Journal of Hazardous Materials 388 (2020) 121814

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Journal of Hazardous Materials

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Microplastics in agricultural soils on the coastal plain of Hangzhou Bay, east T

China: Multiple sources other than plastic mulching film
Bianying Zhoua, Jiaqing Wanga, Haibo Zhanga,*, Huahong Shib, Yufan Feia, Shunyin Huanga,
Yazhi Tonga, Dishi Wena, Yongming Luoc, Damià Barcelód
a
Zhejiang Province Key Laboratory of Soil Contamination Bioremediation, School of Environment and Resources, Zhejiang Agriculture and Forestry University, Hangzhou
311300, China
b
State Key Laboratory of Estuarine and Coastal Research, East China Normal University, Shanghai 200062, China
c
Nanjing Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008, China
d
Water and Soil Quality Research Group, Institute of Environmental Assessment and Water Research (IDAEA), Barcelona, Spain

G R A P H I C A L A B S T R A C T

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

Editor: R Teresa Microplastic contamination in agroecosystems raises great concerns. Here, we investigated the impacts of
Keywords: mulching and irrigation on microplastic accumulation in cropped soils. Sixty soil samples covering mulching and
Agricultural soils no-mulching farmlands, and forty-five irrigation water samples were collected for analysis. Microplastics were
Irrigation water obtained from the soils using continuous air flotation followed by density separation. Stereomicroscopy and
Microplastics micro-Fourier transform infrared spectroscopy (μ-FTIR) were used for identification. Mulching soils contained
Plastic mulching larger amounts of microplastics than non-mulching soils, with 571 pieces kg−1 and 263 pieces kg−1, respec-
Source identification tively, on average. The abundances of films and fibers were significantly (p < 0.05) higher in the mulching soils.
Microplastics in the soils and waters were dominated by fragments and fibers, respectively. The particle size of
the microplastics in soils mostly ranged from 1 to 3 mm, and primarily from 90 μm to 1 mm in waters. Multiple
polymers, e.g. polyethylene, polypropylene, polyester, rayon, acrylic and polyamide, and shapes found in the
soil microplastics indicate contributions from irrigation and plastic waste residues other than plastic mulching.
Future studies might include the long-term accumulation of microplastics in agroecosystems from multiple
sources under intensively managed cropping systems.

⁎
Corresponding author.
E-mail address: hbzhang@zafu.edu.cn (H. Zhang).

