Marine Pollution Bulletin 144 (2019) 61–67

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Marine Pollution Bulletin

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

Study on the capability and characteristics of heavy metals enriched on T

microplastics in marine environment
⁎
Fenglei Gaoa, Jingxi Lia, , Chengjun Suna,b, Letian Zhanga,d, Fenghua Jianga, Wei Caoa,
Li Zhenga,c
a
Marine Ecology Research Center, First Institute of Oceanography of Ministry of Natural Resources, 266061 Qingdao, Shandong, China
b
Laboratory of Marine Drugs and Bioproducts, Qingdao National Laboratory for Marine Science and Technology, 266071 Qingdao, China
c
Laboratory of Marine Ecology and Environmental Science, Qingdao National Laboratory for Marine Science and Technology, 266071 Qingdao, China
d
Qingdao University of Science and Technology, 266042 Qingdao, China

A R T I C LE I N FO A B S T R A C T

Keywords: In this study we examined the adsorption characteristics of heavy metals on microplastic through laboratory test
Microplastics and field test. We demonstrated that polyvinyl chloride, polypropylene, polyethylene, polyamides and poly-
Adsorption formaldehyde could adsorb lead, copper and cadmium in the simulating solution, and the heavy metals showed
Heavy metals higher adsorbance on PVC and PP particles compared with PA, PE and POM. In the field experiment, the ad-
Multiple pollution
sorption rate and concentration of heavy metals varied significantly among different plastic types and locations.
Field measurement
The adsorbability of PP and PVC toward Pb and Mn was strongly correlated with the metal concentration in
seawater. We also compared the adsorption quantity of PP to heavy metals and polycyclic aromatic hydro-
carbons which resulted in an order of magnitude within one month. During the adsorption, the surface mor-
phology of the microplastics which were washed and corroded by seawater underwent a rough-smooth-rough
changing process, and different materials had great differences.

1. Introduction
At present, plastic production has penetrated all aspects of life, from
industry to agriculture and from technology to human life (Andrady,
2011; Fendall and Sewell, 2009). Plastics are widely used globally be-
cause they are cheap, lightweight, durable, and malleable (Boucher and
Friot, 2017). Plastics exhibit a practically unlimited number of possible
applications. However, their extensive use makes plastic waste a feature
in the marine environment (Chen, 2015). More than 300 million tons of
plastic products are globally produced annually (Jambeck et al., 2015),
of which approximately 10% go into the ocean (Thompson, 2007). Two
forms of plastics exist in the ocean, namely, large plastic wastes and
small plastic particulates within 5 mm in size, named microplastics
(Thevenon et al., 2014). Microplastics can pose a serious threat to the
marine environment, not only affecting the photosynthesis of marine
algae (Bhattacharya et al., 2010; Della et al., 2014) and the hatching
and reproduction of certain marine organisms (Carson et al., 2011;
Goldstein et al., 2012; Sussarellu et al., 2016) but also leading to
malnutrition and even death of certain marine organisms (Bond et al.,
2013; Derraik, 2002; Schuyler et al., 2014).
Compared with larger forms of plastic rubbish, microplastics exhibit
large specific surface area, high hydrophobicity, and high tendency to
interact with microbes. These physicochemical properties of micro-
plastics enhance the enrichment capability of certain contaminants,
such as persistent organic pollutants and heavy metals (Guo et al.,
2012; Rochman et al., 2013a, 2013b; Wang et al., 2015), for which
microplastics can play a key role as vectors in the marine system. In
addition, plastic itself contains toxic additives, such as plasticizers,
flame retardants, and antibacterial agents, which are released into the
ocean, causing pollution (Law and Thompson, 2014). Pollutants carried
by microplastics or attached on its surface can be brought into global
distribution, causing complex toxicity to the marine organisms, en-
riched in organisms, and transmitted further along the food chain (Rios
Mendoza and Jones, 2015; Rochman et al., 2013b). Thus, microplastics
pose a serious threat to the survival of marine life and human health
(Cole et al., 2011).
