Effect of polyethylene microplastic biodegradation by algae on their sorption properties and toxicity

Microplastics (MPs) in aquatic environments constitute an ideal surface for biofilm formation, facilitating or hindering the transport of contaminants. This study aims to provide knowledge on the sorption behavior of high-density polyethylene (μ-HDPE) after algal degradation toward UV filters. Up to now, the oxidation of μ-HDPE using the microalga Acutodesmus obliquus has not been studied. The results obtained by infrared spectroscopy (IR), scanning electron microscopy (SEM), and porosimetry analysis revealed a biofilm formation on the surface of μ-HDPE and the presence of carbonyl and double bond functional groups. Also, this is the first time that the simultaneous sorption of benzophenone (BPh), 4-methylbenzylidene camphor (4MBC), benzophenone 3 (BPh3), and benzophenone 2 (BPh2) onto biofilm-covered HDPE (biofilm-HDPE) in water have been studied. Filters' sorption on biofilm-HDPE particles follows pseudo-second-order kinetics, and film diffusion was the stage that limited the sorption rate. The Langmuir isothermal model describes the adsorption process for 4MBC, BPh, and BPh2 well, and the linear model is fit for the sorption of BPh3. Hydrophobic interactions, van der Waals forces, electrostatic, and π-π bon are the main mechanisms responsible for the sorption. Biological analysis indicated that HDPE at concentrations of 500 mg L^-1 inhibits A. obliquus growth and reduces the levels of proteins, sugars, and chlorophylls. In contrast, the activity of antioxidant enzymes and the contents of small molecular weight antioxidants significantly increased in algal cells treated with microplastic. These findings confirm the toxicity of μ-HDPE and demonstrate the induction of defense mechanisms in A. obliquus as a response to environmental pollutants.