https://doi.org/10.1016/j.jhazmat.2019.121814
Received 15 August 2019; Received in revised form 30 November 2019; Accepted 2 December 2019
Available online 05 December 2019
0304-3894/ © 2019 Elsevier B.V. All rights reserved.
B. Zhou, et al.
1. Introduction
Microplastics are defined as polymer particles smaller than 5 mm in
size. They are of great concern globally as environmental pollutants and
most on microplastics have focused on marine ecosystems (Dai et al.,
2018; Thompson et al., 2004). However, recent studies indicate that
microplastics also represent a major threat to terrestrial ecosystems (de
Souza Machado et al., 2018a; Hurley and Nizzetto, 2018; Zhang et al.,
2018a). In agroecosystems there are several possible input pathways by
which microplastics can enter the soil including plastic mulching film,
residues of plastic wastes, application of soil amendments, and irriga-
tion water (Blasing and Amelung, 2018; Steinmetz et al., 2016; Lv et al.,
2019). The abundance of microplastic in soils has increased over time
where successive sewage sludge applications have been made and are
statistically correlated with sludge application rates (Corradini et al.,
2019). It has been estimated that approximately 63,000−430,000 and
44,000−300,000 tonnes of microplastics have been introduced into
agricultural land annually via sludge application in Europe and North
America, respectively (Nizzetto et al., 2016). Weithmann et al. (2018)
have evaluated the microplastics loadings to agricultural land via the
pathway of organic fertilizer application in Germany which amounted
to 35 billion to 2.2 trillion annually. The microplastics burden in ter-
restrial ecosystems through soil amendments has therefore exceeded
the total amount of microplastics estimated to have entered the global
oceans (van Sebille et al., 2015).
Microplastics may persist in soils over the long term due to the low-
light and low-oxygen conditions (Zalasiewicz et al., 2016). However,
ecological impacts of microplastics in the terrestrial environment re-
main poorly understood. Several studies have explored the potential
impacts of microplastic contamination on soil fauna and plant perfor-
mance by disturbing their biophysical environment (de Souza Machado
et al., 2018b; Rillig et al., 2017a; Lwanga et al., 2017; Maass et al.,
2017; de Souza Machado et al., 2019). Significant effects have been
observed on the gut microbiomes of soil collembolans exposed to
polyvinyl chloride (PVC) particles (Zhu et al., 2018). Occurrence of
microplastics may also alter soil chemistry. An incubation experiment
in which a Chinese loess soil was spiked with microplastics suggests
that the microplastics changed the composition of dissolved organic
matter in the soil (Liu et al., 2017). Pervasive microplastic con-
tamination may have consequence for plant performance and thus for
agroecosystems (de Souza Machado et al., 2019). A number of review
articles have therefore highlighted an urgent need to prioritize studies
on microplastics in agroecosystems (de Souza Machado et al., 2018a;
Hurley and Nizzetto, 2018; Ng et al., 2018; Rillig et al., 2017b).
However, only a few studies have been published thus far on mi-
croplastic contamination in soils (Lv et al., 2019; Corradini et al., 2019;
Zhang et al., 2018b; Zhou et al., 2018; Zhang and Liu, 2018; Scheurer
and Bigalke, 2018; Fuller and Gautam, 2016). A high level of up to 7 %
of microplastics by weight in topsoil near roads and industrial areas
around Sydney, Australia, was found by Fuller and Gautam (2016). In
contrast, the amount of microplastics introduced from diffuse sources in
river water or through aeolian transport in Swiss floodplain soils was
comparatively low, with an abundance of up to 55.5 mg kg−1 (593
pieces kg−1) (Scheurer and Bigalke, 2018). Microplastic abundance was
found to be up to 14,712.5 pieces kg−1 in soils of the coastal areas of
north China, derived from a large variety of sources in relation to
fishing, mariculture, and shore protection. The microplastic types pre-
sent were also more diverse than in the Swiss floodplain (Zhou et al.,
2018). Studies on microplastics in arable soils show that microplastic
abundance ranged widely from 78 pieces kg−1 in Shanghai to 18,760
pieces kg−1 in Yunnan province on average, dominated in shape by
fibers and by size fractions < 1 mm in diameter (Lv et al., 2019; Zhang
et al., 2018b; Zhang and Liu, 2018; Liu et al., 2018). In addition, sur-
veys indicate that plastic mulching and irrigation water might con-
tribute substantially to the microplastic accumulation in arable soils.
Plastic mulching is a traditional method of enhancing crop growth and
2
Journal of Hazardous Materials 388 (2020) 121814
more than 128,652 km2 of agricultural land are covered with plastic
films around the world (Zhang et al., 2019). However, the successive
enrichment of plastic fragments in soil by plastic mulching has been
recognized in several studies (Steinmetz et al., 2016; Zhang et al.,
2018b; Ramos et al., 2015).
Therefore, we hypothesized that the cropping lands with long-term
plastic mulching might contain a higher abundance of microplastics
compared to the non-mulching cropping lands due to the fragmentation
of residual films. In order to verify the hypothesis, the area surrounding
the Hangzhou Bay was selected for the study where large areas of
concentrated mulching farmlands are located with a total of forty-seven
thousand hectares of mulching farmlands for vegetable or fruit growing
