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Science of the Total Environment 722 (2020) 137762

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Science of the Total Environment

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

Fenton aging significantly affects the heavy metal adsorption capacity of


polystyrene microplastics
Mengfan Lang a, Xiaoqin Yu a, Jiaheng Liu a, Tianjiao Xia a, Tiecheng Wang a, Hanzhong Jia a, Xuetao Guo a,b,⁎
a
College of Natural Resources and Environment, Northwest A&F University, Yangling, Shaanxi 712100, China
b
Key Laboratory of Plant Nutrition and the Agro-environment in Northwest China, Ministry of Agriculture, Yangling, Shaanxi 712100, 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

• Two aging methods were used to simu-


late aging characteristics and mecha-
nism of PS.
• Fenton aged the PS was stronger than
H2O2 under the same conditions.
• The sorption of heavy metals to PS was
significantly enhanced after aging.
• The sorption of Fenton aging PS was
higher than H2O2 due to more adsorp-
tion sites.

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

Article history: Microplastics released into the environment undergo a variety of aging processes, however, information about
Received 22 January 2020 the influence of aging on the adsorption behavior of microplastics is limited. In order to better understand the
Received in revised form 4 March 2020 effect of aging polystyrene (PS) on the ability to adsorb heavy metal, H2O2 and Fenton reagent were used to in-
Accepted 4 March 2020
vestigate the aging properties of PS. Aging PS with these two different aging agents at pH = 4 and room temper-
Available online 5 March 2020
ature for the same time. Physical and chemical characterization indicated that aging caused oxidation of the
Editor: Damia Barcelo surface of PS and the formation of surface micro-cracks. Based on the 2D-COS analysis, the aging process
of PS functional groups could occur in the following sequence: 1375 (C-OH) N 1739 (C=O) N 1182 cm−1
Keywords: (C−O−C) N 1716 (O−C=O). The adsorption experiments for Cd2+ with two different concentrations were car-
Microplastic ried out by PS with different aging time at room temperature. The adsorption data showed that the adsorption
Aging capacity of Cd2+ was significantly enhanced after aging compared with pristine PS, and the adsorption capacity
Adsorption of PS after Fenton aging treatment is much stronger than that after H2O2 aging treatment. The kinetic analysis of
Cd2+ the adsorption data indicates that the adsorption process is more consistent with the second-order kinetics than
Fenton treatment
the first-order kinetics, and it is further concluded that the adsorption of Cd2+ by PS is a relatively complicated
process. According to the fitting results of adsorption isotherms, the adsorption process of pristine PS mainly oc-
curs on the surface, but with the continuous aging, more adsorption sites may be exposed on the surface of PS, so
it can be concluded that the adsorption mechanism of Cd2+ by PS is the coexistence of physics and chemistry.
This study indicates aging microplastics may have a significant impact on the destination and migration of
metal contaminants, which deserves to be further concerned.
© 2020 Elsevier B.V. All rights reserved.

⁎ Corresponding author at: College of Natural Resources and Environment, Northwest A&F University, Yangling, Shaanxi 712100, China.
E-mail address: guoxuetao2005@nwafu.edu.cn (X. Guo).

https://doi.org/10.1016/j.scitotenv.2020.137762
0048-9697/© 2020 Elsevier B.V. All rights reserved.
2 M. Lang et al. / Science of the Total Environment 722 (2020) 137762

