Environmental Pollution 265 (2020) 114926

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Environmental Pollution
journal homepage: www.elsevier.com/locate/envpol

Adsorption of chlorophenols on polyethylene terephthalate

microplastics from aqueous environments: Kinetics, mechanisms and
influencing factors*
Zheming Liu , Qingdong Qin , Zhixian Hu , Lu Yan , Un-Io Ieong , Yan Xu *
Department of Municipal Engineering, School of Civil Engineering, Southeast University, Nanjing, Jiangsu, 210096, China

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

Article history: Microplastics have received growing attention as carriers of organic pollutants in the water environment.
Received 14 February 2020 To better understand the contribution of hydrophobic interaction, hydrogen-bonding interaction, p-p
Received in revised form interaction and electrostatic interaction on the adsorption of hydrophilic compounds on microplastics
31 May 2020
and their adsorption behavior in natural waters, polyethylene terephthalate (PET, <150 mm) was used as
Accepted 31 May 2020
an adsorbent and 4-chlorophenol (MCP), 2,4-dichlorophenol (DCP) and 2,4,6-trichlorophenol (TCP) were
Available online 6 June 2020
used as adsorbates. The results of batch adsorption experiments showed that chlorophenols (CPs)
reached adsorption sites of PET through film diffusion and intra-particle diffusion. pH greatly affected the
Keywords:
Microplastics
adsorption capacity. Hydrophobic interaction was the main adsorption mechanism of undissociated CPs
Adsorption on PET. Hydrogen-bonding interaction was also an adsorption mechanism between undissociated CPs
Chlorophenols and PET, and the contribution of hydrogen-bonding interaction to adsorption decreased with the in-
Diffusion crease of chlorine content. Meanwhile, the increase of chlorine content was favorable to the hydrophobic
NOM interaction between undissociated CPs and PET. However, higher chlorine content CPs with lower pKa
values tended to dissociate at neutral pH condition and resulted in stronger electrostatic repulsion with
PET. The increase of solution ionic strength and fulvic acid content negatively affected the adsorption of
DCP and TCP on PET, but did not show significant impacts on MCP adsorption. Similarly, the adsorption
capacity obtained using Taihu lake water and Bohai seawater as matrices was much lower than that using
laboratory water for both DCP and TCP, while the adsorption coefficient (Kd) of MCP remained at
approximately 10.6 L/kg to 11.4 L/kg in the three different solution matrices. The Kd values exhibited
using natural water matrices consistently followed the order of DCP > MCP > TCP. This study provides
insights into the fate of CPs in the presence of microplastics and suggests that the potential risks posed by
CPs and microplastics to aqueous ecosystems merit further investigation.
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction
The threat of plastic debris to the marine environment has been
recognized since the end of the 20th century (Derraik, 2002). In the
past decade, microplastics, plastic particles smaller than 5 mm,
have attracted increasing attention due to their evidenced potential
adverse effects on aquatic ecosystems (Arthur et al., 2009;
Thompson et al., 2004). The two primary sources of microplastics
*
This paper has been recommended for acceptance by Eddy Y. Zeng.
* Corresponding author.
E-mail addresses: seulzm@163.com (Z. Liu), qinqingdong@seu.edu.cn (Q. Qin),
huzhixian97@163.com (Z. Hu), luluyan_seu@163.com (L. Yan), 1031680789@qq.
com (U.-I. Ieong), xuxucalmm@seu.edu.cn (Y. Xu).
are believed to be the direct introduction with runoff and weath-
ering breakdown of meso- and macroplastics debris (Andrady,
2011), resulting in a tremendous number of microplastic particles
in aquatic environments (Rezania et al., 2018), terrestrial soil sys-
tems (Wang et al., 2020) and atmosphere (Chen et al., 2020). The
uptake of microplastics by marine organisms has been observed
(Rezania et al., 2018) and is proven to have negative physical im-
pacts on their bodies (Wright et al., 2013). Moreover, microplastics
may enter the human body through commonly consumed items
and the environment (Cox et al., 2019) and pose risks to human
health (Lehner et al., 2019; Wright and Kelly, 2017). Given their
hydrophobic properties, microplastics can both carry organic pol-
lutants (Mato et al., 2001; Van et al., 2012) and release them into
the environment (Teuten et al., 2009). Also, the interaction of

