Elucidating sulfate radical-induced oxidizing mechanisms of solid-phase pharmaceuticals: Comparison with liquid-phase...

As a class of organic micropollutants of global concern, pharmaceuticals have prevalent distributions in the aqueous environment (e.g., groundwater and surface water) and solid matrices (e.g., soil, sediments, and dried sludge). Their contamination levels have been further aggravated by the annually increased production of expired drugs as emerging harmful wastes worldwide. Sulfate radicals (SO₄^•-)-based oxidation has attracted increasing attention for abating pharmaceuticals in the environment, whereas the transformation mechanisms of solid-phase pharmaceuticals remain unknown thus far. This investigation presented for the first time that SO₄^•-, individually produced by mechanical force-activated and heat-activated persulfate treatments, could effectively oxidize three model pharmaceuticals (i.e., methotrexate, sitagliptin, and salbutamol) in both solid and liquid phases. The high-resolution mass spectrometric analysis suggested their distinct transformation products formed by different phases of SO₄^•- oxidation. Accordingly, the SO₄^•--mediated mechanistic differences between the solid-phase and liquid-phase pharmaceuticals were proposed. It is noteworthy that the products from both systems were predicted with the remaining persistence, bioaccumulation, and multi-endpoint toxicity. Therefore, some post-treatment strategies need to be considered during practical applications of SO₄^•--based technologies in remediating different phases of micropollutants. This work has environmental implications for understanding the comparative transformation mechanisms of pharmaceuticals by SO₄^•- oxidation in remediating the contaminated solid and aqueous matrices.