in the raw plastic color
from white to yellow following the UV-O oxidation procedure
(Figure S5), which has also been reported for the degradation
of plastic in environmental conditions.49
The size distribution of suspended particles examined in the
range of 1−10 μm was similar for all plastic samples (including
raw plastic). Upon degradation, more than 99% of the particles
were found to be smaller than 5 μm, and formation of 1−3 μm
particles from the breakdown of larger particles could be
detected. However, only a slight change in large particle
concentration was observed following degradation. This trend
is attributed to the fact that degradation of a few large particles
translates to a large number of smaller particles. Particles
smaller than 1 μm were below the measurement range of the
analytical instrument and could not be quantified using the
applied dynamic image analysis. Therefore, we focused the
PSD discussion on taking the concentration of 1 μm of plastic
particles and the particle size range of 1−10 μm.
The highest concentration of degraded 1 μm plastic particles
was achieved in dry conditions (234k particles/mL of
suspended sample), suggesting that dry plastics are more
greatly impacted by the UV-O oxidation procedure compared
to plastics in wet conditions (Figure 2C). This observation can
be explained by the efficient light absorption in dry conditions
compared to wet conditions where light scattering effects
occur. Based on the changes in surface functionality and PSD
in the range of 1−3 μm, we chose 3 h of dry irradiation as an
optimal UV-O oxidation procedure.
Mechanical Degradation. To mimic mechanical degra-
dation of plastic in aquatic environments, raw-plastic
suspensions were probe sonicated across different times.
Under aquatic environmental conditions, shear forces (from
waves and wind currents) enable the physical aging of plastic
material through erosion,55 which promotes the formation of
MPs.56,57 Specifically, mechanical forces can impose elevated
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Figure 3. Characteristics of PS-based plastic particles following simulated mechanical degradation procedures in wet conditions (DI water and 20%
EtOH) for 10, 20, and 30 min. (A) FT-IR spectra, (B) representative HR-SEM images, and (C) PSD in the range of 1−10 μm.

Figure 4. Characteristics of PS-based plastic particles following simulated thermal procedures in dry (6 and 12 h) and wet conditions (DI water and
20% EtOH; 6 h) (A) FT-IR spectra, (B) representative HR-SEM images, and (C) PSD in the range of 1−10 μm. Arrows in HR-SEM images
represent cracks on the plastic surface.

friction on the surface of plastic against natural shoreline beach
sediments.46
FT-IR analysis did not show any noticeable changes in
surface functionality following sonication in all the tested
conditions (Figure 3A). Unlike photo-degradation, sonication
did impart significant changes in surface morphology as
observed through HR-SEM. Following probe sonication, the
surface morphology of the treated plastic was severely
damaged58 in all three timelines examined, with noticeable
changes in surface morphology appearing with long sonication
times (Figure 3B). The obtained rough surface morphology of
the treated plastics was similar to that of weathered PS-based
plastics as reported in the literature.59 Figure 3C shows that
probe sonication for 20 and 30 min resulted in high
concentrations of 1 μm particles (1.42 × 106 and 1.50 × 106
particles/mL, respectively), which was used as our direct
indicator of levels of degradation, while 10 min of probe
sonication resulted in a lower number of particles in the 1 μm
range (7.44 × 105 particles/mL).
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The EDX of plastic particles formed after sonication showed
the presence of carbon and oxygen elements (from plastic
particles) as well as metallic elements, indicating sample
contamination from abrasion of the probe tip during
sonication (Figure S6). The abrasion from the probe tip at
elevated sonication times was further confirmed by conducting
EDX to control the sample of particles formed following
sonication of DI water (i.e., in the absence of plastic particles),
showing the presence of metallic particles composed of lead,
titanium, iron, and aluminum originating from the probe alloy
(Figure S7). As the probe sonication for 20 and 30 min had a
high contamination rate (∼10% of particles) compared to 10
min of sonication (∼2.5%, Figure S8), we selected probe
sonication for 10 min as the optimal accelerated mechanical
procedure. Separation of the metal particles from the plastic
suspensions can be further achieved by simple centrifugation.