1. Introduction complex (Illés et al., 2020). The initiator of advanced oxidation process
is free radical (Guo et al., 2018b; Hu et al., 2017). Fenton reagent and
Microplastics, refer to plastic particles with small particle size and H2O2 contain large amounts of free radicals (Jia et al., 2018). Therefore,
textile fibers. At present, there is general consensus on the size of we conducted an artificial accelerated aging experiment, which simu-
microplastics in academic circle (P. Liu et al., 2019). Typically, lated some aging factors under natural environmental conditions with
microplastics are defined as plastics particles with particle size less instruments and reagents (Bandow et al., 2017). Through this experi-
than 5 mm (Arthur et al., 2009). It can be detected in various media in ment, we can investigate the aging characteristics and mechanism of
the environment, including freshwater lake, marine areas, soils and microplastics treated with different aging agents (X. Li et al., 2019;
even polar regions (J. Liu et al., 2019). In recent years, the environmental Zhang et al., 2020). Combined with the adsorption experiment, the in-
pollution caused by microplastics has been widely concerned (Liao and fluence of aging process on the adsorption of heavy metals by
Yang, 2020). Due to its small size and large surface area, microplastics microplastics was clarified, so as to further clarify the behavior of
can pose a direct threat to organisms through adsorption and aggrega- microplastics in the environment and provide theoretical basis for the
tion to the surface of the cell membranes (R. Li et al., 2019). Another po- ecological environmental risk assessment under the condition of com-
tential danger is that microplastics may carry and distribute organic pound pollution.
pollutants as well as heavy metal compounds and transfer them into liv-
ing organisms, which could have serious toxic effects (Y. Li et al., 2019). 2. Experimental section
When plastic debris enter the environment, they can be distributed
in the environment for a long period of time, during which they are sus- 2.1. Materials
ceptible to ultraviolet radiation, thermal degradation, biodegradation,
weathering and oxidation, which may change the properties of plastics PS was purchased from Shanghai Aladdin Biochemical Technology
(Jahnke et al., 2017). These processes are called microplastics aging. For Co., LTD. Cadmium nitrate (Cd (NO3)2, purity N 98%) was purchased
the natural aging process, ultraviolet light is the most important factor from Shanghai Aladdin Biochemical Technology Co., LTD and stored at
(Liu et al., 2012). After ultraviolet radiation, a macroscopic micro- 20 °C below zero. 30% of the hydrogen peroxide (H2O2) and concen-
crack network is formed due to the fracture of polymer, which increases trated nitric acid solution were produced by Sichuan Xilong Chemical
with the extension of radiation time (Guo et al., 2018a; Pandey and Co., LTD, and should be kept in the dark. Ferrous chloride (FeCl2), potas-
Singh, 2001). Some studies have shown that microplastics can undergo sium hydroxide solution (KOH) solution and potassium nitrate (KNO3)
the aging process in the environment, which changes their physical and solution were purchased from national pharmaceutical reagent co. LTD.
chemical properties, thereby affecting the absorption properties, colloi-
dal stability and fluidity of these materials (Guo et al., 2018a; J. Liu et al., 2.2. Fenton aging treatment
2019). With the increase of aging time, the surface area of aging
microplastics is increasing, and its ability to adsorb pollutants is also in- Mix 0.3 mL 30% H2O2 and 19.4 mL ultrapure water in a 200 mL glass
creasing (Pandey and Singh, 2001). Despite many studies on vial, then introduce 0.3 mL 200 mM Fe2+ and 0.5 g PS in turn. Since fer-
microplastics adsorption have been published (Fang et al., 2019; Tang ric hydroxide formed under neutral and alkaline conditions inhibits the
et al., 2020; F. Wang et al., 2019; J. Wang et al., 2019), information on catalytic activity of Fe2+, H2O2 or Fe2+ solutions were pre-regulated to
