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Microplastics (MP) are ubiquitous in the environment; their atmospheric relevance is increasingly recognized. Because of their atmospheric concentrations, a question exists as to whether MP can act as ice nucleating particles in the atmosphere. This study investigates the immersion freezing activity of lab-prepared MP of four different compositions—low density polyethylene (LDPE), polypropylene (PP), poly(vinyl chloride) (PVC), and polyethylene terephthalate (PET)—using droplet freezing assays. The MP are also exposed to ultraviolet light, ozone, sulfuric acid, and ammonium sulfate to mimic environmental aging of the plastics to elucidate the role that these processes play in the ice nucleating activity of MP. Results show that all studied MP act as immersion nuclei and aging processes can modify this ice nucleating activity, leading, primarily, to decreases in ice nucleating activity for LDPE, PP, and PET. The ice nucleating activity of PVC generally increased following aging which we attribute to a cleaning of chemical defects present on the surface of the stock material. Chemical changes were monitored with infrared spectroscopy (ATR-FTIR) and the growth of a peak at 1650-1800 cm-1 was associated with a decrease in ice nucleating activity while loss of an existing peak in that region was associated with an increase in ice nucleating activity. The studied MP have ice nucleating activities sufficient to be a non-negligible source of ice nucleating particles in the atmosphere if present in sufficiently high concentrations.
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Confocal Raman Microscopy as a Probe of Material Deconstruction in Processed Low-Density Polyethylene Particles
Confocal Raman microscopy was applied to detect structural change within individual particles of low-density polyethylene (LDPE) following chemical and electrochemical processing steps that aimed to facilitate material decomposition. A high numerical aperture (NA) oil-immersion objective enabled depth-profiling through the near surface region (20 μm–40 μm) of irregularly shaped particles with an axial spatial resolution < 2 μm estimated from measurements of instrument detection efficiency profiles. Changes in vibrational bands sensitive to polyethylene crystallinity were evident following treatments and linked to the release of low molecular weight compounds present as additives and products of processing. Effects of processing were probed by monitoring the rise of Raman scattering intensity in vibrational modes associated with polyethylene chains in a zig-zag (trans) conformation near 1128 cm–1, 1294 cm–1, and 1418 cm–1, signaling chain clustering and development of organized, crystalline-like assemblies. Pristine LDPE particles displayed a uniform structure across the near surface region, while particles treated initially with chemical extractant and then further processed displayed increasingly enhanced crystallinity up to the maximum depth probed (40 μm). As a step toward measurements on ensembles of particles, least squares modeling was adapted to derive pure component spectra reflecting crystallinity change within spectral datasets. The work demonstrates high spatial resolution Raman depth-profiling for the characterization of processed polymers using a high NA immersion objective to overcome the limitations of air-objectives often used for confocal Raman microscopy.
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- Award ID(s):
- 1922956
- PAR ID:
- 10587519
- Publisher / Repository:
- Sage
- Date Published:
- Journal Name:
- Applied Spectroscopy
- ISSN:
- 0003-7028
- Subject(s) / Keyword(s):
- Confocal Raman microscopy Raman depth-profiling low-density polyethylene polymer deconstruction least squares modeling
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript
- Journal Article:
- https://doi.org/10.1177/00037028251322142