(Zhejiang Statistics Bureau, 2018). Mulching soils, non-mulching soils
and irrigation water were sampled simultaneously from the agricultural
fields and analyzed for microplastics. The abundances, shapes, poly-
mers and sizes of the microplastics were determined. This study may
increase our understanding of the sources and accumulation of micro-
plastics in soil media and mulching farmlands.
2. Materials and methods
2.1. The study area
Hangzhou Bay is an inlet of the East China Sea, bordered by the
province of Zhejiang and the municipality of Shanghai. The Qiantang
River flows into the bay. The coastal plain of the Hangzhou Bay is
comprised of Jiaxing city in Zhejiang Province and the south of
Shanghai in the north bank of the bay and the Ningshao Plain in the
south bank of the bay. Three metropolitan cities, Shanghai, Hangzhou
and Ningbo, are located in this region (Fig. 1). The climate is char-
acterized by subtropical monsoon with annual precipitation of
1300−1600 mm and average annual temperature of 15-23℃ (Wei
et al., 2005). The land in the coastal plain was mainly reclaimed from
the sea and has been developed for cotton fields and crops for over 60
years. Agricultural statistical data of the region show that a total of
twenty-nine thousands tons of plastic film was used for vegetable and
fruits planting in this region each year, which covered the total area of
forty-seven thousands hectare approximately (Zhejiang Statistics
Bureau, 2018). This area is also characterized by high density of irri-
gation and drainage networks which are connected with the Hangzhou
Bay eventually.
2.2. Soil and water sampling
Samples were collected from 15 sub-areas each covered 1 km2
within the coastal plain of the Hangzhou Bay in July, 2018 (Table s1 in
the Supplementary). The spatial distributions of the sampling sub-areas
is shown in Fig. 1. The 15 sampling areas were selected because there
are both mulching farmlands and non-mulching farmlands in these
areas, and proportion of the mulching farmlands has reached more than
80 % of the total farmlands area. Meanwhile, these areas have their
own characteristics (Table s1 in the supplementary), e.g. the different
crops and different mulching types. They also have different reclama-
tion history, a longer distance to the coastline corresponding to the
longer history of reclamation (Zhejiang Statistics Bureau, 2018). All
these factors may have impacts on the residue of microplastics in the
farmlands and lead to the spatial variance of the microplastic abun-
dance in soils of the different sampling areas.
At each sub-area, both mulching farmlands and non-mulching
farmlands (rice, corn or sorghum field) were selected for soil sampling
in order to compare the microplastic difference between the two
farmland types. Four surface soil (0−10 cm) samples were collected
from the different sampling sites in a sampling sub-area, including three
samples from mulching cropping fields and one sample from non-
mulching farmlands. Therefore, there are 60 composite soil samples in
total. The landscape photos of the sampling sites could be seen in Fig. 2.
B. Zhou, et al.
Fig. 1. Location of the study area and sampling areas in the study area, the captial letters of each sampling site forms the acronym of sampling area, (BL: Bei Lun, ZH:
Zhen Hai, CXB: Ci Xi Batang Qiao, CXQ: Ci Xi Qiaotou, CXD: Ci Xi Daqiao, CXZ: Ci Xi Zhoutao, YY: Yu Yao, SX: Shao Xing, XS: Xiao Shan, HN: Hai Ning, HYD: Hai Yan
Daheyan, HYF: Hai Yan Funcun, PH: Ping Hu, FX: Fen Xian, NH: Nan Hui).
At each sampling site, six sub-samples were randomly collected from
three selected plots (50 m × 6 m for each) using a stainless shovel and
then bulked to form one composite sample.
All these samples were sieved through a 5 mm mesh screen after air
dried at 25℃, and the visible roots and large pieces of litter were re-
moved from the samples before air drying. Then the air-dried soil
sample was stored in a 500 mL wide-mouth glass bottle at 25℃ and
covered with cap for prevention of contamination.
Meanwhile, one liter water sample were collected using a standard
glass water sampler from surrounding irrigation ditches at the sampling
sites of mulching farmlands and a total of 45 water samples were col-
lected. Water sample was take from the middle of the river and all the
samples were collected in four days without rainfall. The water in the
ditches flows at a very low speed (< 0.1 m s−1). The purpose of col-
lecting the irrigation water samples simultaneously is to determine the
impact of the irrigation water on the microplastic accumulation in the
soils by comparing the abundances, types and sizes of the microplastics
between the soils and waters.
3
Journal of Hazardous Materials 388 (2020) 121814
2.3. Microplastics extraction from the soil samples
Soil samples were treated using a continuous-flow and air floating
device followed by density separation method for microplastics isola-
tion (Dai et al., 2018; Zhou et al., 2018). Briefly, 50.0 g air dried soil
was dispersed thoroughly with 0.5 mol L−1 sodium hexametaphosphate
solution and then transferred to a glass beaker which was placed inside
a 5 L container. Saturated sodium chloride solution (ρ = 1.2 g cm−3)
was pumped into the beaker at a flow rate of 1.0 L min−1 continuously
with air-blowing in the bottom simultaneously. The over-flow suspen-
sion containing microplastics and other low density materials was
collected and moved onto a vibrating sieve (pore diameter: 50 μm). The