https://doi.org/10.1016/j.envpol.2020.114926
0269-7491/© 2020 Elsevier Ltd. All rights reserved.
2 Z. Liu et al. / Environmental Pollution 265 (2020) 114926
microplastics and organic contaminants can aggravate the toxicity
of some chemicals and/or enhance bioaccumulation (Deng et al.,
2018; Ma et al., 2016; Qiao et al., 2019).
Microplastics are capable of adsorbing a variety of anthropo-
genic organic pollutants from the environment (Wang et al., 2018).
The adsorption behaviors of the target organic pollutants onto
microplastics were determined by the properties of microplastics,
organic pollutants as well as water matrices (Tourinho et al., 2019;
Yu et al., 2019). Generally, smaller microplastics, having a larger
specific surface area, tend to exhibit a higher adsorption capacity
(Ma et al., 2019; Zhan et al., 2016). However, when the size reduces
to the nanoscale, the decrease of adsorption capacity caused by the
aggregation of nanoparticles cannot be ignored (Wang et al., 2019).
For the same polymer type, the decrease of crystallinity usually
leads to an increase in the adsorption capacity of microplastics to
hydrophobic organic pollutants (Guo et al., 2012). But for distinct
polymer types, the property of monomer is the main influencing
factor. For instance, the benzene rings of polystyrene microplastics
can produce p-p interaction with an aromatic organic compound to
favor adsorption (Hüffer and Hofmann, 2016; Liu et al., 2019b).
Hydrophobic organic pollutants with higher octanol-water parti-
tion coefficients appear to be more readily adsorbed to micro-
plastics (Velzeboer et al., 2014; Wang et al., 2018). However, the
speciation of dissociable hydrophilic organic contaminants is
commonly pH-dependent, which ultimately affects the interaction
between microplastics and pollutants (Ma et al., 2019; Zhang et al.,
2018). Under certain conditions, microplastics with oxygen-
containing functional groups can readily form hydrogen bonds
with some hydrophilic organic pollutants (Liu et al., 2019b; Zhang
et al., 2018). In addition, ionic strength (Liu et al., 2019a; Ma
et al., 2019), the content of natural organic matter (NOM) (Xu
et al., 2018a; Zhang et al., 2018) as well as temperature (Liu et al.,
2018) could affect the adsorption in varying degrees.
Chlorophenols (CPs) are a class of chlorinated aromatic com-
pounds commonly used for industrial and agricultural production
(Olaniran and Igbinosa, 2011) and killing schistosome intermediate
host snails (Zheng et al., 2012). CPs were found to exhibit chronic
toxic effects on biota (Ge et al., 2017) and have the potential to
cause histopathological changes, mutagenic and carcinogenic ef-
fects (Igbinosa et al., 2013). Among the CPs, 2-chlorophenol, 2,4-
dichlorophenol, 2,4,6-trichlorophenol, and pentachlorophenol are
listed in the Priority Pollutant List of the US Environmental Pro-
tection Agency (ATSDR, 2007). Apart from the direct release, other
sources of CPs include chlorination of humic acid, biodegradation of
some pesticides and herbicides, disinfection of water by chlori-
nating, and so on (Czaplicka, 2004). CPs are ubiquitous in the
aquatic environment (Jensen, 1996). The concentrations of CPs in
surface water generally range from 0.005 to 20 mg/L (Gao et al.,
2008; Ge et al., 2017). Notably, in some treated industrial waste-
water, the concentration can even reach 1.5e3.0 mg/L (Stepanova
et al., 2000). In natural conditions, the degradation of these chlo-
rinated compounds cannot proceed readily, and the degradation
mechanisms are very complex (Ge et al., 2017; Lin et al., 2019).
Moreover, under some circumstances, CPs may even become the
precursor of polychlorinated biphenyls and dioxins (Czaplicka,
2004).
Polyethylene terephthalate (PET), having excellent mechanical
and thermal properties, is widely used in making textile fibers and
packaging with an annual worldwide production of over 50 million
tons (Bornscheuer, 2016; Taniguchi et al., 2019). PET is difficult to
biodegrade, though its monomers are joined together via ester
bonds (Taniguchi et al., 2019). A previous study reported that more
than 1900 fibers were released per garment wash and 78% of fibers
found in marine sediments and sewage were PET fibers (Browne
et al., 2011). Even a single PET plastic teabag could release
approximately 11.6 billion microplastics and 3.1 billion nanoplastics
at brewing temperature (95
C) (Hernandez et al., 2019).
Hydrophobic interaction, hydrogen-bonding interaction and p-
p interaction are the adsorption mechanisms of undissociated hy-
drophilic compounds on microplastics (Tourinho et al., 2019; Yu
et al., 2019). However, the contribution of these mechanisms to
adsorption remains unknown. To better understand these adsorp-
tion mechanisms and other possible adsorption mechanisms, PET
and three typical CPs (4-chlorophenol, 2,4-dichlorophenol and
2,4,6-trichlorophenol) were selected as adsorbent and adsorbate,
respectively. The diffusion process of CPs to PET was studied by
adsorption kinetics. Adsorption isotherms, the effects of solution
pH and chlorine content of CPs were investigated to explore the
adsorption mechanisms. In addition, the effects of ionic strength
and NOM on adsorption were also investigated. Furthermore, to
better understand the adsorption behaviors in complex aquatic
environments, the adsorption of CPs by PET under natural water
matrices were also examined and compared.
2. Materials and methods
2.1. Materials and characterization
4-Chlorophenol (MCP) (purity > 99%), 2,4,6-trichlorophenol
