Environmental Pollution 265 (2020) 114864

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Environmental Pollution
journal homepage: www.elsevier.com/locate/envpol

Laboratory simulation of microplastics weathering and its adsorption

behaviors in an aqueous environment: A systematic review*
Yiran Sun a, 1, Jianhua Yuan c, 1, Tao Zhou a, e, Youcai Zhao a, e, Fei Yu b, d, *, Jie Ma a, d, e
a
Key Laboratory of Yangtze River Water Environment, College of Environmental Science and Engineering, Tongji University, Shanghai, 200092, PR China
b
College of Marine Ecology and Environment, Shanghai Ocean University, Shanghai, 201306, PR China
c
Key Laboratory of Three Gorges Reservoir Region’s Eco-Environment, Ministry of Education, College of Environment and Ecology, Chongqing University,
Chongqing, 400045, PR China
d
Research Center for Environmental Functional Materials, College of Environmental Science and Engineering, Tongji University, 1239 Siping Road, Shanghai,
200092, PR China
e
Shanghai Institute of Pollution Control and Ecological Security, Shanghai, 200092, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Microplastics (MPs) pollution has become a global environmental concern. MPs alone and in combina-
Received 6 November 2019 tion with pollutants can potentially cause significant harm to organisms and human beings. Weathering
Received in revised form of MPs under various environmental stresses increases the uncertainty of their environmental fates.
22 May 2020
Compared with field surveys, laboratory simulation experiments are appropriate to simplify the research
Accepted 22 May 2020
Available online 29 May 2020
procedures and investigate the mechanisms. In this review, the effects of abrasion, solar radiation,
chemical and thermal oxidation, microbial adhesion and colonization, and other environmental factors
on the MPs and the relative laboratory simulation methods were summarized and discussed. Photo-
Keywords:
Weathering
oxidation and abrasion are the most appliable methods due to easy operation and adjustable weath-
Microplastics ering degree. Furthermore, the structural and components changes in weathering process and the
Aging applied characterization methods were generalized. In addition, one of important environmental be-
Adsorption behaviors haviors, adsorption of the weathered MPs towards two typical pollutants was analyzed. Finally, three
Aqueous environment priorities for research were proposed. This paper conducts systematic summarized of the MPs weath-
ering process and provides a reference for future studies to accurately determine the environmental risks
of weathering MPs.
© 2020 Published by Elsevier Ltd.

1. Introduction
In the modern world, plastic is a ubiquitous material in medical,
industrial, agricultural, and many other fields due to its properties
of being lightweight, durable, and cost-effective (Chae and An,
2018). It is estimated that by 2015, a total of 6.30 billion tons of
plastic had been produced in the world. However, only 21% has
been recycled or incinerated (Law, 2017). Recent data also showed
that within the European Union (EU) only 29% of the used plastic is
recycled, and 31% goes into landfills; in the United States (US), up to
53% of plastic waste goes into landfills (Paço et al., 2018). Costal and
* of MPs, which results in changes in their environmental behavior
This paper has been recommended for acceptance by Eddy Y. Zeng.
* Corresponding author.College of Marine Ecology and Environment, Shanghai
Ocean University, Shanghai, 201306, PR China.
E-mail address: fyu@vip.163.com (F. Yu).
1
These authors contributed equally to this work.
marine areas are main depositories of plastic waste, with an esti-
mated accumulative potential of 250 metric tons (Mt) by 2025
(Vince and Hardesty, 2017). Plastic pollution is a worldwide issue,
as it has been detected even in the remote South Pole (Ivar do Sul
and Costa, 2014). The literatures in MPs grow up with exponen-
tial rate (as shown in Figs. S1eS3), indicating the increasing
concern on MPs pollution issues.
Most plastic waste cannot decompose in a short time. Under the
effects of ultraviolet (UV) radiation, mechanical abrasion, fluctu-
ating temperature, and biodegradation, plastic is weathered and
broken down into tiny fragments, which are defined as “micro-
plastics” and “nanoplastics” (White and Turnbull, 1994). The
weathering process changes the physical and chemical properties
(Hu et al., 2019). For example, UV radiation reduces the average
molecular weight of polymers and increases the surface roughness
of MPs (Ma et al., 2019; Suhrhoff and Scholz-Bottcher, 2016). The

https://doi.org/10.1016/j.envpol.2020.114864
0269-7491/© 2020 Published by Elsevier Ltd.
2 Y. Sun et al. / Environmental Pollution 265 (2020) 114864
leaching of additives is also promoted, which increases the
ecological risks (Nakashima et al., 2016). After weathering, the
functional groups of the MPs change, and their hydrophilic may
increase (Andrady, 2011). The adsorption of persistent organic
pollutants (POPs) and Class B and Borderline metals are reported to
be affected by the weathering process (Yu et al., 2019). These
changes affect the transport and final outcome of large amounts of
toxic contaminants (POP) (Koelmans et al., 2013). In addition, the
weathering process affects the sedimentation, ingestion by organ-
isms, pathogen transportation, and so on (Alimi et al., 2018).
Therefore, understanding the MP weathering process and its po-
tential effects is very important for reducing the uncertainty in the
hazard and risk assessments of MPs (Yu et al., 2019).
Assessing the effects of weathered MPs is a difficult task. Mod-
ern plastic is designed to meet diverse application conditions
(Renner et al., 2017; Turner and Holmes, 2011). Thus, many kinds of
polymers and chemical additives have been integrated. Moreover,
under environmental stresses, the adsorption of POPs, Class B and
Borderline metals, and microorganisms and the formation of bio-
films further increase the complexity of the process. To date, lab-
oratory simulations and field monitoring have been conducted to
study weathered MPs. Since field monitoring has limitations and is
impacted by the climate, regional conditions, and many other
complex factors, laboratory simulation is more suitable for the
fundamental study and mechanism investigation of the weathering
process (Kuhn et al., 2018). UV radiation, thermal oxidation, and
chemical oxidation have been frequently used to simulate the
weathering process under diverse environmental stresses. How-
ever, the application of single simulation factors does not
adequately reflect the actual weathering process. In addition, since
the simulation factors influence the weathering degree of the MPs,
a complete evaluation of the weathering degree has not yet been
realized. Therefore, it is crucial to summarize the current studies to
narrow the gap between laboratory simulation and practical
conditions.
