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Science of the Total Environment 628–629 (2018) 740–747

Contents lists available at ScienceDirect

Science of the Total Environment

journal homepage: www.elsevier.com/locate/scitotenv

Observation of the degradation of three types of plastic pellets exposed to


UV irradiation in three different environments
Liqi Cai, Jundong Wang, Jinping Peng ⁎, Ziqing Wu, Xiangling Tan
Faculty of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, China

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Degradation of plastics under UV irradi-


ation in different environments was
studied.
• Changes in chemical/physical properties
were examined by FTIR, Raman, and
SEM.
• Similarities and discrepancies in the
degradation processes were investi-
gated.
• Exposure time, oxygen content and the
water chemistry are the important fac-
tors affecting the degradation degree.

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

Article history: Plastic debris represents one of the most prevalent and persistent pollution problems in the marine environment.
Received 11 December 2017 In particular, microplastics that are mainly degraded from larger plastic debris have become a growing environ-
Received in revised form 22 January 2018 mental concern. However, studies on the degradation of plastics in the aquatic environment that hydrobios re-
Accepted 7 February 2018
side in have been limited, while several studies regarding the degradation of plastics have been conducted
Available online 20 February 2018
under outdoor or accelerated weathering conditions. Thus, observation of the degradation of three types of virgin
Editor: D. Barcelo plastic pellets exposed to UV irradiation in three different environments (i.e., simulated seawater, ultrapure
water, and a waterless (air) condition) was carried out. Data on the changes in physical and chemical properties
Keywords: were collected. The FTIR spectra showed that hydroxyl groups and carbonyl groups developed in three types of
Plastic pellets weathered plastic pellets under the air and ultrapure water environmental conditions after 3 months of UV irra-
Plastic types diation, while only carbonyl groups were found in plastic pellets in the simulated seawater environment. In con-
Different environments trast, the Raman spectra showed no significant changes in the weathered plastic pellets, but there were different
UV irradiation intensities of characteristic peaks after exposure to UV irradiation. In addition, SEM images illustrated that gran-
Degradation
ular oxidation, cracks and flakes were common patterns during degradation, and the plastic pellets in the three
different environments experienced different levels of chemical weathering. We suggest that further studies on
the degradation processes of plastic debris are needed to predict the fate of plastic debris in the environment.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction

The annual production of plastic materials has grown exponentially


⁎ Corresponding author. over the past few decades, with approximately 322 million tons being
E-mail address: Jppeng@gdut.edu.cn (J. Peng). produced in 2015 (PlasticsEurope, 2016). Plastics, due to their

https://doi.org/10.1016/j.scitotenv.2018.02.079
0048-9697/© 2018 Elsevier B.V. All rights reserved.
L. Cai et al. / Science of the Total Environment 628–629 (2018) 740–747 741