residues in the sieve were then transferred and settled in a saturated
solution of sodium iodide (ρ = 1.6 g cm−3) for 48 h. The liquid with
buoyancy materials were filtered through a 5 μm cellulose nitrate filter
(Whatman, AE 98). The same procedures from the air floating to den-
sity separation with sodium iodide were repeated three times for the
same soil sample. All the residues on the filters were washed using
ultrapure water into a glass breaker containing hydrogen peroxide (30
B. Zhou, et al.
Fig. 2. Photos showing the landscape of the sampling areas and some possible sources of microplastics in fields, 1: Greenhouse with sunshade net; 2: Broken mulching
film residue; 3, 4: Weathered package bag; 5: Plastic wastes in field; 6: Plastic basket; 7: Plastic tape; 8: Agrochemical package bags and bottles; 9: Plastic film; 10:
Plastic debris; 11: Non-mulching rice field; 12: Irrigation water.
%, v/v) and the beaker was placed on an electric heating plate at 70℃
for approximately 72 h in order to completely remove organic matter
from the residues. Finally, the mixture in the beaker was transferred
onto a 20 μm glass fiber filter. The filters were then stored inside a glass
petri dish for further identification.
2.4. Microplastics extraction from the water samples
Water samples were treated based on the method of Dai et al.
(2018). Briefly, 1 L water sample was pass through a 5 μm cellulose
nitrate filter (Whatman, AE 98) and the residues were digested using
hydrogen peroxide (30 %, v/v) for removal of organic matter as con-
ducted for soil samples. Finally, the mixture was pass through a 20 μm
glass fiber filter which was kept for further identification.
2.5. Identification, quantification and characterization of microplastics
Micropolastics observation and identification in the filtered residues
was conducted using visual examination under a stereomicroscope
(Nikon SMZ 18, Japan). The 25x-100x magnification range of the ste-
reomicroscope was used to scan all the possible microplastics in the
residues and the minimum observable particle size is around 20 μm. In
order to reduce the possibility of microplastics mis-identification, Rules
were used in the visual identification as proposed by Peng et al. (2017).
Firstly, films or fragments should have no cellular or organic structures.
Secondly, fibers should be equally thick throughout their entire length
and are not tapered. The particles that were clear in shape and color
were selected based on these two rules and were recognized as potential
microplastics. While there were some other particles which was difficult
to be recognized but had some similarities in shape were selected as
suspected microplastics. All these particles were picked up and trans-
ferred to glass petri dish based on their shapes, and the suspected
particles were picked up and stored separately. Photographs were taken
for the potential and suspected microplastics using the camera
equipped in the microscope.
A further polymer identification was carried out to confirm the
4
Journal of Hazardous Materials 388 (2020) 121814
microplastics using micro-transformed infrared spectroscope (μ-FTIR,
Thermo Nicolet iN10 MX) under the transmittance mode. The spectrum
was set ranged of 4000−400 cm−1 with a collection time of 3 s and
scanned 32 times. All spectra were offline processed under an automatic
baseline correction mode via the OMNIC software (Version 9.1, Thermo
Nicolet Corporation). The spectra database of Hummel Polymer and
Additives and Polymer Laminate Films (Thermo Fisher Scientific, USA)
were used to determine the polymer composition of the microplastics.
The algorithm used in result matching was similarity match because it
was recommended and could eliminate the effects of baseline variation
in unknown spectra. Spectrum matches were at least 80 % for identi-
fying polymer compositions.
A part of the extracted microplastics were selected for μ-FTIR
identification. The subsamples numbers were determined based on the
microplastics types. The films contains relatively simple polymer
composition and is easy to be distinguished based on visual inspection.
However, the fragments and fibers which are supposed to be sourced
from different plastic products contain more complicated polymer
composition than films. Therefore, the numbers of films, fragments and
fibers subsamples for μ-FTIR confirmation were 12, 30 and 30 respec-
tively. The selected subsamples covered all the shapes and colors. In
addition, another 8 suspected microplastics including fibers and frag-
ments were also selected for μ-FTIR confirmation. Overall, a total of 80
microplastics samples were analyzed. The abundance of microplastics
was consequently recalculated after excluding false microplastics. The
false microplastic numbers were determined based on the proportion of
that occurred in the subsamples for each type. In this study, the 13 %
and 10 % of the subsamples were confirmed as false microplastics for
fragments and fibers, respectively. All the films were confirmed as true
microplastics in the subsamples, hence no subtraction was required for
for the films. Three particles including 2 fibers and 1 fragment were
confirmed as true microplastics in the 8 suspected particles.
Quantification and size measurement of all the identified micro-
plastics were performed using Nano Measurer 1.2 (Department of
Chemitry, Fudan University, China).
B. Zhou, et al. Journal of Hazardous Materials 388 (2020) 121814