This review aims to explain the MP weathering process and its
adsorption behaviors in an aqueous environment. Laboratory
simulation of environmental stresses that affect the weathering
process are summarized and categorized, and the corresponding
changes in the structures and components of MPs, as well as the
applied characterization methods are generalized. Furthermore,
through a summary and analysis, the adsorption behaviors of two
kinds of contaminant, Class B and Borderline metals and organic
pollutants, onto weathered MPs are discussed.
2. Weathering simulation of microplastics
Once plastics are discharged into the environment, the weath-
ering process would be accelerated by various environmental
stresses. Physical abrasion is caused by waves, tides, sand, stones,
and many other particles. Photo-oxidation and microorganism
colonization also weather the MP to a great extent. In addition,
fluctuations in temperature and salinity influence the weathering
process. To investigate the environmental behaviors of weathered
plastics, laboratory weathering simulations are used to model the
environmental stresses. Here, we summarize the environmental
stresses and classify them into abrasion, Photo-oxidation, chemical
and thermal introduced oxidation, microbial adhesion and coloni-
zation, and other categories of environmental factors. Some typical
simulation methods are shown in Fig. 1. Analysis of these simula-
tion methods shows that the aging simulation of MPs in the labo-
ratory is convenient and the conditions are controllable, but the
simulation is less realistic compared with aging under natural
conditions. The aging of MPs under natural conditions is more
difficult to study and involves uncontrollable factors. Therefore, the
choice of aging method should be carefully considered.
2.1. Abrasion
Physical aging is a common phenomenon for polymers that al-
ters all the temperature-dependent physical properties. Physical
aging makes polymers more fragile (White and Turnbull, 1994).
Microplastics are likely to undergo physical aging due to abrasion
by waves, tides, sand, stones, and other particles.
The most used simulation method of abrasion is exposure to
sand. To simulate a real beach environment, Song et al. (2017a)
collected sand from the beach and pretreated it to remove the
organic matter and plastics. The as-prepared sand was mixed with
low-density polyethylene (PE), polypropylene (PP), and poly-
styrene (PS) pellets; initially, the volumes of the chemicals were
26 ± 0.8, 19 ± 0.9 and 22 ± 2.2 mm3, respectively. The mixture was
rotated for 2 months at 37 rpm. After the mechanical wear treat-
ment of the sand, 8.7 ± 2.5 particles pellet
1 PE, 11 ± 0.7 particles
pellet
1 PP and 4.2  103 ± 33 particles pellet
1 PS were produced.
These results indicated that PS pellets are susceptible to abrasion
with sand, while PE and PP are not easily fragmented by mechanical
abrasion alone. It may be because the glass transition temperature
of polystyrene is 100  C, which is quite different from other types of
plastics. During mechanical wear, polystyrene is more susceptible
to the effects of frictional heat generation, which accelerates its
cracking and fragmentation. This study revealed that the me-
chanical abrasion of MPs is affected by the material type. The me-
chanical strength, tensile strength, density and the glass transition
temperature should be considered when designing the weathering
parameters. The abrasion time is also an important factor that
should be considered when simulating the weathering process.
Kalogerakis et al. (2017) conducted 6 months of laboratory exper-
iments to simulate the weathering of high-density polyethylene
(HDPE) films in onshore and nearshore conditions. As shown in
Fig. 1c, the researchers used rotating glass bottles partially filled
with sand as a mild mechanical stress and found that 12 h
weathering was enough to reach the maximum fragmentation
degree for the microplastic samples. The weathered HDPE films lost
approximately 16% of their area after 5.5 months of mechanical
stress. This loss was the result of sand wear, and a combination of
factors (e.g., with UV light) may have enhanced this effect. In
addition, PE placed in seawater showed a lower fragmentation
degree than those on sand after 6 months of weathering. This result
shows that the presence of seawater reduces abrasion, probably by
reducing the contact of particles with the sediment by suspending
the particles in solution or by buffering the contact (Da Costa et al.,
2018).
Not only does sand accelerate the formation and aging of MPs
but other particles present under natural conditions can play a
similar role. However, there are few studies that focus on the
simulation of the abrasion of sea breeze and grit, stone, and other
substances on MPs. Thus, it is necessary to determine the influence
of various substances on the weathering of MPs and to deepen the
understanding of the physical aging behavior of MPs.
2.2. Photo-oxidation
A wide variety of polymers absorb solar ultraviolet (UV) radia-
tion and undergo photolytic, photo-oxidative, and thermo-
oxidative reactions. Polymers contain many polymer additives,
impurities and other contaminants, and these ingredients contain a
lot of chromophores. Chromophores absorbing in the near-UV re-
gion, along with near-UV absorbing conjugated groups that are
likely to be present at the mildly oxidized surface of waste poly-
mers, are likely to trigger photo-oxidation reactions in the presence
 Y. Sun et al. / Environmental Pollution 265 (2020) 114864
Fig. 1. Typical methods of MP simulation (a and b: seawater immersion and UV irradiation (Oelschl€agel et al., 2018); c: coastal conditions-indoors; d: outdoor chambers-dark and
sun exposure conditions (Rani et al., 2017); e: under the sea surface (Kedzierski et al., 2018); and f: sea surface (Rani et al., 2017).).
of oxygen. Polymer yellowing is a clear indication of the generation
of chromophoric structures whose absorption extends from the
near-UV to the visible region, and of the parallel increasing absor-
bance as the photo-oxidative degradation of the polymeric material
proceeds. Gardette’s et al. (Gardette et al., 2013) research confirmed
that polymers with chromophore groups are likely to adsorb UV
radiation and trigger photooxidation reactions in the presence of
oxygen. Polymer photooxidation reactions generally include four
processes: chain initiation, chain growth, branch formation and
chain termination. If there is a chromophore group in the polymer,
the polymer will absorb more ultraviolet light, which will lead to
the occurrence of chain-initiated reactions, and will generate more
free radicals, thereby accelerating its aging. Under the combined
action of UV and oxygen, the aging rate of the polymer will be
further accelerated. Because of their low-density properties, MPs
often float on the surface of the water and are exposed to Photo-
oxidation. The radiation can change the surface roughness,
morphology, and the chemical characteristics of the plastics, which
severely accelerates the MP weathering process (Andrady et al.,
1998). Therefore, Photo-oxidation is recognized as the dominant
factor in the weathering of MPs. Because of its ease of operation,
Photo-oxidation has been the most frequently applied laboratory
simulation method to study MP weathering.