the effects of microplastics aging on their properties and ultimately on pH 4.0. The mixed liquid was continuously shaken at room temperature
their adsorption behavior is limited. Understanding the sorption inter- (25 ± 2 °C), and 5 mL solution was taken out after shaking 1 d, 3 d, 5 d
actions between contaminants and aged microplastics is still an impor- and 7 d, respectively, and then dried immediately. Finally, the PS solid
tant aspect to evaluate the impact of microplastics on the environment samples before and after aging were obtained for use. Similar experi-
(Hüffer et al., 2018). ments were repeated twice, and the resulting samples were mixed.
Polystyrene (PS) microplastic is one of the most widely used plastics
with an annual output of millions of tons. It is known as the representa- 2.3. H2O2 aging treatment
tive plastic due to its application in various fields (Lambert and Wagner,
2016). Microplastics are easy to undergo different aging processes in the A solution with concentration of 1.5% H2O2 was prepared by mixing
environment, but non-biological mechanisms seem to be more impor- 0.3 mL 30% H2O2 and 19.7 mL ultrapure water in a 200 mL glass vial, and
tant to PS because of its biological durability (L. Li et al., 2019; Zhou the pH of the solution was adjusted to 4.0 for uniform experimental var-
et al., 2019). Some studies have found that, during the aging process, iables. The mixed liquid was continuously shaken at room temperature,
the molecular weight of polymers decreases with the increase of aging and 5 mL solution was taken out after shaking 1 d, 3 d, 5 d, and 7 d, re-
degree, and the morphology of plastic particles also changes with spectively, and then dried immediately. Finally, the PS solid samples be-
aging, which is that the appearance of micro-cracks will be observed fore and after aging were obtained for use. Similar experiments were
on the surface (Pandey and Singh, 2001). Currently, little is known repeated twice, and the resulting samples were mixed.
about the aging degree of microplastics and the potential impact of
aging on pollutant adsorption (Brandon et al., 2016). Consequently, it 2.4. Adsorption kinetics experiment
is essential to study the relationship between the aging performance
of microplastics and the aging degree (Hu et al., 2019; Xia et al., 2019). The experimental method of this experiment was to put the
The purpose of this study is to investigate the aging behaviors of PS microplastics treated by vibrating machine into a glass vial to absorb
microplastics accelerated by Fenton and H2O2 treatments and their ef- Cd2+. First, 1000 mL Cd2+ standard solution with concentration of
fects on heavy metal adsorption after aging. Fenton and H2O2 treatment 2 ppm and 0.5 ppm were prepared. The solution had a pH of 4.0 and
are both advanced oxidation processes (AOPs) (Hu et al., 2019). As a an ionic strength of 0.01 mol of KNO3. Eight samples of 0.01 g
classical redox reaction, Fenton reaction exists in the natural environ- microplastics were weighed with a balance and put into different
ment (Zhang and Chen, 2020). Fenton reaction refers to the oxidation glass bottles and recorded. 20 mL Cd2+ solution with concentration of
of organic substances into inorganic states using a mixture of H2O2 0.5 ppm was added respectively. Prepare three parallel samples and
and Fe2+. It can oxidize large molecules into small ones and small two blank samples for each sample. Then all the samples were shaken
ones into simple inorganic substances such as CO2 and H2O (Farinelli at a constant temperature of 25 ± 2 °C for 0.5 h, 1 h, 3 h, 5 h, 12 h,
et al., 2020). Microplastics are also carbonaceous organic matters, there- 24 h, 36 h and 48 h in the vibrating machine respectively. Take out the
fore, microplastics aging caused by Fenton reaction is common in na- samples after shock at the specified time, 2 mL each time. Repeat the
ture. The factors affecting the natural aging of microplastic are very above experiment, except for changing the concentration of 0.5 ppm
M. Lang et al. / Science of the Total Environment 722 (2020) 137762 3