Thermal Degradation. The Tg of the raw plastic was
determined to be 94.5 °C (Figure S9), suggesting that thermal
treatment at temperatures lower than this Tg should prevent
transition to a viscous or rubbery state of raw plastic.
Environ. Sci. Technol. XXXX, XXX, XXX−XXX
Environmental Science & Technology
Figure 5. Characteristics of PS-based plastic particles subjected to top-down synthesis protocols that combine accelerated oxidation (3 h/dry, UV-
O), thermal (12 h/dry, oven), mechanical (10 min/20% EtOH, probe sonicator) procedures (i.e., Protocol-3). (A) FT-IR (B) PSD in the range of
1−10 μm, and (C) and HR-SEM of representative raw plastic (left) vs preliminary engineered MPs (right).
Therefore, we chose 70 °C for the accelerated thermal
degradation of the raw plastic under dry and wet conditions.
The FT-IR analyses did not show addition of new peaks,
suggesting negligible surface functionalization during thermal
treatment (Figure 4A). However, surface cracks (shown by
arrows, Figure 4B) appeared after both six and 12 h of thermal
treatment. Such observations in surface morphology were also
reported for naturally weathered plastic surfaces.60 Crack
formation most likely occurs during thermal treatment due to
degassing of volatiles, which shrinks the plastic surface and
promotes cracking from surface tensile stress.61
Figure 4C reveals a 1 μm particle concentration for plastics
after 12 h of thermal treatment similar to that of raw-plastic
particles, indicating the limited role of the applied thermal
procedure in fragmentation of the plastic particles. However,
the generated cracks on the plastic surface could predispose
the particles to further fragmentation, especially under post-
mechanical treatment. Thermal treatment for 6 h resulted in a
slight decrease in the 1 μm particle concentration, possibly due
to agglomeration of plastic particles, the effects from which
were not offset by formation of new particles through
fragmentation. Based on the noticeable morphological change,
we chose 12 h (dry) of thermal treatment as an optimal
thermal procedure.
Effect of Combined Accelerated Degradation Proce-
dures on the Properties of PS-Based Plastic. The optimal
accelerated procedures for oxidation (3 h of dry UV-O
oxidation procedure), mechanical degradation (10 min of
probe sonication in 20% EtOH), and thermal (12 h at 70 °C)
degradation were permuted to design a series of multi-stage
protocols (Figure 1B). The three multi-stage protocols were
(1) thermal > mechanical > oxidation; (2) thermal >
mechanical > oxidation > mechanical; and (3) thermal >
oxidation > mechanical. We selected thermal degradation as
the first applied procedure because it results in rough and
cracked surfaces, making the plastic more vulnerable to
subsequent mechanical and oxidation procedures.
The degraded plastics treated in all three protocols showed
the characteristic FT-IR peak of carbonyl groups at ∼1700
cm−1 (Figure 5A), similar to the peak observed for the
individual accelerated UV-O procedure (Figure 2A). Protocol-
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1 resulted in a higher concentration of 1 μm particles (1.9 ×
106 particles/mL) compared to each of the individual
accelerated procedures (Figure 5B). Interestingly, once an
additional probe sonication step was applied (i.e., Protocol-2),
the concentration of 1 μm of particle counts dropped, probably
due to breakage of particles into sizes below the measurement
range. Protocol-3 resulted in the highest concentration of 1 μm
of particles (3.2 × 106 particles/mL) with a noticeable
population of particles in the range of 2−4 μm (Figure 5B).
Representative images of degraded plastic particles following
Protocol-3 show severely damaged particle surfaces as
compared to the smooth surfaces of the raw-plastic particles,
together with a significant change in size (from 90 to 100 μm
for raw-plastic particles to ∼1 μm for plastics treated by
Protocol-3) (Figure 5C). To further examine the smaller
particle size and damaged plastic surfaces in the overall
population, we used ImageJ analysis on a series of HR-SEM
images of raw plastic (Figure S1) and plastic treated by
Protocol-3 (Figure S10). This analysis confirmed a clear shift
of plastic particles’ range from ∼100 μm to below 1 μm. Based
on degradation in particle size and the obtained change in
surface functionality, Protocol-3 was selected as the most
suitable protocol to produce engineered MPs. Moving forward,
we extensively characterized the engineered MP product and
compared its characteristics to those of both a PS microbead
model often used for risk assessment and PS-based semi-
environmental plastic.