(TCP) (purity > 99%) and fulvic acid (purity > 90%) were pur-
chased from Aladdin Bio-Chem Technology Ltd (Shanghai, China).
2,4-dichlorophenol (DCP) (purity > 99.5%) was purchased from
Macklin Biochemical Ltd (Shanghai, China). The polyethylene
terephthalate (PET) powder (guaranteed reagent, < 150 mm) was
provided by DuPont (USA). Acetonitrile was purchased from TEDIA
(HPLC grade, USA). Other chemicals were obtained from Sinopharm
Group (Shanghai, China). Ultrapure water (>18.2 MU cm, Merck
Millipore, Germany) was used in the experiments unless otherwise
specified.
The microscopic surface structure of PET was characterized by
scanning electron microscope (SEM, EVO 18, Carl Zeiss AG, Ger-
many). The surface area and pore size distribution were analyzed by
N2 adsorption with a specific surface area and pore size analyzer
(ASAP2020M, Micromeritics Instrument Corp., USA) using the
Brunauer-Emmett-Teller (BET) method and the Barrett-Joyner-
Halenda (BJH) technique, respectively. The surface functional
groups were determined by attenuated total reflection Fourier-
transform infrared spectroscopy (FTIR, Nicolet iS50, Thermo
Fisher Scientific, USA). The zeta potentials with the change of pH
and the isoelectric point (IEP) of PET were measured using zeta
potential analyzer (Zetasizer Nano ZS, Malvern Panalytical, UK).
2.2. Analytical method
The CPs were analyzed by ultra-performance liquid chroma-
tography (UPLC, ACQUITY UPLC H-Class PLUS, Waters Corp., USA)
equipped with a UV detector and reversed-phase column (BEH C18
100 mm  2.1 mm, 1.7 mm, Waters Corp., USA). The mobile phase
consisted of ultrapure water containing 0.5% acetic acid and
acetonitrile with a ratio of 45:55 (v:v) for MCP and DCP; and 40:60
(v:v) for TCP. The flow rate was 0.3 mL/min and the column tem-
perature was 35
C. The UV detector wavelength was set at 285 nm
for MCP and DCP, and 292 nm for TCP.
2.3. Adsorption experiments
CPs were dissolved in ultrapure water for the preparation of
200 mg/L stock solution and kept in the dark at 4
C. All the ex-
periments were conducted in 30 ml amber borosilicate vials with
PTFE gaskets containing 0.5 g of PET and 20 mL of specific solutions
 Z. Liu et al. / Environmental Pollution 265 (2020) 114926
unless otherwise specified. To inhibit microbial activity, NaN3 was
added to all solutions at a final concentration of 25 mg/L. The initial
pH was adjusted by adding 0.1 M of HCl or NaOH solutions and the
ionic strength was adjusted by adding 1 M of NaCl solution. And
then, the vials were mixed thoroughly at 2500 rpm for 30 s and
shaken continuously at 25 ± 1
C and 150 rpm. All experiments
were conducted in duplicate and the blank controls without PET
were also prepared. All samples were filtered through 0.22 mm
syringe filters (polyethersulfone, AB-GEEKS, China) and 1.5 mL
subsamples were collected to analyze the residual CPs. The first
10 mL filtered solution was discarded to minimize the influence of
membrane adsorption (less than 1%).
In the adsorption kinetic experiments, 20 mL of 5 mg/L of CPs
solutions containing 0.5 g of PET were used and subsamples were
collected destructively at different time intervals (0, 0.17, 0.33, 0.5,
0.75, 1, 2, 4, 8, 12, 24, 36, 48 and 72 h). Adsorption isotherms were
determined using 20 mL different concentrations (2, 3.5, 5, 10 and
20 mg/L) of CPs with 0.5 g of PET. Samples were collected and
analyzed until the adsorption equilibrium was reached. The equi-
librium time was determined by the previous kinetic experiments.
To explore the effect of pH on adsorption, the initial pH of CPs
solution was adjusted to 2.0, 3.0, 4.0, 6.0, 8.0 and 10.0 respectively.
Similarly, CPs with different background ionic strengths (z 0, 0.01,
0.05 and 0.1 M) were prepared to investigate the influence of ionic
strength on adsorption. Fulvic acid was pre-dissolved and passed
through a 0.45 mm membrane (nitrocellulose, Whatman, UK) to
prepare a 440 mg/L fulvic acid stock solution based on the total
Fig. 1. (a) SEM images, (b) N2 adsorption-desorption isotherms with inset the corresponding pore distribution curves and (c) FTIR spectrum of PET microplastics.
3
organic carbon (TOC) determined by the TOC analyzer (Torch, Tel-
edyne Tekmar, USA). To examine the effect of NOM on adsorption,
19.5 mL of different concentrations (1.03, 2.05, 5.13 and 10.3 mg/L)
of fulvic acid solution containing 0.5 g of PET had been completely
mixed for 72 h prior to the addition of 0.5 mL of CPs stock solution
to each vial. And the final total concentrations of fulvic acid in the
system were 1.0, 2.0, 5.0 and 10.0 mg/L, respectively.
Taihu Lake water and the Bohai seawater were used as water
matrices to estimate the adsorption capacity of CPs on PET in the
natural water systems. The lake water was collected at Wuxi
(120
10 E, 31
270 N) and the seawater was sampled from Dalian
(121
90 E, 38
480 N). All water samples were filtered with 0.45 mm
membranes and stored in the dark at 4
C until further use. Similar
to the previous experiments, the filtered water samples and PET
had been pre-mixed for 72 h prior to CPs addition. More details of
the initial conditions of adsorption were listed as annotations un-
der each figure.
2.4. Models
The equilibrium and non-equilibrium adsorption quantity of CPs
on PET were calculated as:
VðC0  CeðtÞ Þ
qeðtÞ ¼ (1)
m
where qe (mg/g) and qt (mg/g) are the amounts of adsorbate uptake
per mass of adsorbent at equilibrium and at any time t (h),
4 Z. Liu et al. / Environmental Pollution 265 (2020) 114926

