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Frontiers of Environmental Science & Engineering

ISSN 2095-2201

ISSN 2095-221X(Online)

CN 10-1013/X

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Front. Environ. Sci. Eng.    2024, Vol. 18 Issue (2) : 19    https://doi.org/10.1007/s11783-024-1779-4
RESEARCH ARTICLE
A potential threat from biodegradable microplastics: mechanism of cadmium adsorption and desorption in the simulated gastrointestinal environment
Timing Jiang1,3, Xiang Wu1,2(), Shushan Yuan1,3(), Changfei Lai1,3, Shijie Bian1,3, Wenbo Yu1,3, Sha Liang1,3, Jingping Hu1,3, Liang Huang1,3, Huabo Duan1,3, Yafei Shi4, Jiakuan Yang1,3,5
1. School of Environmental Science & Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
2. School of Resources and Environmental Science, Hubei University, Wuhan 430062, China
3. Hubei Provincial Engineering Laboratory for Solid Waste Treatment Disposal and Recycling, Wuhan 430074, China
4. School of Civil Engineering, Architecture and Environment, Hubei University of Technology, Wuhan 430068, China
5. State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan 430074, China
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Abstract

● The Cd(II) adsorption capacity followed the order of PA > PLA > PP.

● Oxygen groups played critical roles in Cd(II) adsorption by PLA MPs.

● Degradation of PLA MPs enhanced Cd(II) desorption in human digestive fluid.

● Cd(II) release was easier from PLA during human digestion than from PP or PA.

It has been demonstrated that microplastics (MPs) can accumulate heavy metals from the environment and transfer them into organisms via the food chain. However, adsorption and desorption capacities for biodegradable MPs relative to those for conventional MPs remain poorly understood. In this study, cadmium (Cd(II)) adsorption and desorption characteristics of polylactic acid (PLA), a typical biodegradable MP, were investigated. Two conventional MPs, i.e., polypropylene (PP) and polyamide (PA) were used for comparison. The maximum Cd(II) adsorption capacities of the MPs studied in the adsorption experiments decreased in the order PA (0.96 ± 0.07 mg/g) > PLA (0.64 ± 0.04 mg/g) > PP (0.22 ± 0.03 mg/g). The Pseudo-second-order kinetic model and Freundlich isothermal model described the Cd(II) adsorption behaviors of PLA MPs well. X-ray photoelectron spectroscopy and two-dimensional Fourier transform infrared correlation spectroscopy analysis indicated that oxygen functional groups were the major and preferential binding sites of PLA MPs, which contributed to their high Cd(II) adsorption capacities. Simulated gastric and intestinal fluids both significantly enhanced the desorption capacities of the examined MPs. Notably, degradation of the PLA MPs during in vitro human digestion made the Cd(II) on the PLA MPs more bioaccessible (19% in the gastric phase and 62% in the intestinal phase) than Cd(II) on the PP and PA MPs. These results indicate the remarkable capacities of biodegradable MPs to accumulate Cd(II) and transfer it to the digestive system and show that biodegradable MPs might pose more severe threats to human health than conventional nonbiodegradable MPs.

