Visualization and (Semi-)quantification of submicrometer plastics through scanning electron microscopy and time-of-flight secondary ion mass spectrometry.

Increasing numbers of studies have demonstrated the existence of nanoplastics (1-999 nm) in the environment and commercial products, but the current technologies for detecting and quantifying nanoplastics are still developing. Herein, we present a combination of two techniques, e.g., scanning electron microscopy (SEM) and time-of-flight secondary ion mass spectrometry (ToF-SIMS), to analyze submicron-sized plastics. A drop-casting of a 20-nL particle suspension on a Piranha solution-cleaned silicon wafer with dry ice incubation and subsequent freeze-drying was used to suppress the coffee-ring effect. SEM images were used to quantify particles, and this technique is applicable for 0.195-1.04-µm polystyrene (PS), 0.311-µm polyethylene terephthalate (PET), and 0.344-µm polyethylene (PE) at a minimum concentration of 2.49 × 109 particles/mL. ToF-SIMS could not quantify the particle number, while it could semi-quantitatively estimate number ratios of submicron PE, PET, polyvinyl chloride (PVC), and PS particles in the mixture. Analysis of submicron plastics released from three hot water-steeped teabags (respectively made of PET/PE, polylactic acid (PLA), and PET) was revisited. The SEM-derived sizes and particle numbers were comparable to those measured by a nanoparticle tracking analysis (NTA) regardless of whether or not the hydro-soluble oligomers were removed. ToF-SIMS further confirmed the number ratios of different particles from a PET/PE composite teabag leachate. This method shows potential for application in analyzing more-complex plastic particles released from food contact materials.