Chemosphere 264 (2021) 128556

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Adsorption of three pesticides on polyethylene microplastics in

aqueous solutions: Kinetics, isotherms, thermodynamics, and
molecular dynamics simulation
Hui Li a, Fenghe Wang a, *, Jining Li a, Shaopo Deng b, **, Shengtian Zhang b
a
Jiangsu Provincial Key Laboratory of Materials Cycling and Pollution Control, School of Environment, Nanjing Normal University, Nanjing, 210023, China
b
Nanjing Institute of Environmental Sciences, Ministry of Ecological Environmental (MEE), Nanjing, China

h i g h l i g h t s

Adsorption behavior and mechanism
of pesticides on PE microplastics
were investigated.

Adsorption capacity followed the or-
der
g r a p h i c a l a b s t r a c t
Difenoconazole > Buprofezin > Imidacloprid.

High pH and low NaCl salinity were conducive to the pesticide adsorption.

Adsorption was a spontaneous and endothermic process.

Surface adsorption was the exclusive mechanism for the pesticide adsorption.
of

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

Article history: Microplastics could act as a carrier for pesticides in the water environment and pose a potential risk. This
Received 25 July 2020 study mainly investigated the effects of reaction time, microplastics dosages, pH, and NaCl salinity on the
Received in revised form adsorption characteristics of three pesticides (Imidacloprid, Buprofezin, Difenoconazole) on polyethylene
30 September 2020
(PE) microplastics in aqueous solution. The results showed that high pH and low NaCl salinity were
Accepted 3 October 2020
Available online 7 October 2020
conducive to the adsorption. The adsorption data were well fitted by the Freundlich isotherm model and
the pseudo-first-order kinetics, indicating that it was mainly controlled by physical function. The
Handling Editor: Tamara S. Galloway adsorption capacity of three pesticides on PE microplastics followed the order of
Difenoconazole > Buprofezin > Imidacloprid. The thermodynamic study indicated the adsorption of all
Keywords: pesticides as spontaneous and exothermic processes, and the elevated temperature was favorable to the
Microplastics adsorption. SEM-EDS and FTIR results verified that pesticides were adsorbed on the microplastics but the
Polyethylene adsorption process was mainly controlled by intermolecular Van Der Waals Force and the microporous
Adsorption filling mechanism. Grand Canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulation re-
Pesticides
sults indicated that surface adsorption was the exclusive mechanism for the adsorption of pesticides on
Molecular dynamics simulation
microplastics, and the final adsorption configurations revealed that there were complex interactions

* Corresponding author.
** Corresponding author.
E-mail addresses: wangfenghe@njnu.edu.cn (F. Wang), dsp@nies.org (S. Deng).

