Chemosphere 257 (2020) 127234

Contents lists available at ScienceDirect

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

Microplastic contamination on the lower Chao Phraya: Abundance,

characteristic and interaction with heavy metals
Anh Tuan Ta, Sandhya Babel*
School of Biochemical Engineering and Technology, Sirindhorn International Institute of Technology, Thammasat University, P.O. Box 22, Pathum Thani,
12121, Thailand

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 MPs were found in water and sedi-

ment of Chao Phraya River at Tha Pra
Chan.
 MPs in water were detected at
80 ± 65 items/m3 and
53.3 ± 58.4 mg/m3.
 MPs in sediment were detected at
91 ± 13 items/kg and 4.9 ± 3.4 mg/kg.
 Most MPs were PP, PE and PS with
the dominant size of 0.05e0.5 mm.
 Heavy metals were found with high
concentration of Pb and Cu adsorbed
on MPs.

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

Article history: While a large number of studies on microplastics (MPs) in the western hemisphere have been performed,
Received 6 February 2020 few studies are available in the eastern hemisphere, especially in Southeast Asia. In this study, the
Received in revised form abundance of MPs in water and sediment samples from the Chao Phraya River at the Tha Pra Chan area,
15 April 2020
Thailand, was investigated. Water samples were collected by a manta trawl, and sediment samples were
Accepted 25 May 2020
collected by a Van Veen grab sampler. The average number and concentration of MPs in water samples
Available online 26 May 2020
were 80 ± 65 items/m3 and 53.3 ± 58.4 mg/m3, respectively. The average number and concentration of
Handling Editor: Shane Snyder MPs in sediment samples were 91 ± 13 items/kg and 4.9 ± 3.4 mg/kg, respectively. The main mor-
phologies of MPs were fragments and fibers, mostly white. Polypropylene (PP) was the dominant
Keywords: polymer type found in both water and sediment. Moreover, the content of heavy metals (Cr, Cu, Ni, and
Microplastic Pb) on MPs was extracted by aqua regia solution and analyzed by ICP-OES. Results show high concen-
Freshwater trations of Pb and Cu adsorbed on MPs in the study area. In brief, this study suggests that there are high
Heavy metals levels of MPs in the water and sediments of the Chao Phraya River at the Tha Pra Chan area.
Chao Phraya river
© 2020 Elsevier Ltd. All rights reserved.
Tha Pra Chan
FTIR

1. Introduction (Waters et al., 2016). The annual global production of plastic has
increased steadily from 1.7 to 350 million tonnes over the last 60
Plastics are now considered a signature of human beings years (PlasticsEurope, 2018). As a result, plastic waste is a major
component of riverine and coastal pollution. Currently, 663 species
are known to be impacted by plastic pollution through entangle-
ment or ingestion, including mammals, birds, and reptiles (Dias and
* Corresponding author. Lovejoy, 2012). Ingested plastics can cause internal damage, reduce
E-mail address: [email protected] (S. Babel).

https://doi.org/10.1016/j.chemosphere.2020.127234
0045-6535/© 2020 Elsevier Ltd. All rights reserved.
2 A.T. Ta, S. Babel / Chemosphere 257 (2020) 127234