Fig. 1. SEM images of PS before and after aging.


4 M. Lang et al. / Science of the Total Environment 722 (2020) 137762

Cd2+ solution to 2 ppm. After the sample was taken out, the filtration reagent for 7 days were shown in Fig. 2(a). Fig. 2(b) and (c) shows
membrane was placed in a glass vial and its concentration was mea- FTIR of the original PS and aging with H2O2 and Fenton for 1, 3, 5 and
sured by atomic adsorption spectrometry. 7 days, respectively.

2.5. Adsorption isothermal

The adsorption isothermal experiment was conducted after deter-


mining the shortest time to reach the maximum adsorption quantity
(qe) in the experimental results of adsorption kinetics. Set the concen-
tration gradient to 0.1 ppm, 0.5 ppm, 1 ppm, 1.5 ppm, and 2 ppm for
Cd2+ solution. First, each 20 mL brown glass bottle received the same
mass of PS plastics (0.01 g). Then, different concentrations of Cd2+ solu-
tions were transferred to glass bottles containing PS. All the samples
were placed in thermostatic oscillator at 25 ± 2 °C, and oscillated at
120 rpm for 24 h. After the sample was taken out, it was filtered with
a filtration membrane and its concentration was measured by atomic
adsorption spectrometry.

2.6. Characterization of aging PS

The physical size and morphology of PS before and after aging were
characterized by scanning electron microscopy (SEM) (Nova Nano
SEM-450, FEI). Fourier transform infrared spectroscopy (FTIR)
(Vetex70, Bruker, Germany) was used to identify the functional groups
on PS surface and observe the changes of PS functional groups after
aging. FTIR spectra were recorded in the region of 4000–400 cm−1
with a resolution of 4 cm−1 and 64 scans. The surface chemical compo-
sitions of PS with different aged degree were determined using X-ray
photoelectron spectroscopy (XPS). XPS measurements were performed
on a PHI 5000 Versa Probe spectrometer (ULVAC-PHI Inc., Japan) (P. Liu
et al., 2019), which could detect most essential elements except hydro-
gen on nanometer-thick surface of microplastics. Based on the work of
Noda and Ozaki (Dowrey et al., 2001; Lasch and Noda, 2019; Noda,
2006), information on the composition and changed functional groups
was obtained. FTIR spectra integrated with 2D-COS were used to ob-
serve the changes of aging PS particles. Noda and Ozaki have described
more details about the 2D-COS, which can be found elsewhere (Lasch
and Noda, 2019).

3. Results and discussion

3.1. SEM analysis of PS before and after aging

The effects of aging on the surface structure of PS by SEM are shown


in Fig. 1. Fig. 1(a) represents the pristine PS. It can be roughly inferred
from the figure that the PS particles before aging are uniform spherical
with smooth surface. Fig. 1(b) to (e) is SEM images of PS treated with
H2O2 for 1, 3, 5 and 7 days respectively. As can be seen from these pic-
tures, with the increasing of aging time, the changes of PS surface be-
come more and more obvious (Zhang et al., 2020). The surface of
some PS particles gradually become rough, some of the surface of the
particles have different degrees of folding, and even some individual
particles have broken (Q. Wang et al., 2020). This shows that H2O2
does promote the aging of PS, and these changes increase the surface
area of PS, which is more conducive to absorption of pollutants (Frere
et al., 2016). Fig. 1(f) to (i) represents SEM images of PS aged with
Fenton reagent at 1, 3, 5 and 7 days, respectively. It is not difficult to
see from the Fig. 1 that PS aging with Fenton reagent has a similar effect
to H2O2 aging, and Fenton reagent has a stronger oxidation capacity
than H2O2, thus exposing more surface area to facilitate adsorption
capacity.

3.2. The relationship between aging time and chemical structure


Fig. 2. FTIR images of PS before and after aging; (b) represents the original PS and aging
Fig. 2 shows the oxidation degree of PS surface before and after aging with H2O2 for 1 d, 3 d, 5 d and 7 d respectively; (c) represents the original PS and aging
by FTIR. FTIR of the original PS and PS aging with H2O2 and Fenton with Fenton for 1 d, 3 d, 5 d and 7 d respectively.
M. Lang et al. / Science of the Total Environment 722 (2020) 137762 5

