Induced aging, structural change, and adsorption behavior modifications of microplastics by microalgae

The effects of microalgal biofouling on microplastic (MP) may differ from bacterial biofouling. In this study, the influence of microalgae on MP surface alteration, structural change, and adsorption of organic micropollutants was evaluated. Virgin polyethylene (PE), polyvinyl chloride (PVC), and polyamide (PA) were each immersed in algal photobioreactor and river freshwater for 30 days to simulate algal and river microbe biofouling respectively. Consequently, their physicochemical changes and adsorption potential of a mixture of six bisphenol analogues (BPA, BPS, BPE, BPB, BPF, BPAF) and two parabens (propyl-paraben, benzyl-paraben) were investigated. Owing to the algal bioactive compounds, major microalgae-induced biofouling and more MP aging than the river microbe aging were observed through fractures, pits, cracks, and algal attachments. Intrusion of algal organic matter and scission of polymeric functional groups were revealed during microalgal immersion and the potential MP aging pathways were proposed. Algal biofouling considerably altered the intrinsic properties of the MPs, consequently the adsorption capacity of PE and PVC was enhanced by 3.04-6.72 and 2.14-8.72 times, respectively. Adsorption process onto algal-aged MPs was pH-dependent, endothermic, non-spontaneous, and favored by hydrogen bonds. Meanwhile, the amide group in PA structure was conducive to organic micropollutant adsorption, which was likely reduced by algal aging and the erosion of the N-H stretching. Moreover, higher adsorption capacities of organic micropollutants were shown by the algal-biofilm PE and PVC than virgin and river microbial biofilm MPs. This study discloses that, biofouling and aging of MPs by microalgae through their bioactive components would engender more incidences on MP properties, organic micropollutants adsorption with associated environmental and health hazards.