Fluorescence Correlation Spectroscopy Studies of Dye Diffusion on Fresh and Aged Polyethylene Terephthalate

Microplastics accumulate a wide variety of organic pollutants and thus may serve as efficient vectors for the transport of toxic substances. Much remains to be learned about how organic molecules interact with the surfaces of plastics and how these properties evolve as the microplastics are weathered. In this Letter, we report, for the first time, the application of confocal fluorescence correlation spectroscopy (FCS) to studies of organic molecules adsorbed from aqueous solution onto the surfaces of synthetic secondary microplastics. Both fresh and artificially aged poly(ethylene terephthalate) (PET) plastics are employed. The plastics are artificially aged in a UV-ozone chamber. Raman and infrared spectra confirm the composition of the PET microplastics. Water contact angle and surface roughness measurements reveal, respectively, an increase in wettability and a change in the nature of roughness with aging, consistent with surface oxidation. Rhodamine B (RhB) dye is used as a fluorescent probe in FCS studies and serves as an analogue for organic pollutants commonly found on microplastics. The FCS results reveal the accumulation of dye on the PET surfaces as they age. Dye motion is significantly slower on the plastics than in bulk aqueous solution and occurs by anomalous subdiffusion. The rate of diffusion becomes dramatically slower and more anomalous as the plastics are aged. Surface diffusion is likely slowed by either ionic interactions or hydrogen bonding between the dye and plastic. These results provide new insights critical to the understanding of how microplastics accumulate and transport organic pollutants as they weather in the environment.