respectively; C0 (mg/L) is the adsorbate concentration of blank Table 1

sample; Ce (mg/L) and Ct (mg/L) are the concentrations of adsorbate Part of adsorption kinetic and isotherm parameters of chlorophenols on PET.

at equilibrium and at any time t (h), respectively; m (g) is the mass Model Parameters Chlorophenols
of adsorbent; V (mL) is the volume of the adsorbate solution. MCP DCP TCP
Pseudo-first-order (PFO) model (Eq. (2)) (Lagergren, 1898),
Kinetic
pseudo-second-order (PSO) model (Eq. (3)) (Blanchard et al., 1984)
Pseudo-first-order qea 39.6 76.8 31.4
and intra-particle diffusion model (Eq. (4)) (Weber and Morris, k1 0.139 0.278 1.24
1963) were used to fit the adsorption kinetic data. R2 0.954 0.818 0.945
Pseudo-second-order qe 41.6 70.3 29.8
qt ¼ qe ð1  ek1 t Þ (2) k2  103 5.31 9.78 125
R2 0.985 0.973 0.996
Isotherm
q2e k2 t Langmuir R2 0.997 0.992 0.989
qt ¼ (3) RMSE 0.086 0.071 0.059
1 þ k2 qe t Freundlich R2 0.997 0.978 0.982
RMSE 0.072 0.126 0.096
pffiffi Linear R2 0.998 0.948 0.928
qt ¼ kp t þ C (4)
RMSE 0.089 0.242 0.365

where k1 (1/h), k2 [g/(mg h)] and kp [mg/(g h1/2)] are the rate con-
stants of the PFO, PSO and intra-particle diffusion model, respec-
tively; C (mg/g) is a constant associated with the thickness of
boundary layer.
Langmuir model (Eq. (5)) (Langmuir, 1918), Freundlich model
(Freundlich, 1906) (Eq. (6)) and linear model (Eq. (7)) were used to
fit the adsorption equilibria data.
KL Ce
qe ¼ qmax
1 þ KL Ce
qe ¼ KF Cen
qe ¼ Kd Ce
where KL (L/mg), KF [(mg/g)/(mg/L)n] and Kd (L/kg) are the constants
of Langmuir, Freundlich and linear model, respectively; qmax (mg/g)
is the maximum saturated monolayer adsorption capacity of the
adsorbent; n (dimensionless) is the Freundlich intensity parameter.
3. Results and discussion
3.1. Characteristics of PET microplastics
The SEM images (Fig. 1a) show that the PET microplastic parti-
cles have blocky and layered structure with some cracks and
Adsorption kinetic data after 1 h were used to fix the pseudo-first-order and
pseudo-second-order model. The units of parameters are the same as described
before. R2: regression coefficient; RMSE: root mean squared error. Other fitting
parameters were provided in Table S1.
a
qe values were determined by the maximum measured values (Hai Nguyen
et al., 2017).
macropores. The specific surface area and total pore volume (p/
p0 ¼ 0.990) were 0.864 m2/g and 1.83 mm3/g, respectively. The N2
(5) adsorption-desorption isotherm belonged to Type II and the hys-
teresis loop belonged to Type H3 (Fig. 1b). The types of curves
indicated that the plate-like particles gave rise to slit-shape pores
(6)
form, although the pore structure of PET particles was not devel-
oped (Sing, 1982). According to the FTIR spectra (Fig. 1c), hydroxyl
(7) group [3431 cm1 (stretching vibration of OeH)], methylene group
[2966 and 2907 cm1 (asymmetrical and symmetrical stretching
vibration of CeH)], carbonyl group [1713 cm1 (stretching vibration
of C]O)] and carbon-oxygen single bond [1241 cm1 (stretching
vibration of CeO)] could be identified (Tobin, 1957). The IEP was
estimated to be around 3.6 (Fig. S1).
The zeta potentials and IEP are important surface electro-
chemical properties of microplastics and have significant effects on
the adsorption of dissociable organic pollutants and metals
(Tourinho et al., 2019; Yu et al., 2019). Therefore, it is necessary to
further elucidate the electrification mechanism of microplastics.
Generally, the interface between the untreated microplastics and
water is inert (Liu et al., 2019b). Unexpectedly, for the polymer