https://doi.org/10.1016/j.chemosphere.2020.128556
0045-6535/© 2020 Elsevier Ltd. All rights reserved.
H. Li, F. Wang, J. Li et al.
between the pesticide molecules and the C, H atoms in PE molecules. The results of this study illustrated
that PE microplastics are potential carriers for pesticides in the water environment.
1. Introduction
The widespread use of plastics and their resistance to degra-
dation lead to the accumulation of plastics in the environment (Da
Costa et al., 2016). Plastic debris would continuously degrade into
microplastics as a result of physical, chemical, and microbial effects
(Wang et al., 2017; Hidalgo-Ruz et al., 2012). The microplastics are
defined as plastic particles less than 5 mm in size (Thompson et al.,
2004). Microplastics, as an emerging pollutant, have been almost
ubiquitous in the river, lake, bay, reservoir, sea, and sediment
(Aytan et al., 2016; Di and Wang, 2018; Dean et al., 2018; Hu et al.,
2018; Kapp and Yeatman, 2018; Sutton et al., 2016).
Pesticides could reduce the loss of grain yield and play an
important part in regulating plant growth. During 2018, the pro-
duction of the pesticide in China reached 2.08 million tons,
including 1.40 million tons of exports with $8.07 billion in value
(Yang, 2019). However, the effective utilization rate of pesticides is
usually less than 30%, which means that 70% of pesticides enter the
surrounding environment. There is no doubt that the low utiliza-
tion rate and poor biodegradability of pesticides easily cause the
contamination of water and soil (Zhang et al., 2015). Finally, the
pesticides may enter the human body through the atmosphere,
water, soil, and food, bringing out various chronic or acute diseases
(Jin et al., 2017). In recent years, pesticides have been detected in
surface waters worldwide (Challis et al., 2018; Hladik et al., 2018;
Liu et al., 2015; Struger et al., 2017; Wu et al., 2014), and the
environmental pollution caused by pesticide utilization has
attracted great concern (Morrissey et al., 2015).
Previous studies found that microplastics could carry pollutants
(heavy metals, organic pollutants, antibiotics), affect their mobility,
and cause damage to the ecosystem environment (Hamer et al.,
2014; Massos and Turner, 2017; Velzeboer et al., 2014). Because of
small particle size, large specific surface area, and strong hydro-
phobicity of microplastics, pesticides could be easily adsorbed onto
the microplastics surfaces when microplastics and pesticides
coexist in the water environment (Wang et al., 2017; Wang et al.,
2020). Microplastics carrying pesticides may result in combined
contamination, affecting the distribution of organic pollutants in
water, sediments, and organisms, which could lead to impercep-
tible harm to organisms and even the whole ecosystems (Ling et al.,
2017; Yang et al., 2018). But till now, the research on the driving
process of combined pollution produced by microplastics and
pesticides, the adsorption characteristics of pesticides on micro-
plastics, and the micro-adsorption of pesticides on microplastics at
the molecular level still need to be further studied.
In the present study, polyethylene (PE) microplastics was
selected as it is frequently detected within the scope of the world
(Amrutha et al., 2020; Di and Wang, 2018; Kapp and Yeatman, 2018;
Mak et al., 2020; Mehdinia et al., 2020; Wang et al., 2018a). Three
pesticides (Imidacloprid, Buprofezin, Difenoconazole) which have
been detected in surface waters worldwide in recent years were
selected (Challis et al., 2018; Hladik and Kolpin, 2016; Hladik et al.,
2018; Pazikowska-Sapota et al., 2020; Struger et al., 2017; Xu et al.,
2020; Zhou et al., 2020). The information of three pesticides is
shown in Table S1. The adsorption characteristics of three typical
pesticides (Imidacloprid, Buprofezin, Difenoconazole) on PE
microplastics in aqueous solution environment was investigated. In
2
Chemosphere 264 (2021) 128556
© 2020 Elsevier Ltd. All rights reserved.
particular, the effects of various affecting factors (reaction time,
microplastics dosages, pH, and NaCl salinity) on the adsorption
performance were investigated. The adsorption mechanism be-
tween microplastics and three pesticides were discussed based on
kinetics, adsorption isotherms, thermodynamics, in combination
with SEM, FTIR, Grand Canonical Monte Carlo (GCMC) simulation,
and molecular dynamics (MD) simulation.
2. Materials and methods
2.1. Materials
Certified reference materials of Imidacloprid, Buprofezin, and
Difenoconazole (Beijing-tanmo Co., Ltd., China), PE microplastics
(0.71e0.85 mm) (Beijing institute of standardization, China), HCl
(Sinopharm Chemical Reagent Co., Ltd.), NaOH (Sinopharm Chem-
ical Reagent Co., Ltd), and NaCl (Sinopharm Chemical Reagent Co.,
Ltd) were used in the experiments. All the reagents were analytical
grade without further purification. The stock solutions of all three
pesticides were prepared at 100 mg/L by diluting the certified
reference materials of pesticides with distilled water, and were
stored in brown volumetric flasks in a refrigerator (275 K). A series
of standard solutions (10, 20, 50, 75, and 100 mg/L) were prepared
by diluting the stock solution with distilled water. To remove
organic compounds from microplastics surfaces, microplastics
powders were soaked in ethanol solution for 48 h with a magnetic
stirrer, washed with distilled water, and dried using an oven.
2.2. Adsorption experiments
The effect of reaction time on adsorption behavior was con-
ducted in 20 mL solutions with an initial pesticides concentration of
50 mg/L by adding 0.02 g microplastics at 298 K, and the pesticides
after adsorption experiments were analyzed at time intervals of 2,
5, 8, 11, 14, 17, 20, 23, 26, and 30 h. The effect of microplastic dosages
on adsorption performance was investigated by adding different
amounts of microplastics (0.01, 0.5, 1, 2, and 4 g/L) to 20 mL
pesticide solutions with an initial concentration of 50 mg/L. To un-
derstand the effects of pH on the adsorption behaviors of pesti-
cides, pesticide solutions with a concentration of 50 mg/L were
adjusted to 6, 7, 8, 9, 10 using 1 mol/L NaOH or HCl solutions. NaCl
salinity could affect the coagulation and aggregation state of
microplastics, resulting in the change of the size and surface
properties of microplastics (Velzeboer et al., 2014). The NaCl
salinity of surface water, estuaries, and seawater is 0.05% (Zhang
et al., 2017), 2% (Jiang et al., 2016), and 3.5% (Xu and Gao, 2018),
respectively. Therefore, in NaCl salinity-affected adsorption exper-
iments, 0.05, 2, 3.5 g of NaCl were added to 100 mL of 50 mg/L
pesticide solutions, respectively, and the salinity of the solutions
was adjusted to 0.05, 2, and 3.5%. Experiments for the adsorption
isotherms were performed by adding 0.02 g PE microplastics to
20 mL pesticides solutions with different concentrations
(10e150 mg/L) at 298 K. The adsorption thermodynamics experi-
ment was conducted by 0.02 g PE microplastics (0.02 g) to pesti-
cides solutions (20 mL, 50 mg/L) at temperatures of 278 K, 288 K,
and 298 K. All experiments were conducted in three replicates.
All mixtures were added into 50 mL glass centrifuge tubes
H. Li, F. Wang, J. Li et al. Chemosphere 264 (2021) 128556

