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The growing volume of plastics derived from electronic waste (e-waste) underscores the imperative for environmentally sustainable strategies for the management of this waste. In light of the paramount importance of this issue, a pilot demonstrator for the decontamination of polymers containing Brominated Flame Retardants (BFRs) has been developed. The objective is to investigate the potential for decontaminating BFR-containing polymers from e-waste via UV-visible irradiation using a rotatory laboratory pilot operating under primary vacuum conditions. This report focuses on binary model blends composed of 90 weight% (wt%) poly(Acrylo-Butadiene-Styrene) (ABS) pellets and 10 wt% Deca-Bromo-Diphenyl Ether (DBDE), which is one of the most toxic BFRs. The efficiency of the irradiation process was evaluated as a function of pellet diameter and irradiation time using Fourier Transform InfraRed spectroscopy (FTIR) and High-Resolution Laser Desorption/Ionization Mass Spectroscopy (HR-LDI-MS). As a consequence, ABS + DBDE achieved a decontamination efficiency of 97% when irradiated with pellets of less than 1 mm in diameter for a period of 4 h. Additionally, the thermal behavior of the irradiated samples was investigated through thermogravimetric analysis and differential scanning calorimetry. It was thus established that the application of UV-visible irradiation had no significant impact on the overall thermal properties of ABS. [ABSTRACT FROM AUTHOR]