Fig. 2. Adsorption kinetics of chlorophenols on PET fitted by (a) pseudo-first-order, pseudo-second-order and (b) intra-particle diffusion models. Adsorption conditions: initial
chlorophenol concentration 5.0 mg/L; adsorbent dose 25 g/L; initial pH 8.0; ionic strength 0.01 mol/L. Error bars represent the deviation of replicates.
 Z. Liu et al. / Environmental Pollution 265 (2020) 114926
Table 2
Physical and chemical properties of chlorophenols.
Compound MV (cm3/mol) MD (Å) Sw (g/L) logKow
4-Chlorophenol 99.8 6.82 2.70 2.42
2,4-Dichlorophenol 111.7 7.08 0.45 3.17
2,4,6-Trichlorophenol 123.7 7.32 0.08 3.66
MV: molar volume, inquired from SciFinder at 293 K and 1 atm; MD: molecular
diameter, calculated from MV, assuming that molecules are spherical; Sw: aqueous
solubility from (Davis and Huang, 1990); Kow: octanol-water partition coefficient
from (Davis and Huang, 1990); pKa: dissociation constant from (Davis and Huang,
1990).
surfaces, the IEPs are around 4 and independent of the composition
or hydrophobicity (Zimmermann et al., 2010) which were similar to
the measurements in this study and other literature (Xu et al.,
2018a; Xu et al., 2018b). This phenomenon was likely to be attrib-
uted to the adsorption of hydroxide ions driven by the electrical
potential gradient produced by the first two molecular layers of
water away from the hydrophobic surface (Zangi and Engberts,
2005). The effect of hydrophobicity and multivalent ions on the
zeta potentials of the inert interface between polymer and water
were comprehensively discussed in a previous study (Zimmermann
et al., 2010).
3.2. Adsorption kinetics
The adsorption kinetics of CPs on PET are shown in Fig. 2 and the
parameters calculated with PFO and PSO model are listed in Table 1.
The adsorption equilibrium was achieved within 72 h (Fig. 2a). The
PSO model was more appropriate to describe the adsorption pro-
cess by comparing the R2 values for PFO and PSO models. The intra-
particle diffusion model was also used to fit the data. Apparently,
the curves did not pass through the origin (C s 0) which meant the
adsorption was not solely governed by a single intra-particle
diffusion. However, the data can be fitted well by multiple linear
curves (Fig. 2b) which suggested that the adsorption process was
controlled by a multistep mechanism.
Generally, the transport process of adsorbate to the adsorption
site of adsorbent can be divided into 4 steps (Weber, 1984): (1) bulk
transport (occurs quickly), (2) film diffusion (occurs slowly), (3)
intra-particle diffusion (occurs slowly) and (4) adsorption attach-
ment (occurs quickly). Seen in Fig. 2b, the first stage of the
adsorption could be attributed to the film diffusion driven by
physicochemical interactions (such as hydrophobic interaction,
covalent forces and so on) (Guo et al., 2015). At this stage, about 22%
of total adsorbed MCP, 36% of total adsorbed DCP and 70% of total
adsorbed TCP had successfully occupied the exterior adsorption
Fig. 3. Adsorption isotherms of chlorophenols on PET fitted by (a) Langmuir, (b) Freundlich and (c) linear models. Adsorption conditions: initial pH 8.0; ionic strength 0.01 mol/L;
equilibrium time 96 h.
5
pKa
9.1
7.8
6.1
Fig. 4. Effect of solution pH on chlorophenols adsorption by PET: experimental data
and theoretical values. Adsorption conditions: initial chlorophenol concentration
5.0 mg/L; adsorbent dose 25 g/L; ionic strength 0.01 mol/L; equilibrium time 96 h.
Error bars represent the deviation of replicates.
sites of PET, which was likely due to the differences in hydropho-
bicity (Kow, Table 2). The second stage of adsorption could be
attributed to the surface and intra-particle diffusion (Hai Nguyen
et al., 2017) of CPs. At this stage, chlorophenols with less chlorine
content were more inclined to diffuse into the pores of PET, which
might arise from the differences in the molecule size of CPs (MD,
Table 2) (Qin et al., 2009). The third stage could be attributed to the
dynamic equilibrium of adsorption. In summary, the film diffusion
controlled the adsorption rate at the early stage, while the intra-
particle diffusion at the later stage. The same phenomenon has
been observed in the literature (Guo et al., 2018; Ma et al., 2019).
3.3. Isotherms and effect of pH on chlorophenols adsorption
The adsorption isotherms of CPs on PET fitted by different
models were provided in Fig. 3. The goodness of fit for the isotherm
of DCP and TCP on PET followed the order of Langmuir
model > Freundlich model > linear model by comparing R2 and
RMSE values (Table 1) (Hüffer and Hofmann, 2016). However, for
MCP, these three models could all fit the isotherm well (Table 1).
