Gondwana Research xxx (xxxx) xxx

Contents lists available at ScienceDirect

Gondwana Research
journal homepage: www.elsevier.com/locate/gr

The photo-aging of polyvinyl chloride microplastics under different UV

irradiations
Zhuozhi Ouyang a,b,c,d, Zhiping Zhang e, Yao Jing a, Linjie Bai a, Manyi Zhao a, Xinrui Hao b, Xiaoqin Li b,
Xuetao Guo a,d,⇑
a
College of Natural Resources and Environment, Northwest A&F University, Yangling, Shaanxi 712100, China
b
Guangdong Provincial Key Laboratory of Solid Wastes Pollution Control and Recycling, School of Environment and Energy, South China University of Technology,
Guangzhou, Guangdong 510006, China
c
The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, South China University of Technology, Guangzhou, Guangdong 510006, China
d
Key Laboratory of Plant Nutrition and the Agro-environment in Northwest China, Ministry of Agriculture and Rural Affairs, Yangling, Shaanxi 712100, China
e
School of Earth and Environment, Anhui University of Science & Technology, Huainan, Anhui Province 232001, 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 is becoming a global environmental problem due to the ubiquity.
Received 10 May 2021 Knowledge about transformation process of MPs under ultraviolet (UV) irradiation was critical to under-
Revised 4 July 2021 standing the environmental fate of these particles. In this study, the photo-aging characteristics and
Accepted 10 July 2021
mechanisms of polyvinyl chloride (PVC) under different UV irradiations in the air or water condition were
Available online xxxx
Handling Editor: Wang Jun
comprehensively investigated. When the PVC was exposed to the UVA, UVB and UVC irradiation, the sur-
face morphology, functional group, crystal structure, and elemental composition of PVC were systemat-
ically characterized. With the increasing of aging time, the PVC was identified as more oxygen-containing
Keywords:
functional groups, higher carbonyl index, and higher crystallinity, especially under the UVC irradiation.
PVC Based on the Two-dimensional correlation Fourier transform infrared spectroscopy (2D-FTIR-COS), the
Photo-transformation active sites and aging sequence of functional groups were confirmed under UVA, UVB and UVC irradia-
Reactive oxygen species tion. The reactive oxygen species (ROS) were produced and increased with the aging time as the whole.
Mechanism Corresponding to the aging results, the intensity of ROS and toxicity from leaching under UVC irradiation
Toxicity was greater than that under UVA or UVB. These findings provide direct evidences of photo-aging pro-
cesses of MPs and the potential ecological risks resulting from aging in the aquatic environments.
Ó 2021 International Association for Gondwana Research. Published by Elsevier B.V. All rights reserved.

1. Introduction unexplored areas including the Mount Everest (Napper et al.,

2020), Mariana Trench (Peng et al., 2018) and polar regions
Microplastics (MPs) are defined as plastic particles with size (Peeken et al., 2018). Surprisingly, MPs could transfer to animals
less than 5 mm (Thompson et al., 2004). The pollution of MPs (Li et al., 2018; Lv et al., 2019; Wang et al., 2019a), plants (Li
has become a global environmental problem (Ding et al., 2021; et al., 2020; Mao et al., 2018) and human embryos (Ragusa et al.,
Kane et al., 2020; Lang et al., 2020; Nizzetto et al., 2016; 2021). Therefore, there are an amount of MPs in the environment
Rochman, 2018). Due to their high abundance, small particle size which is closely related to human daily life.
and long-transport distance, MPs are likely harmful to the environ- The residual MPs exposed to the natural environment experi-
ment and human health (Guo et al., 2020; Huang et al., 2021), ence the aging process under the pressure of continuous physico-
which have been widely detected in seas (Mu et al., 2019; Wang chemical factors. Consequently, the surface properties and
et al., 2019b; Zhao et al., 2018), inland waters (Su et al., 2016; microstructure change with the increasing of exposure time,
Zhang et al., 2016), soils (Liu et al., 2018; Lv et al., 2019), and the affecting the environmental behaviors of MPs. According to the dif-
atmosphere (Allen et al., 2019; Chen et al., 2020; Zhang et al., ferent aging processes of MPs reported in the current literature, the
2020). Besides, the MPs have even been found in relatively photo-aging is one of the most important and efficient transforma-
tion (Naik et al., 2020; Zhang et al., 2018). The morphological struc-
ture, element composition and molecular weight of MPs have
⇑ Corresponding author at: College of Natural Resources and Environment, changed dramatically after photo-aging. Additionally, the process
Northwest A&F University, Yangling, Shaanxi 712100, China. makes its surface rough and even disintegrate, which leads to the
E-mail address: [email protected] (X. Guo).

