Are fireworks a significant episodic source of brown carbon?

Abstract

We hypothesize that firework events involving the combustion of charcoal fuel, organic binders, metal salts, and cellulose-based wrapping material could be significant transient sources of aerosol brown carbon (BrC). To test this, we couple high time-resolution (1min) measurements of black carbon (BC) and BrC absorption from a 7-wavelength aethalometer with time-integrated (12-24h) measurements of filter extracts, i.e., UV-visible, fluorescence, and Fourier-transformed infrared (FT-IR) signatures of BrC, total and water-soluble organic carbon (OC and WSOC), ionic species, and firework tracer metals during a sampling campaign covering the Diwali fireworks episode in India. In sharp contrast to BC, BrC absorption shows a distinct and considerable rise of 2-4 times during the Diwali period, especially during the hours of peak firework activity, as compared to the background. Fluorescence profiles suggest enrichment of humic-like substances (HULIS) in the firework plume, while the enhancement of BrC absorption in the 400-500nm range suggests the presence of nitroaromatic compounds (NACs). Considerable contributions of WSOC and secondary organics to OC (44.1% and 31.2%, respectively) and of the water-soluble fraction of BrC to total BrC absorption (71.0%) during the Diwali period point toward an atmospherically processed, polar signature of firework-related BrC, which is further confirmed by FT-IR profiles. This aqueous BrC exerts a short-lived but strong effect on atmospheric forcing (12.0% vis-à-vis BC in the UV spectrum), which could affect tropospheric chemistry via UV attenuation and lead to a stabilization of the post-Diwali atmosphere, resulting in enhanced pollutant build-up and exposure.