Fig. 4 shows the effect of solution pH on the adsorption. Kd
(adsorption coefficient, Kd ¼ qe/Ce) was used to evaluate the effect
of water hydrochemical properties on CPs adsorption by PET.
6 Z. Liu et al. / Environmental Pollution 265 (2020) 114926
As pH increased from 4 to 10, the Kd values decreased sharply
from 12.2 L/kg to 3.9 L/kg for MCP, from 32.7 L/kg to 0.4 L/kg for DCP
and from 43.3 L/kg to 0.2 L/kg for TCP, respectively. The fraction of
undissociated CPs a can be calculated by Eq. (8).
1 adsorbate with aromatic p-system (Keiluweit and Kleber, 2009).
a¼ (8)
1 þ 10pHpKa
When the solution pH was 10, more than 99% of DCP and TCP
were dissociated and the Kd values were close to 0. This indicated
that the negatively charged dissociated CPs could form strong
electrostatic repulsion with negatively charged PET and could not
be adsorbed. Meanwhile, the dissociation of CPs would increase
their hydrophilicity. When the pH was 4, more than 99% of CPs
molecules were undissociated and the Kd reached the maximum
value. Assuming that the pH value remained the same in the
adsorption process and the adsorption isotherm of CPs satisfied the
Langmuir model, the Kd theoretical value could be estimated by Eq.
(9) derivated from Eq. (1), (5) and (8). The derivation process of Eq.
(9) is provided in the Supporting Information.
1 KLð4Þ KLð4Þ
¼ qmaxð4Þ  (9)
a Kd 1þmV Kd
where KL(4) (L/mg) and qmax(4) (mg/g) are parameters of Langmuir
model at pH 4 and are listed in Table S2. As is shown in Fig. 4,
theoretical values were consistent with the experimental data as
the pH increased from 4 to 10. In summary, within the range of pH
that may occur in natural waters, a decrease in pH was favorable for
the adsorption of CPs on PET, especially for the CPs with high
chlorine content.
As the pH decrease from 4 to 2, the Kd values of CPs on PET
decreased apparently (Fig. 4). This implied the hydrogen bond
could form between CPs and PET. With the decrease of solution pH,
more and more H3Oþ could compete for the hydrogen-bonding
adsorption sites with CPs (Qin et al., 2012). Compared with CPs,
the mobility of H3Oþ is greater due to its smaller size. Therefore,
H3Oþ could reach the hydrogen-bonding adsorption sites much
easier and made the surface of PET positively charged (Fig. S1). The
formation of hydrogen bond between CPs and PET could be
attributed to the interaction between the hydroxyl group of CPs and
oxygen-containing functional groups of PET including the carbonyl
group and the terminal hydroxyl group. The interaction between
the hydrogen atom and p-electron was also commonly classified as
a kind of hydrogen bonds (Davis and Huang, 1990) and this inter-
action will be discussed in the next section. If the decrease in
adsorption when pH reduced from 4 to 2 was only caused by the
H3Oþ competition, the contribution of hydrogen bonds to the
adsorption at pH 4 was 37%, 29% and 11% for MCP, DCP and TCP,
respectively. In other words, the contribution of hydrogen-bonding
interaction to the adsorption of undissociated CPs decreased with
the increase of chlorine content.
3.4. Effect of chlorine content on chlorophenols adsorption
When the solution was at pH 2, the electrostatic interaction and
hydrogen-bonding interaction between CPs and PET could be
ignored and the Kd values for MCP, DCP and TCP were 6.9 L/kg,
18.9 L/kg and 34.2 L/kg, respectively. This result indicated that there
were other interactions between CPs and PET besides electrostatic
interaction and hydrogen-bonding interaction. Considering the
presence of hydrophobic groups (benzene ring, chlorine atom and
so on) on CPs and PET, the hydrophobic interaction could not be
excluded. When the pH was 2, the regression of log Kd against log
Kow was log Kd ¼ (0.57 ± 0.10)  log Kow  (0.35 ± 0.29) (R2 ¼ 0.99,
P < 0.05) (Fig. S2a). The significant linear correlation indicated that
the hydrophobic interaction was the main adsorption mechanism
at pH 2.
Cation-p, hydrogen-p, polar-p, n-p EDA and p-p interactions are
often used to explain the interactions between adsorbent and
The adsorption mechanisms involving aromatic p-system of CPs on
PET might also be attributed to the interactions between (1) the
hydrogen atom attached to the oxygen of CPs and the p-electron of
aromatic ring of PET (hydrogen-p interaction), (2) the oxygen atom
of dissociated CPs and the p-electron of aromatic ring of PET (polar-
p interaction) and (3) the p-electron of aromatic ring of CPs and PET
(p-p interaction). The existence of the ester group of PET decreased
the electron density from p-electron of the aromatic ring. This
charge transfer made p-electron an electron acceptor (Fig. S2b)
which is difficult to form hydrogen-p interaction with the hydrogen