2.6. Quality assurance (QA) and quality control (QC)

All instruments and containers were cleaned with MilliQ water be-
fore use. Sample separation and identification were carried out in a
laboratory specified for microplastic studies. Non-textile robes, caps
and gloves were worn in order to prevent contamination from fibers
and hairs when conducting the experiments. The lower and upper limit
of the microplastic size in this method is 50 μm and 5 mm, respectively.
Recovery of the microplastics from the soil under current method
was tested using analytical grade polymers (PVC, polyethylene, poly-
propylene, polystyrene and polyamide, 500 μm to 2 mm in diameter)
which were purchased from Shanghai Yangli Electromechanical
Technology Co. Ltd., China. The recovery tests were conducted for the
five polymers separately. A total of 30 counts of the polymer particles
were spiked into with 50 g relative clean soil and run through the
continuous-flow and air floating device followed by density separation.
The recovered particles were counted in the stereomicroscope. The
average recovery ranged from 75.8%–112.4%, lowest for PVC and
highest for polyethylene.
Duplicate samples which covered 10 % of the total sample numbers
were analyzed to check reliability of the method and the relative
standard deviation (RSD) of the total abundance of the duplicates
ranged from 0 to 14.1 %. Procedural blanks (deionized water absence of
microplastics) were run in parallel with the samples in the laboratory.
Fibers were monitored in the blanks and ranged from 0 to 3 pieces L−1.
Thus, quantification of fibers in the samples was corrected with blanks.
2.7. Statistical analysis
Statistical analysis were performed with the IBM SPSS Statistics
22.0 (IBM Corporation). Graphs were drawn with Origin 9.0 for
Windows software package (OriginLab Corporation). In order to com-
pare the microplastic abundances between the mulching farmlands and
non-mulching farmlands, One-way ANOVA was analyzed for each type
of the microplatics at significance level of 0.05. The Levene’s test was
performed to check the homogeneity of variance and equal variance
was obtained for the two treatments (mulching soil, non-mulching
soils) as shown in Table s2 in the supplementary.
3. Results
Fig. 3. Comparison of the soil abundance of the different microplastic types
between mulching farmlands and non-mulching farmlands. For each micro-
plastic type (films, fragments and fibers), the data for boxplots of mulching
farmlands and non-mulching farmlands counts 48 and 15, respectivelly. The red
star indicates the difference at significance level of 0.05.
values.
The abundance difference between the mulching soils and non-
mulching soils was observed. The total microplastics abundance is
higher in the soils of mulching farmlands than in the non-mulching
farmlands at most of the sampling areas (Fig. s2 in the Supplementary).
Among the different shapes, the abundances of films and fibers are
significantly (p < 0.05) higher in the soils of mulching farmlands than
that in the non-mulching farmland (Fig. 3 and Table s3 in the supple-
mentary). There is no statistical difference of the fragments between the
mulching soils and non-mulching soils, although the mean and median
levels of the fragments are both higher in the mulching farmlands.
Abundances and shapes of the microplastics in the irrigation waters
The average abundance of total microplastics in the irrigation wa-
ters is 3.9 pieces L−1 with the highest abundance of 17 pieces L−1
(Table 1). In contrast to the microplastic types in the soils which
dominated by fragments, fibers are the dominant type in the waters
while the fragments are the least one. The average abundance of fiber is
2.3 pieces L−1 and the highest abundance is 11.0 pieces L−1 in the
water samples, followed by the films. As shown in Fig. s2 in the Sup-
plementary, the microplastics abundance in the irrigation water did not
change with the abundance in the soils.

3.1. Abundances and shapes of the microplastics in the farmland soils

3.2. Size distributions of the microplastics
Three types of the microplastics including films, fragments and fi-
bers could be observed in the farmland soils in this study areas (Fig. s1
The size distributions of miroplastics are different between the
in the Supplementary). As shown in Table 1, average abundance of the
farmland soils and irrigation waters, and it also varies with microplastic
microplastics in the farmland soils is 503.3 pieces kg−1, with the
types both in soils and waters. The histogram with cumulative prob-
highest abundance of 2760 pieces kg−1. The dominated type was
ability was applied to present the size distribution of each microplastic
fragment, followed by fibers and films based on average and maximum
types in the soils and waters (Fig. 4).
In the case of farmland soils, the observed smallest microplastic
Table 1
particle is fragment with 60 μm in diameter. The size distribution of
Statistical description of the microplastic abundance in the soils and waters of
Hangzhou Bay plain.
films show two peaks, the first peak locates at the particle size of
1–1.5 mm and the second one locates at 4–4.5 mm. The size distribution
Microplastic type N Mean S.D. Range Median Detection of fragments show one peak at 0.5−1 mm and more than half of
frequency, %
fragments have the particle size ranged of 0.5−2 mm. The size dis-
Soil (pieces kg−1) tribution of fibers show a peak at 3–3.5 mm and approximate 60 % of
Films 60 57.7 73.3 0 – 420 40 75.0 the fibers have the particle size ranged of 1−3 mm.
Fragments 60 265.5 402.5 0 – 2440 110 86.7 In the case of irrigation waters, the observed smallest microplastic
Fibers 60 183.3 201.8 0 – 980 120 83.3
particle is film with 90 μm in diameter. However, the size distribution
Total 60 503.3 509.2 0-2760 310 93.3
Irrigation waters (pieces L−1) of the microplastics in the waters is generally lower than that of soils.
Films 45 1.0 1.9 0 – 8.0 0.0 30.0 The size distributions of films, fragments and fibers show single peak at
Fragments 45 0.6 1.3 0 – 6.0 0.0 21.7 0-0.5 mm, 0.6-0.8 mm and 1–1.5 mm, respectively. Approximate 70 %
Fibers 45 2.3 2.5 0 – 11.0 2.0 51.7
of the films and fragments have particle size less than 1.0 mm, while the
Total 45 3.9 3.5 0-17.0 3.0 60.0
fibers have the dominant size-fraction ranged from 0.5 mm to 2 mm.
S.D., standard deviation.

