Water Research 233 (2023) 119786

Contents lists available at ScienceDirect

Water Research
journal homepage: www.elsevier.com/locate/watres

Elucidating the characteristic of leachates released from microplastics

under different aging conditions: Perspectives of dissolved organic carbon
fingerprints and nano-plastics
Xiuna Ren a, 1, Ye Han a, 1, Haoran Zhao a, Zengqiang Zhang a, To-Hung Tsui b, c, Quan Wang a, *
a
College of Natural Resources and Environment, Northwest Agriculture and Forestry University, Yangling, Shaanxi Province 712100, PR China
b
NUS Environment Research Institute, National University of Singapore, 5A Engineering Drive 1, Singapore 117411, Singapore
c
Department of Engineering Science, University of Oxford, Parks Road, Oxford, OX13PJ, United Kingdom

A R T I C L E I N F O A B S T R A C T

Keywords: Despite numerous studies that have been devoted to investigating the aging behaviors of microplastics (MPs),
Microplastics dissolved organic carbon (DOC) and nano-plastics (NPs) released from MPs under different aging conditions were
Aging conditions limited. Herein, the characterizations and underlying mechanisms of DOC and NPs leaching from MPs (PVC and
Dissolved organic carbon
PS) in the aquatic environment for 130 days under different aging conditions were investigated. The results
Nano plastics
Risks
showed that aging could reduce the abundance of MPs, and high temperature and UV aging generated small-
sized MPs (< 100 μm), especially UV aging. DOC-releasing characteristics were related to MP type and aging
condition. Meanwhile, MPs were prone to release protein-like and hydrophilic substances except for 60 ◦ C aging
of PS MPs. Additionally, 8.77 × 109–8.87 × 1010 and 4.06 × 109–3.94 × 1010 NPs/L were detected in leachates
from PVC and PS MPs-aged treatments, respectively. High temperature and UV promoted the release of NPs,
especially UV irradiation. Meanwhile, smaller sizes and rougher NPs were observed in UV-aged treatments,
implying higher ecological risks of leachates from MPs under UV aging. This study highlights the leachate
released from MPs under different aging conditions comprehensively, which could offset the knowledge gap
between the MPs’ aging and their potential threats.

1. Introduction et al., 2022). An increasing number of publications have documented

the MPs’ aging behaviors, mainly focusing on the change of surface
Microplastics (MPs), typically defined as plastics with a diameter properties and functional groups (Ding et al., 2020; Liu et al., 2022a,
smaller than 5 mm, have drawn increasing concern due to their wide­ 2022b; Luo et al., 2021). However, little attempt has been made to
spread presence in aquatic environments (rivers, lakes, estuary water explore the variation of the size distribution of MPs under aging envi­
and ocean) and their adverse effect on aquatic organisms (Liu et al., ronments, which is also a non-negligible factor in evaluating their
2019a, 2019b; Chen et al., 2022a, 2022b; Wu et al., 2021). It is well adverse effects on environments (Liu et al., 2022a, 2022b; Sun et al.,
known that MPs are distributed in the environments for a longer period, 2019; Tong et al., 2022). Therefore, this aspect requires more attention.
during which the MPs experience the aging induced by light, tempera­ Besides, MPs in aging environments could lead to the release of
ture and other environmental media (Sridharan et al., 2021; Liu et al., leachates, including dissolved organic carbon (DOC) and nano-plastics
2019a, 2019b). These processes alternate MPs characteristics (surface (NPs), which have attracted more attention recently (Hahladakis
morphology, hydrophobicity, roughness and others) and break MPs into et al., 2018; Lee et al., 2020; Yang et al., 2021). For example, the
smaller debris, which aggravates the destruction of the ecosystem (Ding MPs-sourced DOC could be utilized by microbes in the sea, thereby

Abbreviations: MPs, Microplastics; DOC, Dissolved organic carbon; NPs, Nano-plastics; NTA, Nanoparticle tracking analysis; AFM, Atomic force microscope; PVC,
Polyvinyl chloride; PS, Polystyrene; SEM-EDX, Scanning electron microscopy-energy dispersive X-ray spectroscopy; FTIR, Fourier transform infrared; Eh, Redox
potential; SFS, Synchronous fluorescence spectrum; 3D-EEM, Excitation-emission matrix; DOTP, Two (2-ethyl) terephthalate ester; DOM, Dissolved organic matter;
PE, Polyethylene; GI, Germination index.
* Corresponding author.
E-mail address: [email protected] (Q. Wang).
1
Equally contributing authors.

https://doi.org/10.1016/j.watres.2023.119786
Received 3 January 2023; Received in revised form 16 February 2023; Accepted 20 February 2023
Available online 22 February 2023
0043-1354/© 2023 Elsevier Ltd. All rights reserved.
X. Ren et al. Water Research 233 (2023) 119786