atom attached to the oxygen of CPs (Keiluweit and Kleber, 2009).
The polar-p interaction was negligible compared with the electro-
static repulsion between dissociated CPs and PET inferred from the
experimental results in the previous section. The increase of chlo-
rine content resulted in a decrease of the p-electron density of the
aromatic ring of CPs which made it unfavorable to produce p-p
interaction between CPs and PET (Fig. S2b). Although low-
chlorinated CPs are more prone to form p-p interaction with PET,
the p-p interaction may not be the main adsorption mechanism
compared with hydrophobic interaction and hydrogen-bonding
interaction.
3.5. Effect of ionic strength and fulvic acid on chlorophenols
adsorption
As is shown in Fig. 5a, at pH 8, when the ionic strength increased
from 0 to 0.10 mol/L, the Kd values of DCP and TCP decreased from
25.9 L/kg to 23.8 L/kg and 8.5 L/kg to 6.1 L/kg, respectively. This
indicated Naþ with better migration ability might compete with the
undissociated CPs on the adsorption sites of PET and form steric
hindrance (cation competition). Moreover, the increase of ionic
strength led to a decrease in the solubility of organic pollutants (so-
called salting-out effect) which has been reported to enhance the
adsorption of organic pollutants on microplastics (Ma et al., 2019;
Zhan et al., 2016). To further elucidate the contribution of the
salting-out effect on the adsorption of CPs by PET, the effect of ionic
strength on adsorption was also evaluated at pH 4. When the so-
lution pH was 4, the zeta potential of PET was approximately zero
(Fig. S1) which could minimize the competition of cations to a great
extent and almost all CPs were undissociated. Fig. S3 showed that
the Kd values did not change significantly with the increase of ionic
strength at pH 4. Although the increase in ionic strength decreased
the solubility of CPs, the reduction was less than 5% (Xie et al.,
1994). Meanwhile, the salting-out effect became weaker with the
decrease of CPs concentrations (Kusmierek and Swiatkowski, 2015).
When the pH was 8, more DCP and TCP were dissociated and the
salting effect was negligible. Therefore, the cation competition was
regarded as the main mechanism for low concentrations of DCP and
TCP at pH 8. Notably, in our study, the ionic strength had no sig-
nificant effect on the adsorption of MCP (Fig. 5a). This might result
from both the weak salting-out effect and/or cation competition. A
similar phenomenon was also reported in the literature about the
adsorption of MCP on multi-walled carbon nanotubes (Kusmierek
and Swiatkowski, 2015).
As is shown in Fig. 5b, the existence of fulvic acid negatively
affected the adsorption of DCP and TCP by PET. When the con-
centration of fulvic acid increased from 0 to 2 mg/L, the Kd values of
CPs decreased to some extent. When increasing from 2 mg/L to
10 mg/L, the Kd values remained almost unchanged compared with
 Z. Liu et al. / Environmental Pollution 265 (2020) 114926
Fig. 5. Effect of solution (a) ionic strength and (b) fulvic acid content on chlorophenols adsorption by PET. Adsorption conditions: initial chlorophenol concentration 5.0 mg/L;
adsorbent dose 25 g/L; initial pH 8.0; fulvic acid concentration 0 mg/L when evaluating the effect of ionic strength; ionic strength 0.01 mol/L when evaluating the effect of solution
fulvic acid concentration; equilibrium time 96 h. Error bars represent the deviation of replicates. Different superscript letters within a column indicate significant differences
(P < 0.05) among treatments according to one-way ANOVA test.
the Kd at 2 mg/L fulvic acid concentration. Xu and colleagues had
reported a similar trend in the adsorption of 2,20 ,4,40 -tetra-
bromodiphenyl ether on polyethylene, polypropylene, polyamide
and polystyrene affected by humic acid and fulvic acid content (Xu
et al., 2019). To better explain the effect of fulvic acid, the adsorp-
tion capacity of fulvic acid on PET was also examed. As is shown in
Fig. S4, the adsorption capacity of fulvic acid on PET is much larger
than that of CPs observably at pH 8. The qe of fulvic acid increased
sharply as C0 increased from 0 mg/L to 5 mg/L and the adsorption
tended to saturate gradually when C0 > 5 mg/L. This indicated that
most of the adsorption sites were occupied rapidly by fulvic acid
prior to the addition of CPs, even though the concentration of fulvic
acid might not be high. However, a considerable amount of CPs was
still adsorbed to the microplastics. This was very likely owing to the
fact that undissociated CPs could be associated with fulvic acid by
hydrophobic interaction and p-p interaction (Smejkalov