feeding, disturb the digestive enzyme system or hormone balance, region is well known as a hotspot of mismanaged plastic waste. In
and have an impact on reproduction. In recent years, the more the top 10 countries that have mismanaged plastic waste, 5 coun-
serious and widespread ecological impacts of microscopic plastic tries belong to ASEAN. In total, 3.55 million tonnes of plastic waste
debris, so-called MPs, have become a concern. entered the aquatic environments from Indonesia, Philippines,
Most researchers define MPs as plastic particles that are smaller Vietnam, Thailand, and Malaysia (Jambeck et al., 2015). This creates
than 5 mm in diameter (Moore, 2008; Parliament, 2008; Fendall a threat to water security in the region.
and Sewell, 2009). Generally, MPs are divided into categories of Thailand is a major plastic manufacturer and contributor of
either primary or secondary MPs. Primary MPs are manufactured in plastics in Asia. The plastic pellet and resin production capacity in
micro sizes such as resin pellets and microbeads for cosmetic 2015 was about 6.1 million tonnes (Wichai-utcha and Chavalparit,
products and plastic resin. Secondary sources of MPs are formed 2019). As a result, more than 3 million tonnes of plastic wastes
from the disintegration of larger plastics by biodegradation, pho- were produced in the country, annually. However, only half of the
todegradation, thermooxidative degradation, thermal degradation, amount goes for reuse or recycling (PCD, 2016). The mismanage-
or hydrolysis (Andrady, 2011). Moreover, textile laundering facil- ment of waste in Thailand makes 1.03 million tonnes of plastic
ities and sandblasting are other sources of MPs (Browne et al., 2011; enter the aquatic environment, annually (Jambeck et al., 2015). The
Napper and Thompson, 2016). Pollutants get washed down the sink Chao Phraya River is a major river in Thailand with a length of about
along with wastewater and enter sewage systems. They are too 372 km, exiting in the Gulf of Thailand. On the river, aquatic farming
small to be filtered by sewage-treatment plants and consequently is well developed with an annual production of about 200,000
end up in the river systems and ultimately in the oceans. The effects tonnes. The river is also the major raw water supply for more than
of MPs on the aquatic environment and humans are still being 10 million residents. However, the Pollution Control Department of
studied. However, there is much evidence for significant harm to Thailand (PCD, 2019) reported that the water quality of the river has
biota. MPs are ingested by aquatic organisms including corals, seriously deteriorated in the past decade due to discharges of do-
barnacles, sea cucumbers, zooplankton, rotifers, ciliates, crusta- mestic wastewater, urban runoff, industries, and agriculture. These
ceans, amphipods, and fish (Thompson et al., 2004; Browne et al., pollutant sources can also be sources of MPs in aquatic environ-
2008; Graham and Thompson, 2009; Cole et al., 2011; Set€ al€
a ments. So far, no data on the contamination of MPs in the Chao
et al., 2014). Once ingested, these particles can be transferred to Phraya River have been reported.
higher trophic levels (Farrell and Nelson, 2013; De Sa  et al., 2015). As the above situation, this study investigated MPs in the surface
Toxicity of MPs can be caused by the plastic polymers themselves, water and sediment samples from the Chao Phraya River at Tha Pra
the additives they contain, or by other pollutants adsorbed on the Chan, Bangkok. The main objective is to monitor the current status
MPs. It is reported that MPs in marine environments concentrate of MPs in the river (number and concentration) at Tha Pra Chan, a
various contaminants including persistent organic pollutants densely populated area. For this, both sediment and water samples
(Heskett et al., 2012) and metals (Turner and Holmes, 2015). The were collected. Morphologies and colors of MPs along with the
sorption of the pollutants on MPs is considered an important adsorption of heavy metals on MPs are investigated and reported in
environmental process because this will affect the mobility and this study.
bioavailability of these pollutants. Researchers have reported
adsorption of heavy metals on MPs via several mechanisms. The
2. Methods and materials
adsorption mechanism may be related to the modification of the
MP surface due to the weathering and the attachment of organic
2.1. Study areas
matters. Long-term modification can happen through photooxi-
dation and attrition of charged material (Turner and Holmes, 2015).
Surface water and sediment samples were collected from the
According to Butorn (2002), the mechanism is characterized by
Chao Phraya River at the Tha Pra Chan area of Bangkok, Thailand.
forming water-soluble and water-insoluble complexes with metal
The study area is in downtown Bangkok which is highly populated.
ions and hydrous oxides. With the interaction between MPs and
Therefore, the authors hypothesized that MPs in this area are
silt, clay could also accumulate metals. Moreover, metals and
contributed mainly by treated and untreated domestic wastewater
complexes could directly interact with the charged sites or neutral
and other urban activities.
regions of the MP surface (Ashton et al., 2010). Accumulation of
metals may occur by interactions between bivalent cations and
oxyanions with charged or polar sites of the MP surface. Non- 2.2. Sampling method
specific interactions between neutral metal-organic complexes
and the hydrophobic surface also accumulate metals on MPs 2.2.1. Water samples
(Holmes et al., 2012). Furthermore, the growth of biofilms on MP Surface water samples were collected by a volume-reduced
surface could enhance the accumulation of metals (Tien and Chen, method with a manta trawl. The manta trawl consists of a rectan-
2013; Rochman et al., 2014). The potential effects of MPs on aquatic gular aluminum frame (20 cm high x 50 cm wide) and a 2-m long
organisms can be physical effects such as obstruction, chemical net. The net with a mesh size of 300 mm was connected with a cod-
effects due to the transportation of toxic chemicals, impaired end (25 cm high x 10 cm diameter). The manta trawl was towed
health, impacts on population and ecosystems, and dispersal of behind a research boat to avoid the turbulence of the boat engine.
damaging pathogens (Wright et al., 2013). However, the in- The trawling speed ranged from 5 to 12 km/h. The water volume
teractions between chemicals and MPs in freshwater and marine filtered by the manta trawl was recorded by a flow meter (Hydro-
environments have not been widely reported. Bios model 438110), mounted at the net opening. This enables to
Currently, most MP studies are concentrated in developed calculate the number and concentration of MPs per unit water
countries such as in Europe, North America, and the East Asian volume. Samples were collected on the superficial layer of the
region. Few studies are known in the Southeast Asian region water column (6e10 cm surface layer). The samples were collected
(ASEAN) (Do Sul and Costa, 2014). To highlight this, a literature two times within two months in the dry season of Bangkok. In total,
search on Thomson Reuters’ ISI Web of Science returns 1319 papers twelve water samples were collected. Sampling locations are
containing the term ‘microplastic’, of which only a subset of 31 shown in Fig. 1. All collected samples were rinsed from the net and
publications (2.4%) is in the ASEAN region. However, the ASEAN sieve into 1-L glass containers by deionized water.
 A.T. Ta, S. Babel / Chemosphere 257 (2020) 127234 3