affecting the composition of the base of marine food webs (Romer­ three artificial aging conditions: 60 ◦ C/ dark/ ultrapure water, 25 ◦ C /
a-Castillo et al., 2018). A different phenomenon was found by Zhu et al. UV light / ultrapure water and 25 ◦ C/ dark/ ultrapure water, tersely
(2020), who pointed out that some DOC released from MPs may inhibit marking as 60 ◦ C, UV and 25 ◦ C/Dark respectively (Xu et al., 2022; Chen
microbial activities. Additionally, DOC, as one of the essential envi­ et al., 2022a, 2022b; Qiu et al., 2022). The irradiation energy was
ronmental factors, plays an interactive role with other environmental supplied by two 15 W UV lambs. As for aging experiments, the mixtures
pollutants (heavy metals, antibiotics and others) in the aquatics (Wu of 0.5 grams of MPs and 100 mL ultrapure water were sonicated for 30
et al., 2021; Chen et al., 2022a, 2022b). These findings demonstrated min to make them homogeneously (Luo et al., 2021). Meanwhile,
that different MP-sourced DOC could have varying levels of impacts on treatments in these three aging environments without MPs were recor­
ecological systems (Sun et al., 2022; Qiu et al., 2022; Lithner et al., 2011; ded as the control, and each treatment was set in three parallels. After
Lee et al., 2020; Huffer et L., 2018; Lu et al., 2022). Hence, it is supposed that, all samples were placed in the above three aging conditions for 130
to explore the characterizations of DOC leached from MPs. To the best days of the aging experiment, during which the ultrapure water was
knowledge of the authors, only a few reports discuss the characteriza­ termly replenished to ensure the constant concentration of samples. The
tions of DOC leached from MPs up to date (Romera-Castillo et al., 2018; suspensions were filtrated with 0.45 μm glass fiber filter membrane a
Abolghasemi-Fakhri et al., 2019; Liu et al., 2022a, 2022b). These studies glassware vacuum filtration device at specific aging periods (0, 20, 40,
mainly focused on the final properties of DOC leached from MPs expo­ 60, 80, 100 and 130 days). Then, the aged MPs samples collected above
sure to single or multiple aging conditions (UV, high temperature, the membrane were dried and stored for further analysis, and the
Fenton and seawater) within short periods (4–50 days), while ignoring remaining filtrate (leachate) under the membrane stored in a metal flask
the dynamic changes of DOC leached from MPs under various aging was used for subsequent DOC determination and NPs analysis. The
environments over a prolonged period (Xu et al., 2022; Lee et al., 2020; reasonability for collecting NPs was proven by Lambert and Wagner.
Chen et al., 2022a, 2022b; Qiu et al., 2022). Considering the sensitivity (2016), who pointed out that the NPs released from MPs aging were
of leached DOC and the stability of MPs in water synthetically, it is mainly concentrated from 1–450 nm.
reasonable to hypothesize that the characterizations of MP-sourced DOC
over a prolonged period of aging are different from that obtained from a
short aging time, thereby leading to the distinct effects on environments 2.3. Characteristic analysis of MPs
(Lee et al., 2020; Chen et al., 2022a, 2022b). Herein, further study is
supposed to be explored the variations of DOC leached from MPs under a The surface morphologies of virgin and aged MPs were detected by
long period of aging. Another non-ignoring problem is the release of stereomicroscope (Olympus CX23, Japan) and scanning electron
nano plastics (NPs, plastic particles with size < 1000 nm) with the microscopy-energy dispersive X-ray spectroscopy (SEM-EDX) (S-4800,
fragment of MPs during the aging process (Zhu et al., 2019; Soraman Hitachi, Japan), respectively, which also determined the element
et al., 2022). Different from MPs, NPs are more hazardous due to their abundance on MPs surfaces. Size distribution and the average size of
high diffusion and ability to cross biological barriers, which make it vital MPs were analyzed by measuring particles in stereomicroscope images
to explore the NP’s properties during the aging process of MPs (Allan (SMZ25, Nikon, Japan) using Image-J software. Meanwhile, the Fourier
et al., 2022). At present, although a handful of studies confirm the ex­ transform infrared (FTIR) spectroscopy (Nicolet 8700, America) was
istence of NPs in aging samples (including boiling of plastic tea bags, applied to analyze the functional groups of MPs with a resolution of 2
washing of synthetic textiles and others) by nanoparticle tracking cm− 1 and 64 scanning times over the range of 4000–400 cm− 1.
analysis (NTA), atomic force microscope (AFM) and other means, little
information about the releasing characteristics of NPs from MPs under 2.4. Analytical measurements of DOC leached from different aging
different aging conditions are reported (Hernandez et al., 2019; Yang conditions
et al., 2021).
Therefore, this study primarily investigated the dissolved organic The collected filtrate was divided into several parts, one was used to
carbon fingerprints and NPs released by MPs under different aging measure DOC concentration by TOC-L (TOC-L, Shimadzu, Japan), one
conditions. Commercial polyvinyl chloride (PVC) and polystyrene (PS) was for recording UV -vis spectra and fluorescence spectra, the other was
were selected as the probe plastics for 130 days of aging experiments due for monitoring the FTIR. To eliminate the fluorescence rate, DOC was
to their prevalence in aquatic ecosystems and potential risks (Liu et al., diluted to the same concentration before scanning the UV-vis and fluo­
2022a, 2022b; Luo et al., 2021; Zhu et al., 2019). Moreover, the seed rescence spectra. The UV-vis and fluorescent spectra including syn­
generation test was also done to assess the toxicity of leachate released chronous fluorescence spectrum (SFS) and excitation-emission matrix
from MPs. With the assistance of AFM, NTA, Py-GCMS and spectral (3D-EEM) were recorded by UV-1452 (UV-1452, Shimazu, Japan) and
analyses, it was comprehensive to understand the secondary MPs Fluorospectrometric photometer (F-4600, Hitachi, Japan), respectively.
pollution, and thus evaluate the potential risks of aging MPs to The related details were described in Text S2. Besides, the specific
environments. methods of Cl− concentration and redox potential (Eh) determination
were presented in Text S1.
2. Materials and methods

2.1. Plastic materials 2.5. Determination of nano-plastics and toxicity evaluation

Commercial PVC and PS particles used in this study were purchased Due to the smaller particle size and more complex components of
from Feihong Co., Ltd. (Dongguan, China), and the primary components NPs, different analytical techniques were applied to characterize them.
of PVC and PS are presented in Table S1. Before the aging experiment, In this study, for the physical information, the nanoparticle tracking was
these spherical-shaped PVC and PS were pretreated by washing with analyzed by AFM (Multimode-8, Bruker, America), while the size and
ultrapure water, pulverizing and sieving to determine the particle size number concentration were analyzed by NTA, which could be capable of
below 1000 μm. analyzing particles in size range of 1–2000 nm. Chemically, the Py-
GCMS (GCMS-QP2020, Shimadzu, Japan) was applied to determine
2.2. Aging experiments the nanoparticle composition assisted by a cracker named PY-3030D
Frontier. The operation parameters were exhibited in Text S3. Further­
To simulate the aging of MPs in environments including UV irradi­ more, to assess the toxicity of leachates released from aged MPs, the seed
ation and high temperature, the PVC and PS samples were exposed to germination experiment was carried out according to Li et al. (2012).