Both natural sunlight and direct UV radiation were used to
simulate the Photo-oxidation weathering process (Diffey, 2002).
Zhu et al. (2020) found that MPs may experience photoaging and
breakdown into nanoplastics in aquatic environment as a result of
long-term light irradiation. Under simulated sunlight, they exposed
the PS MPs for 150 days. A large amount of reactive oxygen species
(ROS), were detected in the PS-MP suspension due to light irradi-
ation, which plays an important role in the aging of the PS MPs.
Kalogerakis et al. (2017) weathered 0.1 mm thick HDPE films by
3
natural sunlight, and the results showed that the HDPE began to
fragment at a cumulative luminance of 5.3  106 lux$d with oxygen
and that the film fragmented to “invisible” (maximum length
<100 mm) MPs at a cumulative luminance of 7.2  106 lux$d with a
mild mechanical stress (rotated with sand). Usually, direct UV ra-
diation is used for efficient weathering. UV radiation is classified
according to the wave range into UV-A (320e400 nm), UV-B
(275e320 nm), UV-C (200e275 nm) and UV-D (100e200 nm);
and UV-A, UV-B and UV-C are used to simulate the weathering
process. Due to the different intensities of the UV radiation, the
weathering degree and behaviors of MPs differed among the
studies. UV-B is recognized as the most suitable wave range
because it has the most influence on the polymer lifetime (Andrady
et al., 1998). In addition to the UV type, the radiation time are also
important for the weathering process. Lambert et al. (Lambert and
Wagner, 2016) weathered 1 cm square PS under UV-A at a static
temperature of 30  C. Samples were taken at 7, 14, 28, and 56 days,
and the results showed a difference between the PS sample and the
control sample. After exposure for 56 days, the concentration of
nanoplastics in the PS sample was 1.3  108 particles ml
1
compared to 0.4  108 particles mL
1 in the control. Summarizing
the recent studies, the radiation time varied from 96 h (Liu et al.,
2019a) to 360 days (Song et al., 2017a). Summarizing the recent
studies, the radiation time varied from 96 h (Liu et al., 2019b) to 360
days (Song et al., 2017b). The radiation strengths in recent studies
ranged from 0.04 W m
2 to 50 W m
2 (Wang et al., 2020), and there
has not been a relative systematic study. The exposure dose is a
more reliable parameter to evaluate the weathering process when
the radiation strength and time vary greatly. The inherent proper-
ties of MPs can also affect their weathering behaviors. To date, PS,
PE, polyvinylchloride (PVC), PP, and EPS have been radiated by UV
to simulate the weathering process. Note that the weathering
4 Y. Sun et al. / Environmental Pollution 265 (2020) 114864
behaviors among the different types and sizes MPs under the same
conditions are also diverse. For example, Cai’s (Cai et al., 2018)
study showed that, after 3 months of UV radiation, granular
oxidation and flakes, cracks and flakes, and flakes formed on the PE,
PP and PS pellet surfaces, respectively. In conclusion, both the
properties of MPs and the parameters of Photo-oxidation should be
considered when designing weathering simulation experiments.
2.3. Chemically or thermally induced oxidation
Once MPs are exposed to Photo-oxidation in natural water,
chemical and/or thermal oxidation occurs to weather the MPs.
These weathering processes cause changes in the properties of the
MPs, including their size, surface morphology, and functional
groups, and they cause the leaching of the additives as well
(Gardette et al., 2013).
In the presence of oxygen, MPs may react with the reactive
oxygen species formed during natural processes and interact with
other environmental stressors in the environment to cause chem-
ical oxidation. Chemical oxidation is easily simulated in the labo-
ratory. Liu et al. (2019a) investigated the weathering behaviors of PS
and PE MPs accelerated by Fenton and heat-activated K2S2O8
treatments. The heated-activated K2S2O8 treatment was conducted
in a K2S2O8 solution bath at 70  C for 1, 5, 10, 20, and 30 days. The
Fenton treatment was conducted by adding Fe2þ and H2O2 to the
MPs. Both the K2S2O8 solution and Fenton solution were replaced at
a fixed period to prevent the accumulation of chemicals. Liu et al.
found that the oxygen-to-carbon (O/C) atom ratio and CI increased
with the oxidation time. After 30 d of heat-activated K2S2O8
treatments, the carbonyl index (CI) values ranged from 0 to
approximately 0.7 for PS and 30 to approximately 0.3 for PE, and
the O/C values ranged from 3.0  10
2 to approximately 2.3  10
2
for PS and 2.0  10
2 to approximately 2.4  10
2 for PE. Although
the overall numerical change for the MPs treated by Fenton’s re-
agent were small, the CI and O/C also showed an increasing trend,
which confirmed that an advanced oxidation process is an effective
way to accelerate the weathering process in a laboratory simula-
tion. Additionally, chemical oxidation is often used in combination
with solar UV radiation to simulate the MPs in the presence of
oxygen and the sun. In Huffer’s (Huffer et al., 2018) study, poly-
styrene MP particles were artificially aged in a custom-made
weathering chamber with four 15 W UV-C lights. The particles
were immersed in 50 mL of H2O2 (10 vol-%) to form hydroxyl
radicals and enhance the oxidation. The FT-IR results showed that
the combination of weathering methods accelerated the breaking
of the CeH bonds within the polymer chains and the formation of
eOH, CeO, and CeOH bonds. The study is a combination of mul-
tiple factors, and the photo-oxidation of UV-C may be strong, so it
cannot be completely attributed to chemical oxidation. In sum-
mary, we should also consider different types of photooxidation
when exploring the chemical oxidation of MPs.