5
B. Zhou, et al.
Fig. 4. Histograms with cumulative probability showing the particle size distributions of the microplastics in the cropped soils and irrigation waters. (LOD: Limit of
Detection, The lower LOD is 50 μm in this study).
3.3. Polymer types of the microplastics
Fig. 5 shows the polymer types of the microplastics. A total of ten
polymer types were identified which included three co-polymers. The
polymer composition in the microplastics varies with shapes. Poly-
ethylene (PE) and its co-polymer with polypropylene (PP) dominate
polymer types in the films, accounting for 75 % of the total polymers,
followed by PP and nylon. While PP and it co-polymer with PE dom-
inate the polymer types in the fragments, accounting for 60 % of the
total polymers, followed by polyester and the proportion of PE de-
clining to 10 % approximately. The cumulative proportion of PE, PP
and their co-polymers further decline to 15 % in the fibers, instead
rayon and polyester dominate the polymers, accounting for 41 % and
33 % of the total polymers, respectively. Acrylic and polyamide were
the two polymers only identified in the fibers, accounting for 10 %
cumulatively of the total polymers.
Fig. 5. Polymer compostions of the diffent microplastic types in the cropped
soils; the values within brackets are replicate numbers.
6
Journal of Hazardous Materials 388 (2020) 121814
4. Discussions
4.1. The abundance comparison of microplastics among the different studies
When compared with other study areas as indicated in Table 2, the
farmland soils of Hangzhou Bay plain contain a relatively higher mi-
croplastics abundance than that in Shanghai (Liu et al., 2018) and
northwest China (Zhang et al., 2018b), however extremely lower than
that in Yunan (Zhang and Liu, 2018). The microplastics abundance is
comparable to that in the soils of Swiss floodplain (Scheurer and
Bigalke, 2018) and in the Chile soils where received ten-years sludge
applications (Corradini et al., 2019). This indicated the high variety of
microplastics abundance among the different study areas although most
of the soils were collected from farmlands. Such a variability was also
presented in microplastic shapes. The abundances of films, fragments
and fibers in the farmland soils of Hangzhou Bay plain as well as other
study areas are all higher than that in the coastal beaches of Shandong
peninsula (Zhou et al., 2018). This suggested that microplastics in the
farmlands were characterized of films, fragments and fibers.
The big variety of microplastics abundance among the different
studies might be partly owing to the different methods applied for
miroplastics extraction and quantification (He et al., 2018). The method
of air floating and subsequent density separation was applied to extract
microplastics from soil samples in this study, which has been demon-
strated successfully applied for sediments (Dai et al., 2018; Nuelle et al.,
2014) and coastal soils (Zhou et al., 2018). Prior to the air floating,
sodium hexametaphosphate solution was used to disperse soil samples
thoroughly for destruction of soil aggregates in which microplastics
might be retained and unable to be extracted using density separation
(Zhang and Liu, 2018). Therefore, this method probably could extract
more microplastics from the soils than density separation solely (Liu
et al., 2018). In addition, identification with μ-FTIR in combination of
visual observation may provide a more precise determination of mi-
croplastics abundance compared to the visual method solely (Zhang
and Liu, 2018). The visual inspection has a high risk of missing or
misidentifying particles, for instance, Dekiff et al. (2014). reported that
three independent visual inspections resulted in different quantitative
statements for the same sample extract. In this study, a part of the ex-
tracted microplastics were selected for μ-FTIR identification, which
included all the suspected particles and the representative particles
covered all the microplastic shapes, colors and sampling areas. Selected
a subset of the particles for confirmation using spectroscopic techniques
B. Zhou, et al. Journal of Hazardous Materials 388 (2020) 121814

Table 2
Average abundance of microplastics in the soils of different studies, abundance of films, fragments and fibers and the sum of all the extracted microplastics (total) are
compared.
Study area Analytical method N Microplastic abundance (pieces kg−1) Reference