2
X. Ren et al. Water Research 233 (2023) 119786

3. Results and discussion generation was promoted by these two conditions (Liu et al., 2022a,
2022b; Yan et al., 2022). Notably, the maximum value in fraction with
3.1. Characterization of MPs during different aging processes size < 100 μm was observed in 60 ◦ C-aged PVC (24778 particles/g) and
UV-aged PS (14778 particles/g), revealing that the responses of MPs to a
3.1.1. The changes in the morphology and size distribution of MPs certain aging condition were different. It may be ascribed to the more
SEM images from Fig. 1 and Fig. S2 showed that the cracks, wrinkles straightforward structure and lower tensile strength of PVC than PS,
and pits on the surface of PVC and PS MPs became significant as the which made it easier to decompose more MPs into minor MPs or NPs in
aging continued, especially UV irradiation and high temperature, which PVC-aged samples, especially through UV irradiation (Liu et al., 2019a,
was similar to the finding observed by Tang et al. (2018). While due to 2019b; Tang et al., 2018). The NPs data supported the above result as
the various structure and tensile strengths of PVC and PS, morphological evidence (Fig. 5 a, b).
changes in PVC and PS-aged were different (Zhou et al., 2018).
Compared with PVC MPs, relatively inconspicuous microcracks formed 3.1.2. FTIR analysis of MPs
on the surface of PS MPs. While, the lower final carbon loss (Fig. 1a, b) Compared with virgin MPs, analogous FTIR spectra without any new
and releasing DOC concentration (Fig. 2) in PS than PVC MPs confirmed absorption peaks were recorded in all PVC and PS-aged treatments
this result. (Fig. S3), which was different from the results reported by Ding et al.
As shown in Fig. 1c, d, the total MPs particles significantly (p<0.05) (2022) and Wang et al. (2020). This difference may be due to the
decreased from 48000 to 33000–41667 particles/g in PVC – aged different characteristics of MPs and the aging mechanisms of aging
treatments and 41000 to 20000–35667 particles/g in PS-aged treat­ conditions (Ding et al., 2020). As aging continued, the peak intensities of
ments, respectively, indicating that aging could reduce the abundance of characteristic bands varied in all treatments. The intensities of C− Cl at
MPs. In contrast, one previous study showed that the number of sec­ 782 cm− 1, specific bands of PVC, decreased initially and then increased
ondary MPs in different plastics (PVC, PS, PLA, PBS and PBAT) increased in all PVC samples, which was confirmed by the Cl− concentration in the
undergoing 21 days of UV irradiation (Tong et al., 2022). This difference related filtrate (Fig. S4). This decreasing profile was possibly attributed
may be ascribed to the prolonged aging period in this study, which to the dehydrochlorination by ⋅H induced by aging environments, while
facilitated the exposure of the MPs to further decomposition, and SEM the “concentrated effect” possibly caused by the decomposition of the
images (Fig. 1 a, b) supported this result as evidence. In this study, carbon chain led to the increase of C-Cl (Ren et al., 2022; Tang et al.,
37.50% and 56.91% of virgin PVC and PS were > 200 μm, respectively, 2018). Different from PVC, the peak intensities of CH2 and -CH at 1450
with the dominant size class of 200–500 μm. After 130 days of aging, cm− 1 and 1493 cm− 1 of PS decreased while that of C-O increased in
most secondary MPs in all aged treatments were dominantly concen­ PS-aged treatments as aging proceeded, indicating that the cleavage of
trated on 2–100 μm, indicating the fragmentation of MPs, which was C-H bonds of PS MPs and the oxidation reaction to form C-O induced by
similar to the finding stated by Liu et al. (2019) and Liu et al. (2022). different aging conditions took place (Mao et al., 2020). The further
Meanwhile, high temperature and UV irradiation enhanced the frag­ analysis of 2D-COS based on FTIR indicated that sequential orders of
mentation of MPs, probably because the reactive oxygen species other specific chemical reactions were different among all treatments,

Fig. 1. SEM images and EDS of aged MPs at different aging conditions (a: PVC; b: PS) and size distribution before and after aging (c: PVC; d: PS).

3
X. Ren et al. Water Research 233 (2023) 119786

Fig. 2. The DOC released from MPs (a: PVC; b: PS) under different aging conditions.