wrapped with aluminum foil that prevents light-induced decom- curve.

position of pesticides. All tubes in the experiments were fixed on a
rotating mixer to ensure intensive mixing. After experiments, a pH 2.5. Adsorption thermodynamics
meter (PHSe3C, Raytheon, Shanghai Jingyan, China) was used to
immediately determine the pH values of aqueous solutions. All The thermodynamic calculation was performed by using the
solutions samples were filtered through 0.22 mm organic system Van’t Hoff equation (Eqs. (6)e(8)).
filter membranes before analysis. A UV spectrophotometer (UV-
2550, Shimadzu, Japan) was employed to analyze the pesticide dG ¼  RTlnK (6)
concentrations in all experiments. The information on the standard
curve of three pesticides is shown in the SI material. dG ¼ dH  T dS (7)
The adsorption capacity of microplastics was calculated by Eq.
(1).
dH dS
lnK ¼  þ (8)
ðC  Ct ÞV RT R
Qt ¼ 0 (1)
m where K is the equilibrium constant, R is the gas constant, 8.314 J/
where Qt is the adsorption capacity of microplastics (mg/g), C0 is the (mol$K), T is the temperature (K), DG is the Gibbs free energy
initial concentration of pesticides (mg/L), Ct is the residual concen- change (J/mol); DH is the enthalpy change (J/mol); DS is the entropy
tration of pesticides at any time (mg/L), V is the volume of pesticides change (J/(mol$K)).
solution (L), and m is the mass of microplastics (g).
2.6. Characterization of microplastics
2.3. Adsorption kinetic model
SEM-EDS (ZEISS, GeminiSEM 500, Germany and EDAX, GENESIS,
United States of America) was used to obtain the surface
The adsorption kinetic model could determine the relationship
morphology of microplastics and to determine the element distri-
between adsorption time and adsorption capacity and could be
butions in a micro-area. Fourier transform infrared spectrometer
used to analyze the adsorption mechanism of pesticides on
(FTIR) (Thermo, Nicolet IS5, United States of America) was used to
microplastics. The pseudo-first-order kinetics (Eq. (2)) and pseudo-
detect the types of functional groups contained in substances.
second-order kinetics (Eq. (3)) were used in this study.