Films Fragments Fibers Total

Hangzhou Bay plain Air-floating in saturated NaCl and density separation 45 73.44 304.33 213.56 571.2 This study
(Mulching farmland) in saturated NaI, μ-FTIR confirmed
Hangzhou Bay plain 15 25.67 150.67 89.33 262.7 This study
(Non-Mulching farmland)
Shanghai, China Density separation in saturated NaCl, μ-FTIR 20 5.20 29.31 41.59 78.00 (Liu et al., 2018)
(Vegetable fields, 0−3 cm) confirmed
Yunan, China Density separation in saturated NaI 50 592 816 17530 18,760 (Zhang and Liu, 2018)
(Vegetable fields, 0−5 cm)
Northwest China Floating in distilled water, heating method (3–5 s at 10 n.a. n.a. n.a. 100 (Zhang et al., 2018b)
(Vegetable fields, 0−10 cm) 130 °C) a
Shandong peninsula, China (Coastal Air-floating in saturated NaCl and density separation 120 1.2 8.2 7.3 740.1 (Zhou et al., 2018)
beaches) in saturated NaI, FTIR confirmed
Swiss floodplain Density separation in saturated NaCl, FTIR confirmed 29 n.a. n.a. n.a. 593 b
(Scheurer and Bigalke,
2018)
Chilean soils with ten years of sludge Density separation in distilled water, saturated NaCl 45 n.a. n.a. n.a. 460-3,800c (Corradini et al., 2019)
applications and NaI sequentially

a, the method was developed specified to the low-density microplastics PE and PP; b, maximum concentration rather than average concentration; c, original unit is
pieces (5 g)−1 and the original data were converted to pieces kg−1 here after multiplying by 200; n.a., not available.

has also been used in many other studies to avoiding false microplastics
(Filella, 2015). However, there has not been a consistent method de-
veloped for subsample selection in the microplastics confirmation by
now. In most of the cases, the representativeness of the subsample
would be taken into accounted, which covered the shapes, colors and
sizes of the microplastics (Cozar et al., 2014; Sadri and Thompson,
2014; Doyle et al., 2011).
4.2. Source of plastic mulching to the microplastics in the soils
The abundance of films in soils in this study shows a higher pro-
portion than other studies. The major polymer composition of films are
PE and its copolymers, which was assumed to be sourced from the re-
sidue of plastic mulching used widely in the cropped lands. Because the
most common used polymer is PE in plastic mulching, including high-
density, low-density and linear low density PE (Blasing and Amelung,
2018). The higher films abundance in the mulching soils compared to
the non-mulching soils demonstrated the major contribution of plastic
mulching to the films in the farmlands. The usage of plastic mulching in
cropped land has amounted to 1.5 million tons each year in China and
over 40 % of the used plastic mulching has not been recycled (Zhao
et al., 2017). Meanwhile, the thickness of plastic films used in China are
primary less than 0.005 mm, much lower than the films of 0.02 mm
used in Europe or Japan (Zhao et al., 2017). Such thin films were
supposed to be broken easily under cultivation and hard to be recycled.
The residual plastic mulching in the fields may lose its integrity and
break down into smaller and smaller plastic residues of various sizes
(700 μm2 –2850 cm2), and some of them would eventually form mi-
croplastics (Steinmetz et al., 2016; Ramos et al., 2015; Briassoulis et al.,
2015). The microplastics fragmented from the mulching film in soils are
mainly composed of PE or PP and the sizes of the particles tend to be
larger than other microplastic types. This led the film microplastics to
be identified and quantified easily in the soil samples (Zhang et al.,
2018b). Further effects should be involved in the mechanisms regarding
the fragmentation from the mulching films to microplastics in the dif-
ferent soil environments.
ubiquitously in water (Dai et al., 2018), sludge (Zubris and Richards,
2005), and air samples (Dris et al., 2016). It has been known that
laundry washing machines discharge large amounts of fibrous micro-
plastics into wastewaters and the synthetic fibers persist both in the
treated wastewater effluent as well as the sludge that produced by
wastewater treatment (Corradini et al., 2019; Hernandez et al., 2017).
Therefore, irrigation was supposed to be a major pathway of the syn-
thetic fibers into the cropped soils. Meanwhile, the higher abundance of
synthetic fibers in the mulching soils than in the non-mulching soils
implied that the mulching farmlands might receive more fibers from
irrigation water. The mulching farmlands grown with vegetables or
fruits have more cropping rotations than the rice fields absent of plastic
mulching, hence larger amount of water with fibrous microplastics has
been irrigated in the mulching farmlands than the non-mulching
farmland. In addition, the basin flood irrigation applied in the rice
fields might reduce the retention of fibers in the soils in comparison
with furrow irrigation used in the mulching farmland (Steinmetz et al.,
2016). However, the dynamic loading of fibers in the soils with dif-
ference irrigation modes should be investigated in the future studies.
Notwithstanding, the incoherence of microplastics abundances be-
tween the soils and irrigation waters suggested that there were multiple
pathways of microplastics input into the soils other than irrigation. In
addition, it is noticeable that particle sizes of the microplastics are all
bigger in the cropped soil than in the surrounding waters for the three
shapes (Fig. 4). This implied that the contribution of irrigation water to
the microplastics abundance in the soils was mainly the small sized-
fractions of microplastics. While large sized-fraction (e.g. > 2 mm) of
microplastics was assumed to derive mainly from other sources (Blasing
and Amelung, 2018; Scheurer and Bigalke, 2018). Meanwhile, the
contribution of irrigation water to the microplastics accumulation in
the soils might be underestimated in this study owing to the limitation
of analytical method which is incapable of measuring the microplastics
with size lower than 50 μm. Probably using the mass quantification
methods, e.g. Thermal extraction and desorption coupled with gas
chromatography-mass spectrometry (TED-GC/MS) may provide a more
accuracy estimation (Renner et al., 2018).

