Plastic debris abundance
The mean value was 5.46 ± 3.53 items/m2 on the floodplain. The plastic distribution in riverbanks reported in some studies was 120,632 items in 8411 m2 (≈ 14.34 items/m2) in the Adour River, Southwest France (Bruge et al. 2018), and 27.70 items/m2 in the Thames River, South England (Bernardini et al. 2020). Although these results are higher than ours, they may vary depending on the size of the river and population density.
Plastics in surface water have an average value of 155 ± 100.7 items/m3. During the sampling, river discharges ranged between 6.9 and 29.9 m3/s. No statistically significant correlation was observed between the river discharge rate and the number of plastic items in surface water. We compared our results with those of other river surface water studies conducted using net sampling (Table 1). Some previous studies showed lower average abundance, such as in 29 Japanese rivers (Kataoka et al. 2019), urban Rivers, Chicago (McCormick et al. 2014), and Rhône River, France (Constant et al. 2020) as shown in Table 1. The results for the Saigon River (fragments: 10–223 items/m3), Vietnam (Lahens et al. 2018), and Taichung Rivers, Taiwan (Kunz et al. 2023), were closer to our results. Furthermore, some rivers showed higher amounts of plastic distribution, such as the Yangtze River, China (Zhao et al. 2014), and the Saigon River, (fibers: 172,000–519,000 item/m3) Vietnam (Lahens et al. 2018).
Table 1
The reported plastic concentration, items/m3 in river surface water
Study areas | Dominant plastic types | Plastic concentration, mean ± SD | Net mesh size, [µm] | References |
29 rivers, Japan | PE, PP and PS | 1.6 ± 2.3 | 335 | (Kataoka et al., 2019) |
urban rivers, Chicago, USA | n.r | 1.94 ± 0.81, upstream 17.9 ± 11.0, downstream | 333 | (McCormick et al., 2014) |
Rhône river | PES and PE | 18.8 ± 28.1 | 333 | (Constant et al., 2020) |
Saigon River, Vietnam | PE, and PP | 10–223*, fragment 172000–519000*, fibers | 300 | (Lahens et al., 2018) |
Taichung rivers, Taiwan | PE, and PP | 230, Urban area | 300 | (Kunz et al., 2023) |
Yangtze River, China | PE, and PP | 3088.9 ± 330.6 | 48 | (He et al., 2021) |
* min - max |
The sediment samples demonstrated an average concentration of 128.4 ± 76.3 items/kg. Based on published global data (Table 2), we classified the plastic concentration in river sediment into three categories: low (up to 100 items/kg), moderate (100–1000 items/kg), and high (above 1000 items/kg). Some studies reported low plastic accumulation, such as the Ciwalengke River, Indonesia (Alam et al. 2019), and Po River, Italy (Piehl et al. 2019). The high concentration of plastic in the sediment reached up to four orders of magnitude of items/kg (Hurley et al. 2018; Frei et al. 2019; Singh et al. 2022). Despite these low and high values, plastic density in sediment generally fluctuates within two orders of magnitude on a one-kilogram weight basis. Our result was in the moderate category.
Table 2
The reported plastic concentration, items/kg in other river sediments
Study areas | Predominant plastic types | Plastic concentration, min - max | References |
Ciwalengke River, Indonesia | Polymer mixture and Pes | 30.3 ± 15.9* | (Alam et al., 2019) |
Po River, Italy | PE and PS | 2.92–23.30 | (Piehl et al., 2019) |
Romanian Danube River | PET, PP and PS | 159.2 ± 138.4* | (Pojar et al., 2021) |
Antua River, Portugal | PE and PP | 18–629 | (Rodrigues et al., 2018) |
The River Kelvin, Glasgow, UK | PE, PP, and PS | 161–432 | (Blair et al., 2019) |
Vistula River, Poland | PS, PP and PE | 190–580 | (Sekudewicz et al., 2021) |
River Thames tributaries, UK | Organic dye, PET and PP | 660** | (Horton et al., 2017) |
Ergene River, Turkey | PS and PE | 97.90–277.76* | (Akdogan et al., 2023) |
Qinhuai River, China | PP, PS and PE | 1115–6380 | (Yan et al., 2021) |
Nakdong River, Korea | PE, and PP | 1971 ± 62* | (Eo et al., 2019) |
Pearl River, China | PE, and PP | 1669** | (Lin et al., 2018) |
* mean ± STD **mean |
Plastic composition changes in size, shape and polymer types
Microplastics were dominantly distributed in the surveyed floodplain, surface waters, and sediments (Fig. 2a). Mesoplastics were scarce in surface waters and sediments; however, they were commonly found in floodplains. Macro- and megaplastics were found in floodplains but not in surface water and sediments. The plastic size distribution of the Tuul River floodplain showed a predominance of microplastics and a relatively small number of megaplastics in the previous study (Battulga et al. 2019). The difference in the size composition between the floodplain and the other two compartments was attributed to the difference in the physical and chemical properties of their original materials and degradation stages during their transport processes.
