Heterogeneous photocatalysis increasingly requires rapid polymer degradation tests relevant to aqueous conditions. In this study, a multi-technique approach was developed to monitor the early-stage photo-oxidation of polyethylene (PE) and polystyrene (PS) microplastics in an aqueous ZnO–TiO₂ suspension under combined ultraviolet A and ultraviolet B (UV-A/B) irradiation. The changes were analyzed by ATR-FTIR and Raman spectroscopy, DSC, and gravimetric measurements. For PE, the carbonyl index increased from 0.0189 to 0.1350 after 12 h, mass loss reached 16.98%, and crystallinity decreased from 32.05% to 25.36% after 8 h. The Raman spectra of PE showed band broadening and intensity redistribution, indicating increasing structural disorder. In contrast, PS showed weaker Raman changes, while FTIR revealed a non-monotonic carbonyl-index response, and DSC showed a 2.2 °C increase in Tg after 12 h. Gravimetric analysis also showed measurable mass loss in PS, reaching 18.62% after 12 h. The results demonstrate that the combined use of ATR-FTIR, Raman, DSC, and gravimetry enables reliable distinction between early oxidation, surface modification, and material erosion in photocatalytically treated microplastics.

Sunlight-driven UV weathering is a major transformation pathway of environmental microplastics, promoting surface oxidation, molecular degradation, embrittlement, and progressive fragmentation toward smaller size fractions. However, comparisons across studies remain difficult because weathering is often described using descriptors that probe different aspects of degradation without being clearly distinguished. Surface-sensitive oxidation metrics, such as carbonyl or oxidation indices (CI/OI), are frequently emphasized, whereas fragmentation and embrittlement are more directly governed by bulk molecular-weight loss, mechanical weakening, and particle-size evolution. This review examines UV weathering of common polymers through a coupled chemico-mechanical perspective relevant to the micro-to-nano transition. We distinguish surface chemical descriptors, bulk molecular and mechanical descriptors, and fragmentation-related metrics, and critically assess the analytical methods used to measure them, including FTIR, Raman spectroscopy, GPC/SEC, thermal methods, mechanical testing, and particle-size analyses. We argue that no single metric is sufficient to describe weathering progression, and that meaningful interpretation requires joint reporting of oxidation state, Mn/Mw changes, mechanical deterioration where available, and particle-size distribution as a function of cumulative or spectrum-weighted UV dose. We further propose a minimal QA/QC reporting framework including UV metadata, temperature, oxygen availability, blanks, replicates, recovery tests, and matrix-specific detection limits. By separating what different methods actually probe and linking them to fragmentation mechanisms, this review provides a more operational basis for interpreting UV-aged microplastics in environmental sampling and biomonitoring.