Fig. 1. Sampling sites at Tha Pra Chan area, Bangkok. Sample locations along the river are marked with circles: (M1, M4) Bank 1, (M2, M3) Bank 2, (M5, M6) Middle, (S1) Sediment
bank 1, (S2) Sediment bank 2.

2.2.2. Sediment samples scans. FTIR spectroscopy helps to confirm the polymer types of MPs
Sediment samples were collected from a depth of about 2e4 m in samples.
below the surface water by a 10 L Van Veen grab sampler. Four
samples of sediment were taken at both banks of the Chao Phraya 2.3.1.2. Particles smaller than 0.5 mm. The fractions containing
River at the study area, as shown in Fig. 1. At each position, about particles smaller than 0.5 mm (i.e. retained on sieve mesh sizes of
0.5 kg of sediment was collected and kept in 1 L glass containers. 0.05, and 0.3 mm) were transferred into different beakers by
Both water and sediment samples were kept at 4  C in a laboratory deionized water. Fractions in these size ranges are difficult to
for further analysis. examine visually because they carry much sediment and organic
debris. Thus, hydrogen peroxide (30%) with iron (II) as a catalyst
2.3. Sample processing was used to remove organic material. Moreover, sodium iodide
(NaI) with a density of 1.5 g/cm3 was also used to remove sediment
A procedure designed for the analysis of MPs concentration in and some organics from the samples in these size ranges. The
the marine environment by Masura et al. (2015) was adopted with remaining solids after density separation were filtered on cellulose
modifications for this study. Water samples were first sieved nitrate membrane filters by vacuum filtration and dried in an oven
through stainless-steel mesh sizes of 0.05, 0.3, 0.5, 1.0, and 5.0 mm. at 60  C. After drying, the size fraction of 0.3 mm was inspected by
To transfer all solids to the sieves, deionized water was used for an optical microscope and FTIR, similar to the particles larger than
rinsing. On the sieve of 5.0 mm, organics such as leaves, bugs, larger 0.5 mm. However, the efficiency of the organic digestion process
algae, and wood were carefully rinsed with deionized water and could not reach 100% for the size fraction of 0.05 mm. The
picked out of the samples with tweezers. remaining organic debris impeded the inspection of small MPs on
the optical microscope. Therefore, filter papers that contain parti-
2.3.1. Water samples cles of the size fraction of 0.05 mm were stained with Nile Red (NR)
2.3.1.1. Particles larger than 0.5 mm. The fractions containing par- solution. The method for staining was adopted from Tamminga
ticles larger than 0.5 mm (i.e. retained on sieves mesh sizes of 0.5 et al. (2017). NR was dissolved in chloroform with a concentration
and 1.0 mm) could be examined visually without instruments. of 1 mg/ml. The NR solution was applied with a microliter pipette to
Therefore, suspected plastic debris in this size range was picked out the center of each filter to provide an even distribution and a
on Petri dishes using stainless-steel tweezers. The total solids for complete moistening of both filters and particles. Stained mem-
these particles were determined by drying in an oven at 60  C for brane filters were examined under a fluorescence microscope
24 h. Suspected plastics larger than 0.5 mm were inspected by an (DeltaVision™ Elite cell imaging system) using an excitation DAPI
optical microscope (Olympus CX41) at 4x and 10x magnification. of 390/18 nm and an emission DAPI of 435/48 nm. After visual
Under the microscope, MPs were inspected for the number, sorting, 10 spots on each membrane filter were randomly chosen
morphology, and colors. After visual sorting, all particles were and identified by a Thermo Science micro-FTIR (Nicolet iN10MX).
inspected by Fourier transform infrared (FTIR) spectroscopy. A
Thermo Science FTIR (Nicolet iS50) spectrometer was equipped 2.3.2. Sediment samples
with a diamond micro-tip resolution of 8 cm 1 using a diamond For sediment samples, duplicate 50-grams wet sediment sam-
micro-tip with a range of 4000-650 cm 1 with an average of 8 ples were used for MP analysis. The samples were dried in the oven
4 A.T. Ta, S. Babel / Chemosphere 257 (2020) 127234