Turner and Holmes (2015) used original and aged PE particles to
adsorb metal ions of Cr, Cu, Ag, Cd, Hg, Ni, Co, Pb, and Zn in fresh
water and found that the difference in ion concentration between the
liquid phase (metal solution) and the solid phase (PE particles) was the
main factor affecting the adsorption and the metal ion concentration
eventually reached equilibrium. Due to the oxidation and weathering of

⁎
Corresponding author.
E-mail address: jxli@fio.org.cn (J. Li).

https://doi.org/10.1016/j.marpolbul.2019.04.039
Received 14 September 2018; Received in revised form 24 March 2019; Accepted 15 April 2019
Available online 10 May 2019
0025-326X/ © 2019 Elsevier Ltd. All rights reserved.
F. Gao, et al.
aging particles, the surface morphology of the particles changed, which
made it easy to obtain electric charge and to adsorb metal ions to
achieve charge balance. Moreover, in addition to pH, the time of mi-
croplastics existed in the environment also affects the adsorption ca-
pacity crucially. Early reports testified the adsorption of virgin poly-
styrene beads and aged polyvinyl chloride fragments to heavy metals,
such as Cu and Zn, leached from an antifouling paint in seawater during
14 days of experimental manipulation. The heavy metal on the surface
of the plastic particles was 800 times higher than that of in seawater.
The aged PVC fragments adsorb more Cu than the PS particles, which
may be due to the specific surface area of PVC fragments increased after
cracking and crushing, and the presence of adhering biomass on the
surface of the particles also enhances the behavior of adsorbing heavy
metals (Brennecke et al., 2016).
Moreover, a limited number of recent studies reported the adsorp-
tion of heavy metals on the microplastics in the actual ocean environ-
ment and the adsorption characteristics of different types of micro-
plastic particles. In this study, static simulating experiment and field
measurements were conducted to investigate the adsorption of heavy
metals on the microplastics and their adsorption characteristics.
2. Materials and methods
2.1. Materials
The microplastics used throughout the study were purchased from
Shaoxing City Yixin Ball Industry Co., Ltd., China. Five types of pre-
production microplastic particles, namely, PP, PE, PA, PVC, and POM
with a diameter of 4 mm were cleaned by washing in high purity
(18.2 MΩ cm at 25 °C) Millipore Milli-Q water and then ultrasonicating
for 5 min with 2% nitric acid to remove impurities. These particles are
the most common raw materials used in the plastic industry and are
abundantly observed and collected from oceans. All solvents and re-
agents used were of analytical grade and purchased from Merck,
Germany.
2.2. Simulation experiment
We prepared 5 mg/L of Pb, Cu, and Cd solutions, equivalent to ion
concentrations of class IV seawater. We performed the adsorption ex-
periments with 50 mL PE bottles, each containing 30 mL of metallic
solutions and 0.5 g precleaned particles of PP, PE, PA, PVC, POM. Each
experiment was performed in triplicate. We suspended these bottles by
using a shaking table at 160 r/min and room temperature for a period of
13 days. The particles were collected on the 1 d, 3 d, 5 d, 9 d, 11 d and
13 d respectively to observe the influence of adsorption time on the
adsorption process, and three days after adsorption to observe the in-
fluence of other factors.