Comparison of Engineered MPs to the Polymeric
Microbead Model and Environmental Plastic. The overall
surface morphology of the obtained engineered MPs was
fragmented, markedly different from the smooth, spherical
morphology of the PS microbead particles but similar to
environmental PS plastics (Table S1).53,54,62,63 The color of
real environmental PS plastic appears to be yellow,64 similar to
that of engineered MPs (Figure S5). An additional peak (i.e.,
not a pristine PS plastic peak) was reported in the range of
1650−1750 cm−1 for many extracted PS-based environmental
MPs (corresponding to the insertion of oxygen functionalities
due to environmental weathering), which also appeared for
engineered MPs.50−54,63 We have also collected large PS-based
MPs from the Israeli coast of the Mediterranean Sea (Tel Aviv,
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Figure 6. Representative HR-SEM images of (A) 1 μm of PS microbeads, (B) PS-based plastic particles subjected to top-down synthesis protocols
that combine accelerated oxidation, thermal, mechanical procedures (Protocol-3), and (C) semi-environmental plastic (raw-plastic particles
naturally weathered for 11 months on a Tel Aviv University rooftop).

Figure 7. Comparison of characteristics of raw plastic, engineered MPs, and semi-environmental plastics by means of (A) FT-IR spectra, (B) PSD
in the range of 1−10 μm, and (C) zeta potential, and (D) XRD (inset: zoom in to show similarity in peak intensity to engineered MPs and the
semi-environmental sample).

Israel), which had a similar fragmented and rough morphology
with an oxidized surface (Figure S11).
However, bulk properties of environmental PS MPs are hard
to assess due to the difficulty in collecting large volumes of
environmental plastics of a single plastic origin. Additionally,
surface impurities50,51 and heterogeneity in plastic sizes and
aging periods65 also hinder the use of extracted MPs as a
reference material for assessing the environmental relevance of
engineered MPs.66
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Controlled aging of plastics may be the best available
reference for comparison to engineered MP properties. Semi-
environmental plastic may hold many advantages as a reference
as (1) the raw plastic to be aged is identical to the one used to
produce engineered MPs, (2) it is produced in a controlled
environment, where aging time and aging conditions are
known, (3) impurity content decreases and, (4) large volumes
of MPs can be produced for bulk and surface analyses. For
these reasons and as past studies used controlled simulated-
Environ. Sci. Technol. XXXX, XXX, XXX−XXX
Environmental Science & Technology
PS59,67,68 as a standard reference to assess the bulk properties
of MPs, we used semi-environmental plastic aged for 11
months in outdoor conditions (Figure 6) as our reference.
The appearance of semi-environmental plastic is also yellow,
similar to that of engineered MPs and real environmental PS
plastic.64 The FT-IR patterns of both engineered MPs and
semi-environmental plastic are similar in nature, with the
emergence of the characteristic peak associated with carbonyl
groups for both (Figure 7A). PS microbeads did not show any
characteristic peak at 1700 cm−1, implying that the PS
microbeads lack oxygen functionalities. To determine the
aging time of the engineered MPs, we compared its normalized
carbonyl index (CI)defined as the integrated area ratio of
the carbonyl bond to the carbon−carbon bond and often used
as an aging index69 to that of semi-environmental plastic.
The calculated CI index suggests that the engineered MPs
(Figure S12) produced through the accelerated protocol
(roughly <16 h) was equal to 10−11 months of environmental
weathering.
PSD analysis shows similar size distributions of the
engineered MPs and the semi-environmental plastic; however,
even with similar initial starting particle concentrations, the
two degradation processes resulted in a significant difference in
their resultant 1 μm particle concentrations (Figure 7B). This
difference in final particle count could be attributed to the fact
that the semi-environmental plastic was kept under sunlight
irradiation with no external mechanical forces (which also
hinder it from reaching true environmental realism), whereas
the engineered MPs were subjected to both chemical and
mechanical aging. The PS microbeads had a narrow PSD
(single peak at 1 μm) compared to that of the semi-
environmental plastic and the engineered MPs.
