Are fireworks a significant episodic source of brown carbon?

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 (1 min) measurements of black carbon (BC) and BrC absorption from a 7-wavelength aethalometer with time-integrated (12-24 h) 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 400-500 nm 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.

Brown carbon aerosols in the Indo-Gangetic Plain outflow: insights from excitation emission matrix (EEM) fluorescence spectroscopy.

We report the first characterization of the aerosol brown carbon (BrC) composition in the Indian context using excitation emission matrix (EEM) fluorescence spectroscopy coupled with parallel factor (PARAFAC) analysis. We find that biomass burning (BB)-dominated wintertime aerosols in the Indo-Gangetic Plain (IGP) outflow are characterized by two humic-like (HULIS) (C1_aq and C2_aq) and one protein-like/fossil fuel-derived (C3_aq) component for aqueous-extractable BrC (BrCaq), and by one humic-like (C1_me) and one protein-like (C2_me) component for methanol-extractable BrC (BrCme). Strong correlations of the BB tracer nss-K+ with C1_aq and C2_aq (r = 0.75-0.84, p < 0.01) and C1_me (r = 0.77, p < 0.01) point towards the BB-dominated IGP outflow as the major source. This is also supported by the analysis of fluorescence indices, which suggest extensive humification of BB emissions during atmospheric transport. The HULIS components correlate significantly with BrC absorption (r = 0.85-0.94, p < 0.01), and contribute substantially to the BrC relative radiative forcing of 13-24% vis-à-vis elemental carbon (EC). There is strong evidence that the abundant BB-derived NOX leads to NO3- formation in the IGP plume and drives the formation of water-soluble nitroaromatics (NACs) that constrain BrCaq light absorption (r = 0.56, p < 0.01) to a considerable degree. Overall, the study uncovers complex atmospheric processing of the IGP outflow in winter, which has important implications for regional climate.