2.3. Field experiment
We selected two mass-produced plastic types, PP and PVC, which
were launched at three locations along the China coastline on January
17th, 2016 and commonly found in the marine environment (Cózar
et al., 2014) (Fig. 1). We assigned three typical sites: one was a sewage
treatment plant near Maidao, and the other two were offshore scallop
culture areas in Huangdao and Baian. Maidao and Huangdao are lo-
cated along the coast of Qingdao (Monsoon climate of medium lati-
tudes), which belongs to the yellow sea. Baian is located in the south-
east of Shanwei city, Guangdong province (Subtropical monsoon
climate), which belongs to the south China sea. At each site, we ar-
ranged two replicate samples at a distance of 1 m from each other. To
promote seawater exchange and removal of organisms, we placed 30
glass fiber bags (15 bags contained PP, and the other 15 contained PVC)
inside a nylon mesh (10 mm) bag supported by a frame. Each replicate
contained 20 g of one plastic type placed into individual mess bags of
62
Marine Pollution Bulletin 144 (2019) 61–67
glass fiber with a diameter of 1 mm. Particles of PP and PVC were both
cylindrical (3 mm in length, 2 mm in diameter). We suspended the
plastic samples at a depth of approximately 1 m below the sea surface
for future collection after 1, 3, 6 and 9 months. During collection, we
retrieved three bags of each plastic type of particle samples from each
replicate and collected the seawater samples.
2.4. Metal and particles characteristics analysis
We rinsed all microplastic particles from each site in ultrapure water
to remove fouling organisms. Then, 0.5 g of particles from each sample
was subjected to extraction by sonication (120 W, 10 min) in 2% nitric
acid. The extraction solution was collected and determined using in-
ductively coupled plasma-mass spectrometry (Agilent 7500 series,
USA). 50 μg/L of Li, Sc, Ge, Y, In, Tb, Bi was added into the standard
solution and sample solution as internal standard. For heavy metal
analysis in seawater, water samples collected from the field were
acidified with nitric acid and stored under −20 °C until analysis. Virgin
particles of each type were used as laboratory blanks and 0-month
controls, representing the background metal concentration. The acid-
ified plastic pellets were cut into thin slices with a dissection scalpel and
fixed with a conductive tape on the sample stage to expose the selected
external surface for testing. After the sample was gold plated, the mi-
crostructure of the surface was observed by using a scanning electron
microscope (FEI Quanta 200, Netherlands).
3. Results and discussion
3.1. Adsorption characteristics of microplastics to metals
To examine the adsorbability of different kinds of microplastics to
metals, we suspended five types of clear microplastic particles (PP, PE,
PA, PVC, and POM, in a diameter of 4 mm) in metallic solutions (Pb, Cu,
and Cd) under other identical conditions for three days. The con-
centrations of three metals extracted from microplastics varied from
plastic types (Fig. 2). The microplastic particles of PVC, PP consistently
sorbed higher concentrations of heavy metals than PA, PE and POM.
Notably, the concentration of lead among microplastic particles was
relatively large. Mean concentration was up to 1.318 μg/g with PVC
and 0.627 μg/g with PP. Cd concentration on the microplastic particles
maintained lower value compared with Pb and Cu, only 0.002 μg/g on
POM. Similar to Cu on PE and POM, Cu levels in the microplastic
particles of PVC, PP, and PA presented slight variation. In general, the
adsorption metal ion concentration trends of PP, PVC and PE were
Pb > Cu > Cd; while the adsorption trends of PA and POM were
Cu > Pb > Cd. Previous studies have found that the different type
plastic particles may have different adsorption properties to metal ions
because of the physicochemical properties of their surfaces, such as
hydrophobicity and diffusivity (Brennecke et al., 2016). In this study,
compared to the other four types of particles, PVC particles showed a
high adsorption capacity due to the PVC particles' polar groups con-
taining chlorine.
Significant differences in adsorption of Pb, Cu, and Cd on PP par-
ticles were relative to adsorption time and metal ion concentration
(Fig. 3a and c). With the increase in adsorption time and metal ion
concentrations, the adsorption efficiency of PP particles to heavy metals
initially increased and then flattened out, except toward Cu. During
adsorption of PP particles, sorption time strongly influenced the ad-
sorption effect. At the beginning, adsorption capacity increased rapidly
because the heavy metal ions were mainly adsorbed on the outer sur-
face of the microplastic particles. With the extension of adsorption time,
PP particles and metal ions became in contact with each other fully. The
results showed that the adsorption reached equilibrium until the 9th
day. The adsorption amount of PP particles to Cu increased firstly and
then gradually decreased after a certain time and concentration. At the
initial stage of adsorption (1 d), the adsorption amount of PP particles
F. Gao, et al.
Baian
Fig. 1. Three study locations at which particles were sampled and where the suspension experiment was conducted.