inexpensive, lightweight, and durable properties, are suitable for a large studies on the degradation of plastics in the aquatic environment that
variety of consumer products used in everyday life (Thompson et al., hydrobios reside in have been limited, especially for plastic particles of
2009; Wang et al., 2016). However, the accumulation of plastic waste in small size (b5 mm). In addition, knowing the degradation process of
the environment, especially in the ocean, has been of great concern lead- plastics in different environments is critical for calculating their resi-
ing to long-term environmental, economic, and pollution management dence times in different environments and providing a basis for evaluat-
problems (Singh and Sharma, 2008). Some studies indicated that there ing the status of plastic pollution in these environments. This study
may be N5 trillion pieces of plastic in the oceans globally (Eriksen et al., focuses on the secondary source of microplastics (i.e., degradation)
2014), and 4.8 to 12.7 million tons of plastic waste was estimated to and intends to investigate similarities and discrepancies in the degrada-
enter the oceans in 2010 (Jambeck et al., 2015). In addition, it was re- tion process of plastics for different environments. Thus, observation of
ported that 60% to 80% of floating litter in the oceans consisted of plastic the degradation of three types of virgin plastic pellets exposed to UV ir-
debris, and the amount of plastic debris in the environment increases radiation in three different environments (i.e., simulated seawater, ul-
each year (Moore, 2008; Gewert et al., 2015) because most plastic prod- trapure water, and a waterless (air) condition) was carried out. Data
ucts are used in single-use applications that have a low recovery value on the changes in physical and chemical properties were collected,
and are difficult to degrade in the environment (Wang et al., 2016). Nota- and comparisons of plastic pellets in three different environments and
bly, it has been predicted that the total weight of plastic debris in the under different exposure times were also performed.
oceans could be heavier than the total weight of fish by 2050 unless effec-
tive measures are taken (Neufeld et al., 2016; Song et al., 2017). 2. Materials and methods
Among the plastic debris in the ocean, microplastics (i.e., plastic par-
ticles b5 mm in diameter) have been reported to compose the majority 2.1. Samples and experimental setting
of debris (Goldstein et al., 2013; Hidalgo-Ruz et al., 2012). Sources of
microplastics include primary sources (i.e., plastics of microscopic size Three types of commonly used plastics (i.e., polyethylene (PE), poly-
that are purposefully used) and secondary sources (i.e., fragmentation propylene (PP), and polystyrene (PS) virgin plastic pellets; 150 items,
and degradation from larger plastic items). The continuous degradation respectively) were obtained from DuPont Engineering Polymers, and
of plastics could result in an amount of microplastics that would inevi- three different simulation environments (i.e., simulated seawater
tably increase in the environment with time (Wang et al., 2016). In (26.5 g/L NaCl +24 g/L MgCl2 + 0.73 g/L KCl + 3.3 g/L MgSO4 +
addition, because plastic debris of small size can be easily transported 0.2 g/L NaHCO3 + 1.1 g/L CaCl2 + 0.28 g/L NaBr), ultrapure water, and
by ocean currents, wind, tides and tsunamis in the environment a waterless (air) condition) were established. In addition, UVA340
(Collignon et al., 2012; Wang et al., 2016), microplastics have become lamp was selected as simulated natural sunlight because it can give a
a prevalent component and can be found worldwide in the global envi- good reproduction of natural sunlight (Brennan, 1987). First, the sam-
ronment, including seas (Van Cauwenberghe et al., 2013; Thompson et ples were placed evenly on glass dishes, and the samples were just sub-
al., 2004), freshwater lakes (Fischer et al., 2016; Ballent et al., 2016), riv- merged in the simulated seawater or ultrapure water solution
ers (Peng et al., 2017; Morritt et al., 2014; Wang et al., 2017), terrestrial environments (Fig. 1) using a dropper. Then, the glass dishes were
environments (Jambeck et al., 2015), and atmospheric fallout (Dris et transferred into homemade environmental chamber (Fig. 2; 60 cm
al., 2016; Cai et al., 2017). Meanwhile, these environmental forces × 30 cm × 30 cm for length, width, height, respectively) that was
(mainly physical effects) could also contribute to the fragmentation equipped with a UV lamp (UVA340).
and degradation of plastics in the environment to some extent. In addi- This aging experiment, with a period of 3 months (one month was
tion, there is a particular concern that microplastics have been reported 30 days, which was defined as a cycle), were conducted with continu-
to be ingested by a wide variety of organisms (Gall and Thompson, ous UV irradiation. 15 of the plastic pellets in each solution environment
2015; Zhao et al., 2016; Li et al., 2016; Sanchez et al., 2014), which can were randomly removed in each cycle, and then the surface solutions of
be transferred through the food web (Setälä et al., 2014). More impor- the removed samples were dried with absorbent papers. After that,
tantly, microplastics contain various chemicals, such as additives these samples were dried at 60 °C and stored in glass containers in the
(Rochman et al., 2013; Lithner et al., 2011) and metals (Holmes et al., dark (Brandon et al., 2016). Meanwhile, 15 of the plastic pellets in the
2014; Turner and Holmes, 2015), which have also been widely reported. air environment were also randomly selected out of each cycle for
For example, some additives are added into plastics during the analysis.
manufacturing process to obtain better stability. However, there addi-
tives could leach out from the plastics as they degrade in the environ- 2.2. FTIR analysis
ments because they are usually not covalently bonded to the polymers
(Lenz et al., 2015; Gewert et al., 2015). Thus, the chemicals carried by For the FTIR analysis, 5 items of each type of virgin plastic pellet (PE,
plastics can bioaccumulate in organisms when the plastics are mistaken PP and PS) were analyzed using FTIR spectroscopy (Nicolet 6700, Thermo
by organisms, which causes adverse effects on the normal functioning of Fisher, USA) equipped with an attenuated total reflectance (ATR) dia-
organisms and even poses a potential health hazard to human beings mond crystal attachment in order to establish their reference spectra.
(Eerkes-Medrano et al., 2015). Ranges of the spectra were set from 4000 to 500 cm−1, and the collection
Plastic debris, including microplastics, could persist in the environ- time was 16 s for each measurement. In addition, 5 items of each type of
ment for hundreds or even thousands of years due to its stability and weathered plastic pellets (treated by different UV irradiation times, i.e.,
durability (Barnes et al., 2009; Gewert et al., 2015).In addition, larger 1 month, 2 months and 3 months) were randomly selected and analyzed
plastics in the environment would continually degrade into by FTIR spectroscopy. Three different points (i.e., the central point and
microplastics (Andrady, 2011; Wang et al., 2016) as a result of physical, two different edge points) of each sample were examined. Among
chemical and microbial effects, resulting in an annual increase in the these resulting spectra, the representative resulting spectra were selected
amount of microplastics. Thus, it is essential to understand the degrada- and compared with their reference spectra without post-processing or
tion processes of plastic particles to increase our understanding of the transformation after each experimental cycle.
source of microplastics, predict the fate of microplastics in the environ-
ment, and evaluate the potential environmental hazards to organisms. 2.3. Raman analysis
Currently, although some studies regarding the degradation of plastics
have been conducted under outdoor conditions (Rajakumar et al., For the Raman analysis, 5 items of each type of virgin plastic pellet
2009; Azuma et al., 2009) or accelerated weathering conditions in labo- (PE, PP and PS) were examined using a Raman spectroscopy (LabRAM
ratory experiments (Stark and Matuana, 2004; Song et al., 2017), HR 800, HORIBA, France) with a laser wavelength of 632.8 nm in
742 L. Cai et al. / Science of the Total Environment 628–629 (2018) 740–747

