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Microplastic Crystallinity and Its Influence on Emerging Contaminant Adsorption and Environmental Persistence
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This review summarizes existing research on how the internal structure of microplastics, specifically their crystalline versus amorphous regions, affects how they absorb and release chemical pollutants. It also examines how this structure influences how plastics break down over time, and suggests structural features that could be targeted to reduce pollutant transport.
Microplastics are often perceived as a diffuse and complex contaminant class, yet their growing ecotoxicity and persistence demand a mechanistic view. Beyond source tracking, occurrence, leaching and bulk sorption that has been explored in detail, there still remains an overlooked driver that links these facets together based on microstructure. This review argues that crystallinity and the resulting domain architecture of lamellae along with amorphous regions governs how microplastics form, age, sorb, and release emerging contaminants (ECs). We synthesize evidence for regioselective interactions between contaminants and distinct polymer domains. Surface-limited adsorption predominantly occurs on crystalline domains, whereas amorphous phases facilitate contaminant partitioning. The review relates ultrastructure to the generation of micro and nanoplastics under quiescent and mechanical weathering, and compile kinetics frameworks that couple diffusion and sorption to crystallinity and other physico-chemical properties. Finally, these mechanisms are placed within the plastic value chain to highlight current bottlenecks and opportunities for mitigation. Focusing on microstructure offers clear guidance for mitigation such as altering crystallinity or surface chemistry to reduce persistence, contaminant transport, and exposure risk.
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