to the three metals increased rapidly, which was about 50% of the total;
at the 3 d to 5 d, the adsorption rate of the three metals slowed down;
after 5 days, the adsorption rate decreased significantly, and after
9 days, the adsorption amount did not increase significantly, indicating
the adsorption of the three metal reaches a dynamic equilibrium. The
change of this trend was mainly due to the fact that the adsorption of
heavy metals on PP particles was mainly on the outer surface. With the
prolongation of adsorption time, PP particles and metal ions were in full
contact, and metal ions were continuously accumulated in the particles.
On the surface, the adsorption capacity increases, and finally reaches
the adsorption equilibrium, and the adsorption amount of Cu decreases.
The adsorption amount of PP particles has similar changes in different
series of solutions; between 0.01 and 0.1 mg/L, PP particles adsorbed
metals rapidly because probably each metallic solution at low con-
centration could provide several adsorption sites for microplastic par-
ticles. On the contrary, when the concentration was higher than
Fig. 2. The adsorbance of Pb, Cu and Cd on different types of microplastics.
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Marine Pollution Bulletin 144 (2019) 61–67
Maidao
Huangdao
0.1 mg/L, the adsorption rate decreased possibly because the surface
exhibited a certain coverage rate, which affected the subsequent ad-
sorption rate. In addition, adsorption capacity toward copper ions de-
creased at high concentrations probably because copper ions in solution
react with air or water, leading to variation in the state of copper ions.
We employed four PP particles in regular shape of different size
(diameter in 2, 3, 4, and 5 mm) to identify relations with the enrich-
ment of heavy metals. Concentrations of heavy metals adsorbed to PP
varied significantly on account of particle size (Fig. 3b). Regardless of
Pb, Cu, or Cd, the heavy-metal adsorbance on microplastics decreased
with increasing particle size. This phenomenon may be due to dimin-
ished specific surface area, resulting in a decrease in adsorption sites on
the particle surface, and the amount of adsorption to metal ions is also
reduced. From the influence of particle size on the adsorption amount
of the three metal ions above, it may be inferred that the adsorption
amount of microplastics to other metal ions also increases with the
F. Gao, et al. Marine Pollution Bulletin 144 (2019) 61–67

Fig. 3. Effect of time (a), diameters (b), ions concentration (c) on adsorption of Pb, Cu and Cd on PP particles. Selective adsorption of metal ions by four types of
microplastics (d).

Table 1 metal adsorption to the microplastic pellets owing to the different

Metal concentrations in seawater and on PP, PVC particles, partitioning coef- concentrations of heavy metals in the seawater (Holmes et al., 2014).
ficient (Kpw) with data collected in six months at HuangDao. Kpw is calculated according to the following equation:
Seawater (μg/L) PP (μg/g) Kpw PVC (μg/g) Kpw
[MeP ]
Kpw =
Cr 0.952 ± 0.019 0.003 ± 0.001 3.15 0.000 ± 0.001 0.00 [MeW ]
Mn 29.661 ± 17.336 11.848 ± 0.864 399.45 3.040 ± 0.864 102.49
Cu 7.564 ± 0.015 0.223 ± 0.030 29.48 0.079 ± 0.030 10.44
where [MeP] (μg/g) and [MeW] (μg/mL) are metal concentrations
Zn 75.569 ± 2.884 0.000 ± 0.121 0.00 0.000 ± 0.121 0.00
As 22.011 ± 0.058 0.008 ± 0.003 0.36 0.000 ± 0.003 0.00 adsorbed to microplastic pellets and originally existed in the sur-
Cd 0.377 ± 0.001 0.023 ± 0.000 61.01 0.000 ± 0.000 0.00 rounding seawater.