Fig. 1. Three types of plastic pellets in different environments. Plastic pellets are shown in the (a) air environment and the (b) solution environments (i.e., ultrapure water and simulated
seawater (a drop of Prussian blue was added in order to obtain a better visual effect)). (For interpretation of the references to colour in this figure legend, the reader is referred to the web
version of this article.)

order to establish their reference spectra. Ranges of the spectra were set weathered plastic pellet were studied by scanning electron microscopy
according to their characteristic peaks in the Raman spectrum (i.e., (SEM) on a JEOL JSM-6510 microscope. Because the surface textures of
1000–1500 cm−1 for PE, 300–1500 cm−1 for PP, and 500–2300 cm−1 the weathered plastic pellets were heterogeneous, visualization was re-
for PS), and the integration time was 16 s. Then, 5 items of each type peated at different surface sites (i.e., at least three relatively smooth or
of weathered plastic pellet were randomly selected and analyzed by rough sites; Wang et al., 2017). In addition, comparisons of the changes
Raman spectroscopy. Three different points (i.e., the central point and in the surface textures of virgin plastic pellets and weathered plastic
two different edge points) of each sample were examined. Among pellets were carried out.
these resulting spectra, the representative resulting spectra were se-
lected and compared with their reference spectra. 3. Results and discussion

2.4. SEM analysis 3.1. Changes in FTIR spectra

The surface textures of the plastic pellets could be clearly illustrated Three types of plastic pellets treated by different UV irradiation
in SEM images. Thus, 5 items of each type of virgin plastic pellet and times (i.e., blank, 1 month, 2 months and 3 months) in three different

