Chemical and Light-Absorption Properties of Water-Soluble Organic Aerosols in Northern California and Photooxidant Production by Brown Carbon Components.

Atmospheric brown carbon (BrC) can impact the radiative balance of the earth and form photooxidants. However, the light absorption and photochemical properties of BrC from different sources remain poorly understood. To address this gap, dilute water extracts of particulate matter (PM) samples collected at Davis, CA over one year were analyzed using high resolution aerosol mass spectrometry (HR-AMS) and UV-vis spectroscopy. Positive matrix factorization (PMF) on combined AMS and UV-vis data resolved five water-soluble organic aerosol (WSOA) factors with distinct mass spectra and UV-vis spectra: a fresh and an aged water-soluble biomass burning OA ( _WS BBOA _fresh and _WS BBOA _aged ) and three oxygenated OA ( _WS OOAs). _WS BBOA _fresh is the most light-absorbing, with a mass absorption coefficient (MAC _365 nm ) of 1.1 m ² g ^-1 , while the _WS OOAs are the least (MAC _365 nm = 0.01-0.1 m ² g ^-1 ). These results, together with the high abundance of _WS BBOAs (∼52% of the WSOA mass), indicate that biomass burning activities such as residential wood burning and wildfires are an important source of BrC in northern California. The concentrations of aqueous-phase photooxidants, i.e., hydroxyl radical (·OH), singlet molecular oxygen ( ¹ O ₂ *), and oxidizing triplet excited states of organic carbon ( ³ C*), were also measured in the PM extracts during illumination. Oxidant production potentials (PP _OX ) of the five WSOA factors were explored. The photoexcitation of BrC chromophores from BB emissions and in OOAs is a significant source of ¹ O ₂ * and ³ C*. By applying our PP _OX values to archived AMS data at dozens of sites, we found that oxygenated organic species play an important role in photooxidant formation in atmospheric waters.
Competing Interests: The authors declare no competing financial interest.
(© 2023 The Authors. Published by American Chemical Society.)