Pb 0.823 ± 0.019 0.144 ± 0.008 174.97 0.028 ± 0.008 34.02 We selected the most representative 6-month adsorption data col-
lected simultaneously from the three stations for analysis. The metal
concentrations and partition coefficients of the microplastic particles
decrease of particle size, indicating that smaller microplastic has placed at Huangdao, Maidao and Baian and local seawater were shown
stronger adsorption capacity to heavy metals, and the microplastics in Tables 1, 2 and 3. In general, for most of the metal ions, PP almost
present in the marine environment are mainly in the form of particle showed a higher adsorption capacity than PVC, contrary to the results
size less than1 mm (Programme, 2005) which facilitating the combi- of simulation experiment in lab, perhaps because of the formation of
nation of microplastics and heavy metals. organic matters and microorganisms on the surface of microplastics,
We prepared the Pb, Cu, and Cd-coexisting solution systems (with which affects its adsorption of metals (Hua et al., 2012 and Turner and
Pb, Cu, and Cd concentrations of 0.05 mg/L) and studied the selectivity Holmes, 2015). Among the three experimental sites, the adsorption law
and amount of adsorption of three metals on different materials (PP, PE, of PVC to metal ions was about the same, Huangdao was Mn >
PA, PVC, in a diameter of 4 mm) (Fig. 3d). A competitive adsorption Pb > Cu > Cd, Maidao was Mn > Pb > Cu > Zn > Cd, Baian was
phenomenon was observed when Pb, Cu, and Cd coexisted. Under Mn > Pb > Cu > Cr > Cd, and the adsorption of PVC to the three
identical conditions, the adsorption capacity of mixed solutions (Pb, Cu, metal ions in the indoor simulation experiment was consistent (Pb >
and Cd coexisting) was lower than that in single metallic solution. The Cu > Cd), this was similar to the results of adsorption of these three
adsorption of metal ions on the surface of microplastics was competitive metal ions on other hydrophobic substrates in fresh water by Hua et al.
because of the existence of three metal ions. In addition, the results and Turner et al. (Hua et al., 2012 and Turner and Holmes, 2015); but
shown that the coexistence of ions had little effect on the adsorption of the adsorption capacity of PP to the metal ions in the seawater at
PE materials, and the adsorption amount of the three metal ions was Huangdao was different: Pb > Cd > Cu, the other two sites were
about the same, while the adsorption of PVC on the three metal ions in consistent with the result in the indoor simulation experiment. Com-
the mixed solution and the single metal solution were almost con- pared with the other two places, microplastic particles placed at Baian
sistently, only the corresponding adsorption amount was reduced; the
adsorption law of PA material in the mixed solution and the single
Table 2
solution was significantly different. In a single solution, the adsorption Metal concentrations in seawater and on PP, PVC particles, partitioning coef-
amount of PA to Cu was higher than that of Pb, but in the mixed so- ficient (Kpw) with data collected in six months at MaiDao.
lution, the adsorption amount of Cu was lower than that of Pb, in-
Seawater (μg/L) PP (μg/g) Kpw PVC (μg/g) Kpw
dicating that when Pb and Cu are present simultaneously, Pb has more
affinity with PA particles, and Cu has lower binding ability with PA. Cr 0.881 ± 0.003 0.011 ± 0.004 12.49 0.000 ± 0.007 0.00
Mn 7.225 ± 3.875 4.855 ± 0.555 671.97 8.931 ± 0.985 1236.13
Cu 2.790 ± 0.257 0.117 ± 0.006 41.94 0.145 ± 0.008 51.97
3.2. Field measurement Zn 60.903 ± 2.070 0.014 ± 0.269 0.23 0.011 ± 0.023 0.18
As 3.271 ± 0.269 0.000 ± 0.002 0.00 0.000 ± 0.004 0.00
Cd 0.142 ± 0.018 0.000 ± 0.001 0.00 0.000 ± 0.000 0.00
3.2.1. Metal content of microplastic particles at three stations Pb 0.898 ± 0.136 0.109 ± 0.011 121.38 0.107 ± 0.016 119.15
Partition coefficients (Kpw) can appropriately describe the rate of

64
F. Gao, et al.
Table 3
Metal concentrations in seawater and on PP, PVC particles, partitioning coefficient (Kpw) with data collected in six months at BaiAn.
