Nitrogen-containing heterocyclic volatile organic compounds (VOCs) are important components of wildfire emissions that are readily reactive toward nitrate radicals (NO3) during nighttime, but the oxidation mechanism and the potential formation of secondary organic aerosol (SOA) and brown carbon (BrC) are unclear. Here, NO3 oxidation of three nitrogen-containing heterocyclic VOCs, pyrrole, 1-methylyrrole (1-MP), and 2-methylpyrrole (2-MP), was investigated in chamber experiments to determine the effect of precursor structures on SOA and BrC formation. The SOA chemical compositions and the optical properties were analyzed using a suite of online and offline instrumentation. Dinitro- and trinitro-products were found to be the dominant SOA constituents from pyrrole and 2-MP, but not observed from 1-MP. Furthermore, the SOA from 2-MP and pyrrole showed strong light absorption, while that from 1-MP were mostly scattering. From these results, we propose that NO3-initiated hydrogen abstraction from the 1-position in pyrrole and 2-MP followed by radical shift and NO2 addition leads to light-absorbing nitroaromatic products. In the absence of a 1-position hydrogen, NO3 addition likely dominates the 1-MP chemistry. We also estimate that the total SOA mass and light absorption from pyrrole and 2-MP are comparable to those from phenolic VOCs and toluene in biomass burning, underscoring the importance of considering nighttime oxidation of pyrrole and methylpyrroles in air quality and climate models.
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This content will become publicly available on January 1, 2025
Molecular analysis of secondary organic aerosol and brown carbon from the oxidation of indole
Abstract. Indole (ind) is a nitrogen-containing heterocyclic volatile organic compound commonly emitted from animal husbandry and from different plants like maize with global emissions of 0.1 Tg yr−1. The chemical composition and optical properties of indole secondary organic aerosol (SOA) and brown carbon (BrC) are still not well understood. To address this, environmental chamber experiments were conducted to investigate the oxidation of indole at atmospherically relevant concentrations of selected oxidants (OH radicals and O3) with or without NO2. In the presence of NO2, the SOA yields decreased by more than a factor of 2, but the mass absorption coefficient at 365 nm (MAC365) of ind-SOA was 4.3 ± 0.4 m2 g−1, which was 5 times higher than that in experiments without NO2. In the presence of NO2, C8H6N2O2 (identified as 3-nitroindole) contributed 76 % to all organic compounds detected by a chemical ionization mass spectrometer, contributing ∼ 50 % of the light absorption at 365 nm (Abs365). In the absence of NO2, the dominating chromophore was C8H7O3N, contributing to 20 %–30 % of Abs365. Indole contributes substantially to the formation of secondary BrC and its potential impact on the atmospheric radiative transfer is further enhanced in the presence of NO2, as it significantly increases the specific light absorption of ind-SOA by facilitating the formation of 3-nitroindole. This work provides new insights into an important process of brown carbon formation by interaction of two pollutants, NO2 and indole, mainly emitted by anthropogenic activities.
more » « less- Award ID(s):
- 2039985
- NSF-PAR ID:
- 10493042
- Publisher / Repository:
- EGU
- Date Published:
- Journal Name:
- Atmospheric Chemistry and Physics
- Volume:
- 24
- Issue:
- 4
- ISSN:
- 1680-7324
- Page Range / eLocation ID:
- 2639 to 2649
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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