at 60  C and the total solids were determined. Due to the whereas the lowest concentration is detected at bank 1. This dif-
complexity of sediment samples, plastic debris needs to be ference may be explained by the turbulence and morphology of the
extracted from the sediment by floatation in NaI solution. The so- river at the study area. As shown in Fig. 1, before the sampling
lution with a density of 1.5 g/cm3 was used as most plastic types points, the river has a curve that affects the river flow. Moreover,
have specific gravities < 1.4 g/cm3. The dried sediment was mixed busy activities of boats at the banks may also make materials flow
with 200 ml of the NaI solution in a beaker for 30 min by a magnetic into the middle position of the river. However, further studies are
stirrer. The mixture was transferred into a glass funnel for settling. needed to confirm and explain the differences in MPs concentra-
After 24 h of settling, the floating particles were collected and tions at different positions in the river.
treated, similar to the surface water samples. Since the standards for the collection, identification, and eval-
uation of MPs are still not developed, the results in this study were
2.4. Heavy metal analysis only compared with studies using the same units (item/m3, and
mg/m3). The number of MPs at the Tha Pra Chan area in the Chao
After analysis by FTIR, thirty to fifty particles of MPs from each Phraya River is fewer than in other rivers in Asia but higher than
sampling position were transferred into 10 ml glass vials for the rivers in Europe. Some studies on rivers in China such as the
analysis of heavy metals. These particles were weighted to deter- Yangtze River, the Hanjiang River, and the Pearl River have a higher
mine the total mass. Aqua regia solution (3 ml of 50%) was trans- MP number than the Chao Phraya River (Table 1) (Wang et al.,
ferred into each vial for metal extraction. The contents were shaken 2017b; Yan et al., 2019). In the Saigon River of Vietnam, the num-
on an orbital shaker at 150 rpm for 48 h. The extracted solution was ber of MPs was 172000e519000 items/m3. This is also much higher
diluted with deionized water. Arsenic (As), cadmium (Cd), copper than that of the Chao Phraya River (Lahens et al., 2018). Studies on
(Cu), chromium (Cr) lead (Pb), and nickel (Ni) were analyzed by rivers in European countries, such as the Danube River (Austria)
Perkin Elmer inductively coupled plasma - optical emission spec- and the Seine River (France), have lower numbers of MPs than this
troscopy (ICP-OES, model Avio 200). The calibration curve was study (Lechner et al., 2014; Dris et al., 2015). Many studies reported
prepared by using five mixed-standard solutions (Perkin Elmer that waste management practices and high population density are
N9300281). directly related to the high level of MP pollution in regions
(Lambert and Wagner, 2018). Therefore, the number of MPs in this
2.5. Contamination control study and other studies may demonstrate the level of waste man-
agement systems in each study area. Moreover, the data also
To minimize the contamination of samples during sampling and highlight the unsound waste management systems in Asian
analysis, the following procedure was strictly followed. Standard countries, compared to European countries (Wu et al., 2018a).
non-plastic equipment, i.e. metal and glass, was used as much as The concentration or mass of MPs was not widely reported in
possible. The researchers wore 100% natural fiber clothing and lab freshwater studies. During the sampling and analysis processes, the
coats. Samples and glassware were covered with aluminum foil number of MPs can be under/overestimated because MPs are easily
during analysis steps to avoid air exposure. The equipment was lost or fragmented into smaller particles. Therefore, the mass of
thoroughly rinsed using distilled water, prior to use. All experi- MPs is important to indicate and compare the levels of MP pollution
ments were carried out inside a laminar flow hood. Control ex- in different regions. In this study, the mean concentration of MPs in
periments with a known type and number of MPs were conducted the surface water is 53.3 ± 58.4 mg/m3. This is much higher than
to investigate the recovery efficiency of the applied method. Blank the concentration of MPs in the Danube River, the Meuse River, and
samples (deionized water only) were conducted parallel with the Rhine River (Table 1) (Lechner et al., 2014; Urgert, 2015). This
samples to determine the contamination level during experiments. phenomenon is reasonable since the number of MPs in the rivers of
Europe is much lower than that of the Chao Phraya River.
2.6. Unit and data expression
3.1.2. Sediment samples
The abundance of MPs in the water in this study was expressed MPs were also detected in sediment samples collected at two
as the number (items/m3) and concentration (mg/m3) per unit banks of the Chao Phraya River. At the middle position, sediment
volume of water. For sediment, MPs were also reported as the samples could not be collected because the river is too deep. The
number (items/kg) and concentration (mg/kg) per unit of dried mean number and concentration of MPs are 91 ± 13 items/kg and
sediment. Adsorption of heavy metals on MPs was expressed as the 4.9 ± 3.4 mg/kg, respectively. In comparison with other studies, the
concentration of metals per unit of dried MPs (mg/g). The data are number of MPs in this study is higher than that of the Ciwalengke
expressed as the mean and standard deviation (SD) at each sam- River, Indonesia (Alam et al., 2019). However, the number of MPs in
pling position. sediment at the Thames River (UK) and Beijiang River (China) is
significantly higher than the Chao Phraya River (Horton et al., 2017;
3. Results and discussion Wang et al., 2017a). At the Rhine and Main River (Germany), both
the number and concentration of MPs are higher than this study
3.1. Microplastic abundance (Klein et al., 2015). A possible explanation for the differences in MPs
levels between this study and others is the sampling methods. At
3.1.1. Water samples the study area of the Chao Phraya River, artificial riverbanks made
MPs were found in all surface water samples collected from the of concrete were completely built. Therefore, benthic sediment
Chao Phraya River at the Tha Pra Chan area. As shown in Table 1, the samples were collected under the surface water from 2 to 4 m by
lowest and highest numbers of MPs are 48 ± 11 and 155 ± 16 items/ the Van Veen grab sampler. While the other studies collected sur-
m3 for bank 2 and the middle position, respectively. The mean face sediment by a stainless-steel scoop or spoon.
number of MPs in all samples at the study area is 80 ± 65 items/m3.
In terms of concentration, MPs ranged from 17.9 ± 1.1 to 3.2. Microplastic size
120.7 ± 8.1 mg/m3. As presented in Fig. 2, the number and con-
centration of MPs do not have the same trend. The highest con- 3.2.1. Water samples
centration of MPs is found at the middle position of the river, The percent distribution of MPs by size varies among different
 A.T. Ta, S. Babel / Chemosphere 257 (2020) 127234 5