except the prior destruction of the C=O in UV aging of PVC and PS crystallinity of the polymer, and thereby restricting the adsorption
(Fig. S6, Table S2 and Table S3). These results indicated aging behaviors relationship between DOC and MPs (Anjana et al., 2023). The higher
of MPs varied with the MPs type and aging condition, like the findings of carbon contents on MPs under 60 ◦ C aging confirmed the reasonability
Ding et al. (2020). of this result (Fig. 1a, b); 2) The decomposition was promoted by high
temperature, consistent with the relatively higher Eh values observed in
3.2. The characteristics of DOC-MPs under different aging conditions 60 ◦ C-aged treatments (Fig. S5). The DOC released from MPs could not
only be integral to many processes of ecological, like the carbon cycle
3.2.1. The DOC concentration variation and climate change but also be served as heterogenous sites for the
As exhibited in Fig. 2, PVC and PS MPs released DOC into the sur­ binding of pollutants, thus aggravating the environmental risks (Qiu
rounding water under aging conditions, which consisted of truly dis­ et al., 2022). To assess the risks of MPs aging to the ecological envi­
solved substances and polymeric NPs fragmented from the plastic ronment, it is important to investigate the characteristics of DOC.
surface (Romera-Castillo et al., 2018). During the aging experiments, the
DOC leached from PVC MPs showed a gradual upward trend, which 3.2.2. Spectroscopic characterization of DOC leached from MPs-aged
increased rapidly in the first 20 days and then fluctuated with the extent process
of aging time in all PS-aged treatments. These results indicated that the
trend of DOC leached from PVC and PS MPs differed, except for the 3.2.2.1. UV-vis characterization analysis. As presented in Fig. S7,
initial increase within 20 days in all treatments. This temporary increase regardless of the MPs type, the absorbance fluctuated with the prolon­
was like the results pointed out by Lee et al. (2020), in which MPs gation of aging time in PVC and PS-aged treatments, and there were no
structures became more vulnerable to being dissolved (Lee et al., 2020; pronounced characteristic peaks, like the observation reported by Xu
Lambert and Wagner, 2016). Meanwhile, the DOC leached from PS-aged et al. (2022). These results indicated that the component and molecular
treatments on the 20th was higher than that of in PVC-aged treatments, weight of DOC differed in all treatments and varied as aging proceeded
possibly due to the 2-ethyl terephthalate ester (DOTP) in PVC (Table S1) (Cook et al., 2017).
resulting in its aging-resistant in the short period (Tang et al., 2018). To obtain more information, SUVA254, representing the molecular
After 20 days, the fluctuated leaching of DOC in PS-aged treatments was weight, was calculated according to the published formula and defini­
possibly ascribed to the adsorption of DOC on the PS surface and con­ tion (Chen et al., 2022a, 2022b). As exhibited in Table S4, whatever the
version of DOC in the surrounding water, which was promoted by the MP type, the SUVA254 value fluctuated with the aging continued, indi­
extended contact of MPs with aging environments (Chen et al., 2022a, cating the conversion between high-molecular-weight fractions and
2022b; Meng et al., 2021). The variation of carbon content on the PS low-molecular components during the aging process. A different profile
surface (Fig. 1a, b) and spectral signatures of DOC (Fig. S7 and Fig. S8) was observed by Chen et al. (2022), who pointed out that SUVA254
could also provide evidence for this result. While the intense release of increased within 40 days of PS aging. This difference was possible
DOC in all PVC-aged treatments was possibly due to the rapid dissolu­ because of the prolonged aging period in this study, during which the
tion of DOTP (additive detected in PVC) from confined matrices, which dynamic transformation of DOC took place, and the variation of fluo­
was also facilitated by the more substantial fragmentation (Lee et al., rescent signatures provided evidence for this result (Fig. S8, S9). Addi­
2020; Do et al., 2022). tionally, SUVA254 might reflect aromatic degree, that is, identify the
In this study, the final DOC values in PVC-aged treatments DOC properties from the perspectives of hydrophobicity and hydrophi­
(3.38–7.60 mg/L) were higher than that of PS (1.19–4.69 mg/L), which licity (Chen et al., 2022a, 2022b; Weishaar et al., 2003). Most SUVA254
may be ascribed to the existence of benzene ring structures in PS poly­ values in PVC and PS MPs-aged treatments were < 3 under all aging
mers made it insensitive to environments (Liu et al., 2019a, 2019b). conditions except 60 ◦ C aging of PS, in which SUVA254 values were > 4
Furthermore, the highest DOC concentration was observed in 25 on the 20th, 60th and 100th. This result demonstrated that though most
◦
C-aged treatments regardless of the MP type. A different profile was DOC was composed of hydrophilic substances; high temperature facili­
reported by Chen et al. (2022), who described that UV irradiation pro­ tated the formation of the hydrophobic substance of PS-sourced DOC.
moted the release of DOC from PS and polyethylene (PE) MPs aging Meanwhile, this generated hydrophobic substance was beneficial for
within 7 days. This difference was probably because of the fragmenta­ strengthening the absorption of DOC on PS MPs (Zheng et al., 2023),
tion accelerated by high temperature and UV under a prolonged aging thereby possibly leading to the highest carbon content (Fig. 1b) in PS
time, during which adsorption of DOC on MPs surface and the decom­ MPs and the rapid decrease of DOC (between 20–40 days) undergoing
position of DOC were promoted (Ding et al., 2020; Fan et al., 2021). 60 ◦ C (Fig. 2b). Additionally, it was reported that the substances char­
Additionally, the DOC values detected in UV-aged were higher than acterized with hydrophilia/ hydrophobicity played the distinctive roles
those in 60 ◦ C-aged treatments. It could be explained by two perspec­ on the fate of organic pollutants (Zheng et al., 2023; Seidensticker et al.,
tives: 1) High temperature accelerated the diffusion of DOC, thereby 2017). Therefore, it was reasonable to hypothesize that the effect of DOC
facilitating the adsorption of DOC by MPs while UV increased the leached from MPs on the fate of pollutants differed among different