https://doi.org/10.1016/j.gr.2021.07.010
1751-7311/Ó 2021 International Association for Gondwana Research. Published by Elsevier B.V. All rights reserved.

Please cite this article as: Z. Ouyang, Z. Zhang, Y. Jing et al., The photo-aging of polyvinyl chloride microplastics under different UV irradiations, Gondwana
Research, https://doi.org/10.1016/j.gr.2021.07.010
Z. Ouyang, Z. Zhang, Y. Jing et al. Gondwana Research xxx (xxxx) xxx

formation of porous surface and increases the specific surface area dong Microbial Culture Collection Center, China. The other
of MPs (Liu et al., 2019b; Tang et al., 2018; Velzeboer et al., 2014). reagents used were guaranteed reagents (GR) without further
At the molecular level, the chemical structures of MPs were influ- purification.
enced, such as chain breaking, degree of crosslinking and surface
functional groups (Wang et al., 2020). Meanwhile, the different 2.2. Experimental procedures
environmental conditions, irradiation intensity and time have an
impact on the efficiency of photo-aging (Guo and Wang, 2019; The PVC samples were exposed to two photo-aging environ-
Luo et al., 2020). ments: air and pure water. The temperature and humidity during
Our previous studies have confirmed that ultraviolet light (UV) the experiment were recorded (Supplementary Data, Fig. S1). The
could induce a natural photocatalytic reaction to influence the PVC of the air-aged and water-aged test group were placed in
transformation of pollutant and purify water (Ouyang et al., 15.0 cm petri dish and customized quartz reaction tube (4.6 cm
2020a). As an important component of sunlight, UV light might inner diameter and 17.0 cm high) containing 200 mL reaction solu-
be a significant factor which determines the environmental fate tion. Especially, the solution containing PVC was homogenized
of MPs. Compared with visible light, it is more efficient in affecting with magnetic stirrer in the water-aged reaction and regular
the transformation of MPs in most of environmental conditions. replenishing pure water was essential every two days. The
Generally, The UV-mediated photo-aging of MPs includes direct photo-aging experiments were carried out in different reaction
and indirect photolysis. The direct photo-transformation refers to chamber with three types of low-pressure mercury lamp, which
the MPs directly absorbing at a certain UV wavelength. The excited simulate different wavelength range of UV light sources, including
state of MPs were produced when exposure to light source. There- UVA, UVB and UVC. The results of spectral measurement showed
fore, the MPs could be degraded through direct photolysis or that the main wavelength of three light sources was 365 nm,
through sensitized photo-processes reacting with reactive oxygen 302 nm and 254 nm, respectively. The dark control was set in
species (ROS) formed in aquatic environment. UV lights are divided air-aged and water-aged test group. The solution and PVC samples
into UVA (320–420 nm), UVB (280–320 nm) and UVC (180– were periodically taken after aging 4, 8, 12 and 16 days. The solu-
280 nm) according to their wavelengths (Cao et al., 2021; Zhong tion sample was filtered with 0.45 lm membrane before use and