Keywords Biodegradable microplastics      Cadmium      Adsorption and desorption      Gastrointestinal environment      Two-dimensional correlation spectroscopy      Bioaccessibility     
Corresponding Author(s): Xiang Wu,Shushan Yuan   
Issue Date: 12 October 2023
 Cite this article:   
Timing Jiang,Xiang Wu,Shushan Yuan, et al. A potential threat from biodegradable microplastics: mechanism of cadmium adsorption and desorption in the simulated gastrointestinal environment[J]. Front. Environ. Sci. Eng., 2024, 18(2): 19.
 URL:  
https://academic.hep.com.cn/fese/EN/10.1007/s11783-024-1779-4
https://academic.hep.com.cn/fese/EN/Y2024/V18/I2/19
Fig.1  SEM images of PLA, PP, and PA microplastics (MPs) on a scale of 5 μm: original MPs (a, b, c), MPs after adsorption (d, e, f), MPs in the gastric phase (g, h, i), and MPs in the intestinal phase (j, k, l).
Kinetic model Parameters PLA PP PA
Pseudo-first-order k1 (h−1) 0.84 ± 0.27 0.19 ± 0.05 0.14 ± 0.03
qe (mg/g) 0.40 ± 0.03 0.18 ± 0.01 0.76 ± 0.05
R2 0.763 0.861 0.916
Pseudo-second-order k2 (g/(mg?h)) 2.35 ± 0.67 1.50 ± 0.48 0.22 ± 0.07
qe (mg/g) 0.44 ± 0.02 0.20 ± 0.01 0.85 ± 0.06
R2 0.903 0.929 0.943
Tab.1  Fitting parameters of kinetic models for adsorption of Cd(II) on PLA, PP, and PA microplastics (MPs) (the Cd(II) concentration = 100 mg/L, and the MP dose = 10 g/L)
Fig.2  Kinetics for adsorption of Cd(II) on PLA, PP, and PA microplastics (MPs) and fits with the (a) Pseudo-first-order and Pseudo-second-order models, (b) film diffusion model, and (c) intraparticle diffusion model.
Isotherm model Parameters PLA PP PA
Langmuir qm (mg/g) 1.65 ± 0.30 0.34 ± 0.03 1.76 ± 0.24
kL (L/mg) 0.0042 ± 0.0011 0.0126±0.0030 0.0079±0.0019
R2 0.811 0.927 0.887
Freundlich kF (mg/g) 0.0087 ± 0.0018 0.0091 ± 0.0022 0.0223 ± 0.0057
n 1.16 ± 0.07 1.56 ± 0.14 1.31 ± 0.11
R2 0.976 0.946 0.956
Dubbin-Radushkevich kDR (kJ/mol) 27.6 ± 6.4 38.8 ± 8.0 32.4 ± 6.3
R2 0.718 0.763 0.785
Tab.2  Fitting parameters of Isotherm models for Cd(II) adsorption on PLA, PP, and PA microplastics (MPs) (Cd(II) concentration = 10–200 mg/L, and equilibrium time = 72 h)
Fig.3  Isotherms for adsorption of Cd(II) on PLA, PP, and PA microplastics (MPs): (a) original data, (b) Langmuir model, and (c) Freundlich model.
MPs Cd(II) adsorption C 1s O 1s N 1s Cd 3d a) O/C N/C b)
PLA Before adsorption 61.83 37.62 0.53 0.02 0.61
After adsorption 60.99 38.38 0.61 0.02 0.63
PP Before adsorption 97.23 2.48 0.87 0.05 0.03
After adsorption 94.60 4.59 0.78 0.03 0.05
PA Before adsorption 77.47 15.01 7.49 0.03 0.19 0.10
After adsorption 76.37 13.20 10.38 0.05 0.17 0.14
Tab.3  Atomic percentages (%) from XPS analyses of the elements on the PLA, PP, and PA microplastics (MPs) before and after Cd(II) adsorption
Fig.4  XPS C 1s spectra of (a) PLA, (b) PP, and (c) PA microplastics (MPs) before and after Cd(II) adsorption.
Core level Assignment Before Cd(II) adsorption After Cd(II) adsorption
Binding energy (eV) Area Component percentage (%) Binding energy (eV) Area Component percentage (%)
C 1s C–C/C–H 284.77 68743 38.63 284.78 52128 27.80
C–O–C=O 286.68 40873 23.00 286.73 52128 28.05
O–C=O 288.77 68089 38.37 288.83 82591 44.16
O 1s C=O 532.14 86304 33.27 532.10 154682 54.11
C–O–H 533.49 143543 55.40 533.47 102958 36.05
O=C–O 538.48 29248 11.33 537.69 27995 9.84
Tab.4  C 1s and O 1s component peaks for the PLA microplastics (MPs) before and after Cd(II) adsorption
Fig.5  2D FTIR COS maps for the microplastics (MPs): (a) synchronous and (b) asynchronous maps for the PLA MPs; (c) synchronous and (d) asynchronous maps for the PA MPs; (e) synchronous and (f) asynchronous maps for the PP MPs. The red and blue colors in the maps indicate positive and negative correlations, respectively.
Fig.6  In vitro assay results for PLA, PP, and PA microplastics (MPs) in the simulated gastric and intestinal phases: (a) adsorbed (initial) and desorbed Cd(II) amounts (mg/g); (b) bioaccessibility (%) of Cd(II) adsorbed on MPs; (c) lactic acid concentrations (mmol/L) of the filtered gastric and intestinal fluids. Statistically significant differences were determined with one-way ANOVA (n.s.: not significant; ***P < 0.001; **P < 0.01; *P < 0.05).
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