Microplastics (MP), consisting of particles under 5 mm in size, and fibrous microplastics (FMPs), which originate from textiles and are shed during the washing process, are acknowledged as a new and expanding category of pollutants. This study aimed to conduct an analytical evaluation of the defragmentation process of polyester fabrics featuring a prominent tri-color pile surface. The evaluation involved washing the fabrics with detergent and water and employing various methods to assess the fabric, wastewater, and filter cake both prior to, and following, cryogenization. The specificity of a pile polyester fabric provided a baseline for evaluating the detergent and water system. Subjecting the polyester fabric to five cycles of washing in a detergent solution and water resulted in a measurable loss of mass. The pristine polyester fabric was analyzed microscopically and by FTIR, while the fabrics before and after washing were subjected to gravimetric analysis. The physico–chemical characteristics of the wastewater, such as the conductivity, turbidity, and chemical oxygen demand, were impacted by the composition of the washing bath. The application of pyrolysis, combined with gas chromatography and mass spectrometry (Py-GC/MS), on the filter cake demonstrated the value of using blank samples. The results indicated that both the detergent and the water significantly affected the release of FMPs during the washing process. Polyester fabric sample 1, which was washed in a detergent solution for five cycles, exhibited a mass loss of 1619 mg kg−1. In contrast, sample 2, consisting of a polyester fabric washed solely in water, showed a mass loss of 1707 mg kg−1 over the same number of cycles.
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