53.3 ± 58.4
21.3 ± 20.9
120.7 ± 8.4
17.9 ± 1.1

4.9 ± 3.4
6.4 ± 2.5
1.3 ± 1.1
Total

1228e3763 items/kg; 21.8e932 mg/kg

43.5e459 items/kg; 43.5e459 mg/kg
178 ± 69 to 544 ± 107 items/kg
0.05e0.3

0.6 ± 0.3

4.9 ± 3.4
0.3 ± 0.1
0.5 ± 0.5
0.8 ± 0.2

6.4 ± 2.5
1.3 ± 1.1

Number; concentration

30.3 items/kg

660 items/kg
0.5 ± 0.6
0.2 ± 0.0
0.2 ± 0.1
1.2 ± 0.2
0.3e0.5
Concentration (water, mg/m3), (sediment, mg/kg)

e
e

Fig. 2. Number and concentration of MPs in surface water and sediment with SD.
0.5e1.0

Ciwalengke River, Indonesia (Alam et al., 2019)

16.1 ± 2.1

positions in the river, as presented in Fig. 3. MPs with a size of

8.4 ± 7.4
7.6 ± 4.9
1.4 ± 0.3

0.5e1 mm are dominant in samples collected at bank 1 of the

Chao Phraya River. At bank 2, size ranges of 0.05e0.3 and
e
e

0.3e0.5 mm are more abundant than other sizes. Samples at the

middle position give the lowest percentage of MPs with a size of
Main River (Germany)
Beijiang River (China)

0.05e0.3 mm. In general, MPs with a size of 0.3e1.0 mm (middle

43.8 ± 51.1
19.1 ± 20.2
102.5 ± 5.9

Horton et al., (2017)

Wang et al., (2017a)

Thames River (UK)

Klein et al., (2015)

9.8 ± 3.7

size) account for a higher proportion (60%) than other size ranges
1.0e5.0
Number and concentration of microplastics in water and sediment samples in the study area, as compared to other rivers in the world.

(mean data, Fig. 3). In comparison with other studies, MPs in this
Rhine River
e
e

study had smaller sizes. In the Yangtze estuary and estuaries of

Sediment

Minjiang, Oujiang, and Jiaojiang (China), MPs with a size of

0.5e1.0 mm were the most abundant (Zhao et al., 2014, 2015). MPs
detected at the Three Gorges Reservoir (China) were mostly
155 ± 16
80 ± 65

91 ± 13
48 ± 11
38 ± 30

96 ± 12
86 ± 17

0.5e1.6 mm (Zhang et al., 2015). The MP size distribution is related

Total

to the sources of MPs and reflects the degree of weathering.