et al., 2011). Currently, most of studies only concentrated on the solid samples were dried for testing.
photo-transformation of MPs under full spectrum UV light or a
specific light band (e.g. UVC) (Lin et al., 2020; Mao et al., 2020). 2.3. Characterization of PVC
There was no investigation on the photo-transformation of MPs
under different UV irradiations to the best of our knowledge. The surface morphologies, functional groups, crystal structures,
Whether the three different light irradiations could accelerate and elemental compositions were characterized by scanning elec-
the aging of MPs or not is scarcely documented. Besides, little is tron microscope (SEM, ProX, Phenom-World), Fourier transform
known about the production of active substance, aged mechanism, infrared spectroscopy (FTIR, Vetex70, Bruker), X-ray diffraction
and the environmental risk of MPs under UVA, UVB and UVC (XRD, D8 Advance, Bruker) and X-ray photoelectron spectroscopy
irradiation. (XPS, Escalab 250Xi, Thermo Fisher Scientific). Based on the FTIR
Due to the excellent physicochemical properties, polyvinyl spectra of PVC before and after aging, the Two-dimensional corre-
chloride (PVC) plastics were widely used in product. The presence lation Fourier transform infrared spectroscopy (2D-FTIR-COS) were
of macro and micro sized particles of PVC has been ubiquitously produced by 2D-Shige software (Noda et al., 2000; Noda and Ozaki,
detected in the environment (Wang et al., 2020). PVC ranked as 2005; Zhou et al., 2017) and some detailed information was dis-
the most hazardous MPs with strong mutagenicity and carcino- played in our previous studies (Ouyang et al., 2020a). Besides,
genicity (Wei et al., 2019). Waste PVC causes serious environmen- the carbonyl index (CI) obtained from the absorbance ratio of car-
tal pollution because of the production of toxic intermediate bonyl stretch vibration (C@O) and methylene vibration (ACH2) in
through abandoning or incinerating (Miao et al., 2020). Therefore, FTIR spectrum to reflect the degree of aging (Brandon et al., 2016).
PVC was selected as the model plastic fragment. In this study,
the photo-aging behaviors and mechanism of PVC under the 2.4. The leaching of aging
UVA, UVB and UVC irradiation were explored. Overall, the major
objectives of the present work were to: (1) discuss the changes The solution samples of aged test group were periodically with-
in physicochemical properties of PVC under three different UV irra- drawn. The PVC obtained from the air-aged test group was added
diations; (2) confirm the substances leaching and production of to the deionized water. The mixed samples were shaken and pass
ROS during aging; (3) investigate the photo-aging mechanism through the 0.45 lm membrane. The three-dimensional
and the potential environmental risk of PVC. This study is impor- excitation-emission matrix (3D-EEM) spectra and concentrations
tant for further understanding the natural aging behavior and envi- of total organic carbon (TOC) in solution were measured by fluores-
ronmental fate of MPs. cence spectrometer (Shimadzu, RF-6000) and TOC analyzer system
(Elementar, Vario), respectively.