lnðQe  Qt Þ ¼ lnQe  K1 t (2) 3. Results and discussions

t 1 t 3.1. Effects of reaction time

¼ þ (3)
Qt K2 Qe2 Qe
Fig. 1 shows the adsorption of pesticides by microplastics with
where Qe is the unit adsorption capacity of microplastics at increasing reaction time. The adsorption of Imidacloprid increased
adsorption equilibrium (mg/g), Qt is the unit adsorption capacity of rapidly at 2e8 h, then the rate of adsorption slowed down, and
microplastics at any time (mg/g), K1 is the pseudo-first-order ki- equilibrium was reached at about 30 h. The adsorption of Bupro-
netics rate constant (1/h), K2 is the pseudo-second-order kinetics fezin on microplastics increased rapidly in the range of 8e26 h and
rate constant (g/(mg$h)), and t is the adsorption time (h). reached equilibrium at about 30 h. The adsorption of difenocona-
zole by microplastics increased rapidly in the early period of
0e20 h, and the adsorption tended to be flat after 20 h, then the
2.4. Adsorption isotherms model
adsorption reached dynamic equilibrium in about 30 h. Therefore,
30 h was selected as the equilibrium time in the following
The Langmuir model assumes that the surface of the adsorbent
is uniform and there are no effects between the adsorbents. It is
single layer adsorption, that is, the adsorption occurs only on the
outer surface of the adsorbent (Eq. (4)). The Freundlich equation is
an empirical adsorption isothermal equation for uneven surface,
which could describe the adsorption mechanism of the uneven
surface and is applicable for low concentration adsorption (Eq. (5)).

Ce 1 Ce
¼ þ (4)
Qe Qm KL Qm

1
lnQe ¼ lnKF þ lnCe (5)
n

where Qm is the monolayer saturated adsorption capacity (mg/g), Ce

is the equilibrium mass concentration of pesticides (mg/L), KL is the
Langmuir adsorption equilibrium constant (L/mg), Qe is the equi-
librium adsorption capacity of microplastics (mg/g), KF is the
Freundlich adsorption equilibrium constant, and n is the concen-
tration index, which is used to indicate the adsorption capacity and
the surface evenness of the adsorbent. If n is in the range of 2e10, Fig. 1. Effects of adsorption time on the adsorption of pesticides onto microplastics
the reaction is favorable for adsorption. Qm, KL, KF, and n could be (microplastics amount ¼ 0.02 g, V ¼ 20 mL, initial concentration of pesticides ¼ 50 mg/
obtained by calculating the slope and intercept of the linear fitting L and temperature ¼ 298 K).

3
H. Li, F. Wang, J. Li et al. Chemosphere 264 (2021) 128556

Fig. 2. Adsorption kinetics, (a) pseudo-first-order kinetics, (b) pseudo-second-order kinetics (microplastics quality ¼ 0.02 g, V ¼ 20 mL, initial concentration of pesticides ¼ 50 mg/L,
adsorption time ¼ 30 h and temperature ¼ 298 K).

Table 1
Adsorption kinetic model and related parameters.

Pseudo-first-order kinetics Pseudo-second-order kinetics

Pesticides K1 (1/h) Qe (mg/g) R2

K2 (g/(mg$h)) Qe (mg/g) R2

Imidacloprid 0.1477 3.537 0.9534 162.5 0.1325 0.1178

Buprofezin 0.1619 3.607 0.9982 0.01455 5.008 0.8186
Difenoconazole 0.1343 13.05 0.9304 0.0001304 55.55 0.1637

experiments. The adsorption capacities at equilibrium followed the

order of Difenoconazole > Buprofezin > Imidacloprid. As shown in
Fig. 2 and Table 1, the pseudo-first-order model was more suitable
for describing the adsorption kinetics process of three pesticides on
PE microplastics. This indicates that physical adsorption instead of
chemisorption was the leading force for the adsorption of pesti-
cides on microplastics (Li et al., 2017). These results were incon-
sistent with the study of Wang et al. (2020), in which the adsorption
of five pesticides on PE agricultural soil film-derived microplastics
were investigated and the experimental data fitted better with the
pseudo-second-order model.

