Microplastics as an emerging anthropogenic vector of trace metals in freshwater: Significance of biofilms and comparison with natural substrates

Microplastics (MPs) are ubiquitous in freshwater environments, and represent an emerging anthropogenic vector for contaminants, such as trace metals. In this study, virgin expanded polystyrene (PS) particles were placed in a eutrophic urban lake and a reservoir serving as the resource of domestic water for 4 weeks, to develop biofilms on the surface. For comparison, natural adsorbents in the form of suspended particles and surficial sediment were also sampled from these waterbodies. The trace metal adsorption properties of anthropogenic (virgin and biofilm covered microplastics) and natural substrates were investigated and compared via batch adsorption experiments. The adsorption isotherms fitted the Langmuir model, revealed that biofilms could enhance the trace metal adsorption capacity of MPs. However, natural substrates still had a greater adsorption capacity. Biofilms also alter the adsorption kinetics of trace metals onto MPs. The process of adsorption onto virgin MPs was dominated by intraparticle diffusion, whereas film diffusion governed adsorption onto biofilm covered microplastics and natural substrates. The trace metal adsorption of all the substrates was significantly dependent on pH and ionic strength. The adsorption mechanisms were further analyzed by SEM-EDS and FT-IR. The enhancement of adsorption was mainly attributed to complexation with functional groups contained in the biofilms, including carboxyl, amino, and phenyl-OH. Collectively, biofilm development intensifies the role of MPs in the migration and fate of trace metals in freshwater, since it does not give MPs an edge over natural substrates in adsorption.