The wavelength of the adsorption peak of some chemical bonds in PS shown in Fig. 3. From XPS spectra, only aliphatic C−H bonds and aro-
can be obtained by referring to the literature (Ma et al., 2019). The ad- matic C−H bonds were observed for pristine PS. However, the aging
sorption peak at 3000–3100 cm−1 is speculated to be the stretching vi- PS showed adsorption peaks that had never been observed before, in-
bration of benzene ring = C−H bond (Fang et al., 2019). The two cluding C−O, C_O and O−C=O bonds, due to the oxidation of the sur-
adsorption peaks near 2922 cm−1 and 2848 cm−1 can be inferred as face. In the early stage of aging, excessive free radicals lead to rapid
the asymmetric stretching vibration of -CH2 and symmetric stretching oxidation of the surface of PS. Therefore, for aging samples, C−O and
vibration of -CH2, respectively, whereas the peaks at 1597, 1498 and O−H bonds are initially formed, and then as the aging degree increased,
1444 cm−1 are attributed to the deformation an skeletal vibrations of some of them change to C_O bonds, and eventually a small part will be
-CH2 (Chia et al., 2012). The spectra of the aged PS shows additional converted to O−C=O bonds. Meanwhile, the relative proportion of al-
bands (F. Wang et al., 2019). iphatic C−H increased, while aromatic C−H decreased. This may be
By analyzing the FTIR figures, it can be seen that no matter which due to the opening of the benzene ring or the volatilization of small
kind of aging agent aging the PS, it did not affect the adsorption charac- molecules (Chen et al., 2017) containing the benzene ring from the PS
teristic peak band of the PS before aging, but only added several new ad- main chain (Liao and Yang, 2020).
sorption peaks. For example, a new characteristic peak of C−OH bond of Thus, the aging process of PS results in the oxidation of certain
phenol appears near the wavelength of 1375 cm−1, which is not ob- bonds, such as C−H and C−C bonds. The structure of PS determines
tained for pristine PS (Hüffer et al., 2018). Furthermore, the O−C=O its physical and chemical properties. Due to wrinkles or cracks gener-
and C_O stretching bands at 1716 cm−1 and the peaks of C−O−C at ated during the aging process, the surface of PS releases more active
1182 cm−1 were observed for the two aged PS. XPS regional spectra sites, which will affect its affinity to pollutants and thus affect the ad-
of C1s of pristine and aged PS in H2O2 and Fenton treatments are sorption process of pollutants.

Fig. 3. XPS regional spectra of C1s of pristine and aged PS in H2O2 and Fenton treatments.
6 M. Lang et al. / Science of the Total Environment 722 (2020) 137762

3.3. 2D-COS maps on the aging process of PS 1182 cm−1, most cross peaks Ψ (x1, 1739) showed a positive signals.
In addition, five negative cross peaks at Ψ(1182, 1375/1716/1739)
2D-COS is based on a set of FTIR spectra in response to certain exter- and Ψ(1739, 1375/1716) were observed, indicating that the change se-
nal disturbances, which can potentially reveal the sequence changes of quence of bands at 1375/1739 cm−1 occurred earlier than those at 1182
different functional groups. 2D-COS analysis is a powerful way to reveal and 1716 cm−1 (Liu et al., 2020). In conclusion, the aging process of PS
the mechanism of interaction between PS and Cd2+, and to better un- could occur in the following sequence: 1375 (C-OH) N 1739 (C=
derstand the dynamic aging process of PS. As can be seen from Fig. 4, O) N 1182 cm−1 (C−O−C) N 1716 (O−C=O) (C. Li et al., 2019; Liu
the distribution of the peak of the synchronous maps under different et al., 2018). Likewise, according to the sign of 2D-COS maps in Fig. 4
aging agents is almost similar. Red indicates a positive correlation and (c) and (d), the sequential order of band changes followed
blue indicates a negative correlation. Darker colors represent higher in- 1375 N 1182 N 1739 N 1716 cm−1.
tensity and therefore have a stronger positive or negative correlation.
In 2D-COS maps, the peaks on the diagonal are called auto-peaks, 3.4. Adsorption kinetics of Cd2+ on PS
while cross peaks are located off the diagonal (Zhou et al., 2017). Five
major auto-peaks were discovered at 1030, 1385, 1460, 1500 and In order to better understand the influence of aging on PS adsorption
1600 cm−1 along the diagonal (T. Wang et al., 2020). capacity and whether its adsorption process conforms to the kinetic
Regardless of the aging agent, peaks at 1385 and 1460 cm−1 involv- law, pseudo-first-order and pseudo-second-order adsorption models
ing in the C−H bond had the highest intensity, followed by the peaks at were used to fit the experimental data. The fitting results of the adsorp-
1500 and 1600 cm−1 involving in the C_C bond of benzene ring, while tion data are shown in Fig. 5 and the relevant adsorption parameters are
the C−H of benzene ring at 1030 cm−1 had the lowest intensity (Zhang listed in Tables S2 and S3. It is not difficult to see from Tables S2 and S3
et al., 2019). In Figs. 4(a) and 2(c), most of cross peaks had a positive that with the increase of aging time, the ability of PS to adsorb Cd2+ is
sign, suggesting that almost all the functional groups underwent syn- increasing, which indicates that the aging PS is more conducive to the
chronously changes during the aging process. Moreover, when Fenton adsorption of Cd2+. By comparing the maximum adsorption quantity
was used as an aging agent, these auto-peaks had higher intensity (qe), it can be found that the qe of the second-order kinetics is closer
than of H2O2. This clearly demonstrates that Fenton has a better aging to the experimental value than the qe of the first-order kinetics, and it
effect than H2O2. Asynchronous correlation spectra can reveal the se- can be concluded that the qe of PS after Fenton aging is much higher
quence of specific chemical reactions during the aging of PS. The asyn- than that of H2O2, so the aging effect of Fenton is much better than
chronous map is anti-symmetric relative to diagonals and therefore do that of H2O2.
not show auto-peak. In Fig. 4(b) and (d), distinctive differences in the According to the adsorption kinetics data analysis, the adsorption
sign of cross peaks were found among two aging agent. As shown in process of Cd2+ by PS can be roughly divided into three stages: from 0
Table S1, in the case of H2O2 aging PS, except for the cross peak at to 6 h to the first stage, in which the PS rapidly adsorbed Cd2+ ions