3.2. Effects of microplastics dosages

As shown in Fig. 3, the adsorption capacity of pesticides

decreased sharply with increasing the microplastics dosages. The
total surface area of the microplastics increases with the micro-
plastics dosages, therefore, the number of blank adsorption sites on
the surface of microplastics increases, resulting in the decrease of
microplastics unit adsorption (Li et al., 2018). Besides, the concen-
tration of pesticides in the solution decreased gradually with the
adsorption of microplastics. According to Fick’s law, the mass
transfer force is proportional to the concentration of the absorbed
component, therefore, the mass transfer force in the solution was
reduced, resulting in weakened solute diffusivity and the reduction
adsorption of pesticides by microplastics (Zhang et al., 2018).
Consequently, the microplastic dosage at 0.25 g/L was applied for
further adsorption experiments in this study.
3.3. Effects of pH
As depicted in Fig. 4, the adsorption of pesticides on micro-
plastics increased with pH range of 6e10. The pKa of Imidacloprid
was 7.16, and the molecular state of Imidacloprid decreased as the
pH value increased from 6 to 10 (Fig. S2). We suggested that the
ionic state of Imidacloprid was beneficial to the Imidacloprid
4
Fig. 3. Effects of microplastics dosages on the adsorption of pesticides onto micro-
plastics (microplastics amount ¼ 0.005, 0.01, 0.02, 0.04, 0.08 g, V ¼ 20 mL, initial
concentration of pesticides ¼ 50 mg/L, adsorption time ¼ 30 h and
temperature ¼ 298 K).
adsorption onto PE microplastics. In comparison, 99% of Buprofezin
and Difenoconazole were ionic state at pH values ranging from 6 to
10 (Fig. S2). Wang et al. (2018b) suggested that high alkalinity
would cause erosion on the surface of the microplastics and enlarge
the surface area of microplastics, thus increasing the adsorption of
pesticides by microplastics. Besides, Bakir et al. (2014) confirmed
that low pH could increase the desorption of pollutants from the
surface of microplastics, thereby reducing the adsorption of pesti-
cides by microplastics.
3.4. Effects of NaCl salinity
The adsorption capacities of three pesticides on PE microplastics
H. Li, F. Wang, J. Li et al.
Fig. 4. Effects of pH on the adsorption of pesticides onto microplastics. (pH ¼ 6.0, 7.0,
8.0, 9.0, 10.0, microplastics amount ¼ 0.02 g, V ¼ 20 mL, initial concentration of
pesticides ¼ 50 mg/L, adsorption time ¼ 30 h and temperature ¼ 298 K).
Fig. 5. Effects of NaCl salinity on the adsorption of pesticides onto microplastics (NaCl
salinity ¼ 0.05, 2, 3.5%, microplastics amount ¼ 0.02 g, V ¼ 20 mL, initial concentration
of pesticides ¼ 50 mg/L, adsorption time ¼ 30 h and temperature ¼ 298 K).
Fig. 6. Adsorption isotherms, (a) Langmuir, (b) Freundlich (microplastics amount ¼ 0.02 g, V ¼ 20 mL, initial concentration of pesticides ¼ 50 mg/L, adsorption time ¼ 30 h and
temperature ¼ 298 K).
5
Chemosphere 264 (2021) 128556
decreased with the increase of NaCl salinity (Fig. 5), and the extent
of decrease followed the order: Buprofezin > Difenoconazole >
Imidacloprid. This was consistent with the previous study (Wang
et al., 2020) where high NaCl concentration caused decreases in
the adsorption capacity of pesticides on microplastics from agri-
cultural polyethylene films. However, it has been reported that the
increase of solution salinity can improve the adsorption of hydro-
phobic organic pollutants on microplastics (Fei et al., 2015; Ma
et al., 2019). The NaCl addition might produce strong hydration of
electrolyte ions, reducing the effective water volume in the solvent
and salting out of the pesticides, after which the pesticides would
be easily adsorbed onto microplastics through distribution. Also,
the presence of NaCl will partially neutralize the negative charge at
the adsorption site on the surface of microplastics, thus reducing
the electrostatic interaction between PE microplastics and pesti-
cides. These inferences were unable to explain our results. We
suggested that high NaCl salinity resulted in the increase of Naþ
concentration nearby the surface of microplastics, and the elevated
Naþ might compete with undissociated pesticides for adsorption
sites thereby excluding pesticide attachment (Huang et al., 2019;
Liu et al., 2020).
3.5. Adsorption isotherms
The Langmuir and Freundlich models were used to fit the
adsorption processes of three pesticides on PE microplastic (Fig. 6
and Table 2). The Langmuir model had a poor linear fit, indicating
that the process of pesticides by microplastics is not molecular
adsorption on the uniform surface (Fig. 6a). The Freundlich model
fitted the adsorption data well (Fig. 6b), which was consistent with
previous studies (Fang et al., 2019; Wang et al., 2020). It indicated
that the adsorption processes were multilayer adsorption (Fig. 6b).
The value of n in the Freundlich model has been used to determine
the type of adsorption process. Adsorption is a chemical process
when n is less than 1, and a physical process when n is greater than
1. In the present study, the n values were 3.113, 3.804, and 3.082 for
Imidacloprid, Buprofezin, and Difenoconazole, respectively, and
Table 2
Adsorption isotherms model and related parameters.
Langmuir Freundlich
Pesticides Qm KL R2 KF n R2
Imidacloprid 2.630 0.03036 0.9280 0.4234 3.113 0.9566
Buprofezin 1.892 0.04745 0.9851 0.4441 3.804 0.9940
Difenoconazole 2.365 0.03115 0.9425 0.3796 3.082 0.9509
H. Li, F. Wang, J. Li et al. Chemosphere 264 (2021) 128556

