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Deciphering the carrier potential of microplastics aged in freeze-thaw soils: Multiscale insights into mechanisms for
Wen-Hao Yang1, Jian-Yong Wu2, Kong-Yan Luo1
1Key Laboratory of the Three Gorges Reservoir Region's Eco-Environment, Ministry of Education, Chongqing University, Chongqing 400045, China.
Abstract:
Aged microplastics (MPs) have attracted growing concern about their carrier effects. Yet, the impact of soil freeze-thaw cycles (FTCs) on MPs as contaminant carriers remains poorly understood. This study assessed changes in the carrier potential of FTC-aged MPs for antibiotics (ATs) through adsorption experiments, and disentangled their underlying mechanistic pathways by innovatively integrating characterization, batch adsorption and density functional theory (DFT) data within a partial least squares structural equation modeling (PLS-SEM) framework. Results showed that soil FTCs roughened surfaces, altered wettability and surface charges, and increased oxygen-containing functional groups (OCFGs) of MPs. The adsorption capacities for sulfamethoxazole (SMX) and enrofloxacin (ENR) were generally enhanced on FTC-aged MPs across MP types and environmental conditions, indicating strengthened carrier potential. Mechanistically, the dominant driver was the FTC-altered surface morphology of MPs that promoted pore-filling, while FTC-generated OCFGs played a limited and polymer-specific role by remodeling the electronic structure of MPs, thereby modulating their electrostatic and hydrogen-bonding interactions with ATs. This study establishes a transferable framework for adsorption research, advances understanding of the carrier potential of MPs undergoing FTCs in soils, and calls for greater attention to the overlooked role of FTCs in shaping co-contamination risks in cold region ecosystems under climate change.
Insights
Soil freeze-thaw cycles (FTCs) enhance microplastics' (MPs) ability to carry antibiotics. FTCs alter MP surfaces, increasing adsorption capacity for common antibiotics like SMX and ENR.
Area of Science:
- Environmental Science
- Materials Science
- Chemistry
Background:
- Aged microplastics (MPs) are a growing concern due to their potential to transport contaminants.
- The influence of soil freeze-thaw cycles (FTCs) on the contaminant-carrying capacity of MPs is not well understood.
Purpose of the Study:
- To investigate how soil FTCs affect the carrier potential of MPs for antibiotics (ATs).
- To elucidate the mechanisms behind these changes using a combination of experimental and computational methods.
Main Methods:
- Adsorption experiments were conducted using FTC-aged MPs and antibiotics (sulfamethoxazole and enrofloxacin).
- MP characterization included surface morphology, wettability, and surface charge analysis.
- Density functional theory (DFT) and partial least squares structural equation modeling (PLS-SEM) were used to analyze mechanistic pathways.
Main Results:
- FTCs roughened MP surfaces, altered wettability and surface charges, and increased oxygen-containing functional groups (OCFGs).
- Adsorption capacities for SMX and ENR generally increased on FTC-aged MPs, indicating enhanced carrier potential.
- FTC-induced surface morphology changes were the primary driver of increased adsorption, with OCFGs playing a minor, polymer-specific role.
Conclusions:
- Soil FTCs significantly enhance the carrier potential of MPs for antibiotics.
- Surface morphology alterations due to FTCs are key to increased adsorption, impacting contaminant transport in cold regions.
- This study provides a framework for understanding MP-contaminant interactions under environmental stress and highlights the importance of FTCs in climate change contexts.
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