2. Materials and methods 2.5. EPR analysis

2.1. Chemicals The signals of singlet oxygen (1O2), hydroxyl radicals (OH) and
superoxide anion (O
2 ) were analyzed using an electron parameter
The pristine PVC was purchased from Dongguan Jingtian Raw resonance system (EPR, EMXmicro-6/1/P/L, Bruker). The using of
Materials of Plastics Co., Ltd. (CHN). Before the experiment, the radical trap was provided in our previous studies (Ouyang et al.,
PVC was washed with ethanol and deionized water, respectively. 2020a; Ouyang et al., 2020b).
After that, the MPs were dried and passed through a 60 mesh steel
standard sieve. 5,5-Dimethyl-1-pyrroline N-oxide (DMPO), 2,2,6,6- 2.6. Toxicity measurement
Tetramethylpiperidine (TEMP) and dimethyl sulfoxide (DMSO)
were purchased from Aladdin Co., Ltd. (CHN). Escherichia coli The toxicity of the leaching and intermediates under three
ATCC11303 (E.coli) was a standard strain, provided from Guang- UV irradiations was evaluated by using E. coli as the reference
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microorganism. In brief, the toxicity tests were performed by dis- To further analyze the crystallinity and micro-structure of PVC
persing bacterial suspension and the photo-aging treated samples, before and after aging, the XRD analysis was carried out and the
which were cultivated in Luria-Bertani (LB) agar plates (1% w/v patterns of three aged PVC were recorded in Fig. 2. As for the pris-
tryptone, 0.3% w/v yeast extract, and 0.5% w/v NaCl). The plates tine PVC, there were some peaks between 10° and 30°. After the
were then incubated shaking at 150 rpm at 30 °C for 5 h and treatment of aging, some sharp peaks were observed, which indi-
24 h. All tests were performed in triplicate. The index of OD600 (op- cated the increasing of crystallinity under three UV irradiations.
tical density at 600 nm) represented the concentration or growth The highest value of crystallinity was shown in the condition of
of E. coli, which measured with UV–Vis spectrophotometer UVC irradiation. Generally, because of structure and functional
(GENESYS 10S, Thermo Fisher Scientific, USA). groups destruction after degradation, the crystallinity of polymer
increased (Liu et al., 2019a; Taghizadeh et al., 2012). We specu-
3. Results and discussion lated that the destruction and production of some characteristic
functional groups occurred. The aged PVC might be fragile and
3.1. Surface morphology of PVC smaller particles were produced after the aging. In the actual envi-
ronment, the aged MPs are much more fragile (Mao et al., 2020).
The morphology change of MPs is an important indicator to The particle size of MPs decreases with aging time, which may
reflect the degree of aging process. The Fig. 1 depicted the surface be more harmful to organisms than the large particles (Jeong
morphology under different UV irradiations. The surfaces of pris- et al., 2016).
tine PVC were relatively smooth. With the increasing of aging time,
the surface gradually became coarse. More cracks and flakes 3.2. Surface chemical characteristics of PVC
appeared on the aged PVC and some debris adhered to the surface
of PVC. Some published literatures also proved the phenomenon of To further reveal the aging characteristics of PVC exposure to
aging PVC under irradiation (Lin et al., 2020; Tang et al., 2018). three UV irradiations, the XPS spectra of the pristine and aged
Both in the water and air condition under different UV irradiations, PVC were exhibited (Supplementary Data, Fig. S2). Compared to
the degree of aging were obvious. pristine PVC, O1s proportion of aged PVC increased from 17.63%

Fig. 1. SEM images of PVC treated by different UV irradiations and times in (a) water and (b) air condition.

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Fig. 3. FTIR spectra of pristine and aged PVC treated by UVC irradiations in (a) water
and (b) air condition with aged time.