Table 3 water at different seasons in the Yangtze River, China. As a result,

Adsorption thermodynamics and related parameters. we suggested that the summer season favors the association of
Pesticides T (K) DG (kJ/mol) DH (kJ/mol) DS (J/(mol$K)) these three pesticides with PE microplastics, which further affects
Imidacloprid 278 6.16 7.08 45.56
the mobility and transformation of pesticides in the water
288 6.27 environment.
298 6.49
Buprofezin 278 4.79 4.15 31.61
3.7. Characterization of microplastics
288 4.96
298 5.26
Difenoconazole 278 4.89 4.66 33.87 As shown in Fig. 7, there were irregular structures such as folds
288 5.14 and fractures on the surface of PE microplastic. It was expected that
298 5.42 these irregular structures on the surface of microplastics provide
sufficient adsorption sites for pesticides. It was found that there are
freeze-dried particles on the surfaces of PE microplastics after
thus they represented a physical adsorption process between three pesticide adsorption. Fig. S3 illustrates the EDS analysis of several
pesticides and PE microplastics. Besides, the results suggested that selected dots. The composition elements of PE microplastics are C
the adsorption processes of pesticides on microplastics were and H, while Cl was not displayed. The composition elements of
favorable, and the adsorption will be enhanced with the increased Imidacloprid are C, H, N, O, and Cl. The existence of Cl in Fig. S3 (f)
concentration of pesticides in the solution (Kong et al., 2016). and (g) demonstrated that Imidacloprid was adsorbed on the
microplastics. The composition elements of Buprofezin are C, H, N,
3.6. Adsorption thermodynamics S, and O, while the composition elements of Difenoconazole are C,
H, N, O, and Cl. Similarly, elemental analysis proved that Buprofezin
Table 3 shows the values of the thermodynamic parameters. The and Difenoconazole were adsorbed on microplastics.
DG value was negative, and the absolute values of DG increased as FTIR spectra of microplastics, pesticides, and pesticides-
the adsorption temperature increased. This indicated that the adsorbed microplastics are shown in Fig. S4. The characteristic
adsorption was spontaneous. The DH value was positive, indicating infrared absorption peaks of PE microplastics were as follows:
that the adsorption process was endothermic. The DS value was 3449 cm1 as OeH stretching vibration; 2921 cm1 and 2850 cm1
positive, indicating the randomness of the microplastic/pesticide as CeH stretching vibration; 1468 cm1 and 719 cm1 as CeH in-
interface increased with temperature during the adsorption pro- plane and out-of-plane deformation vibration, respectively. None
cess. All together, increasing the temperature favors the adsorption of the new peaks appeared after pesticide adsorption, indicating
of three pesticides on PE microplastics, and this is in accord with a that no new covalent bonds were formed during the adsorption
previous study (Wang et al., 2020). The temperatures of 278 K, process. As discussed above, the adsorption of pesticides on PE
288 K, and 298 K in the present study referred to the temperature of microplastics was probably physical adsorption. Hendrickson et al.

Fig. 7. SEM images of microplastics (a), microplastics adsorbed Imidacloprid (b), microplastics adsorbed Buprofezin (c), and microplastics adsorbed Difenoconazole (d).