a and


Piccolo, 2008; Smejkalov 
a et al., 2009), fulvic acid might act as a
bridge with the surface of PET and CPs. The existence of fulvic acid
or humic acid even enhanced the adsorption of oxytetracycline on
polystyrene foam particles mainly attributed to the bridging effect
(Zhang et al., 2018). Therefore, the effect of fulvic acid on the
adsorption of DCP and TCP on PET was relatively limited but not
negligible.
3.6. Adsorption of chlorophenols on PET microplastics in natural
water matrices
More complex interactions were expected between PET micro-
plastics and CPs in natural water. The Kd value of each equilibria
data was analyzed for the statistical difference of the adsorption in
different water matrices (Fig. 6) and the linear model was used to
evaluate the adsorption capacity (Table 3). The properties of the
natural water matrices were also provided in Table 3. The con-
centrations of CPs were below the detection limit (10 mg/L) in the
natural water matrices. It was also reported that the concentration
of each CP was less than 1 mg/L in the sampling area (Gao et al.,
2008). Also, the filtration before the experiment could remove
most of the microplastics in natural waters. Thus, the effect of
preexisting CPs and microplastics in natural water on the
7
experiment was negligible. As is shown in Fig. 6a, there was no
significant difference among the Kd values of MCP in different water
matrices at 0.05 level. The Kd values of DCP and TCP were signifi-
cantly lower in natural waters than in laboratory water. These re-
sults were similar to the previous study involving the effect of
solution ionic strength and NOM content on adsorption. Regardless
of the water matrix we used in this study, the adsorption capacity of
DCP was much higher than that of MCP and TCP. Compared with
TCP, more DCP existed in the undissociated form at pH 8, therefore,
DCP is easier to be adsorbed onto PET. However, the hydrophobicity
played a crucial role in the adsorption of MCP and DCP. Although
the pKa of CPs decreases with the increase of chlorine content
(Garba et al., 2019), the contribution of hydrophobicity to adsorp-
tion cannot be overlooked, especially under acidic conditions.
Multiple CPs often coexist in the environment, therefore, the
adsorption of CPs mixture in laboratory water was also investi-
gated. The mixture of three CPs was added to the vials right before
reaction occurred and the equilibrium data for each CP was fitted
using linear model, respectively (Fig. S5). The fitting parameter Kd
was 10.0 L/kg for MCP (R2 ¼ 0.998), 27.5 L/kg for DCP (R2 ¼ 0.996)
and 9.8 L/kg for TCP (R2 ¼ 0.995). The Kd value of each component
in the mixed CPs reduced by less than 10% compared with that in a
solution with the sole component. This indicated that the adsorp-
tion of each CP by PET was less affected by the presence of other CPs
when the concentration of CPs was low.
4. Conclusion
In this study, we examined the adsorption behaviors of three
typical CPs with distinct chlorine contents on PET under different
pHs, ionic strengths and the concentrations of fulvic acid. The
adsorption isotherms were well fitted by Langmuir model for DCP
and TCP. For the lowest chlorine content MCP, Langmuir model,
Freundlich model and linear model could all fit the adsorption
isotherm well. Multiple adsorption mechanisms were identified for
the adsorption of CPs on PET. Generally, hydrophobic interaction
was the main adsorption mechanism of undissociated CPs on PET.
Hydrogen bonds formed between CPs and PET enhanced the
adsorption of the undissociated CPs and the contribution of
8 Z. Liu et al. / Environmental Pollution 265 (2020) 114926

Fig. 6. Adsorption isotherms of chlorophenols on PET in different water matrices fitted by linear model with inset the distribution of adsorption coefficient (Kd) of each point in
different water matrices. To compare with the natural waters, laboratory water was the ultrapure water and the initial pH has been adjusted to 8.0 before experiments. Natural
waters have not been adjusted before experiments.

Table 3
The basic properties of different water matrices and the isotherm parameters of chlorophenols on PET in different water matrices fitted by linear model.

pH Conductivity TOC MCP DCP TCP

(mS/cm) (mg/L)
Kd R2 Kd R2 Kd R2

Laboratory water 8.0 <0.01 Not detected 10.6 0.992 29.4 0.995 10.5 0.983
Bohai seawater 7.9 53.2 4.7 11.4 0.993 21.7 0.995 5.7 0.997
Taihu lake water 8.0 0.55 5.2 10.7 0.990 18.0 0.993 4.6 0.992

TOC: total organic carbon; The unit of Kd: L/kg.

hydrogen-bonding interaction to adsorption increased with the Acknowledgments

decrease of chlorine content. The increase of chlorine content
facilitated hydrophobic interaction between undissociated CPs and
PET. Meanwhile, higher chlorine content CPs having lower pKa
values tended to dissociate at neutral pH condition and resulted in
stronger electrostatic repulsion with PET. Remarkably, the adsorp-
tion of CPs on PET was greatly influenced by pH, with adsorption
capacity increasing rapidly from pH 2 to 4, then decreasing grad-
ually from pH 4 to 10. At pH 8, both ionic strength and the con-
centration of fulvic acid did not affect the adsorption of MCP
significantly, while the adsorption of DCP and TCP decreased with
the increase of ionic strength or concentration of fulvic acid. These
findings were further confirmed in natural water matrices. The
adsorption capacity of MCP on PET in both Taihu lake water and
Bohai seawater was similar to that observed in laboratory water,
while the adsorption of DCP and TCP greatly reduced in Taihu Lake
water and Bohai seawater. This work contributed to the under-
standing of the adsorption mechanisms of hydrophilic compounds
on microplastics and adsorption behavior in natural waters.
The work was funded by the National Natural Science Founda-
tion of China (41671468, 41301546), the Natural Science Foundation
of Jiangsu Province (BK20171356), the National Key Research and
Development Program of China (2018YFA0901200), the Under-
graduate Innovation and Entrepreneurship Training Program of
Jiangsu Province (201810286044X), Qing Lan Project of Jiangsu
Province, Science and Technology Service Network Initiative (KFJ-
STS-QYZX-051), the Priority Academic Program Development of
Jiangsu Higher Education Institutions and the Fundamental
Research Funds for the Central Universities. The authors are
grateful to collaborators at the Analytical Center of NIGLAS for their
in-kind support in laboratory facilities.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.envpol.2020.114926.

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.
CRediT authorship contribution statement
Zheming Liu: Writing - original draft, Data curation, Visuali-
zation. Qingdong Qin: Conceptualization, Writing - review &
editing, Supervision. Zhixian Hu: Investigation, Writing - original
draft. Lu Yan: Investigation. Un-Io Ieong: Investigation. Yan Xu:
Conceptualization, Methodology, Writing - review & editing,
Supervision.
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