Fig. 2. XRD patterns of pristine and aged PVC treated by three different UV
irradiations in (a) water and (b) air condition after 16 d.
aging conditions was calculated and shown in Fig. 4. The obvious
increasing of CI was observed after three treatments, suggesting
the production of a large amount oxygen containing groups on
to 19.05%, 17.76% and 19.39% under UVA, UVB and UVC treatment, the PVC surface. Therefore, there results showed the aging effect
respectively. The corresponding oxygen-to-carbon (O/C) ratio also under UVC irradiation stronger than irradiation motivated by
increased from 0.265 to 0.292, 0.272 and 0.297. These results con- UVA and UVB.
firmed that the surface of the PVC was oxidized during aging. To
further verify the changes in functional groups and elemental com- 3.3. The leaching of photo-aging
positions of PVC with aging times, the FTIR spectrum were showed
(Fig. 3 and Supplementary Data, Fig. S3). In water or air condition, To investigate the leaching of PVC during the photo-aging pro-
new oxygen-containing absorption peaks appeared at 1736 and cess, the amount of dissolved organic matter in solution were
3456/3602 cm
1 after the different UV irradiation treatments, detected by TOC analysis, which reflected the decomposition of
belongs to the stretching vibrations of C@O and AOH groups, polymer chains into solution. As illustrated in the Fig. 5, a high
respectively (Lin et al., 2020). The intensity of C@O and AOH amount of TOC was measured under different UV irradiations.
groups increased with the reaction. Peaks at 2907 and 763 cm
1 Especially, the concentration was increased to 98.5 ± 3.53 mg/L
were observed, representing the stretching vibrations of CAH in after 16 d UVC irradiation. The TOC slowly enhanced under UVA
the methyl and methylene groups, respectively. The intensity in or UVB irradiation, which indicated the intermediates potentially
605 cm
1 could be assigned to the stretching vibrations of CACl mineralized with the aging time.
groups (Wang et al., 2020). Therefore, the above results proved that Furthermore, 3D-EEM was used to study the leaching compo-
the PVC was aged after UV irradiation, and new oxygen-containing nents. The EEMs of the leaching of PVC under different aging con-
functional groups were generated. ditions are shown (Supplementary Data, Fig. S4). Several peaks
Both the FTIR and XPS results showed the oxidation of PVC dur- appeared in the protein-like fluorescence spectra region. Based
ing aging. Further, the value of CI provided the quantitative data to on the peak-picking method, this region was typically defined as
verify these variations, which was introduced to evaluate the aging peak B (-225 (-280)/-305 nm) and peak T (-225 (-280)/-350 nm),
degree of PVC under UV irradiations. The CI of PVC at different representing tyrosine-like and tryptophan-like substances
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3.4. The photo-aging mechanism of PVC

