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Accurate spectral identification of weathered plastics and analyses that provide insight into environmental degradation and age are desirable for source tracking and understanding hazards. The objectives of this study were to (1) evaluate the kinetics of spectral changes for lab-weathered polymers and compare to spectra from environmental microplastics (MPs), and (2) assess the accuracy of spectral databases in identifying weathered polymers. For objective 1, polyethylene (PE) and polypropylene (PP) fragments were exposed to simulated solar radiation in water for 90 days. FTIR spectra were collected periodically and degradation was quantified using carbonyl and hydroxyl bond indices. Significant linear increases in carbonyl indices for PP, but not PE, were observed as a function of exposure time. Spectra (via principal component analysis) and bond indices from lab-weathered polymers were then compared to environmental MPs collected from urban stormwater and the Delaware Bay estuary. Estuarine PP carbonyl and hydroxyl indices varied as a function of spectral collection mode (i.e., ATR vs. transmission) and by sampling site, potentially indicating the bond indices provide insight into sources/fate/transport of PP and are worthy of further study. In contrast, no significant differences were observed for PP in stormwater samples, possibly due to the close proximity of collection locations. PE exhibited non-linear trends in bond indices in the laboratory study and showed no significant association with sampling location in environmental samples, suggesting these indices may be less useful for PE degradation analysis. For objective 2, 14 different polymers, eight of which were polymer blends, were exposed to simulated solar radiation for up to 90 days, in dry and wet conditions. FTIR spectra were collected periodically and analyzed with two spectral identification software. OpenSpecy achieved an 88 % true positive rate compared to siMPle's 57 % at a 70 % hit quality threshold. Expanding reference libraries, to include weathered polymers and polymer blends, could improve spectral identification accuracy, and manual interpretation of FTIR spectra is recommended for low-confidence matches.
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What Determines Accuracy of Chemical Identification When Using Microspectroscopy for the Analysis of Microplastics?
Fourier transform infrared (FTIR) and Raman microspectroscopy are methods applied in microplastics research to determine the chemical identity of microplastics. These techniques enable quantification of microplastic particles across various matrices. Previous work has highlighted the benefits and limitations of each method and found these to be complimentary. Within this work, metadata collected within an interlaboratory method validation study was used to determine which variables most influenced successful chemical identification of un-weathered microplastics in simulated drinking water samples using FTIR and Raman microspectroscopy. No variables tested had a strong correlation with the accuracy of chemical identification (r = ≤0.63). The variables most correlated with accuracy differed between the two methods, and include both physical characteristics of particles (color, morphology, size, polymer type), and instrumental parameters (spectral collection mode, spectral range). Based on these results, we provide technical recommendations to improve capabilities of both methods for measuring microplastics in drinking water and highlight priorities for further research. For FTIR microspectroscopy, recommendations include considering the type of particle in question to inform sample presentation and spectral collection mode for sample analysis. Instrumental parameters should be adjusted for certain particle types when using Raman microspectroscopy. For both instruments, the study highlighted the need for harmonization of spectral reference libraries among research groups, including the use of libraries containing reference materials of both weathered plastic and natural materials that are commonly found in environmental samples.
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- Award ID(s):
- 1935028
- PAR ID:
- 10441775
- Date Published:
- Journal Name:
- Chemosphere
- Volume:
- 313
- ISSN:
- 0045-6535
- Page Range / eLocation ID:
- 137300
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1016/j.chemosphere.2022.137300