Fig. 2. Experimental setup: (a) a homemade environmental chamber equipped with a UV lamp (UVA340) and (b) a structure diagram of this experimental setup.
L. Cai et al. / Science of the Total Environment 628–629 (2018) 740–747 743

environments were analyzed by FTIR spectroscopy. As shown in Fig. 3, of identical plastic pellets in the air environment was significantly
the FTIR spectra showed new absorption peaks that appeared at ap- higher than that in the solution environments (i.e., simulated seawater
proximately 3300 cm−1 and 1712 cm−1 in three types of weathered and ultrapure water), which may be related to the exposure level of ox-
plastic pellets in the air and ultrapure water environments after ygen in the environment. Compared with the solution environments, a
3 months of UV irradiation, while there was only one set of new absorp- higher oxygen content was available in the air environment, and the uti-
tion peaks that appeared at approximately 1712 cm−1 in plastic pellets lization rate of UV light was also higher for the plastic pellets under air
in the simulated seawater environment. The appearance of new absorp- conditions than for those in the solution environments (i.e., light reflec-
tion peaks indicated that hydroxyl groups (OH, ~3300 cm−1) and car- tion, diffusion and deflection were relatively low). Thus, the photo-oxi-
bonyl groups (C=O, ~1700 cm−1) developed (Zbyszewski and dative degradation of the plastic pellets was more effective in the air
Corcoran, 2011; Cooper and Corcoran, 2010), and plastic pellets in the environment. In addition, the FTIR spectra also showed that the degra-
three different environments experienced different levels of chemical dation degree of identical plastic pellets in the ultrapure water solution
weathering (i.e., photo-oxidative degradation) after UV irradiation. In (where hydroxyl and carbonyl groups developed) was higher than that
addition, the level of chemical weathering of the plastic pellets in the of the plastic pellets in the simulated seawater environment (where
same environment increased with the exposure time, which could be only carbonyl groups developed), which might be associated with a sa-
a result of the increased absorbance intensity of hydroxyl groups (OH, linity difference between the solution environments. One important
~3300 cm−1) and carbonyl groups (C=O, ~1700 cm−1) in the FTIR spec- factor affecting the degradation degree is UV light intensity, which
tra (shown in Table 1 and Table 2 in S1). could be affected by the water chemistry. According to the empirical
Based on observation of the degradation of identical plastic pellets in equation for the refraction index of seawater mentioned by Quan and
three different environments, it was found that the degradation degree Fry (1995), the refractive index of water increases with salinity. Thus,

Fig. 3. FTIR spectra of three types of virgin and weathered plastic pellets (treated by different UV irradiation times, i.e., 1 month, 2 months and 3 months) in three different environments.
744 L. Cai et al. / Science of the Total Environment 628–629 (2018) 740–747

for plastic pellets in the simulated seawater environment, the utilization groups (C=O, ~1700 cm−1) developed after photo-oxidative degra-
rate of UV light was relatively low compared with that in the ultrapure dation. In addition, the presence of hydroxyl and carbonyl groups
water environment, which led to plastics that degraded more efficiently was found in many environmental plastics according to the reported
in the ultrapure water environment when compared with the simulated literature (Zbyszewski and Corcoran, 2011; Corcoran et al., 2009),
seawater environment. indicating that chemical weathering plays a key role in the degrada-
The mechanism for the plastic pellets in this experiment was tion of microplastics in the natural environment.
photo-oxidation that was caused by free-radical chain reactions.
For plastics, UV irradiation has sufficient energy to cleave C\\C 3.2. Changes in Raman spectra
bonds (375 kJ/mol) and C\\H bonds (420 kJ/mol) (Singh and
Sharma, 2008; Plotnikov, 1988); thus, parts of the free radicals Three types of plastic pellets that were treated by different UV ir-
formed as a result of cleavage of C\\C bonds and C\\H bonds under radiation times in three different environments were examined
the condition of UV irradiation. In addition, some chromophoric using Raman spectroscopy. As shown in Fig. 4, the Raman spectra
groups (e.g., several unreacted monomers (C=C), carbonyl groups showed that there were no significant changes in the weathered
(C=O), and hydroperoxide groups (ROOH)) introduced from the plastic pellets in the three different environments compared with
manufacturing of plastics were also initiated by UV irradiation the virgin plastic pellets, but there were different intensities in the
(Singh and Sharma, 2008), which resulted in the formation of free characteristic peaks after exposure to UV irradiation. These results
radicals and thereby completed the chain initiation reactions. After were in accord with Lenz et al., (2015), where both PE and PP
a series of complicated chain propagation, chain branching and showed a slight reduction in the intensity of characteristic peaks
chain termination, chain scission and crosslinking occurred in these after exposure to simulated sunlight in air for 1634 h. In addition,
polymers. And, hydroxyl groups (OH, ~3300 cm −1) and carbonyl Raman spectroscopy has been widely used in the qualitative analysis