Seawater (μg/L) PP (μg/g)
Cr 1.201 ± 0.361 0.084 ± 0.009
Mn 3.465 ± 0.185 31.252 ± 0.879
Cu 2.763 ± 0.736 0.174 ± 0.002
Zn 31.553 ± 11.610 0.000 ± 0.026
As 5.718 ± 0.425 0.037 ± 0.004
Cd 0.128 ± 0.001 0.006 ± 0.000
Pb 0.846 ± 0.177 0.434 ± 0.019
can adsorb Cd and As to a certain extent, perhaps because the tem-
perature and pH of surrounding seawater are higher (see Table 4 in
Supplementary material), which was beneficial to the adsorption of Cd
and As by microplastic particles (Holmes et al., 2014). In addition,
compared with Pb, Cu and Cd in laboratory simulation experiments, it
was found that the adsorption concentration of Cr on PP and PVC was
slightly different. PP showed higher adsorption capacity than PVC, and
PVC had almost no adsorption to Cr. However, the adsorption capacity
of microplastics at Baian to Cr was higher, because the adsorption of Cr
on microplastic particles decreased with the increase of pH and the
decrease of salinity (Holmes et al., 2014). It was worth noting that the
adsorption of the two microplastic to Mn was significantly higher than
that to the other six metals, and exhibited higher adsorption capacity at
Huangdao and Baian. The partition coefficients of PP and PVC reaches
9019.34 and 5183.26 at Baian. Although the concentration of Zn and As
in seawater was high, the adsorption amount on both PP and PVC was
negligible.
The abnormal content of Mn in seawater may be due to the large use
of fodder in scallop culture areas, and elements such as Cu and Zn are
often added to fishery feeds (Ali, 2000), indicating that aquaculture can
cause serious metal contamination. In addition, the good adsorption
properties of microplastics such as PP and PVC to heavy metals such as
Mn and Pb indicate that microplastics can transport pollutants globally
by means of seawater flow and ocean migration (Engler, 2012; Zarfl
and Matthies, 2010). Despite the low content of Cd, Cr and Pb in sea-
water, indoor simulation experiments and field experiments have
shown that microplastics such as PP and PVC can adsorb and enrich
these metal ions, indicating that microplastics are not only carriers, but
also beneficial to the enrichment of heavy metals on its surface.
3.2.2. Time-dependent change of metal concentration adsorbed on
microplastics
During 9 months of on-site adsorption experiments, the adsorption
of metal ions in seawater on microplastic particles showed different
trends. Four kinds of metal ions (Cr, Pb, Cu, Mn) with obvious changes
in adsorbance on microplastics during 9 months were selected and
compared. The adsorbance of PP and PVC and the concentration of
metal ions in surrounding seawater in Maidao was shown in Fig. 4.
Although the adsorption of heavy metals on microplastics was closely
related to its concentration in seawater, the time at which the adsorp-
tion peaks was different between different types of heavy metals. The
change trend of adsorption of Cr and Pb on microplastics was almost
consistent with the trend of the metal ions in seawater. The adsorption
of both ions peaks at 3 months, indicating that microplastics have a
faster adsorption rate to Cr and Pb. Then, in 6 months and 9 months, the
ion concentration first decreased and then increased, indicating that in
the actual seawater environment, the adsorption of metal ions on mi-
croplastics has been in dynamic exchange, and there is always a process
of ion transfer between the solid interface of the microplastic surface
and the liquid interface of seawater. The concentration of Cu and Mn on
the microplastics was basically accumulated over time, but there was
no correlation with the change of seawater concentration. The ion
concentration on the microplastics peaks in sixth month. However, the
concentration of seawater around was the lowest in 6 months. By
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Marine Pollution Bulletin 144 (2019) 61–67
Kpw PVC (μg/g) Kpw
69.94 0.046 ± 0.002 38.30
9019.34 17.960 ± 1.200 5183.26
62.98 0.110 ± 0.011 39.81
0.00 0.000 ± 0.020 0.00
6.47 0.000 ± 0.004 0.00
46.88 0.001 ± 0.000 7.81
513.00 0.441 ± 0.001 521.28
comparing the difference in adsorption between the two materials, it
was found that the adsorbance of PP to Cr and Pb was higher than that
of PVC, but the opposite was true for Cu and Mn, and PVC was larger
than PP.
