This study examined the effects of
simulated solar irradiation
on a model system of atmospheric aqueous secondary organic aerosol
(aqSOA) formed from oxidation of guaiacyl acetone (GA) by reactions
with triplet excited carbon (3C*) generated by photoexcitation
of 3,4-dimethoxybenzaldehyde (DMB). Both GA and DMB are common components
of biomass burning emissions, and their mixture was selected as a
case study to investigate the influence of aqueous-phase photochemistry
on the light absorption properties of atmospheric brown carbon (BrC)
pertinent to aqSOA formation. Irradiation was performed in a photoreactor
designed to mimic sunlight irradiation, and samples were collected
at different times of the experiment, which lasted for 6 h. Chemical
components of the samples were separated using high-performance liquid
chromatography and analyzed with a photodiode array detector and Orbitrap
mass spectrometer operated simultaneously to record both UV–visible
spectra and high-resolution mass spectra. This allowed us to obtain
molecular characterization of the aqSOA individual components, as
well as information on their light-absorbing properties and how they
change over time when irradiated. The results indicate that three
generations of products formed at different stages of the experiment:
monomeric products, dimeric products, and less polar aromatic products
similar to those formed during oxygen-deprived pyrolytic processes.
The monomeric and dimeric products result from oxidation reactions
initiated by 3C*, while the less polar aromatic products
form as a result of radical recombination. Prior to irradiation, the
BrC absorbance is dominated by monomeric species, but it is later
dominated by pyrolytic-like products as the monomeric and dimeric
products begin to photodegrade. Comparison with previously defined
BrC classes based on optical properties suggests that the aqSOA formed
in this experiment initially fall outside of these classes but then
become more absorbing, consistent with the “very weak”
to “weak” BrC classes.