The immense production of plastic polymers combined with their discordancy with nature has led to vast plastic waste contamination across the geosphere, from the oceans to freshwater reservoirs, wetlands, remote snowpacks, sediments, air and multiple other environments. These environmental pollutants include microplastics (MP), typically defined as small and fragmented plastics less than 5 mm in size, and nanoplastics (NP), particles smaller than a micrometer. The formation of micro and nanoplastics in aqueous media to date has been largely attributed to fragmentation of plastics by natural (i.e., abrasion, photolysis, biotic) or industrial processes. We present a novel method to create small microplastics (≲ 5 μm) and nanoplastics in water from a wide variety of plastic materials using a small volume of a solubilizer liquid, such as n-dodecane, in combination with vigorous mixing. When the suspensions or solutions are subjected to ultrasonic mixing, the particle sizes decrease. Small micro- and nanoparticles were made from commercial, real world and waste (aged) polyethylene, polystyrene, polycarbonate and polyethylene terephthalate, in addition to other plastic materials and were analyzed using dark field microscopy, Raman spectroscopy and particle size measurements. The presented method provides a new and simple way to create specific size distributions of micro- and nanoparticles, which will enable expanded research on these plastic particles in water, especially those made from real world and aged plastics. The ease of NP and small MP formation upon initial mixing simulates real world environments, thereby providing further insight into the behavior of plastics in natural settings.

Polyethylene (PE) is an intensely utilized polymer, which has consequently led to it becoming a common environmental contaminant. PE and other plastic waste are known to be highly persistent in surface waters; however, chemical and physical changes do take place over time, dependent mostly on highly variable natural conditions, such as oxygen (O₂) availability. Gamma radiation was used to generate reactive oxygen species, namely hydroxyl radicals, in initially aerated aqueous solutions to simulate the natural weathering of microplastics in waters where there are fluctuations and often depletions in dissolved O₂. The headspace of the irradiated PE-containing solutions was probed for the formation of degradation products using solid-phase microextraction (SPME) fibers in combination with gas chromatography mass spectrometry (GCMS). The major species detected were n-dodecane, with trace levels of tridecane, 2-dodecanone, and hexadecane, which were believed to be predominately adsorbed in the PE microplastics in excess of their aqueous solubility limits. Surface characterization by Raman spectroscopy and light and dark field microscopy indicated no change in the chemical composition of the irradiated PE microplastics under low O₂ to anaerobic conditions. However, morphological changes were observed, indicating radical combination reactions.