Because the temperature varies with the climate constantly, the
movement of the macromolecular chains in MPs is affected. On the
one hand, once the dissociation energy of the chemical bond is
exceeded, random fracture and side group decomposition occur,
which accelerates the rate of the polymer degradation. Tempera-
ture fluctuation is also an important factor that influences the MP
weathering process, heating and cooling usually have a strong ef-
fect on cracking (Copinet et al., 2004). On the other hand, tem-
perature has a kinetic acceleration effect on any occurring reaction,
which accelerating the thermal decomposition of newly formed
peroxides to form new free radical species in sunny days, on the
surface of an object, or even at room temperature. Besides, me-
chanical fragmentation can be induced even without external
mechanical stress in the amorphous phase of aged and
hydrophilized polymeric materials due to swelling/shrinking ef-
fects as a result of the combination of temperature jumps and of the
presence of moisture. Temperature fluctuation is always simulated
by thermal oxidation. Thermal oxidation is often combined with
Photo-oxidation. Bandow et al. (2017) weathered PS, HDPE, and
PVC MPs using a Global UV-Test 200 weathering device at a tem-
perature of 80 ± 1.6  C and a UV irradiance of 25 ± 3.0 W m2. The
artificial exposure for 2000 h was the equivalent of 4 months of
outdoor exposure, and the additive thermal oxidation increased the
overall equivalence by a factor of at least 5 to 10. Like Bandow,
Kenneth et al. studied a method for estimating the equivalent
natural age due to heat, humidity and UV exposure. Tire and road
wear particles were placed in baskets with semiporous Teflon liners
that were transparent to UV light, and they were exposed to UVA-
340 lamps with an irradiance of 7.7  10
2 W m2 nm
1 at 340 nm
(Unice et al., 2015). The results showed that the average chamber
acceleration factor was 24-times the natural age (range: 15 to 33).
Which also indicated that the combination of thermal oxidation
and UV radiation is an effective way to accelerate the weathering
process in simulated experiments.
2.4. Microbial adhesion and colonization
The Microplastic weathering process is not only affected by
physical and chemical factors but also largely susceptible to mi-
croorganisms (Harrison et al., 2011). Microorganisms are ubiqui-
tous and possess an inherent ability to adapt to different
environments and utilize different substances, which typically ac-
celerates the weathering of MPs by biodegradation (Kalogerakis
et al., 2017). Generally, microorganisms colonize on MPs and pro-
mote biodegradation and biotransformation by adhering to the
surface of the MPs and forming biofilms (Oberbeckmann et al.,
2015). Studies have shown that there are several criteria for mi-
crobial degradation of microplastics (Yuan et al., 2020). First, mi-
croorganisms must be present that can depolymerize the target
substance and mineralize the monomeric compounds with en-
zymes of an appropriate metabolic pathway. Second, the environ-
mental parameters, such as temperature, pH, moisture, and salinity
must provide conditions that are necessary for biodegradation.
Third, the morphology of MPs must render the attachment of mi-
croorganisms and the formation of a biofilm (Klein et al., 2018).
At present, studies of microbial weathering of MPs under labo-
ratory conditions focus on the degradation of MPs by pure bacteria
and fungi (Paço et al., 2018). In recent years, increasingly pure
bacteria and fungi that degrade MPs have been isolated in the
laboratory, and their MP degradation properties have received
increasing attention. Most microbial degradation studies have
included pretreatment with UV radiation or thermal treatment. In
Auta’s (Auta et al., 2018) study, polypropylene MPs were pretreated
by UV light, and the PP MPs were put into an inoculum with
nutrient broth. After 40 days of incubation, the polypropylene MP
weight loss included a 6.4% loss due to Rhodococcus sp. strain 36
and a 4.0% loss due to Bacillus sp. strain 27, and the microbially
treated PP MPs exhibited attachment or colonization of the bacte-
rial isolates on the surface of the MPs. Various pores and irregu-
larities formed simultaneously. These results implied that these
two pure bacteria were able to adhere and colonize the surface of
the PP MPs and cause surface damage. Comparing with bacteria,
the degradation efficiency of fungi seems to be lower. Sepulveda
et al. (Volke-Sepúlveda et al., 2002) thermooxidized (80  C, 15 days)
low-density polyethylene (TO-LDPE) by Aspergillus niger and Peni-
cillium pinophilum. They found that after 31 months of incubation,
the TO-LDPE MPs weight loss included only a 0.6% loss due to the
Aspergillus niger and a 0.4% loss due to the Penicillium pinophilum
fungi (Volke-Sepúlveda et al., 2002). In addition to the weight loss,
 Y. Sun et al. / Environmental Pollution 265 (2020) 114864
the functional groups (Auta et al., 2017), molecular weights and
tensile strengths (Jeon and Kim, 2013) also changed quickly when
the MPs were inoculated with microorganisms. The structural
changes and corresponding characterizations are discussed in
detail in section 3. The process of microbial degradation of MPs
involves many biochemical reactions. First, the microorganisms
adhere to the surface of the MPs and changes its surface properties
such as hydrophilicity and adhesion. Second, the leaching of addi-
tives and monomers out of the MPs by cell and enzyme degradation
is increased. Third, the enzymes or biological radicals attack the
MPs and additives, leading to both embrittlement and loss of me-
chanical stability. The particle size of MPs is relatively large
compared to the pore size of the cell membrane. Microplastics are
too large to pass through cellular membranes, so they must first be
depolymerized to smaller monomers before they can be absorbed
and biodegraded within microbial cells.
The colonization of microorganisms on MPs can lead to the
formation of biofilms, which can mask the surface properties,
degrade the additives, attack the surface by enzymes, and release
metabolic biochemical substances (Miao et al., 2019). The presence
of biofilms may also increase the density of plastics changing the
exposure to other factors involve in the degradation. Generally, the
simulation of biofilm formation is quite simple. Chen et al. tied
square PP sheets to a steel wire and floated them on the East Lake.
The biofilm appeared on the surface on the 3rd day of summer, and
the biomass showed an increasing trend over time (Chen et al.,
2019). However, MPs immersed in natural water are easily
disturbed by wind, wave, fish and so on. Therefore, some re-
searchers collected sea water, pretreated it by filtration, and
developed an MP biofilm at a constant temperature (Wieczorek
et al., 2019). In addition, microfibers are also targeted for degra-
dation. Zambrano et al. (2019) used aerobic organisms in activated
sludge to degrade polyester microfibers, cotton and rayon micro-
fibers. The results shown that cotton and rayon microfibers are
expected to degrade in natural aquatic aerobic environments. The
researchers also inoculated a pure bacteria sample and added cul-
ture medium to accelerate the formation of a biofilm (Hossain et al.,
2019). Hossain’s study also showed that UV radiation pretreatment
can promote the biofilm formation, which may be because the
microorganisms can more easily adhere to the rough surface and
functional groups of the MPs. Therefore, the combination of mi-
crobial weathering and other processes is an alternative solution.