3.4.1. The production of ROS

Generally, the UV irradiation determines the lifetime of poly-
mer in outdoor, resulting in the decomposition of the MPs at envi-
ronmental conditions. (Geburtig and Wachtendorf, 2010; Naik
et al., 2020). Based on the existing experimental results, the irradi-
ation at different wavelengths influences the efficiency of photo-
aging. Besides, the physicochemical characteristics of PVC were
changed in different degrees under three UV irradiations. The aging
efficiency of PVC is most obvious in UVC band. During the photo-
aging, the ROS were also produced, such as hydroxyl radicals
(OH), the singlet oxygen (1O2) and superoxide anion (O
2 ), which
were important to the transformation of pollutants. As illustrated
in Fig. 6, the ESR signals of three free radicals increased with the
aging time as the whole. Corresponding to the aging results, the
intensity of ROS under UVC irradiation was greater than that under
UVA or UVB.
The general steps for degradation of polymers included initia-
tion, propagation, autocatalysis, and termination (Gewert et al.,
2015; Naqash et al., 2020). Dechlorination was the first aging step
of PVC and the UV irradiation has enough energy to cleave CAC or
CAH bond (Feldman, 2002; Gardette et al., 2013). The mechanisms
of the photo-aging reactions were identified by the extraneous
groups or impurities in the PVC, which absorbed photon and form-
ing the triplet excited state. The short-lived singlet state of PVC
was transformed to the long-lived the triplet excited state (Singh
and Sharma, 2008; Turro et al., 2012). And 1O2 came from the
quenching reaction between oxygen molecule and the triplet
excited state of PVC due to the energy transfer. Our previous stud-
ies have mentioned that 1O2 is the lowest excited singlet state of
Fig. 4. The carbonyl index of aged PVC treated by three different UV irradiations oxygen molecule and more reactive, which further attacked the
and times in (a) water and (b) air condition. C-H bond leading to the formation of alkyl radicals or macroradical
(Ng et al., 2018; Turro et al., 2012). However, no environmentally
persistent free radicals (EPFRs) were detected during the aging of
PVC. The generation of EPFRs was mainly related to the molecular
structure of MPs. Generally, the formation of EPFRs usually occurs
on MPs with conjugated benzene-ring structures like polystyrene
(PS) (Feld-Cook et al., 2017; Zhu et al., 2019). In the propagation
reaction, the hydroperoxide groups were formed. Further, the
alkoxy radicals and OH were formed in the autocatalytic reaction
(Ng et al., 2018). The published studies have also confirmed the
production of OH in the photodegradation of PVC, enhancing the
release of organotin (Chen et al., 2019). The macroradical could
react with oxygen molecule to generate O
2 , which was beneficial
for the formation of H2O2. In addition, the different physicochem-
ical properties of PVC caused by photo-aging in three conditions
affected the generation of ROS. The formation of more oxygen-
containing functional groups has been verified by the available
data. The published studies also had confirmed the products with
oxygen-containing functional groups during photo-aging of PVC,
such as, esters, aldehyde, alcohols and polymer fragments with
Fig. 5. The concentration of TOC leaching from aged PVC treated by three different carboxylic acid end groups (Gewert et al., 2018; Miao et al.,
UV irradiations and times in water condition. 2020). As the photosensitizer, these groups could enhance the light
absorption and the production of ROS, which promoted the aging
of PVC (Gewert et al., 2015; Singh and Sharma, 2008). The reactions
(Carstea et al., 2016). Generally, the peak T was used to describe in the photo-aging of PVC under UV irradiations are concluded in
microbial activities. And the fluorescence EEM regions Table 1.
(Em < 380 nm) reflected some compounds in wastewater (e.g.,
phenols, etc.) (Lee et al., 2020). Interestingly, the leaching under 3.4.2. 2D-FTIR-COS investigation
UVC irradiation on the 12th day showed additional peaks in the The 2D-FTIR-COS maps (synchronous and asynchronous) of PVC
humic-like fluorescence region, which was defined as peak A under different UV irradiations in water and air condition are
(250-300/400-450 nm). In addition, fluorescence intensities gradu- showed (Fig. 7 and Supplementary Data, Fig. S5). Based on the
ally increased and then decreased with longer exposures time. This spectrum of FTIR, 500–1800 cm
1 and 2800–3800 cm
1 bands
phenomenon could be due to photolysis of fluorescent substances were selected to carry out 2D-FTIR-COS analysis. According to
derived from the aging of PVC. the synchronous maps, total seven major auto peaks were
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Fig. 6. The EPR signals of (a) 1O2, (b) .OH and (c) O.-2 under three different UV irradiations with aged time.

‘‘CAH”, ‘‘HAC@O”, ‘‘C@O”, ‘‘CAH” and ‘‘OAH”, respectively. The

Table 1
Compilation of reactions in the photo-aging system of PVC under UV
intensity of ‘‘HAC@O” and ‘‘C@O” groups for samples treated by
irradiations. UVC irradiation were much higher than UVA or UVB. This result
was consistent with the data obtained by mentioned characteriza-
No. Reactions
tion, which further demonstrated the aging efficiency of UVC
hv hv
1-1 PVC
H !  PVC
HðSinglet stateÞ !  PVC
HðTriplet stateÞ higher than UVA and UVB. In the synchronous maps, positive signs
1-2
Energy transfer
PVC
HðTriplet stateÞ þ O2 ƒƒƒƒƒƒƒƒ! PVC
H þ 1 O2 were observed for all cross peaks under three different UV irradia-
1-3 PVC
H þ ROS ! PVC þ ROS
H tions (Supplementary Data Table S1), implying synchronous
1-4 PVC þ 2O2 ! PVC
OO þ O
2 change for almost all the functional groups during the aging (de-
1-5 O

2 þ H
þ
HO2 crease of bands intensity).

