Biomass burning emits large amounts of phenols, which can partition into cloud/fog drops and aerosol liquid water (ALW) and react to form aqueous secondary organic aerosol (aqSOA). Triplet excited states of organic compounds ( 3 C*) are likely oxidants, but there are no rate constants with highly substituted phenols that have high Henry's law constants (K H ) and are likely important in ALW. To address this gap, we investigated the kinetics of six highly substituted phenols with the triplet excited state of 3,4-dimethoxybenzaldehyde. Second-order rate constants at pH 2 are all fast, (2.6−4.6) × 10 9 M −1 s −1 , while values at pH 5 are 2−5 times smaller. Rate constants are reasonably described by a quantitative structure−activity relationship with phenol oxidation potentials, allowing rate constants of other phenols to be predicted. Triplet-phenol kinetics are unaffected by ammonium sulfate, sodium chloride, galactose (a biomassburning sugar), or Fe(III). In contrast, ammonium nitrate increases the rate of phenol loss by making hydroxyl radicals, while Cu(II) inhibits phenol decay. Mass yields of aqueous SOA from triplet reactions are large and range from 59 to 99%. Calculations using our data along with previous oxidant measurements indicate that phenols with high K H can be an important source of aqSOA in ALW, with 3 C* typically the dominant oxidant.

Abstract. Aerosol liquid water (ALW) is a unique reaction medium, but its chemistry is poorly understood. For example, little is known of photooxidant concentrations – including hydroxyl radical (●OH), singlet molecular oxygen (1O2*), and oxidizing triplet excited states of organic matter (3C*) – even though they likely drive much of ALW chemistry. Due to the very limited water content of particles, it is difficult to quantify oxidant concentrations in ALW directly. To predict these values, we measured photooxidant concentrations in illuminated aqueous particle extracts as a function of dilution and used the resulting oxidant kinetics to extrapolate to ALW conditions. We prepared dilution series from two sets of particles collected in Davis, California: one from winter (WIN) and one from summer (SUM). Both periods are influenced by biomass burning, with dissolved organic carbon (DOC) in the extracts ranging from 10 to 495 mg C L−1. In the winter sample, the ●OH concentration is independent of particle mass concentration, with an average value of 5.0 (± 2.2) × 10−15 M, while in summer ●OH increases with DOC in the range (0.4 − 7.7) × 10−15 M. In both winter and summer samples, 3C* concentrations increase rapidly with particle mass concentrations in the extracts, and then plateau under more concentrated conditions, with a range of (0.2 − 7) × 10−13 M. WIN and SUM have the same range of 1O2* concentrations, (0.2 − 8.5) × 10−12 M, but in WIN the 1O2* concentration increases linearly with DOC, while in SUM 1O2* approaches a plateau. We next extrapolated the relationships of oxidant formation rates and sinks as a function of particle mass concentration from our dilute extracts to the much more concentrated condition of aerosol liquid water. Predicted ●OH concentrations in ALW (including mass transport of ●OH from the gas phase) are (5 − 8) × 10−15 M, similar to those in fog/cloud waters. In contrast, predicted concentrations of 3C* and 1O2* in ALW are approximately 10 to 100 times higher than in cloud/fogs, with values of (4 – 9) × 10−13 M and (1 – 5) × 10−12 M, respectively. Although ●OH is often considered the main sink for organic compounds in the atmospheric aqueous phase, the much higher concentrations of 3C* and 1O2* in aerosol liquid water suggest these photooxidants will be more important sinks for many organics in particle water.

Oxidizing triplet excited states of organic matter ( 3 C*) drive numerous reactions in fog/cloud drops and aerosol liquid water (ALW). Quantifying oxidizing triplet concentrations in ALW is difficult because 3 C* probe loss can be inhibited by the high levels of dissolved organic matter (DOM) and copper in particle water, leading to an underestimate of triplet concentrations. In addition, illuminated ALW contains high concentrations of singlet molecular oxygen ( 1 O 2 *), which can interfere with 3 C* probes. Our overarching goal is to find a triplet probe that has low inhibition by DOM and Cu(II) and low sensitivity to 1 O 2 *. To this end, we tested 12 potential probes from a variety of compound classes. Some probes are strongly inhibited by DOM, while others react rapidly with 1 O 2 *. One of the probe candidates, (phenylthiol)acetic acid (PTA), seems well suited for ALW conditions, with mild inhibition and fast rate constants with triplets, but it also has weaknesses, including a pH-dependent reactivity. We evaluated the performance of both PTA and syringol (SYR) as triplet probes in aqueous extracts of particulate matter. While PTA is less sensitive to inhibition than SYR, it results in lower triplet concentrations, possibly because it is less reactive with weakly oxidizing triplets.

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 (WSBBOAfresh and WSBBOAaged) and three oxygenated OA (WSOOAs). WSBBOAfresh is the most light-absorbing, with a mass absorption coefficient (MAC365 nm) of 1.1 m2 g–1, while the WSOOAs are the least (MAC365 nm = 0.01–0.1 m2 g–1). These results, together with the high abundance of WSBBOAs (∼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 (1O2*), and oxidizing triplet excited states of organic carbon (3C*), were also measured in the PM extracts during illumination. Oxidant production potentials (PPOX) of the five WSOA factors were explored. The photoexcitation of BrC chromophores from BB emissions and in OOAs is a significant source of 1O2* and 3C*. By applying our PPOX 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.