4
X. Ren et al. Water Research 233 (2023) 119786

aging conditions, resulting in potential damage to the ecological envi­ substrate were observed in all treatments, and the location of these two
ronment, which was supposed to be further investigated. more substantial peaks varied with MPs type (PVC: C1 (Ex/Em=220
(275) / 310 nm) and C2 (Ex/Em=225 (275)/ 300 nm); PS: C1 (Ex/
3.2.2.2. Fluorescent signatures analysis. Fluorescent spectra are notable Em=220 (275)/310 nm) and C2 (Ex/Em=275/330 nm)). These results
tools for detecting the location and intensity of fluorescence components illustrated that the aging of MPs facilitated the release of degradable
in dissolved organic matter (DOM) (Lee et al., 2020; Xu et al., 2022). In organic substances. A similar finding was also reported by Sun et al.
this study, fluorescent spectra (SFS and 3D-EEM maps) of DOC under (2022) that more liable compounds, including lipid-like, protein/amino
different aging conditions were compared for the different MPs. No sugar-like and carbohydrate-like compounds, were observed in DOC
fluorescence peak was detected for the control sample, that is, the leached from MPs. Besides, the elaboration of the PARAFAC model
distilled water without MPs, which was enough evidence that the fluo­ confirmed a two-component model regardless of MP type, like the re­
rescence peaks observed in other samples originated from the MPs sults described by Xu et al. (2022). Furthermore, to quantifiably eval­
(Fig. S8). As aging continued, SFS spectra differed between PVC and PS uate the change of two more vital components, the temporal variations
MPs-aged treatments. Three peaks representing the protein-derived were calculated. As shown in Fig. S10 and Table S5, Fmax values varied
substances (~280 nm), soluble microbial byproduct-like materials with the prolonged aging time, and Fmax values exhibited apparent dif­
(~320 nm) and humic-like fluorescence regions (~380 nm) occurred in ferences in different MPs regardless of aging conditions. Higher Fmax
PVC-aged treatments except for 60 ◦ C-aged, while one strong peak values were observed in C1 (accounting for 82.38%–99.60%) of the DOC
(~280 nm) and two weaker peaks (~330 nm and ~380 nm) were derived from PS in all aging conditions, which was also confirmed by the
detected in all PS-aged treatments. The peak intensities of these fluo­ previous report that the higher correlations of C1 with the initial
rescent peaks varied with aging time, revealing that the chromogenic amounts of PS provided adequate evidence (Lee et al., 2020). Oppo­
components of DOC changed (Zhang et al., 2021; Chen et al., 2022a, sitely, C2 was regarded as the dominant component in DOC leached
2022b). from PVC-aged treatments except under 60 ◦ C conditions, in which the
Commonly, the EEM map can be split into several regions, repre­ main component changed between C1 and C2 with the increase of aging
senting the protein-like substance, fulvic acid-like substrate, the soluble time.
microbial byproduct-like substrate as well as humic acid-like substance,
respectively (Chen et al., 2022a, 2022b). As presented in Fig. S9, the 3.2.2.3. 2D-COS maps analysis. To explore the aging mechanism deeply
locations and intensities of three fluorescent components in PVC and PS from the perspectives of DOC characterizations, 2D-COS was used to
MPs-aged treatments varied during the experiment, indicating that the expand the dynamic spectrum (Ding et al., 2020; Lin et al., 2020). In this
dynamic evolution of DOC differed in all samples (Xu et al., 2022; Lee study, FTIR and SFS integrated with 2D-COS were used to analyze the
et al., 2020). The variation of DOC concentration (Fig. 2) and SFS DOC-MPs according to the reported rules (Noda, 2006; Dowrey et al.,
(Fig. S8) supported this result as evidence. In this study, the protein-like 2001; Lasch and Noda, 2019). After analyzing the 2D-COS images
substances and soluble microbial byproduct-like substrates were the (Fig. 4), it was found that the transformation mechanisms of DOC
main components of DOC in all samples, similar to the report by Zhang released from MPs aging varied when exposed to different aging con­
et al. (2021). The dominant presence of the bio-labile substances was ditions. The related details were that the FTIR bands at 810 and 1660
consistent with the previous findings that 60% of MPs-sourced DOC cm− 1 were positively correlated with the SFS bands at 280 nm in all
could be utilized by microbes (Romera-Castillo et al., 2018). Besides, a DOC-PVC treatments, and the color of these red points became darker in
weaker peak representing the humic-like substance was exhibited in 60 ◦ C and UV-aged treatments regardless of the aging conditions. These
EEM maps, which was also observed by Lee et al. (2020) in commercial results indicated that the degradation of protein-like substances was
plastics after UV irradiation. Furthermore, the regions of humic-like attributed to the destruction of C=O and C-Cl in PVC MPs-aged treat­
substances were relatively more pronounced in PVC than PS aged ments, and high temperature and UV irradiation promoted this process.
treatments, likely because the DOTP contained in PVC manufacture was Besides, humic-like substances were positively connected with C=O in
released during the aging process, which exhibited the fluorescent DOC derived from 25 ◦ C-aged, while that in UV aging treatment pre­
response in the region of humic-like (Zhang et al., 2021). sented negative correlations, indicating that the change mechanisms of
To obtain more valuable information, PARAFAC modeling was humic-like substances were different under 25 ◦ C and UV aging. Due to
applied in this study. As illustrated in Fig. 3, two more robust compo­ the weak humic-like peak that occurred in 60 ◦ C aging of PVC, no
nents representing the protein-like substances and two weaker fluores­ apparent relationship between humic-like substances and C=O was
cent components representing soluble microbial byproduct-like observed, as discussed in section 3.2.2.2. As for PS-aged treatments, the

Fig. 3. PARAFAC model output showing the two different fluorescent components (above) and the corresponding excitation/emission loading (below).

5
X. Ren et al. Water Research 233 (2023) 119786

Fig. 4. Synchronous maps obtained via 2D heterospectral correlation analysis of the FTIR and synchronous fluorescence spectroscopy of DOC-MPs under different
aging conditions.

negative correlations between functional groups (C-O and C=O) and in Fig. 5a, b, there was a substantial release of NPs in all treatments, and
protein-like substances were observed in PS-aged samples except for 25 the size mainly concentrated from 1–450 nm, like the finding by
◦
C aging, and blue points became darker in 60 ◦ C-aged samples. Lambert and Wagner (2016). It was observed that the abundance of
Concluded from these results demonstrated that the correlations be­ detectable NPs in PVC and PS MPs-aged treatments were 8.77 ×
tween fluorescent substances and functional groups could be affected by 109–8.87 × 1010 NPs/L and 4.06 × 109–3.94 × 1010 NPs/L, respectively,
MPs type and aging conditions, and thereby leading to the differences in which was like the NPs concentration (1.47 × 1010 particles) reported in
DOC transformation. The concentration (Fig. 2) and spectral charac­ thermal aging of plastics teabags (Hernandez et al., 2019). Meanwhile,
terizations (Fig. S7-S10 and Table S4-S5) of DOC leached from all higher abundances of NPs were detected in PVC-aged treatments, which
treatments confirmed this result. was because the open structure and lower tensile strength of PVC make
it easier to be fragmented (Liu et al., 2019a, 2019b). Besides, in both
PVC and PS MPs-aged treatments, the highest abundance of NPs was
3.3. Nanoparticles characterizations during the MPs-aged process observed in UV- aged treatments, followed by 60 ◦ C and 25 ◦ C/dark,
indicating that photochemical oxidation and thermochemical oxidation
The 3D AFM height images in Fig. 5 showed that nano-particles were aggravated the release of NPs during the aging process, especially the
generated in all PVC and PS-aged treatments. These nanoparticles were UV irradiation, confirmed by the roughness obtained from AFM analysis
characterized by irregular shapes and rough surfaces, and the roughness (Table S6).
values were 1.35–2.33 nm and 1.08–4.09 nm in PVC and PS-aged As presented in Fig. 5c, d, the average size of NPs released from PVC
treatments, respectively (Table S6). Furthermore, the maximum and PS MPs-aged samples was 156.81–289.50 nm and 236.52–253.89
roughness values were observed in UV aging treatments, followed by 60 nm, respectively, which was larger than the results observed in the
◦
C and 25 ◦ C/dark. Similar studies were reported by Ding et al. (2020) mechanical aging of polyester textiles (188 ± 68 nm) (Yang et al., 2021).
and Zhu et al. (2020), who stated that high temperature and UV irra­ This difference could be due to the different aging conditions and MP
diation promoted the generation of cracks, flakes and pits on MPs sur­ properties (Ding et al., 2020; Bao et al., 2022). Besides, it was noted that
face, and thereby enhancing its roughness. Though AFM confirmed the the generated NPs mainly concentrated at 200–300 nm in PS (44.89%–
release of nanoparticles during the aging of MPs by visualized images, 46.54%) and PVC-aged treatments (38.37%–39.71%) except UV-aged of
the composition of these nanoparticles was unclear in this study. The PVC, in which smaller NPs (1–100 nm) were generated. The simpler
Py-GCMS data showed that PVC-NPs and PS-NPs were released under structure and lower tensile strength of PVC and the rougher MPs surface
the aging of PVC and PS MPs (Table S7). Considering the findings that promoted by UV irradiation were responsible for this phenomenon, and
additives and oligomers leached from MPs are soluble in water (Yang the SEM images and size distribution (Fig. 1) confirmed this result.
et al., 2021; Hernandez et al., 2019; Lee et al., 2020). Herein, coinciding Obviously, compared with PS MPs-aged treatments, more NPs charac­
with NTA results, it pointed out that UV irradiation and high tempera­ terized with sizes ranging from 50–100 nm were generated in all PVC
ture promoted the release of NPs, especially UV irradiation, during MPs-aged treatments. Hence, more attention should be paid to the
which MPs became more vulnerable and rougher to be fragmented (Liu UV-aged of PVC to reduce its potentially hazardous effect on ecology
et al., 2022a, 2022b). The release of NPs fitted with rougher surfaces from the perspective of NPs generation.
affected the transport of environmental contamination, based on the
investigations of relationships between MPs-aged and environmental
contamination (Ding et al., 2020; Wang et al., 2020; Meng et al., 2021). 3.4. Seed germination and seedling growth
However, due to the different properties of MPs and NPs, the specific
effect of NPs on environmental contamination should be further studied The data showed that the GI values in leachate-PVC differed from
to assess its potential risks to ecology (Lee et al., 2020). those of leachate-PS treatments, and the specific information was that GI
To further detect the size and distribution of released NPs, NTA was values were 86.18%–95.00% and 100.51%–114.67% in PVC MPs-aged
applied in this study (Rocca et al., 2014; Yang et al., 2021). As presented treatments and PS MPs-aged treatments, respectively (Fig. S11). The