Fig. 4. Raman spectra of three types of virgin and weathered plastic pellets (treated by different UV irradiation times, i.e., 1 month, 2 months and 3 months) in three different environments.
L. Cai et al. / Science of the Total Environment 628–629 (2018) 740–747 745

of microplastics (Imhof et al., 2016; Lenz et al., 2015). Because plastic the exposure time was an important factor in the degradation of
particles of small size (N1 μm) can be identified by Raman spectros- plastics. However, based on the observation of the patterns of degra-
copy, it appeared to be a good method for identification. However, dation of the three types of plastic pellets, it was found that the crack
in reality, some inorganic additives added into plastics during the pattern did not appear on the PE pellet surfaces, which might be re-
manufacturing process could interfere with the determination of lated to insufficient UV exposure time. In Song et al. (2017), crack
plastics (Lenz et al., 2015). Thus, there are some deficiencies in the patterns appeared on PE after 6 months of UV exposure. In addition,
Raman analysis for the identification of plastics, especially in the the common pattern of degradation for PP pellets was also the crack
analysis of aging experiments. pattern. The formation of cracks is primarily attributed to continuous
In comparison with Raman spectra, FTIR spectra can directly reflect photo-oxidative degradation. In addition, cracks are an extension of
the functional groups of polymers. For example, in this experiment, fractures, which act as stress concentrators and fracture loci
the formation of polar oxidative functional groups (i.e., the hydroxyl (Rabek, 1996; Cooper, 2012); thus, it is possible for cracks to pro-
and carbonyl groups) can be easily observed in the FTIR spectra (Lenz mote the further degradation of plastic pellets. The common pattern
et al., 2015), but cannot be observed in the Raman spectra. Thus, of degradation of PS pellets was the flake pattern, which involves the
whether plastic pellets experienced chemical weathering in the envi- formation of a brittle surface area or layer on plastic pellet surfaces
ronment or not could be easily identified by using the FTIR spectra, (Cooper, 2012), where embrittlement occurs on the brittle surface
but not by the Raman spectra. However, for suspected plastic particles areas or layers of the plastic pellets.
experienced a high level of chemical weathering in the environment, Cracks and flakes were the common patterns of degradation in the
several new oxidative functional groups developed can increase the dif- chemical weathering of plastics. However, plastics with cracks and/or
ficulty of identification. Thus, the identification methods used for the flakes were prone to experience further fragmentation in the natural
analysis of microplastics in the environment need to be improved be- environment (including biotic and abiotic effects), which resulted in
cause there were several deficiencies in both the FTIR and Raman the production of smaller microplastics or nanoplastics.
analyses.
4. Conclusion
3.3. Changes in surface textures
Three types of virgin plastic pellets exposed to UV irradiation in
SEM images of the three types of plastic pellets treated by differ- three different environments for 3 months were carried out. The FTIR
ent UV irradiation times in three different environments were ob- spectra showed that new absorption peaks appeared at approximately
tained by using SEM. As shown in Fig. 5a, three types of virgin 3300 cm−1 and 1712 cm−1 in three types of weathered plastic pellets
plastic pellets exhibited relatively homogeneous and compact tex- under air and ultrapure water environmental conditions after 3 months
tures. In contrast, the weathered plastic pellets exhibited relatively of UV irradiation, while only one set of new absorption peaks appeared
rough surface textures (Fig. 5b, Fig. S2 and Fig. S3). In the case of the at approximately 1712 cm−1 for plastic pellets in the simulated seawa-
PE pellets (Fig. 5b), granular oxidation and flakes were found on PE ter environment, indicating that hydroxyl groups (OH, ~3300 cm−1)
pellet surfaces after 3 months of UV irradiation. Among these pel- and carbonyl groups (C=O, ~1700 cm−1) developed, and plastic pellets
lets, flakes were apparent after 1 month of UV irradiation, while in the three different environments experienced different levels of
granular oxidation appeared on PE pellet surfaces after 2 months chemical weathering (i.e., photo-oxidative degradation) after UV irradi-
of UV exposure. For the PP pellets (Fig. S2), cracks and flakes were ation. In contrast, the Raman spectra showed that there were no signif-
common patterns of degradation. Cracks were apparent after icant changes in the weathered plastic pellets in three different
1 month of UV exposure in all three different environments. How- environments compared with the virgin plastic pellets, but there were