The surface charge of the synthesized engineered MPs was
determined through zeta potential measurements and was
compared to the surface charge of semi-environmental plastic
and PS microbeads. The zeta potential of the engineered MPs
product (−22.65 mV) was not statistically significantly
different from that of the semi-environmental sample
(−16.86 mV) but statistically significantly different than that
of PS microbeads (p value: 0.046, Figure 7C). The similarity in
zeta potential between engineered MPs and the semi-
environmental sample could be attributed to similar phys-
icochemical changes occurring in both the engineered MP
product and semi-environmental plastic (e.g., weathering-
induced carbonyl functional groups, which influence the
surface charge).
Similar XRD spectra were observed for both the engineered
MPs and the semi-environmental sample (Figure 7D),
suggesting that they have similar crystallinities (determined
by both the location and intensity of XRD peaks). However,
lower crystallinity was observed for PS microbeads as
compared to engineered MPs and semi-environmental plastic.
Interestingly, the XRD spectra of raw plastics was also similar
to that of engineered MPs (Figure S13), which can be
explained by two contradictory processes occurring simulta-
neously. Photo-oxidation may increase crystallinity in polymers
because the amorphous regions within the plastic are more
susceptible to photo-degradation than those of crystalline
regions.70,71 On the contrary, due to insertion of oxygen
groups in the polymeric chains, amorphous or crystalline
domains in polymer chains are interrupted, subsequently
lowering the polymeric crystallinity.72,73 These contradictory
H https://doi.org/10.1021/acs.est.1c02196
pubs.acs.org/est Article
effects may result in similar crystallinities when comparing
degraded and non-degraded plastics.
Surprisingly, we noticed a smaller SSA for engineered MPs
(0.379 m2/g) than those of raw plastic (0.581 m2/g) and semi-
environmental plastic (0.618 m2/g), most likely because of the
method by which oxygen surface functionalities were imparted
on the engineered MPs during the accelerated photo-
degradation procedure. Functionalization by carbonyl groups
may occupy sites available for Kr adsorption during SSA
measurements, thus resulting in a decreased SSA.74 The
moderate oxygen functionalization occurring during environ-
mental weathering in semi-environmental plastic, however,
resulted in a negligible difference in the SSAs of raw plastic and
semi-environmental plastic.
Altogether, the physicochemical characteristics of engi-
neered MPsincluding surface functionality, surface morphol-
ogy, PSD, surface charge, and crystallinitywere comparable
to those of the semi-environmental sample but inherently
different from those of PS microbeads. The inherent
differences between the characteristics of PS microbeads as
compared to their environmental counterparts suggest that
they are not an ideal model for environmental plastics,
especially in fate, transport, and toxicity studies, which are
driven by weathering and surface characteristics.69 For
example, the presence of oxygen functionalities in weathered
plastic may alter its interactions with surrounding substances59
and generation of asymmetric rough morphologies of
weathered plastics can affect the toxicity67 and transport
phenomenon.59,71
In this study, weathering processes are mimicked through
lab-simulated techniques in such a way that they combine
maximal effects of high environmental relevance. Of particular
note, the engineered MPs were synthesized over 10 times with
consistent similarity to the semi-environmental sample
(demonstrated in PSD error bars and relative standard
deviation of 7.4−9.4%, Figure 7B), indicative of the high
reproducibility and reliability of the engineered MPs. There-
fore, our engineered MPs bolster its relevance as a more robust
representative of environmental MP in controlled risk
assessment.
We calculated the energetic efficiencies per particle
produced of single degradation procedures and compared
them to the overall energetic efficiency of Protocol-3 (detailed
calculation in the Supporting Information) to learn about the
synergistic effects which occur through the combination of
several degradation mechanisms. Using equations S1−S3, we
showed that the probe sonication procedure was the most
energy-efficient procedure requiring 1.66 J/L per particle
produced. UV-O treatment in the selected conditions (i.e., 3 h
of dry treatment) requires 76.05 J/L per particle produced,
while thermal treatment requires 540 J/L per particle
produced. The combined top-down synthesis protocol had a
lower energy consumption (0.37 J/L per particle produced)
compared to individual procedures, which was also 5 times
lower than that of the most efficient procedure (i.e., probe
sonication). This energy calculation suggests that combination
of all three procedures into one protocol is critical not only to
increase environmental relevance but also to enable a
synergistic effect and decrease the energy consumption of
the overall process.