6
X. Ren et al. Water Research 233 (2023) 119786

Fig. 5. Atomic force microscopy of nano plastics in leachate-MPs and related size distribution (a, c: PVC; b, d: PS).

GI values in PVC MPs-aged treatments were lower than 100%, demon­ corn (Zea mays L.) seedlings which due to the PS NPs trigging root
strating the inhibition effect of leachates released from PVC MPs on seed antioxidant enzyme system (Zhang et al., 2022). Furthermore, regard­
germination, which was dominantly explained by followed two per­ less of the MPs type, the lowest GI values were observed in UV-aged
spectives: 1) More NPs particles generated in PVC-aged (Fig. 5a) which treatments, which was consistent with the more NPs released from
could accumulate in the stoma of the seed skin of the germinating plant UV-aged (Fig. 5).
and form a physical barrier, thereby restricting the germination of seeds
and root growth (Bosker et al., 2019); and 2) As confirmed, additive in 4. Conclusions
PVC production (Table S1), the main organic additives in MPs are
plasticizers like dibutyl phthalate (2-ethylhexyl) ester, which might Data obtained from artificial aging experiments showed that the total
inhibit amylase activity and induce oxidative stress in plants, thus abundance of MPs decreased after aging and the formation of smaller
leading to the negative effect on seed germination (Hahladakis et al., MPs was facilitated especially by UV aging. With the aging proceeding,
2018; Fauser et al., 2022). While the GI values in PS MPs-aged treat­ the DOC-releasing tendency of PVC differed from that of PS, and high
ments were above 100%, indicating that the leachates released from PS temperature and UV irradiation promoted the adsorption and decom­
MPs-aged treatments benefited the plant growth, like its positive role on position of DOC. Most MPs-sourced DOC was composed of protein-like