The shape composition of the materials was different between the floodplain and the other two surveyed compartments (Fig. 2b). The floodplain areas were dominated by foams (77.2%), followed by films, fibers, and fragments. The latter three types are evenly distributed in surface water and sediments (Fig. 2b).
Seven common types of plastics, namely polyethylene (PE), polypropylene (PP), low-density polyethylene (LDPE), polystyrene, nylon (NYL), polyethylene terephthalate, and polyvinylchloride (PVC), were identified from the total collected samples, which were identified by the micro-FTIR analysis (Figs. 3 and 4). The composition was largely different between the collected plastic debris on the floodplain, in the surface water, and in sediments. The predominance of PSF was characteristic of the floodplain samples, while it was only 2.7% in the surface water and 1.6% in the sediments. PSF has a high buoyancy due to its structure, resulting in the release of PSF into surface water washed ashore along the floodplain, as observed during field survey (Fig. S1). Additionally, the large consumption of PSF results in the generation of plastic debris in a wide size range as it undergoes degradation. In surface water samples, most of the polymer debris consisted of LDPE, PE, and PP, whereas sediment plastics were dominated by PE and PP. Moreover, polymer composition of surface water and sediment plastics were correlated significantly (p < 0.01). Two major plastics, PE and PP, are common plastic debris in surface water and sediments, indicating that sedimentary plastic debris undergoes density transformation during in-stream processes. PVC was not detected in the surface water and sediment samples analyzed.
Structural changes on the surface of microplastics
PE was the most representative and comparable plastic type in river compartments, and the CI was calculated a using total of 75 PE samples from each compartment (25 pieces). The average FTIR spectra of PE are shown in Fig. 5. The spectra of pristine PE were obtained from the Shimadzu library (Fig. 5.d).
In comparison to the pristine spectra, degraded plastics in the field exhibited multiple peaks, as shown in Fig. 5. a, b, and c. In particular, the C = O double bond peak appeared on most of the samples observed at 1715–1730 cm− 1, which indicated the photodegradation process of saturated aliphatic moieties (Guo et al. 2023). Moreover, a weak spectral band appeared at 1629–1647 cm− 1 for all three compartment samples, which corresponds to C = O stretching vibrations or the amide I band (Celina et al. 2021).
Floodplain samples exhibited C–O stretching vibrations, which appeared at 1180, 1082, and 1029 cm− 1, and C–H bending vibrations at 895 cm− 1 corresponding to the C–H stretching vibrations at 2920 and 2850 cm− 1 (Tofa et al. 2019).
In surface water samples, C–O stretching vibrations appeared at 1029 cm− 1, and bands appeared at 877 cm− 1 and 781 cm− 1, which might be attributed to unsaturated groups during photodegradation, respectively (Gardette et al. 2013; Yagoubi et al. 2015; Tofa et al. 2019).
Sediment plastics showed a strong absorption at 1022 cm− 1, which can be attributed to silica oxide stretching vibrations (Hahn et al. 2019). This indicates that sedimentary minerals may reside on the surface of the plastic debris and form plastic-associated minerals (PAM) during the accumulation process.
Photodegradation stages
The CI value of the floodplain PE plastics was 0.56 ± 0.35. A slightly higher CI value (0.61 ± 0.26) was found in the PE in the surface water. The highest average value of CI (0.90 ± 0.68) was recorded in the PE in the sediments (Fig. 6). There was a statistically significant (p < 0.05) difference between the PE in the three river compartments, as observed by one-way ANOVA. The highest CI value reached 2.83, recorded in the sedimentary PE, whereas the lowest CI was 0.06 in the PE in the floodplain. Although there was a slight difference in the average CI values of the PE in the floodplain and surface water, the sedimentary PE indicated a highly deteriorated surface with high CI values.
The difference in the CI between the river compartments was not well recognized in other studies. A few studies report the CI values for naturally weathered plastics in river water and sediment. Rodrigues et al., 2018 reported two times higher CI average values for the PE in sediments than for those in surface water, indicating that relatively deteriorated PE could reside in sediments.
Among the four shapes, except for foams, the CI of fragment plastics was the highest (0.75 ± 0.06), followed by fiber (0.67 ± 0.15), and that of film was the lowest (0.62 ± 0.24). Fragments are typically bulk and solid plastics compared with fibers and films, which have thin and narrow shapes. Fragment plastic durability can be tougher than that of film and fibers. Therefore, its high CI values may be related to its long durability in the environment.