Fig. 4. (a) and (c) are respectively the synchronous 2d correlation maps of PS after H2O2 and Fenton aging. (b) and (d) are respectively the asynchronous correlation maps of PS after H2O2
and Fenton aging. (For interpretation of the references to color in this figure, the reader is referred to the web version of this article.)
M. Lang et al. / Science of the Total Environment 722 (2020) 137762 7

Fig. 5. (a) and (b) are the first and second order adsorption kinetics fitting diagrams before and after PS aging when Cd2+ concentration is 0.5 ppm. (c) and (d) are the first and second
order adsorption kinetics fitting diagrams before and after PS aging when Cd2+ concentration is 2 ppm. The red line represents the first order dynamics. The blue line represents second
order dynamics.

and reached the maximum adsorption capacity of 70%–80% at 6 h. The 3.5. Adsorption isotherm of Cd2+ on PS
second stage is from 6 h to 24 h, when the adsorption rate is relatively
slow, reaching 90%–100% of qe at 24 h. At the third stage after 24 h, Adsorption isotherm is very vital to design adsorption system.
the adsorption rate is almost 0, which means that the adsorption Therefore, Henry, Freundlich and Langmuir isotherm adsorption models
amount of Cd2+ by PS basically reaches the saturated qe value, from were used to fit the adsorption data (Gao et al., 2019). The fitting results
which the saturated adsorption time can be determined to be 24 h. of isothermal adsorption of Henry model are shown in Fig. 6. As can be
It can be seen from the fitting correlation coefficient (R2) that, com- seen from the Table S4, the parameter k of the three adsorption models
pared with the first-order kinetics, the adsorption of Cd2+ by aging PS is increased with the aging time, and the parameter k of Fenton treatment
more consistent with the pseudo-second-order kinetics model was much larger than that of H2O2 at the same aging time, and the
(Almeida et al., 2019). It is speculated that the adsorption of Cd2+ by fitting coefficient of Henry model is the highest, indicating that Henry
PS is a complex process, which may include both physical adsorption model is more suitable for adsorption experimental data. In addition, ac-
and chemical adsorption (G. Liu et al., 2019; Yin et al., 2018). cording to the poor fitting effect of Langmuir model, it can be seen that

Fig. 6. (a) Henry model adsorption isotherms of PS aged with H2O2 for 1, 3, 5, and 7 days respectively. (b) Henry model adsorption isotherms of PS aged with Fenton for 1, 3, 5, and 7 days
respectively.
8 M. Lang et al. / Science of the Total Environment 722 (2020) 137762

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