Structural Identification and Observation of Dose Rate-Dependent Beam-Induced Structural Changes of Micro- and Nanoplastic Particles by Pair Distribution Function Analysis in the Transmission Electron Microscope (ePDF).

Micro- and nanoplastics (MNPs) are considered a possible threat to microorganisms in the aquatic environment. Here, we show that total scattering intensity analysis of electron diffraction (ED) data measured by transmission electron microscopy, which yields the electron pair distribution function (ePDF), is a feasible method for the characterization and identification of MNPs down to 100 nm. To demonstrate the applicability, cryo ball-milled powders of the most common polymers [i.e., polyethylene , polypropylene, polyethylene terephthalate, and polyamide] and nano-sized polystyrene and silica spheres were used as model systems. The comparison of the experimentally determined reduced pair density functions (RDFs) with model RDFs derived from crystallographic data of the respective polymers allows the distinction of the different types of polymers. Furthermore, carbon-based polymers are highly beam-sensitive materials. The degradation of the samples under the electron beam was analyzed by conducting time-resolved ED measurements. Changes in the material can be visualized by the RDF analysis of the time-series of ED patterns, and information about the materials in question can be gained by this beam damage analysis. Prospectively, ePDF analytics will help to understand and study more precisely the input of MNPs into the environment.