2.5. Other environmental factors
In addition to the abrasion and the solar, chemical and microbial
oxidation, some other environmental factors, including the pH,
salinity, presence of water and humic acid (HA) concentration, also
influence the MP weathering process. The presence of water in-
dicates whether the MPs are on the beach or in the seawater, while
the salinity is used to simulate fresh water and water with different
salt contents. The pH and HA represent different water qualities.
Most recent studies have focused on the presence of water and
salinity; however, changes in the salinity, pH, and HA concentration
have not been widely studied. Cai et al. (2018) investigated the
process of weathering PP, PE and PS exposed to UV irradiation in
simulated seawater, ultrapure water, and a waterless (air) envi-
ronment. The results showed that after 3 months of weathering,
both hydroxyl groups and carbonyl groups were found in the PP, PE
and PS in the air and ultrapure water, while in the simulated
seawater, only carbonyl groups developed. The weathering degree
of the MPs in the tested environments followed the order
beach > ultrapure water > seawater. This result indicated that the
MPs on the beach were more weathered than those in fresh water
and seawater, which may be attributed to the adsorption of UV
5
radiation by the water. The effects of water and salinity on the aging
of MPs are mainly considered in this study. The combined effect of
temperature has not been considered, and related research can be
continued in the future. Shen et al. investigated the adsorption
capacity of tetracycline onto MPs with different aging factors,
including salinity, pH, HA concentration, and so on. The study found
that pH and salinity had little impact on the adsorption capacity.
However, HA significantly decreased the adsorption capacity of the
MPs. Thus, not only can HA cover the surface of the MP but its
functional group can change the hydrophobicity of the MP and
compete for the adsorption of tetracycline (Yu et al., 2019). Note
that Shen’s study did not use any other oxidation weathering
methods, and in this case, the weathering degree of the MPs was
too low to reflect the effect of pH and salinity effectively. Therefore,
the combined weathering method is recommended in the
following studies to simulate the real conditions.
2.6. Methods comparison
According to the operability of the method, the aging effect and
influencing factors, etc., we conducted a comprehensive evaluation
and ranking of various aging methods. (shown in Table 1).
Comparing the above methods, photo-oxidation is widely used in
the simulation of MP weathering process. Which is easy-operated
and needn’t pretreatment or separation. It is also recognized as
the dominant factor when the density of MPs is low. Because MPs
tend to float on the water, resulting in long time exposure. so that
the light is sufficient, thus accelerating its aging. In addition, some
polymers are more prone than others to photooxidative degrada-
tion, a few others may undergo preferential hydrolytic degradation
(Celina, 2013; Feldman, 2002). The weathering degree is also
adjustable according to intensity, time, temperature and so on.
Normally, the longer the oxidation time and the higher the tem-
perature, the higher the weathering degree of MPs. It is noticeable
that exposure dose or irradiance is a more reliable parameter since
factors like distance, time and presence of water, varied a lot in
different studies. The second dominant weathering parameter is
abrasion. Abrasion is ubiquitous and easy operated. But the sepa-
ration procedure is complicated, and the MPs size is limited.
Another significant weathering parameter is microbial adhesion
and colonization. Microorganism covered the MPs surface and
changed their density and surface properties. Also, MPs could be
degraded by microorganisms. As described in section 2.4. There are
many studies on the use of microorganisms to degrade MPs, but the
related research on microbial aging MPs is insufficient because of
its complex operating procedures and quantitative methods. The
weathering caused by chemically and thermally induced oxidation
and other environmental factors are not common, so further
research is needed.
3. Physicochemical properties of weathered microplastics
and characterization methods
Under the different environmental stresses, the structure and
components of weathered MPs changed greatly. We classified these
changes into 5 categories, i.e., size and surface pores, crystallinity,
functional groups, leaching of additives and biofilm formation. In
the following discussion, we introduce the changes in these prop-
erties and the corresponding characterization methods (shown in
Fig. 2).
3.1. Size and surface pores
Most plastic litter enters the marine environment in the form of
bags, foams, bottles, and fishing nets. Under oxidation and other
6 Y. Sun et al. / Environmental Pollution 265 (2020) 114864

Table 1
Comparison of different weathering simulation methods of MPs.

Environmental Stresses Simulation Method Conducting Parameters Operability Appropriateness

Abrasion Sand; Rotation Sand type and size; Speed Need separation ***
Photo-oxidation UV, Sunlight UV type; Intensity; Duration Easy *****
Chemically induced Chemical reagents Oxidizability; Dose; Need separation **
oxidation
Thermally induced Heating Temperature Easy **
oxidation
Microbial adhesion and Microorganisms Species; Degradation capacity; Cultured conditions Need Pretreatment, cleaning and separation ***
colonization
Other environmental Salt; acid; alkali; HA; Salty; pH; HA concentration Need separation **
factors

Fig. 2. Results of different test instruments for detecting aged MPs (a: optical microscope images of PE and PP(Wang et al., 2017); b: scanning electron microscope (SEM) images of a
virgin pellet-HDPE-12 and debris (Ter Halle et al., 2017); c: fluorescence microscopy (FESEM) images of the MPs (Tiwari et al., 2019); d: full range and (insert) magnification of the
1400-1280 cm
1 range of MPs (Shen et al., 2018); e: attenuated total reflection FTIR (ATR-FTIR) spectra of MP pellets collected along the Goa coast (Veerasingam et al., 2016); f:
Raman spectra of the most common synthetic polymers (Kappler et al., 2016); g: PVC, PE and PET energy dispersive spectrometer (EDS) spectra (Tiwari et al., 2019); h: diffuse
reflectance spectra (DRS) visible spectra for PE (Fotopoulou and Karapanagioti, 2015); and i: X-ray diffractomer (XRD) patterns of pristine and aged PS MPs(Liu et al., 2019a).).

weathering processes, the plastics first fragment into smaller pieces
(Hidalgo-Ruz et al., 2012; Miranda-Urbina et al., 2015). As the
weathering proceeds, the size of the MPs decreases (Pan et al.,
2019). This phenomenon has been observed in both field surveys
and laboratory simulations. Because of the complexity of the
samples and limited characterization methods, the MPs found in
the field surveys were relatively large. However, small-sized MPs
are predominant in weathered plastics. Pan (Pan et al., 2019)
surveyed the MP pollution in the Northwestern Pacific Ocean. The
MPs were counted and identified using a microscope and Raman
microscope coupled with an optical microscope. The small-sized
MPs (0.5e1.0 mm, 50%) were detected in the highest amounts,
followed by the medium-sized MPs (1.0e2.5 mm, 30%) and then
the large-sized MPs (2.5e5.0 mm, 17%). In the laboratory simulation
process, more characterization methods were utilized, and the MPs
with much smaller size were able to be detected. Lambert et al.