Fig. 4(a2–b2) showed the changes in PP and PVC adsorption and the
metal concentration of surrounding seawater in Huangdao within
6 months. In addition to Cr, the other three metal ions gradually ac-
cumulated over time and reached the peak concentration in June. Ex-
cept for Pb, the concentration of metal adsorbed on microplastics was
consistent with the trend of surrounding seawater concentration. It
could be found that whether in Maidao or Huangdao, the adsorption of
four metals on PVC was higher than that of PP in January, indicating
that the adsorption rate of PVC to metal ions was higher than that of PP.
3.2.3. Comparison of PAHs and metals adsorbed by microplastics
Heavy metals and persistent organic pollutants (POPs) are two ty-
pical pollutants that people are concerned about at present. In this
study, we measured 16 EPA priority polycyclic aromatic hydrocarbons
(PAHs)-naphthalene (Nap), acenaphthene (Ace), acenaphthylene (Acy),
fluorene (Flu), phenanthrene (Phe), anthracene (Ant), fluoranthene
(Fla), pyrene (Pyr), benzo(a)anthracene (BaA), chrysene (Chr), benzo
(b)fluoranthene (BbF), benzo(k)fluoranthene (BkF), benzo(a)pyrene
(BaP), dibenzo(a,h)anthracene (DBahA), indeno(1,2,3-cd)pyrene(InP)
and benzo(g,h,i)-perylene (BghiP), to investigate the difference in ad-
sorption of heavy metals and PAHs by microplastics. The PAHs ad-
sorbed on the PP particles recovered from Maidao and Huangdao
during 1 month were extracted with dichloromethane/hexane (1:1, v/
v) and analyzed by using gas chromatography-mass spectrometer
(Agilent 6890N GC/5973N MSD, USA). The results showed that 13
kinds of PAHs were detected on the surface of microplastics except InP,
DBahA and BghiP (see Table 5 in Supplementary material). The total
PAHs concentrations (sum of the 16 EPA priority pollutants) on PP
particles from Maidao ranged from 0.072 to 0.261 μg/g, with a mean
concentration of 0.167 μg/g. The total PAHs concentrations on PP
particles from Huangdao ranged from 0.114 to 0.245 μg/g, with a mean
concentration of 0.180 μg/g. According to Baumard et al. (Baumard
et al., 1998), the contamination levels of ΣPAHs could be classified into
four groups: low (0 ∼ 0.1 μg/g), moderate (0.1 ∼ 1 μg/g), high
(1 ∼ 5 μg/g), and very high (> 5 μg/g). Based on these definitions, the
level of adsorption of ΣPAHs on PP at Maidao was in low and moderate
pollution, and ΣPAHs on PP at Huangdao was in moderate pollution.
Nevertheless, in this experiment, the adsorption of Mn, Pb, Cu, and Cr
on the PP particles at Maidao and Huangdao after one month was 0.352
and 0.787 μg/g, 0.018 and 0.015 μg/g, 0.018 and 0.018 μg/g, 0.007
and 0.010 μg/g respectively. Compared with the adsorption of heavy
metals on microplastic particles, it was found that the adsorption of
PAHs on microplastic particles was basically in the same order of
magnitude as that for metals, and the adsorption capacity for heavy
metals was slightly higher.