The suggested method provides high levels of control over
the model particles’ properties and thus could be tuned to
produce PS-based engineered MPs of various sizes (e.g., NPs
Environ. Sci. Technol. XXXX, XXX, XXX−XXX
Environmental Science & Technology
vs MPs) or age by altering the accelerated weathering
procedures (e.g., degrading at various temperatures and
sonication intensities). In fact, these engineered MPs can be
(post) modified through sorption of typical co-existing
substancessuch as biomacromolecules (i.e., eco-corona)
and micropollutantsto evaluate their role in the behavior
of MPs in the aquatic environment. Furthermore, the protocol
can form the basis for the future development of engineered
MPs derived across polymer types (e.g., PET or PP-based
MPs, which are abundant in the aquatic environment). We
outlined the design, fabrication, and characterization of the first
prototype of an environmentally relevant PS-based plastic
model, which can be ultimately used as an improved model for
future risk assessment studies as well as general standardized
MPs of high environmental relevance. In future studies, the
shelf-life of engineered MPs as well as their performance in
fate, transport, and toxicity assays as compared to environ-
mental plastics should be determined to validate the hypothesis
claiming engineered MPs in this work as an emerging, highly
representative plastic model augmenting the field of risk
assessment.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.est.1c02196.
PSD for raw plastic; spectral distribution of UV
irradiation; negligible particle contamination during
filtration; functionalization following UV-O treatment
across various conditions; change in color following UV-
O treatment; elemental analysis of particles obtained
following probe sonication; particle count of probe
sonicated solutions in the presence and absence of
plastics; DSC spectrum of raw plastic; PSD for
engineered MPs; FT-IR spectra and their corresponding
sizes, and digital images of real PS-based environmental
plastic collected from the Israeli coast of the
Mediterranean Sea, Tel-Aviv, Israel; FT-IR spectra and
calculation of CI; XRD spectra of raw plastic and
engineered MPs; and characteristics of extracted PS-
based environmental MPs (PDF)
■
AUTHOR INFORMATION
Corresponding Author
Ines Zucker − School of Mechanical Engineering, Faculty of
Engineering, Tel Aviv University, Tel Aviv 69978, Israel;
Porter School of the Environment and Earth Sciences, Faculty
of Exact Sciences, Tel Aviv University, Tel Aviv 69978,
Israel; orcid.org/0000-0001-7408-6757; Phone: (+972)
73-3804581; Email: ineszucker@tauex.tau.ac.il
Authors
Amit Kumar Sarkar − School of Mechanical Engineering,
Faculty of Engineering, Tel Aviv University, Tel Aviv 69978,
Israel; Porter School of the Environment and Earth Sciences,
Faculty of Exact Sciences, Tel Aviv University, Tel Aviv
69978, Israel; orcid.org/0000-0002-8262-7485
Andrey Ethan Rubin − Porter School of the Environment and
Earth Sciences, Faculty of Exact Sciences, Tel Aviv University,
Tel Aviv 69978, Israel
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.est.1c02196
I https://doi.org/10.1021/acs.est.1c02196
pubs.acs.org/est Article
Author Contributions
§
A.K.S. and A.E.R. are co-first authors.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
A.K.S. acknowledges funding by the Tel Aviv University
Matching Fellowship and Planning and Budget Committee
(PBC) Postdoctoral Fellowship. A.E.R. acknowledges funding
by the Aaron Frenkel Pollution Initiative at Tel Aviv
University. The authors also acknowledge Dr. Yinon Yecheskel
for his technical and scientific support. They thank Dr. Vered
Cohen and Prof. Hadas Mamane for help with PSD analyses
and Eliran Hamo and Dr. Brian Rosen for help with XRD
analyses. The authors also would like to thank Dr. Adi Radian
and Yael Zvulunov for the assistance with BET measurements.
■
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