1-6 2HO2 ! H2 O2 þ O2
In Supplementary Data (Table S1), significant differences in the
1-7 HO2 þ O

2 þ H2 O ! H2 O2 þ O2 þ OH

hv
sign of cross peaks of asynchronous map were found in the water
1-8 H2 O2 ! 2  OH
and air condition, especially for the oxygen-containing functions
1-9 PVC
H þ OH !  PVC þ H2 O
1-10 PVC
H þ HO2 !  PVC þ H2 O2 (‘‘HAC@O”, ‘‘C@O”, and ‘‘OAH”). In the water condition, three neg-
1-11 PVC
OO þ PVC
H ! PVC
OOH þ  PVC ative cross peaks were found at 2907 and 3456 cm
1, indicating
1-12
hv
PVC
OOH !  PVC
O þ  OH change sequence of bands at 2907 cm
1 occurred before that at
1-13 PVC
O þ PVC
H ! PVC
OH þ PVC 3456 cm
1. While for the air condition, those sequences changed
1-14
chaincleavage
PVC
O ƒƒƒƒƒƒƒ! Aging
PVC þ Products to 2907 cm
1 later than 3456 cm
1. Peaks in the lower bands
(500–1800 cm
1) undergo larger change in the reaction sequence
between different functional groups. For example, sign of cross
identified at 605, 1248, 1435, 1636, 1736, 2907 and 3456 cm
1 peaks between 605 and 1248 cm
1 in the water condition showed
along the diagonal line, and represented peaks of ‘‘C-Cl”, ‘‘ACH2”, significant different values (‘‘
”, ‘‘o”, ‘‘+”) under UVA, UVB and UVC
6
Z. Ouyang, Z. Zhang, Y. Jing et al. Gondwana Research xxx (xxxx) xxx

Fig. 7. Synchronous and asynchronous 2D-FTIR-COS maps of PVC aging under different UV irradiations of the (a) water and (b) air condition in bands of 500–1800 cm
1. Red
color and blue color represents positive and negative correlation, respectively. The peaks located at the diagonal line are called auto peaks while cross peaks are located off-
diagonal positions. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

irradiation, respectively. The reaction sequences between different water condition; in air condition under UVB irradiation,
functional groups in bands 500–1800 cm
1 under different reaction 1736 < 605/1248/1435/1636; (3) in water and air condition under
conditions were summarized as follows: (1) in water and air condi- UVC irradiation, 1636 < 1736/605 < 1435 < 1248 and
tion under UVA irradiation, 1636/1736 < 1248/1435 < 605 and 605/1248/1435 < 1636 < 1736. In general, regardless of the
1736 < 1435 < 1248 < 605 < 1636; (2) in water condition under treatments, the aging of PVC induced by three different UV irradia-
UVB irradiation, no cross peak generated among functional groups tions was basically similar except for the diverse reaction rate of
in this bands range, no correlation for their reaction sequences in functional groups of PVC.

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Xuetao Guo: Conceptualization, Review, Project administration,

Funding acquisition.

Declaration of Competing Interest

The authors declare that they have no known competing finan-

cial interests or personal relationships that could have appeared
to influence the work reported in this paper.

Acknowledgements

The study was supported by the Open Fund of Guangdong

Provincial Key Laboratory of Solid Wastes Pollution Control and
Recycling (No. 2020B121201003), Natural Science Foundation of
Shaanxi Province (No. 2021JQ-167), Chinese Universities Scientific
Fund (No. 2452020225), China Postdoctoral Science Foundation
(No. 2021M692652) and National Natural Science Foundation of
Fig. 8. The OD600 of E. coli treated by the leaching from aged PVC under different UV
China (No. 41977307).
irradiations.
Appendix A. Supplementary material
3.5. Environmental risk assessment
Supplementary data to this article can be found online at
The toxicity of aging intermediates was determined using the https://doi.org/10.1016/j.gr.2021.07.010.
bacterium E. coli so as to evaluate the environmental risk of
photo-aging process of PVC. The variation of OD600 represented References
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