6
H. Li, F. Wang, J. Li et al.
(2018) also suggested that the adsorption behaviors that happened
on microplastics were mainly affected by the intermolecular Van
Der Waals Force and the microporous filling mechanism. As a
result, the content of pesticides adsorbed on the microplastics was
likely to be too low to be detected by FTIR analysis.
3.8. GCMC-MD simulation
Materials Studio (MS) software was used to simulate the mo-
lecular dynamics of the pesticide adsorption on microplastics. The
model construction for PE microplastics and pesticides was
described in the SI material. The “Sorption” and “Forcite” module of
MS software was used for Grand Canonical Monte Carlo (GCMC)
simulation and molecular dynamics (MD) simulation, respectively.
The details are described in the SI material. There are two ways for
the pesticide adsorption on PE microplastics: the internal adsorp-
tion and the surface adsorption. The key point for internal
adsorption was whether there was enough space in PE to accom-
modate pesticide molecules. It could be pre-judged in advance by
comparing the occupied volume of pesticide molecules with the
internal free volume of PE. In this study, the total volume of PE
model was 26711.6 Å3, and the free volume was 4752.2 Å3. The
occupied volume of pesticide molecules was 212.3 Å3 (Imidaclo-
prid), 309.5 Å3 (Buprofezin), and 350.0 Å3 (Difenoconazole).
Although the total free volume inside the PE model reached
4752.2 Å3, the volume of a single void may not be able to accom-
modate a pesticide molecule, which needed to be further verified
by simulating the isothermal isobaric adsorption of pesticide mol-
ecules in PE model. The adsorption amount and energy obtained by
simulating the adsorption of three pesticide molecules in PE were
Fig. 8. Adsorption process of an Imidacloprid (a), Buprofezin (b), and Difenoconazole (c) molecule on PE surface.
7
Chemosphere 264 (2021) 128556
zero. Therefore, the surface adsorption should be considered in the
adsorption mechanism of three pesticide molecules on PE.
The results of MD calculation showed that the three pesticides
could be adsorbed on PE surface and reached equilibrium after 200
ps (Fig. 8). The final adsorption configurations showed that there
were complex interactions between the pesticide molecules and
the C, H atoms in PE molecules (Fig. 9). The adsorption energy
followed the order of Buprofezin (25.0 kcal/
mol) > Difenoconazole (22.4 kcal/mol) > Imidacloprid
(20.2 kcal/mol). The adsorption energies of three pesticides have
no big differences and the results of theoretical simulation tally
with the data of adsorption thermodynamics within the error
range. It shows that MD simulation could be used as a tool to study
the micro-adsorption behavior of three pesticide molecules on PE.
4. Conclusions
This study investigated the adsorption properties of three pes-
ticides (Imidacloprid, Buprofezin, Difenoconazole) by PE micro-
plastics in aqueous solutions. Elevated pH and low NaCl salinity
favored the adsorption of pesticides on microplastics. The adsorp-
tion process of pesticides on microplastics followed the Freundlich
isotherm model and the pseudo-first-order kinetics, indicating that
it was multilayer adsorption and mainly controlled by physical
action. Adsorption thermodynamic studies showed that high
temperature was conducive to adsorption. SEM-EDS, FTIR, and
GCMC-MD simulation results verified the adsorption of pesticides
on PE microplastics surfaces but the dominant adsorption mecha-
nism was surface adsorption. This study simulated the adsorption
process of pesticides on microplastics in the water environment,
H. Li, F. Wang, J. Li et al.
Fig. 9. The final adsorption configurations of pesticide molecules on the surface of PE (The pink dotted lines expressed the close contact of atoms less than 3 Å). (For interpretation
of the references to colour in this figure legend, the reader is referred to the Web version of this article.)
which may provide a reference for further studying the environ-
mental behavior of microplastics and pesticides in the water
environment.
CRediT author statement
Hui Li, Conceptualization, Methodology, Investigation, Formal
analysis, Validation, Writing - original draft, Writing - review &
editing. Fenghe Wang, Conceptualization, Methodology, Writing -
review & editing, Funding acquisition, Supervision. Jining Li,
Methodology, Writing - review & editing, Visualization. Shaopo
Deng, Methodology, Writing - review & editing, Supervision.
Shengtian Zhang: Methodology, Writing - review & editing.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgments
We acknowledge the financial support received from the Na-
tional Natural Science Foundation of China (41473071), the Six
Talent Peaks Project in Jiangsu Province (JNHB-008), the Natural
Science Foundation of Jiangsu Province (16KJA610001), and the
Priority Academic Program Development of Jiangsu Higher Edu-
cation Institutions (PAPD, 164320H116) for this study. We thank
Prof. Dr. X.D. Gong for his help in MD simulation.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.chemosphere.2020.128556.
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