3.2.4. Surface morphology of microplastic particles
Different types of microplastic particles exhibited substantially dif-
ferent surface morphologies (Fig. 5). The surface roughness of PP par-
ticles was lower than that of PVC. The virgin PP particle surface
F. Gao, et al.
presented a large number of massive protrusions and a uniform cov-
erage. Meanwhile, the virgin PVC particle surface showed evident
cracks, which may be related to the production methods, which result
in mechanical damage. Compared with virgin microplastic particles of
the same type, microplastic particles placed in the actual seawater en-
vironment exhibited significantly altered surface morphology over
time. The PP particles were washed, impacted, and eroded by seawater.
Thus, the degree of surface protrusion weakened and was weathered
severely, and fine linear microgrooves occurred at 6 months, increasing
the specific surface area of microplastic particles and the surface ad-
sorption sites. The adsorption to heavy metals also peaked in 3 or
6 months. The surface protrusions of the particles almost disappeared.
The surface was smooth and showed some small hole-shaped depres-
sion, which increased the adsorption to metal elements. The result
agreed with the conclusion made by (Ashton et al., 2010) who thought
that plastic aging and polarization can improve the adsorption capacity.
PVC particles possessed a rough surface and complex features; after
a long period of actual corrosion by the marine environment, the sur-
face cracked gradually and became regularly wavy, showed serious
aging (9 months)increased tendency to adsorb metal elements (Antunes
et al., 2013). In addition, microplastic particles are exposed to seawater
environments for extended periods of time, and organic attachments
adhere easily to the particle surface (Reisser et al., 2014); such biolo-
gical membranes may exhibit selective adsorption toward different
PP
0 month 1 month 3 months
PVC
Fig. 5. SEM image of PP and PVC particles showing changes in surface morphology with time.
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Marine Pollution Bulletin 144 (2019) 61–67
Fig. 4. Content of heavy metals (Pb, Cr, Cu,
and Mn) sorbed to two plastic types (PP and
PVC) over time in Maidao and Huangdao.
Purple and blue lines respectively represent
the contents of heavy metals on the PP and
PVC (μg/g of particles). Orange lines re-
present the concentrations of heavy metals
in the surrounding seawater (μg/L of sea-
water). (For interpretation of the references
to colour in this figure legend, the reader is
referred to the web version of this article.)
metal elements. This phenomenon may also explain the different ad-
sorbability of microplastic particles toward different metal elements.
4. Conclusions
While microplastics had been proved to have the enriching cap-
ability of contaminants like heavy metals, this work not only reinforce
this phenomenon existed through indoor simulation experiment, but
also studied the characteristics of microplastics adsorb typical heavy
metals existed in marine environment. Our research indicated that
certain types of microplastics had different adsorbability toward dif-
ferent heavy metals with a correlation of ion concentration, adsorption
time and particles size. Meanwhile, we observed a competition among
different heavy metals when adsorbed onto microplastics and exhibited
diverse selectivity, but the in-depth principle is to be studied in the
future. Sewage outfall and culture zones are typical pollution sources of
heavy metals, and microplastics can be a key vector for its transpor-
tation in marine systems. Inspite of the content of certain heavy metals
are low in seawater, they can still show adsorbance on microplastics
when aggregating to a certain amount. In the study, it was found that
the adsorption amount of metals and PAHs on PP particles was similar
in order of magnitude. All results of the study could provide a theore-
tical basis for studying the combined pollution of microplastics and
pollutants in the marine environment.
6 months 9 months
F. Gao, et al.
Acknowledgements
This work was supported by the Basic Scientific Fund for National
Public Research Institutes of China (No. 2016Q02/2017Y03), the
Research Cooperation and Exchange of Marine Litter and Microplastics,
China (No. QY0518011), The Special Operational Funding Project of
the State Oceanic Administration-Marine Environmental Monitoring/
Assessment and Capacity Upgrading. C. Sun would also like to thank
Taishan Scholar Project of Shandong Province for funding support. The
authors also thank Wanru Wu from Qingdao No.2 Middle School and
Mindy Luo from Campolindo High School in Moraga, CA, USA for
helping with some sample analysis.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.marpolbul.2019.04.039.
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