Therefore, the higher degree of weathering in Thailand compared
to the other study areas might result in a higher abundance of
smaller MPs (Wu et al., 2018a). Moreover, the percent distribution
0.05e0.3

11 ± 16

91 ± 13
96 ± 12
86 ± 17

of MPs by size range is an important parameter to indicate the

10 ± 2
15 ± 1
7±1

severity of MP pollution in the study areas. The smaller the size of

172000 to 519000 items/m3

9.7 items/m3; 0.14 mg/m3

MPs detected, the more severe the threat to the ecosystem

Number; concentration

56 items/m; 0.56 mg/m3

2516.7 ± 911.7 items/m3

0.317 ± 4.665 items/m3;

(Haegerbaeumer et al., 2019).

Number (water, items/m3), (sediment, items/g)

933 ± 305.5 items/m3

In this study, samples were collected by a manta trawl net with

0.3e0.5

4.8 ± 24.2 mg/m3

22 ± 16
13 ± 10

19860 items/m3
12 ± 1

41 ± 2

a mesh size of 0.3 mm. However, MPs smaller than 0.3 mm were
0.35 items/m3

still detected in the samples. These smaller MPs might be stuck to

e
e

larger particles due to cake filtration in the aquatic environment.

0.5e1.0

25 ± 20
23 ± 8

47 ± 8
6±6

e
e

Meuse River (Netherlands) Rhine River (Urgert, 2015)

1.0e5.0

22 ± 26
9 ± 12
52 ± 5

Danube River (Austria) (Lechner et al., 2014)

6±3

e
e

Yangtze River (China) (Zhao et al., 2014)

S bank 1
S bank 2
Middle
Bank 1
Bank 2

Mean

Mean

Saigon Rivers (Vietnam)

Hanjiang River (China)
Wang et al., (2017b)

Lahens et al., (2018)

Seine River (France)

Pearl River (China)

Dris et al., (2015)

Yan et al., (2019)
Surface water
Surface water
Size (mm)

Sediment
Samples
Table 1

Fig. 3. Percent distribution of each size range of MPs in surface water.

6 A.T. Ta, S. Babel / Chemosphere 257 (2020) 127234

Moreover, small organisms that may contain the small sizes of MPs organisms.
such as plankton, fish, and shrimp were also collected by the manta
trawl. These MPs might be released through the digestion step by 3.3. Microplastic morphology
H2O2. Therefore, the number and concentration of MPs that are
smaller than 0.3 mm may be lower than the number and concen- 3.3.1. Water samples
tration in the river. In this study, MPs were classified into fragments, pellets, films,
and fibers. Briefly, films are thin pieces of plastic debris, pellets are
3.2.2. Sediment samples spherical or cylindrical pieces, fibers are thin and long items, and
MPs with a size range of 0.05e0.3 mm were found in sediment fragments are unidentified morphology. The morphologies of MPs
samples in the Chao Phraya River. This is because samples were were not much different for the three sampling positions in the
collected under the surface water by 2e4 m. At this depth, the small Chao Phraya River (Fig. 4A). At both banks, the proportions of
MPs may sink to the bottom of the river by cake filtration or morphologies are similar, with the dominance of fragments (>50%)
agglomeration rather than by density. and fibers (>40%), while in the middle location, fragments were the
According to Lusher et al. (2017), various types of MPs with a most abundant (~80%). Pellet and film MPs were lower than 5% in
size up to 0.15 mm have been demonstrated to translocate from the all water samples. The morphology of MPs can be used to indicate
mammalian gut into the lymphatic system. Polyvinyl chloride (PVC) their potential origins. According to Peng et al. (2018) and Zhao
particles with sizes lower than 0.11 mm have been detected in the et al. (2015), fragment MPs mainly come from fragmented plastic
portal veins of dogs. Currently, human data on the absorption of containers, tableware, furniture, and toys. Fibers can originate from
MPs are not available. However, MPs with particle sizes from domestic effluent (Browne et al., 2011), breakdown of fishing nets
0.0002 to 0.15 mm were found in human lymph (Hussain et al., and lines (Cole et al., 2011), and the deposition of airborne matter
2001). In this study, both surface water and sediment samples (Dris et al., 2016). Pellets are typically used in air-blasting or as
were contaminated with MPs in a size range that can access the feedstock for plastic production (Eerkes-Medrano et al., 2015).
lymphatic system of mammals (0.053e0.3 mm). Therefore, the MPs Films may come from the fragmentation of larger plastic wrappings
found in the Chao Phraya River can cause serious threats to the and bags (Nor and Obbard, 2014). The study area is located in a
ecosystem and people inhabiting the river basin. However, further famous tourist attraction of the Bangkok capital with a high pop-
studies need to be done to clarify the impacts of MPs on living ulation density. Plastic wastes from urban activities with improper
waste management may contribute to fragments and films.
Household sewage may be an important carrier that can conveys
fibers to aquatic systems.
In comparison with other studies, a high proportion of frag-
ments and fiber MPs were found in the Saigon River of Vietnam and
Taihu Lake of China (Su et al., 2016; Lahens et al., 2018). While the
study on the Pearl River of China reported the largest percentages
of film and granule MPs (Yan et al., 2019), fibers were the most
frequently detected in water samples from the Seine River (France),
Yangtze River (China), and Hanjiang River (China) (Dris et al., 2015;
Wang et al., 2017b). This indicates that MP characteristics may be
related to the sampling area and the source of plastic wastes in the
water.
The color of the MPs was also inspected in this study. As shown
in Fig. 4B, white MPs accounted for the largest proportion, at
51.7e66.7%. White is the base color of most plastic resin. To
improve the market appeal of plastic products, external or internal
coloration is conducted. In external coloration, plastics are printed,
coated, or plated with colors on their surface. In Internal coloration,
colorants are kneaded into resins. MPs can inherit their colors from
the original plastic products. However, their colors can fade due to
weathering, especially in external coloring products. The high
percentages of white MPs in this study show the abundance of
white plastic products or externally colored products in the study
area. Colored MPs, such as green, blue, red, and yellow, were found
in the water samples, corresponding to the common colors of daily
plastics. There were also transparent MPs. Other colors (including
black) might have originated from vehicles (Wagner et al., 2018).