7
X. Ren et al. Water Research 233 (2023) 119786

and hydrophilic substances except for the 60 ◦ C aging of PS MPs. Be­ Hahladakis, J.N., Velis, C.A., Weber, R., Iacovidou, E., Purnell, P., 2018. An overview of
chemical additives present in plastics: migration, release, fate and environmental
sides, high temperature and UV irradiation promoted the release of MPs-
impact during their use, disposal and recycling. J. Hazard. Mater. 334, 179–199.
NPs under the aging of MPs, especially UV, which promoted the for­ Hernandez, LM., Xu, E., Larsson, H.C.E., Tahara, R., Maisuria, V.B., Tufenkji, N., 2019.
mation of smaller and rougher NPs and thus adversely affected ecolog­ Plastic teabags release billions of microparticles and nanoparticles into tea. Environ.
ical environments. The finding first revealed the characteristics of Sci. Technol. 53, 12300–12310.
Huffer, T., Weniger, A., Hofmann, T., 2018. Sorption of organic compounds by aged
leachates (DOC and NPs) released from MPs under different aging polystyrene microplastic particles. Environ. Pollut. 236, 218–225.
conditions, which was helpful for offsetting the knowledge gap between Lambert, S., Wagner, M., 2016. Characterization of nanoplastics during the degradation
the MPs’ aging and assessing their potential threats to ecology. of polystyrene. Chemosphere 145, 265–268.
Lasch, P., Noda, I., 2019. Two-dimensional correlation spectroscopy (2D-COS) for
analysis of spatially resolved vibrational spectra. Appl. Spectrosc. 73 (4), 359–379.
Lee, Y., Murphy, K., Hur, J., 2020. Fluorescence signatures of dissolved organic matter
Declaration of Competing Interest leached from microplastics: polymers and additives. Environ. Sci. Technol. 54,
11905–11914.
Li, R., Wang, J.J., Zhang, Z., Shen, F., Zhang, G., Qin, R., Li, X., Xiao, R., 2012. Nutrient
The authors declare that they have no known competing financial transformations during composting of pig manure with bentonite. Bioresour.
interests or personal relationships that could have appeared to influence Technol. 121, 362–368.
the work reported in this paper. Lin, J., Yan, D., Fu, J., Chen, Y., Ou, H., 2020. Ultraviolet-C and vacuum ultraviolet
inducing surface degradation of microplastics. Water Res. 186, 116360.
Lithner, D., Larsson, A., Dave, G., 2011. Environmental and health hazard ranking and
Data availability assessment of plastic polymers based on chemical composition. Sci. Total Environ.
409, 3309–3324.
Liu, P., Li, H., Wu, J., Wu, X., Shi, Y., Yang, Z., Huang, K., Guo, X., Gao, S., 2022.
Data will be made available on request.
Polystyrene microplastics accelerated photodegradation of co-existed polypropylene
via photosensitization of polymer itself and released organic compounds. Water Res.
214, 118209.
Liu, P., Qian, L., Wang, H., Zhan, X., Lu, K., Gu, C., Gao, S., 2019a. New insights into the
Acknowledgment aging behavior of microplastics accelerated by advanced oxidation processes.
Environ. Sci. Technol. 53, 3579–3588.
The research was supported by the National Natural Science Foun­ Liu, X., Deng, Q., Zheng, Y., Wang, D., Ni, B-J., 2022a. Microplastics aging in wastewater
treatment plants: Focusing on physicochemical characteristics changes and
dation of China (Grant No. 42007349). corresponding environmental risks. Water Res. 221, 118780.
Liu, X., Shi, H., Xie, B., Dionysiou, D., Zhao, Y., 2019b. Microplastics as both a sink and a
source of bisphenol A in the marine environment. Environ. Sci. Technol. 53,
Supplementary materials
10188–10196.
Lu, J., Yu, Z., Ngiam, L., Guo, J., 2022b. Microplastics as potential carriers of viruses
Supplementary material associated with this article can be found, in could prolong virus survival and infectivity. Water Res. 225, 119115.
the online version, at doi:10.1016/j.watres.2023.119786. Luo, H., Zeng, Y., Zhao, Y., Xiang, Y., Li, Y., Pan, X., 2021. Effects of advanced oxidation
processes on leachates and properties of microplastics. J. Hazard. Mater. 413,
125342.
References Mao, R., Lang, M., Yu, X., Wu, R., Yang, X., Guo, X., 2020. Aging mechanism of
microplastics with UV irradiation and its effects on the adsorption of heavy metals.
J. Hazard. Mater. 393, 122515.
Abolghasemi-Fakhri, L., Ghanbarzadeh, B., Dehghannya, J., Abbasi, F., Adun, P., 2019.
Meng, J., Xu, B., Liu, F., Li, W., Sy, N., Zhou, X., Yan, B., 2021. Effect of chemical and
Styrene monomer migration from polystyrene based food packaging nanocomposite:
natural ageing on the release of potentially toxic metal additives in commercial PVC
effect of clay and ZnO nanoparticles. Food Chem. Toxicol. 129, 77–86.
microplastics. Chemosphere 283, 131274.
Allan, I., Samanipour, S., Manoli, K., Gigault, J., Fatta-Kassinos, D., 2022. Examining the
Noda, I., 2006. New approaches to generalized two-dimensional correlation spectroscopy
relevance of the microplastic-associated additive fraction in environmental
and its applications. Appl. Spectrosc. Rev. 41 (5), 515–547.
compartments. ACS Environ. Sci. Technol. Water 2, 405–413.
Qiu, X., Ma, S., Zhang, J., Fang, L., Guo, X., Zhu, L., 2022. Dissolved organic matter
Anjana, R.K., Keerthana, S., Arnepalli, D.N., 2023. Coupled effect of UV ageing and
promotes the ageing process of polystyrene microplastics under dark and ultraviolet
temperature on the diffusive transport of aqueous, vapour and gaseous phase organic
light conditions: The crucial role of reactive oxygen species. Environ. Sci. Technol.
contaminants through HDPE geomembrane. Geo. Geomembranes. 51, 316–329.
56, 10149–10160.
Bao, R., Cheng, Z., Hou, Y., Xie, C., Pu, J., Peng, L., Gao, L., Chen, W., Su, Y., 2022.
Ren, J., Li, J., Zhen, Y., Wang, J., Niu, Z., 2022. Removal of polyvinyl chloride
Secondary microplastics formation and colonized microorganisms on the surface of
microplastic by dielectric barrier discharge plasma. Sep. Purif. Technol. 290,
conventional and degradable plastic granules during long-term UV aging in various
120832.
environmental media. J. Hazard. Mater. 439, 129686.
Rocca, A., Liberto, G., Shayler, P.J., Parmenter, C.D.J., Fay, M.W., 2014. Application of
Bosker, T., Bouwman, L.J., Brun, N.R., Behrens, P., Vijver, M.G., 2019. Microplastics
nanoparticle tracking analysis platform for the measurement of soot-in-oil
accumulate on pores in seed capsule and delay germination and root growth of the
agglomerates from automotive engines. Tribol. Int. 70, 142–147.
terrestrial vascular plant Lepidium sativum. Chemosphere 226, 774–781.
Romera-Castillo, C., Pinto, M., Langer, T.M., Alvarez- Salgado, X.A., Herndl, G.J., 2018.
Chen, M., Liu, S., Bi, M., Yang, X., Deng, R., Chen, Y., 2022a. Aging behavior of
Dissolved organic carbon leaching from plastics stimulates microbial activity in the
microplastics affected DOM in riparian sediments: From the characteristics to
ocean. Nat. Commun. 9, 1430.
bioavailability. J. Hazard. Mater. 431, 128522.
Seidensticker, S., Zarfl, C., Cirpka, O.A., Fellenberg, G., Grathwohl, P., 2017. Shift in
Chen, M., Xu, J., Yuan, S., Xu, Q., Shi, P., 2022b. Roles of microplastic-derived dissolved
mass transfer of wastewater contaminants from microplastics in the presence of
organic matter on the photodegradation of organic micropollutants. J. Hazard.
dissolved substances. Environ. Sci. Technol. 51, 12254–12263.
Mater. 440, 129784.
Sorman, C., Edo, C., Gonzalez-Pleiter, M., Femandez-Pinas, F., Leganes, F., Rodriguez, A.,
Cook, S., Peacock, M., Evans, C.D., Page, S.E., Whelan, M.J., Gauci, V., Kho, L.K., 2017.
Rosal, R., 2022. Ageing and fragmentation of marine microplastics. Sci. Total
Quantifying tropical peatland dissolved organic carbon (DOC) using UV-visible
Environ. 827, 154438.
spectroscopy. Water Res. 115, 229–235.
Sridharan, S., Kumar, M., Bolan, N.S., Singh, L., Kumar, S., Kumar, R., You, S-M., 2021.
Ding, L., Mao, R., Ma, S., Guo, X., Zhu, L., 2020. High temperature depended on the
Are microplastics destabilizing the global network of terrestrial and aquatic
ageing mechanisms of microplastics under different environment conditions and its
ecosystem services? Environ. Res. 198, 111243.
effect on the distribution of organic pollutants. Water Res. 174, 115634.
Sun, S., Sui, H., Zhang, J., Wang, D., Zhou, Z., 2022. Effect of freeze-thaw cycle aging and
Ding, L., Yu, X., Guo, X., Zhang, Y., Ouyang, Z., Liu, P., Zhang, C., Wang, T., Jia, H.,
high-temperature oxidation aging on the sorption of atrazine by microplastics.
Zhu, L., 2022. The photodegradation processes and mechanisms of polyvinyl
Environ. Pollut. 307, 119434.
chloride and polyethylene terephthalate microplastic in aquatic environments:
Sun, Y., Xu, W., Gu, Q., Chen, Y., Zhou, Q., Zhang, L., Gu, L., Huang, Y., Lyu, K., Yang, Z.,
important role of clay minerals. Water Res. 208, 117879.
2019. Small-sized microplastics negatively affect rotifers: changes in the key life-
Do, A.T.N., Ha, Y., Kwon, J-H., 2022. Leaching of microplastic-associated additives in
history traits and rotifer− phaeocystis population dynamics. Environ. Sci. Technol.
aquatic environments: a critical review. Environ. Pollut. 305, 119258.
53, 9241–9251.
Dowrey, A.E., Marcott, C., Story, G.M., Ozaki, Y., 2001. Comparison of principal
Tang, C., Chen, H., Brimblecombe, P., Lee, C., 2018. Textural, surface and chemical
component analysis and generalized two-dimensional correlation spectroscopy:
properties of polyvinyl chloride particles degraded in a simulated environment. Mar.
spectral analysis of synthetic model system and near-infrared spectra of milk. Appl.
Pollut. Bull. 133, 392–401.
Spectrosc. 55 (1), 29–38.
Tong, H., Zhong, X., Duan, Z., Yi, X., Cheng, F., Xu, W., Yang, X., 2022. Micro- and
Fan, X., Zou, Y., Geng, N., Liu, J., Hou, J., Li, D., Yang, C., Li, Y., 2021. Investigation on
nanoplastics released from biodegradable and conventional plastics during
the adsorption and desorption behaviors of antibiotics by degradable MPs with or
degradation: Formation, aging factors, and toxicity. Sci. Total Environ. 833, 155275.
without UV ageing process. J. Hazard. Mater. 401, 123363.
Fauser, P., Vorkamp, K., Strand, J., 2022. Residual additives in marine microplastics and
their risk assessment – a critical review. Mar. Pollut. Bull. 177, 113467.