 Y. Sun et al. / Environmental Pollution 265 (2020) 114864
weathered 1 cm square PS under UV-A for 7, 14, 28 and 56 days, and
a nanoparticle tracking analysis (NTA) was used to determine the
MP size distribution in the liquid samples. After 56 days of
weathering, the concentration of the nanoplastics increased to
1.3  108 particles mL
1, with an average particles size of 224 nm
(Lambert and Wagner, 2016). In Liu’s study, with the assistance of
FESEM ImageJ software, the average size of PS and PE MPs was
found to decrease from approximately 40-50 mm to less than 30 mm
after 10 days of advanced oxidation (Liu et al., 2019a).
Regarding the surface pores, it is widely reported that there are
many wrinkles and cracks on the surface of weathered MPs, which
has been observed by SEM. Luo et al. (2020) reported that the
surface area of commercial pigmented PE MPs increased from
3.4 ± 0.1 m2 g
1 to 5.8 ± 0.3 m2 g
1 after aging treatment. Cracks
and fragmentation of MPs facilitated the accessibility of light and
oxygen to internal layer and therefore accelerated the aging pro-
cess. Zhang’s study further investigated the specific surface area
(SSA) and pore properties of virgin and weathered PS MPs by a
surface area and porosimetry analyzer. The results showed that the
SSA of weathered PS MPs was 7.9 ± 0.2 m2 g
1, while that of virgin
PS MPs was only 2.0 ± 0.1 m2 g
1, and the average pore diameter of
weathered PS MPs (5.1 ± 0.2 nm) was much lower than that of
virgin PS MPs (39.3 ± 0.5 nm), indicating that smaller pores were
formed during the weathering process.
3.2. Crystallinity
Early stages of weathering increased the degree of crystallinity
of the oxidized plastic. Two factors contribute to this increase
(Rouillon et al., 2016). The amorphous polymer is preferentially
degraded in weathering, increasing fractional crystallinity. Also, the
short segments of polymer generated by chain scission in degra-
dation migrate together and crystallize by ‘chemi-crystallization’.
This increase in crystallinity is relatively more likely in the surface
layer where oxidation primarily occurs (Carrasco et al., 2001; Lv
et al., 2015). Müller et al. (Muller et al., 2018) found that the crys-
tallinity of PP and PS increased by approximately 50% after 4 weeks
of weathering under UV radiation at 60  C, which was due to the
post-crystallization process of oxidative chain scission and subse-
quent rearrangement to an ordered structure. Partial crystallinity
generally makes the plastic tougher but at very high degrees of
crystallinity it can render the material brittle. This morphological
model of plastics is important because of its bearing on ease of
crack formation and fragmentation of semi-crystalline plastics such
as PE, PP and PET in weathering (Andrady, 2017). In Kathrin
Oelschla €gel’s study (Oelschla€gel et al., 2018), PET and low-density
polyethylene (LDPE) were weathered in artificial seawater under
UV radiation, and the crystallinity of the two MPs was also
increased. In addition to UV radiation, Karlsson et al. (2018) studied
the influence of thermo-oxidation on the crystallinity variation, but
they found that different thermo-oxidation degree did not signifi-
cantly change the crystallinity. Since higher crystallinity leads to
higher light scattering and reflection and thus reduces the distance
light can penetrate, smaller MPs showed higher crystallinity than
that of larger MPs after UV radiation (Ter Halle et al., 2017). How-
ever, to clarify the environmental behaviors caused by the weath-
ering of MPs, the crystallinity variation of different MP types,
additives, and weathering conditions and degrees requires further
study.
The characterization method most commonly applied in recent
studies was differential scanning calorimetry (DSC), in which the
crystallinity can be precisely quantified by the expression:
crystallinityð%Þ ¼ DHm
ref  100, where Hm is the melting enthalpy
DH m
and Hmref is the theoretical value of the melting enthalpy (Ter
7
Halle et al., 2017). In addition, researchers can choose suitable
characterizations among XRD, the density gradient method, IR
spectroscopy, and inverse gas chromatography (IGC) based on the
MP structure.
3.3. Surface chemical properties
As MPs weather under the environmental stresses, the physical
integrity of the MPs are destroyed and the surface chemical prop-
erties of MPs may change. The mechanism of free radical reaction
shows that the aging of polymers under the action of light, heat and
oxygen is an automatic catalytic process. The products of the re-
actions involved are capable of further increase the number of
reactive species as a result of secondary processes, thus resulting in
an auto-acceleration of the overall photo-oxidative degradation.
MPs weathering is mainly carried out according to the free radical
reaction process, including three processes (Celina et al., 2019):
chain initiation: RH/R þ H  , RH þ O2 /R þ HO2  , R þ
O2 / RO2  ; chain propagation and transfer: RO2  þ RH/ROOH þ
R , ROOH / R O þ  OH ROOH þ RH/RO þ R þ H2 O,RO þ
RH/ROH þ R ; Termination of the chain: R þ R /R
R, R þ
RO2  /ROOR, RO2  þ RO2  /ROOR þ R þ O2 The species and
quantity of functional groups on the MP surface change as a result
of the weathering process (Oelschla €gel et al., 2018). In laboratory
simulations, the weathering process often leads to an increase in
the oxygen-containing functional groups, and the changing degree
of the functional groups is determined by the weathering process
and the type of plastic (Huffer et al., 2018; Liu et al., 2019a; Liu et al.,
2019c). For example, in Liu’s study (Liu et al., 2019a), PS and PVC
MPs were weathered under UV radiation for 96 h, and hydroxy
groups formed in both the aged PS and PVC samples, while carbonyl
and vinyl esters groups formed in the aged PVC samples, indicating
that the formation of oxygen functional groups varies with the MP
type. The comparison of collected beached MPs and virgin MPs also
proved that weathered plastics have more oxygen-containing
functional groups due to the oxidization (Huffer et al., 2018;
Tiwari et al., 2019; Turner and Holmes, 2015).
