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Gas Chromatography-Atmospheric Pressure Chemical Ionization (GC-APCI) Expands the Analytical Window for Detection of Large PAHs (≥24 Ringed-Carbons) in Pyroplastics and Other Environmental Matrices
Summary
Researchers developed a new analytical method using gas chromatography with atmospheric pressure chemical ionization to detect very large polycyclic aromatic hydrocarbons (PAHs) in pyroplastics — partially burned plastic from fires and maritime incidents. These large PAHs, which conventional methods miss, could serve as chemical fingerprints for identifying pyroplastic contamination in environmental samples including microplastics. This matters because pyroplastics from open burning are an underappreciated source of highly toxic compounds entering marine and terrestrial environments.
Open waste burning, large-scale fires, and maritime disasters produce partially burnt plastic called "pyroplastic". Chemical markers would provide a complementary method to appearance and physical properties for identifying pyroplastics in environmental samples, particularly with respect to microplastics. Pyroplastic can contain significant quantities and unique distributions of parent polycyclic aromatic hydrocarbons (PAHs) with molecular weights up to 278 Da. Because of this enrichment, we considered whether large PAHs (≥24 ringed-carbons) could serve as chemical markers for pyroplastics. To address this, we developed a high-temperature method for gas chromatography atmospheric pressure chemical ionization (GC-APCI) coupled with tandem mass spectrometry (MS/MS) to target large PAHs with molecular weights ranging from 314-424 Da. Method development was performed using National Institute of Standards and Technology standard reference materials (SRMs) previously characterized for PAHs greater than 302 Da. A PAH class-specific MS/MS acquisition scheme combined with a simple, generic microextraction provided sensitive and specific detection without the need for sample fractionation or cleanup. Pyroplastics collected during the 2021 M/V <i>X-Press Pearl</i> ship fire and plastic spill were analyzed. A semiquantitative comparison showed that the pyroplastic samples contained over 2 orders of magnitude more of the 16 large PAHs (314-424 Da) than unburnt plastic pellets, reflecting previously observed trends for parent PAHs up to 278 Da. Qualitative comparison of samples and SRMs revealed multiple potential candidates (including 1,3,5-triphenylbenzene) suitable for further study as markers of pyroplastics in complex environmental samples. A suite of chemical markers for pyroplastics should prove helpful in monitoring efforts for air quality, waste management, microplastic pollution, and fires at the forest-urban interface.
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