4.3. Source of irrigation water to microplastics in the soils 4.4. Source of plastic wastes and compost to microplastics in the soils

This study demonstrated that the synthetic fibers were the dominant The fragments are the dominated microplastics in the soils with a
microplastic form in the soil as well as irrigation waters. The fibers diversified polymer compositions. The proportion of PP and its copo-
including polyester, polyamide, rayon etc. have been detected lymers is approximate 60 % for the fragments and the remaining

7
B. Zhou, et al.
identified polymers include PE, polyester, nylon and rayon. The
polymer of PP was more susceptible to be fragmentation than other
polymers such as PE and polystyrene under ultraviolet (UV) exposure
due to the lower bond dissociation energy of the chemical bonds in PP
(Song et al., 2018; Weinstein et al., 2016). A weathering experiment
performed in the laboratory indicated that a 12-months UV exposure
and 2-months mechanical abrasion of PP pellets could produce
6084 ± 1061 particles pellet−1 (Song et al., 2018). Therefore, the
fragments in the soil were assumed to be mainly sourced from the de-
gradation of residual plastic wastes under long-term weathering. Plastic
package bags and bottles of PP for agrochemicals and fertilizers could
be found residue in fields regardless of mulching or not in the study
areas (Fig. 2), which probably contributed significantly to the sources of
fragments in the soils.
In addition to the degradation of plastic wastes, compost application
in the cropped fields was supposed to be another major source to the
fragments. The composts have been found containing substantial
amount of microplastics. Weithmann et al. (2018) collected compost
samples with different substrate pretreatment, plant and waste and
found that all samples were found microplastics and abundance of the
particles > 1 mm in diameter was up to 895 pieces kg−1. Meanwhile,
most of the microplastics were fragments, accounting for 75%–100%.
Whereas, the contribution of composts application to the microplastics
accumulation in the cropped soils are not clear yet. In particular of the
mulching farmlands grown with vegetables, the input of microplastics
through composts application deserved to be concerned about since the
application rate of composts is almost ten times higher than that in the
conventional rice field (Zhang et al., 2016). Future studies may focus on
the microplastics accumulation in the cropped soils after a long-term
application of different composts.
5. Conclusions
This study demonstrated that the mulching cropped soils contained
much higher microplastics than the non-mulching cropped soils, which
is 571.2 pieces kg−1 and 262.7 pieces kg−1 on average, respectively.
Nonetheless, the contribution of higher microplastics abundances in the
mulching cropped soil is not only sourced from the plastic mulching
which is primary composed of polyethylene and its copolymers. The
multiply polymers and shapes found in the mulching cropped soils in-
dicated that other sources (e.g. irrigation water, plastic wastes de-
composition, or composts application) may play important roles.
Fragments of polypropylene could be traced to the plastic package bags
and bottles for agrochemicals. While fibers of polyester or raynon ori-
ginated from clothing probably entered into the cropped soils by the
pathway of irrigation. A continue studies deserved to be carried out
regarding the development of the mass quantification methods for the
soil microplastics and revealing the long-term loading of microplastics
in the agroecosystems from different source contributions under the
intensive cropping patterns.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
CRediT authorship contribution statement
Bianying Zhou: Writing - original draft. Jiaqing Wang:
Investigation. Haibo Zhang: Supervision. Huahong Shi: Resources.
Yufan Fei: Software, Visualization. Shunyin Huang: Formal analysis.
Yazhi Tong: Investigation. Dishi Wen: Investigation. Yongming Luo:
Methodology. Damià Barceló: Writing - review & editing.
8
Journal of Hazardous Materials 388 (2020) 121814
Acknowledgments
This research was funded by the National Natural Science
Foundation of China (No. 41771351), Zhejiang Provincial Natural
Science Foundation of China (No. LZ19D010001), Zhejiang Agriculture
and Forestry University Research Fund (2017FR021), Key Research
Program of Frontier Sciences, CAS (No. QYZDJ-SSW-DQC015) and the
“111” Project (D18008). Thanks are given to the anonymous reviewers
for their suggestive comments on the improvement of the manuscript.
We also appreciate the contribution of Dr. Peter Christie in the language
polish for this manuscript.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.jhazmat.2019.121814.
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