3.3.2. Sediment samples

The morphologies of MPs in sediment samples are presented in
Fig. 4A. At bank 1, the number of fragment MPs was much more
than the others, accounting for 48.5% of the total. While bank 2
shows an abundance of fibers with 52.2%. The same trend has been
reported in the sediment of freshwater environment studies such
as the River Thames, UK (Ferreira et al., 2019) and East Dongting
Fig. 4. Relative abundance of MPs: (A) by morphology; (B) color. (For interpretation of
Lake, China (Yin et al., 2019). As mentioned above, MPs in sediment
the references to color in this figure legend, the reader is referred to the Web version of samples were small sizes (0.05e0.3 mm). Therefore, the MPs need
this article.) to be stained with Nile red for visual sorting under the fluorescence
 A.T. Ta, S. Babel / Chemosphere 257 (2020) 127234 7

microscope. Thus, the original color of the MPs was not determined. 3.5. Interaction with heavy metals

3.4. Polymer composition Previous studies detected heavy metals such as cadmium (Cd),
chromium (Cr), copper (Cu), and lead (Pb) in the water and sedi-
3.4.1. Water samples ment of the Chao Phraya River (McLaren et al., 2004; Wijaya et al.,
To confirm and identify the polymer types of MPs, particles were 2013). This depicts the high potential of interaction of the metals
inspected by FTIR and micro-FTIR (depending on sizes). The pro- from the surrounding environment onto MPs, shown by laboratory
portion of polymers in water samples at both banks and middle experiments (Holmes et al., 2014; Turner and Holmes, 2015).
positions of the river is not much different. PP accounts for the In this study, the concentration of heavy metals on MPs was only
highest percentage (40.1e48.8%) of all samples. Polystyrene (PS) analyzed with surface water samples. In sediment samples, MPs
and Polyethylene (PE) were the second (26.1e29.8%) and third were found with small sizes, and the mass was not large enough to
(18.3e23.2%) abundant polymers. Copolymers and others (i.e. cel- extract metals by the aqua regia solution. Table 2 summarizes the
lophane, polyurethane, and polybutylene) were found in small normalized concentrations of heavy metals (dry weight) on MPs. As
percentages. The high quantity of production of PP, PS, and PE in shown in the table, Ni and Pb were detected at the lowest and
Thailand may be the main reason for their large abundance highest concentrations on MPs, respectively. However, the con-
(Wichai-utcha and Chavalparit, 2019). These polymers are centrations of Cu and Ni in the water river were higher than Pb and
commonly used to produce consumer products such as containers, Cr. This may be explained by a study of Turner and Holmes, (2015)
bottles, plastic bags, and tableware. PP, PE, and PS MPs likely who conducted control experiments on the adsorption of the
originated from the fracture of larger debris (Cole et al., 2011). PP metals on MPs. According to their results, Cu and Pb were reported
and PE polymers are also used in personal care and cosmetics to adsorb in higher amounts on the surface of MPs, compared to Cr
products (Leslie, 2014). According to PlasticsEurope (2018), PP and and Ni. Concentrations of heavy metals in the surface water of the
PE are the most widely produced polymers around the world and Chao Phraya does not exceed the Thailand standard for freshwater
are also the most frequently detected MPs in the marine and (Table 2). However, in the long term, heavy metals can accumulate
freshwater environment (Hidalgo-Ruz et al., 2012; Wu et al., in higher concentrations in the river ecosystem. The heavy metals
2018a). In comparison with other studies, PP and PE were also re- in the Chao Phraya River may be contributed by anthropogenic
ported with the highest percentages at Jiaojiang, Oujiang, and activities, such as industrial effluents, municipal waste combustors,
Minjiang estuaries (Zhao et al., 2015). Polyamide and cellophane vehicular emissions, inland canals from upstream, and the Bangkok