Fourier transform infrared spectrometer (FTIR), the most
commonly used characterization method, is a classical method to
determine the functional groups on the MP surface. In addition to
FTIR, attenuated total reflection-infrared spectroscopy (ATR-IR)
and Micro-FTIR has also been used to characterize the functional
groups of MPs. Compared with FTIR, ATR-IR can be used to analyze
samples in situ without the need to prepare them with Potassium
bromide, and the infrared reflection can be used to better charac-
terize the surface information of MPs. The ratio of two typical IR
bands, i.e., the ratio of carbonyl groups at 1726 cm
1 to the meth-
ylene groups at 2851 cm
1, defined as the CI, have often been used
to characterize the weathering degree of MPs. The CI can be utilized
to evaluate the weathering degree of different types of MPs under
different weathering conditions. However, the functional groups of
the additives in the MPs, which may influence the estimation, need
to be considered. Mylla €ri et al. (Myllari et al., 2015) proved that the
O/C ratio obtained by X-ray photoelectron spectroscopy (XPS) is
also an effective method to evaluate the weathering degree.
Moreover, the C 1s and O 1s regions of high-resolution XPS spectra
can be used to analyze the changes in the bonds of the functional
groups (Liu et al., 2019a), which is useful for suppressing the
interference of additives.
3.4. Leaching of additives and adsorbed pollutants
During the production of plastics, the toxic additives are mixed
with polymers to improve the properties of the plastics for diverse
8 Y. Sun et al. / Environmental Pollution 265 (2020) 114864
applications, including antioxidants, flame retardants, coloring
agents, etc. During the weathering process, the toxic additives may
leach from the MPs, leading to ecological risks. There was an clear
increase in opacity and yellowness in MPs, which may be caused by
the oxidation of additives and adsorbed substances (Brandon et al.,
2016). The investigation found that antioxidants are one of the
additives in polymers. Their main functions include capturing free
radicals generated by polymers during aging and preventing or
stopping chain reactions, so antioxidants can slow the aging rate of
plastics to a certain extent, but as exposure time increases, the
leaching of additives decreases the resistance of the polymers and
may thus accelerate the rate of MP weathering (Nakashima et al.,
2016).
Bejgarn et al. (2015) chose plastic made from different polymers
and investigated their leaching properties before and after artificial
sunlight irradiation. The results showed that the type of leachate
differed before and after irradiation, while there was no common
trend in how the toxicity of the leachate changed as a function of
irradiation time. However, the additive type was not identified in
this study. Recently, the greatest amount of attention has been
focused on additives for brominated flame retardants (BFRs), which
have been categorized as POPs because of their high biotoxicity,
environmental persistence, bio-accumulative tendencies, and long-
range transportability. Rani et al. (2017) studied hex-
abromocyclododecane (HBCDD) leaching from expanded PS in
dark, sun exposure, and open sea-surface conditions. The results
showed the rapid leaching of HBCDD from the outer surface of the
expanded PS in the first 5 days, followed by a slow release or
nonrelease for 6 months. Among the 3 conditions, the greatest
release of HBCDDs from expanded PS occurred on the open sea
surface (approximately 42.9 mg g
1; 61%), followed by sun expo-
sure (approximately 34.4 mg g
1; 49%) and dark exposure
(approximately 25.6 mg g
1; 37%). These results showed that the
weathering process, including Photo-oxidation and water leaching,
may accelerate the leaching of HBCDD. In addition to the additives,
the contaminants that adsorbed onto the MPs also leached into the
environment. Bandow et al. (2017) recycled plastic granules, i.e.,
HDPE, PVC and PS, and investigated the leaching of contaminants in
a simulated weathering process of solar and thermal oxidation. The
study found that the total organic carbon, Cl, Ca, Cu, and Zn were
affected by the weathering process, and the leaching was increased
more by solar oxidation than by thermal oxidation. Schellenberger
(Schellenberger et al., 2019) found that functional textiles will
release aging MP fibers during the washing process. After testing,
MP fibers will release perfluoroalkyl acid to affect the aquatic
environment. An understanding of the leaching properties in
different conditions, for example, the digestive fluids of organisms,
is also needed to further clarify the ecological risks of MPs.
3.5. Biofilm formation
When MPs are in the water, they come into contact with the
inorganic particles, organic matter, as well as the microorganisms
(Parrish and Fahrenfeld, 2019). As a result, microorganisms of
different sizes and kinds, including protists, algae, bacteria, fungus,
and even viruses, attach to the surface of MPs (Michels et al., 2018;
Oberbeckmann et al., 2015). The colonization of these microor-
ganisms forms biofilms on the surface of MPs that may cover the
surface of the MPs and influence the ingestion, sinking, trans-
portation, and many other environmental behaviors (Wieczorek
et al., 2019). A biofilm is mainly composed of water, extracellular
polymer substances, microorganisms, and entrapped organic and
inorganic particles, which create a small complex ecosystem
(Shabbir et al., 2020). Lobelle et al. (Lobelle and Cunliffe, 2011)
investigated the early biofilm formation on a PE surface for the first
3 weeks. After 1 week, the biofilm was apparent on the PE surface
and continued to increase during the following two weeks. The
number of culturable heterotrophic bacteria on the submerged
plastic also increased from 1.4  104 cells cm
2 at week
1e1.2  105 cells cm
2 at week three. The hydrophily also increased
significantly during the 3 weeks and began sinking in the seawater-
air interface. However, the PE MPs did not show significant
degradation by microorganisms. Since the surface of MPs is quite
different from that of other substances, the biofilm on its surface
also varies. Miao’s study (Miao et al., 2019) evaluated the incuba-
tion of biofilms on typical MPs (polyethylene and polypropylene)
and natural substrates (cobblestone and wood) using high-
throughput sequencing of 16S rRNA and revealed that the alpha
diversity (richness, evenness, and diversity) was lower in the MP-
associated communities than in those on the natural substrates.
The biofilm on MPs showed higher abundances of Pirellulaceae,
Phycisphaerales, Cyclobacteriaceae, and Roseococcus than that of
natural substrates. These phenomena showed that the biofilm on
the surface of MPs is different from that on other substances, which
was also verified by Jiang’ s study. Jiang et al. (2018) applied high-
throughput sequencing to investigate the bacterial communities
that attached to MP samples from intertidal locations around the
Yangtze estuary in China, and the metabolic pathway analysis
suggested that these bacterial assemblages adapted to the plastic
surface-colonization lifestyle by reducing “cell motility” and
increasing “xenobiotics biodegradation and metabolism.” Even for
biofilms of MPs, different types, sizes, and surface properties of the
MPs, as well as the water source quality, influences the biofilm
(Hossain et al., 2019; Parrish and Fahrenfeld, 2019). Parrish et al.