8
X. Ren et al. Water Research 233 (2023) 119786

Wang, C., Xian, Z., Jin, X., Liang, S., Chen, Z., Pan, B., Wu, B., OK, Y.S., Gu, C., 2020. Zhang, Y., Yang, X., Luo, Z., Lai, J., Li, C., Luo, X., 2022. Effects of polystyrene
Photo-aging of polyvinyl chloride microplastic in the presence of natural organic nanoplastics (PSNPs) on the physiology and molecular metabolism of corn (Zea mays
acids. Water Res. 183, 116082. L.) seedlings. Sci. Total Environ. 806, 150895.
Weishaar, J.L., Aiken, G.R., Bergamaschi, B.A., Fram, M.S., Fujii, R., Mopper, K., 2003. Zhang, Y., Zhou, L., Zhou, Y., Zhang, L., Yao, X., Shi, K., Jeppesen, E., Yu, Q., Zhu, W.,
Evaluation of specific ultraviolet absorbance as an indicator of the chemical 2021. Chromophoric dissolved organic matter in inland waters: Present knowledge
composition and reactivity of dissolved organic carbon. Environ. Sci. Technol. 37 and future challenges. Sci. Total Environ. 759, 143550.
(20), 4702–4708. Zheng, R., Li, Q., Li, P., Li, L., Liu, J., 2023. Total organic carbon content as an index to
Wu, X., Liu, P., Gong, Z., Wang, H., Huang, H., Shi, Y., Zhao, X., Gao, S., 2021. Humic estimate the sorption capacity of micro- and nano-plastics for hydrophobic organic
acid and fulvic acid hinder long-term weathering of microplastics in lake water. contaminants. Chemosphere 313, 137374.
Environ. Sci. Technol. 55, 15810–15820. Zhou, Q., Zhang, H.B., Zhou, Y., et al., 2018. Surface weathering and changes in
Xu, Y., Huang, D., Liu, P., Ouyang, Z., Jia, H., Guo, X., 2022. The characteristics of components of microplastics from estuarine beaches, 63. Science China Press,
dissolved organic matter release from UV-aged microplastics and its cytotoxicity on pp. 214–224.
human colonic adenocarcinoma cells. Sci. Total Environ. 826, 154177. Zhu, K., Jia, H., Zhao, S., Xia, T., Guo, X., Wang, T., Zhu, L., 2019. Formation of
Yan, W., Chen, Y., Han, L., Sun, K., Song, F., Yang, Y., Sun, H., 2022. Pyrogenic dissolved environmentally persistent free radicals on microplastics under light irradiation.
organic matter produced at higher temperature is more photoactive: Insight into Environ. Sci. Technol. 53, 8177–8186.
molecular changes and reactive oxygen species generation. J. Hazard. Mater. 425, Zhu, L., Zhao, S., Bittar, T.B., Stubbins, A., Li, D., 2020. Photochemical dissolution of
127817. buoyant microplastics to dissolved organic carbon: rates and microbial impacts.
Yang, T., Luo, J., Nowack, B., 2021. Characterization of nanoplastics, fibrils, and J. Hazard Mater. 383, 121065.
microplastics released during washing and abrasion of polyester textiles. Environ.
Sci. Technol. 55, 15873–15881.