were found to be dominant in the Pearl River and Taihu Lake of city center (Wijaya et al., 2013). In this study, the possible mecha-
China (Su et al., 2016; Yan et al., 2019). Different trends detected in nism of the interaction between MPs and heavy metals may be
these study areas suggest that the sources of the MPs may differ related to the modification of the MP surface. The high degree of
considerably in different regions. weathering at the Chao Phraya River could modify the MP surface
through photooxidation and attrition of charged material (Turner
3.4.2. Sediment samples and Holmes, 2015). In the study area, wastewater from urban ac-
The MPs in sediment samples were inspected by micro-FTIR due tivities are also discharged into the river. Therefore, accumulation
to their small sizes. As shown in Fig. 5, the proportion of polymer of metals on MPs may also occur by interactions between neutral
types is not much different between sediment and surface water metal-organic complexes (Holmes et al., 2012). Furthermore, the
samples. PP is the most abundant polymer, from 42.8 to 50.0%. PE growth of biofilms on MP surface could enhance the accumulation
and PS MPs were also found in sediment samples. However, of metals (Tien and Chen, 2013; Rochman et al., 2014). Currently,
copolymer MPs were not detected in any samples. Polyesters were studies about the interaction of heavy metals on MPs in freshwater
found in a small amount, from 7.1 to 12.5%. This appearance of environments are still insufficient. In the Beijiang River of China,
polyester MPs may be due to their high density (1.4 kg/m3) that concentrations of metals adsorbed on MPs were reported to be
make the MPs sink to the bottom of the river. Moreover, many large much higher than those of this study. This may be because their
black particles were also visually detected, which are mostly study focuses on MPs in sediment where there is more accumula-
confirmed as ash particles by FTIR. tion of heavy metals.
Impacts of heavy metals on the ecosystem and human health
were shown in many studies (Jiang et al., 2017; Wu et al., 2018b).
The risks associated with heavy metals are due to their environ-
mental stability, difficult degradation, easy accumulation, and
tendency to transform into toxic organic forms (Zhu et al., 2017).
The metals can be a threat to human life at high levels. They also
tend to aggravate environmental degradation and disturb the
biochemical functions of environmental components. According to
Martin and Griswold (2009), long term exposure to Pb can affect
the nervous system; generate weakness in fingers, wrists, or an-
kles; increase blood pressure; and lead to anemia. Ingesting a
higher concentration of Cu than a normal level can show symptoms
such as vomiting and stomach cramps. Moreover, long term
exposure to Cr can damage the liver, kidney, circulatory system, and
nerve tissues, as well as provoke skin irritation. The impacts of MPs
associated with heavy metals are still controversial and not well
understood. However, some studies indicated that MPs can be
vectors for heavy metals in aquatic systems (Brennecke et al., 2016).
Cr(VI) adsorbed on MPs can decrease predatory behavior and
reduce individual performance, ultimately leading to death with
Fig. 5. Relative abundance of MPs by polymer types. negative effects on the population fitness of the goby fish (Luís
8 A.T. Ta, S. Babel / Chemosphere 257 (2020) 127234

Table 2
Concentration of heavy metals on MPs in this study, compared to other studies.

Samples Cr Cu Ni Pb

This study MPs (mg/g) 2.95 ± 2.96 13.02 ± 18.26 0.78 ± 1.11 17.61 ± 18.26
Water (mg/L) 1.1 ± 0.00 0.05 ± 0.03 0.05 ± 0.06 0.01 ± 0.00
Thailand standard of fresh surface water 0.05 0.1 0.1 0.05
(mg/L) (Government, 1994)
Beijiang River (mg/g) e 80.9e500.6 0.54e2.39 38.24e131.11
Wang et al., (2017a)

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