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.

Extraction method development for nanoplastics from oyster and fish tissues.

Nanoplastics are now found in some environmental media and consumer products. However, very limited data on nanoplastics are available for one of the main human consumption sources of microplastics: seafood. Unlike microplastics, a method for extracting nanoplastics from seafood is still lacking. Herein, a combination of common extraction techniques including enzymatic digestion, sequential membrane filtration, centrifugal concentration, and purification (dialysis and sodium dodecylsulfate (SDS) incubation), was developed to extract nanoplastics from oyster and fish tissues. Corolase with subsequent lipase treatment achieved the highest digestion efficiencies (88- 89%) for non-homogenized tissues compared to other proteases and additional cellulase or H2O2 treatment. With the exception of polyethylene terephthalate (PET), enzymatic digestion did not change the morphology or structure of polyvinyl chloride (PVC), polyethylene (PE), or polystyrene (PS) nanoplastic particles, and the subsequent extraction procedures had good recoveries of 71- 110% for fluorescence-labeled 76-nm PVC and 100- and 750-nm PS, as validated by a Nanoparticle Tracking Analysis (NTA). Few of the 1011 digested residual particles of 150- 300 nm in diameter per oyster or per serving of fish tissue were left in the method blank. Consequently, this efficient approach could be used as a pretreatment protocol for current potential nanoplastic detection methods.