Ionic Strength Enhances the Multiphase Oxidation Rate of Sulfur Dioxide by Ozone in Aqueous Aerosols: Implications for Sulfate Production in the Marine Atmosphere

Multiphase oxidation of sulfur dioxide (SO2) by ozone (O3) in alkaline sea salt aerosols is an important source of sulfate aerosols in the marine atmosphere. However, a recently reported low pH of fresh supermicron sea spray aerosols (mainly sea salt) would argue against the importance of this mechanism. Here, we investigated the impact of ionic strength on the kinetics of multiphase oxidation of SO2 by O3 in proxies of aqueous acidified sea salt aerosols with buffered pH of ∼4.0 via well-controlled flow tube experiments. We find that the sulfate formation rate for the O3 oxidation pathway proceeds 7.9 to 233 times faster under high ionic strength conditions of 2–14 mol kg–1 compared to the dilute bulk solutions. The ionic strength effect is likely to sustain the importance of multiphase oxidation of SO2 by O3 in sea salt aerosols in the marine atmosphere. Our results indicate that atmospheric models should consider the ionic strength effects on the multiphase oxidation of SO2 by O3 in sea salt aerosols to improve the predictions of the sulfate formation rate and the sulfate aerosol budget in the marine atmosphere

Contribution of Charge-Transfer Complexes to Absorptivity of Primary Brown Carbon Aerosol

Light-absorbing organic aerosol, or brown carbon (BrC), has significant but poorly constrained effects on climate. A large fraction of the absorptivity of ambient BrC is unassigned, and organic charge-transfer (CT) complexes have the potential to contribute to this fraction. Here, the contributions of CT complexes to the absorptivity of laboratory-generated BrC and ambient aerosol material influenced by biomass burning have been investigated, using a wide range of chemical, spectroscopic, and physical analyses. Chemical functionalization experiments are inconclusive about the role of CT complexes, whereas fluorescence spectra exhibit distinct spectral features indicative of individual chromophores. Determinations of the concentration and temperature dependences of absorbance are more conclusive. In particular, for laboratory-generated BrC extracted in either water or methanol, absorbance scaled linearly with orders-of-magnitude changes in concentration, indicating that intermolecular complexes do not contribute to the absorptivity. Furthermore, whereas the absorbance of BrC extracts in dimethyl sulfoxide exhibited a slight temperature dependence, consistent with a 15% contribution from intramolecular CT complexes at 15 °C, the complete temperature independence of absorbance of water-soluble extracts from surrogate and ambient BrC indicates a negligible role for CT complexes. Overall, our results find little evidence for CT complexes in the primary BrC studied, suggesting that they do not contribute significantly to the missing absorptivity of ambient BrC

Secondary Organic Aerosol Formation from Urban Roadside Air in Hong Kong

Motor vehicle emissions are an important but poorly constrained source of secondary organic aerosol (SOA). Here, we investigated in situ SOA formation from urban roadside air in Hong Kong during winter time using an oxidation flow reactor (OFR), with equivalent atmospheric oxidation ranging from several hours to several days. The campaign-average mass enhancement of OA, nitrate, sulfate, and ammonium upon OFR aging was 7.0, 7.2, 0.8, and 2.6 μg m–3, respectively. To investigate the sources of SOA formation potential, we performed multilinear regression analysis between measured peak SOA concentrations from OFR and the concentrations of toluene that represent motor vehicle emissions and cooking OA from positive matrix factorization (PMF) analysis of ambient OA. Traffic-related SOA precursors contributed 92.3%, 92.4%, and 83.1% to the total SOA formation potential during morning rush hours, noon and early afternoon, and evening meal time, respectively. The SOA production factor (PF) was approximately 5.2 times of primary OA (POA) emission factor (EF) and the secondary particulate matter (PM) PF was approximately 2.6 times of primary particles EF. This study highlights the potential benefit of reducing secondary PM production from motor vehicle emissions in mitigating PM pollutions

Dynamic Wood Smoke Aerosol Toxicity during Oxidative Atmospheric Aging

Wildfires are a major source of biomass burning aerosol to the atmosphere, with their incidence and intensity expected to increase in a warmer future climate. However, the toxicity evolution of biomass burning organic aerosol (BBOA) during atmospheric aging remains poorly understood. In this study, we report a unique set of chemical and toxicological metrics of BBOA from pine wood smoldering during multiphase aging by gas-phase hydroxyl radicals (OH). Both the fresh and OH-aged BBOA show activity relevant to adverse health outcomes. The results from two acellular assays (DTT and DCFH) show significant oxidative potential (OP) and reactive oxygen species (ROS) formation in OH-aged BBOA. Also, radical concentrations in the aerosol assessed by electron paramagnetic resonance (EPR) spectroscopy increased by 50% following heterogeneous aging. This enhancement was accompanied by a transition from predominantly carbon-centered radicals (85%) in the fresh aerosol to predominantly oxygen-centered radicals (76%) following aging. Both the fresh and aged biomass burning aerosols trigger prominent antioxidant defense during the in vitro exposure, indicating the induction of oxidative stress by BBOA in the atmosphere. By connecting chemical composition and toxicity using an integrated approach, we show that short-term aging initiated by OH radicals can produce biomass burning particles with a higher particle-bound ROS generation capacity, which are therefore a more relevant exposure hazard for residents in large population centers close to wildfire regions than previously studied fresh biomass burning emissions

Fostering a Holistic Understanding of the Full Volatility Spectrum of Organic Compounds from Benzene Series Precursors through Mechanistic Modeling

A comprehensive understanding of the full volatility spectrum of organic oxidation products from the benzene series precursors is important to quantify the air quality and climate effects of secondary organic aerosol (SOA) and new particle formation (NPF). However, current models fail to capture the full volatility spectrum due to the absence of important reaction pathways. Here, we develop a novel unified model framework, the integrated two-dimensional volatility basis set (I2D-VBS), to simulate the full volatility spectrum of products from benzene series precursors by simultaneously representing first-generational oxidation, multigenerational aging, autoxidation, dimerization, nitrate formation, etc. The model successfully reproduces the volatility and O/C distributions of oxygenated organic molecules (OOMs) as well as the concentrations and the O/C of SOA over wide-ranging experimental conditions. In typical urban environments, autoxidation and multigenerational oxidation are the two main pathways for the formation of OOMs and SOA with similar contributions, but autoxidation contributes more to low-volatility products. NOx can reduce about two-thirds of OOMs and SOA, and most of the extremely low-volatility products compared to clean conditions, by suppressing dimerization and autoxidation. The I2D-VBS facilitates a holistic understanding of full volatility product formation, which helps fill the large gap in the predictions of organic NPF, particle growth, and SOA formation