(Parrish and Fahrenfeld, 2019) investigated the biofilm microbial
communities on MPs of different types and sizes and in water from
different quality sources. The study found that the MP type in-
fluences the biofilm more than does the size, due to the variation of
morphology/surface texture. In addition, water source quality
significantly influences the biofilm because it affects the external
environment and the source community.
4. The adsorption behaviors of weathered microplastics
Due to their small size, low density, large surface area, and
complex components, MPs pose considerable ecological risks.
Microplastics transferred into a variety of invertebrates and verte-
brates after adsorbing organic pollutants, which seriously threatens
the growth and reproduction of marine life (Jupp, 2008). Class B
and Borderline metals, as one of the most persistent pollutants in
aqueous environments, pose serious environmental and health
risks (Guo and Wang, 2019) (Buccolieri et al., 2006). Microplastics
can be ingested by the aquatic animals and birds, which impacts the
whole food chain. Additionally, the adsorption of contaminants
onto MPs greatly increases the ecological risks of MPs (Antunes
et al., 2013; Fossi et al., 2012; Yu et al., 2019). Moreover, the
weathering of MPs caused by various environmental stresses
changes their structure and properties, such as SSA and hydrophily,
thus changing their adsorption behaviors towards contaminants
(Alimi et al., 2018).
There is increasing awareness of the adsorption of organic pol-
lutants onto MPs, including the commonly used pharmaceutical
and personal care products (PPCPs) and polycyclic aromatic hy-
drocarbons (PAHs), as well as some banned organic pollutants,
which changed the migration and transformation behaviors of the
contaminants (Koelmans et al., 2016). We summarized recent
studies of the adsorption of organic pollutants on weathered MPs
(S. Table 2). We found that weathering can decrease the adsorption
of organic MPs because weathering can increase the hydrophilicity
of MPs by introducing functional groups, and the partition
 Y. Sun et al. / Environmental Pollution 265 (2020) 114864
coefficient decreases because most of the organic pollutants are
hydrophobic (Endo et al., 2005; Huffer et al., 2018; Muller et al.,
2018; Teuten et al., 2009). However, other studies proved that the
weathering process can enhance the adsorption of organic pollut-
ants (Hartmann et al., 2017; Liu et al., 2019a; Liu et al., 2019c; Zhang
et al., 2018), and the enhancement was generally ascribed to the
increase in the specific surface area and adsorption sites caused by
the oxygen-containing functional groups. This difference is likely
caused by the hydrophilicity of organic pollutants, which could be
determined by some index, such as Partition coefficient of n-octa-
nol/water (logKow). In addition, the complex structure of organic
pollutants should also be taken into consideration due to the varied
adsorption mechanism, such as hydrogen bonding, p-p interaction
and hydrophobic force.
The association of many kinds of Class B and Borderline metals,
including Ag, Cd, Co, Cr, Cu, Hg, Ni, Pb and Zn, with MPs has been
reported in both laboratory studies and field surveys (Ashton et al.,
2010; Massos and Turner, 2017). The weathering process brings
higher specific surface area and more functional groups, which
increases the adsorption capacities of Class B and Borderline metals
on MPs (as summarized in S. Table 3). Turner et al. (Turner and
Holmes, 2015) studied the adsorption of Class B and Borderline
metals (Ag, Cd, Co, Cr, Cu, Hg, Ni, Pb, Zn) onto virgin PE and beached
(weathered) MP pellets in river water under laboratory conditions.
Both the rate constants of the kinetics and the distribution co-
efficients of isotherms showed that the beached MPs had higher
adsorption capacities than the virgin MPs. The maximum distri-
bution coefficients for the virgin pellets (Hg and Pb) and beached
pellets (Ag and Pb) were 6.0 mL g
1 and on the order of
1.0  102 mL g
1, respectively. Moreover, Wang’s study (Wang et al.,
2020) showed that the increasing weathering time (UV radiation,
200 he500 h) could increase the adsorption capacity of Cu2þ
(55e60 to 160e175 mg g
1) and Zn2þ (45e50 to 75e80 mg g
1). The
adsorption mechanism of Class B and Borderline metals on MPs
mainly includes hydrophobic partitioning and chemical bonding
between anions and cations, which is influenced by the specific
surface area, hydrophobicity and adsorption sites on the MP surface
(Wang et al., 2020).
5. Conclusion and outlook
In order to clarify the environmental behaviors of weathered
MPs, laboratory simulation experiments are appropriate to simplify
the research procedures and investigate the mechanisms. Sum-
marizing the five types environmental stresses and laboratory
simulation methods in this review, it is found that the most
commonly used methods of MP weathering currently include
photo-oxidation, abrasion and microbial adhesion and coloniza-
tion, and less research on chemically and thermally induced
oxidation and other environmental factors. Comparing the opera-
bility, the order is Photo-oxidation > thermally induced
oxidation > abrasion > chemically induced oxidation > other
environmental factors > microbial adhesion and colonization. The
correlations between the weathering degree and the variations in
the structure and components can help to simplify the simulation
method of the weathering process. Moreover, more attention
should be paid on MPs with smaller size (nano plastics) and various
micro-morphologies (micro fibers, micro films).
Weathering increases the adsorption capacities of Class B and
Borderline metals on MPs, while the effect of weathering on
organic pollutant adsorption depends on the pollutant types. Cur-
rent studies focused mainly on the adsorption of individual pol-
lutants onto MPs. However, there are multiple contaminants that
coexist in the environment, and MPs as well as many natural sub-
stances (e.g., sediments) act as the adsorbents. Thus, the
9
competitive and cooperative adsorption of contaminants onto MPs,
and the partition of these contaminants between MPs and other
substances in an aqueous environment are also priorities for
research to determine the environmental risks of MPs.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgements
This research is supported by the National Key R&D Program of
China (Grant no. 2018YFC1901401). We are also thankful to the
anonymous reviewers for their valuable comments to improve this
manuscript.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.envpol.2020.114864.
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