ever, PP cracks in the air environment were obviously thicker than different intensities in the characteristic peaks after exposure to UV irra-
those in the solution environments after 3 months of UV exposure, diation. Thus, whether the plastic pellets experienced chemical
indicating that the level of chemical weathering of the PP pellets weathering in the environment or not could be easily identified using
in the air environment was highest among the three different envi- the FTIR spectra, but not the Raman spectra. However, there were sev-
ronments at the same UV exposure time. In addition, the level of eral deficiencies in both the FTIR and Raman analyses. Thus, identifica-
chemical weathering of the PP pellets illustrated in the SEM images tion methods for the analysis of microplastics in the environment
was consistent with their respective FTIR spectral results (Fig. 3), need to be improved. In addition, the SEM images illustrated that gran-
where the intensities of the hydroxyl absorption peaks in the air en- ular oxidation, cracks and flakes were common degradation patterns in
vironment were also stronger than those in the solution environ- the chemical weathering of plastics. Specifically, granular oxidation and
ments. For the PS pellets (Fig. S3), the surfaces of the PS pellets flakes were found on the PE pellet surfaces, cracks and flakes were
exposed to UV irradiation for 1 month began to develop flakes, found on the PP pellet surfaces, and flakes were found on the PS pellet
and the level and range of degradation also increased with exposure surfaces after 3 months of UV exposure. It should be noted that plastics
time in all three environments. The abiotic degradation of plastics with cracks and/or flakes were prone to further fragmentation in the
can be divided into physical and chemical weathering. Currently, natural environment (including biotic and abiotic effects), resulting in
the degradation of microplastics is mainly based on their surface to- the production of smaller size microplastics or nanoplastics. Meanwhile,
pographies. In this study, the surface topographies of plastic pellets these experimental results indicated that UV irradiation and oxygen
only exposed to UV irradiation had similar textures to those in the were important factors in the initiation of the photo-oxidative degrada-
natural environment (Zbyszewski et al., 2014; Zbyszewski and tion of polymers. Observations and comparisons of the degradation of
Corcoran, 2011; Cooper and Corcoran, 2010; Corcoran et al., identical plastic pellets in three different environments revealed that
2009). However, the mechanisms of degradation need to be further the level of chemical weathering of plastic pellets was in the following
studied. The selected plastic pellet samples were cut to be observed order: air environment N ultrapure water environment N simulated sea-
by SEM in our study. In other words, these samples were influenced, water environment. The level of chemical weathering of the plastic pel-
to some extent, by physical forces. lets increased with the exposure time in all three environments,
In general, there were some differences in the patterns of degra- indicating that the UV exposure time and the environmental differences
dation and the levels of chemical weathering of plastic pellets in associated with the differences in the utilization rate of UV light, the
three different environments. Similarly, the level of chemical salinity and the exposure level of oxygen were the important
weathering of the plastic pellets increased with the exposure time factors that affected the degradation degree of plastic pellets. Because
in all three environments, in other words, this study showed that smaller polymers formed by photo-oxidative degradation are more
746 L. Cai et al. / Science of the Total Environment 628–629 (2018) 740–747

Fig. 5. SEM images of the three types of virgin and PE weathered plastic pellets (treated by different UV irradiation times, i.e., 1 month, 2 months and 3 months) in three different
environments. (a) SEM images of the three types of virgin plastic pellets; (b) SEM images of the PE weathered plastic pellets in three different environments (all the SEM images were
obtained by a scanning electron microscope operating at 10 keV and ×1000 magnification).

susceptible to biodegradation, abiotic degradation is expected to pre- are needed; this would help increase our understanding of the source
cede biodegradation (Gewert et al., 2015). Thus, more investigations of microplastics, predict the fate of microplastics in the environment,
on the degradation processes of plastic particles in the environment and evaluate the potential environmental hazards to organisms.
L. Cai et al. / Science of the Total Environment 628–629 (2018) 740–747 747

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