Ambient measurements of chemical and physical properties of organic aerosols: Insights into formation, growth, and heterogeneous chemistry

Organic aerosols are a ubiquitous component of the troposphere, from heavily polluted cities to the remote Arctic. In Chapters II, III, and V of this dissertation, the formation of organic aerosol through observations of ambient size distributions is addressed. Chapter IV presents a new pathway for the formation of nitrous acid (HONO) in the urban atmosphere. In Chapter II, the size-resolved chemical composition of sub-micron aerosol was measured at a suburban forested site in North Carolina. Two events were identified in which particle growth, presumably by gas-to-particle conversion, was dominated by accumulation of organic aerosol mass. Growth rates between 1.2 nm hr-1 and 4.9 nm hr-1 were observed. Using a mass-spectral deconvolution method coupled with linear regression analysis, the sub-micron organic aerosol mass observed during the campaign, and during events, was determined to have been influenced by both local and regional secondary processes with only a minor influence from combustion sources. In Chapter III, the chemical characteristics of sub-10-micron aerosol were explored as a function of ambient particle size at a coastal and inland site in New England. Average organic carbon (OC) concentrations of 4.9 microg C m-3 and 3.4 microg C m-3 were observed at the coastal site at the Isles of Shoals (IOS) and at the slightly inland site at Thompson Farm (TF), respectively. An average of 84 and 72% of OC was found to be water-soluble at IOS and TF, respectively. Size distributions indicate that the formation of dicarboxylic acids, especially oxalic acid, is driven by aqueous-phase reactions. A chemical fingerprint analysis suggests that all water-soluble OC at IOS resembles secondary organic aerosol (SOA), while WSOC at TF appears to result from mixed sources. In Chapter IV, a newly identified formation pathway for nitrous acid (HONO) is presented. HONO is an important precursor to hydroxyl radicals in the troposphere and thus contributes to the oxidative capacity of the atmosphere. The proposed pathway is shown to depend on the surface chemical characteristics of primary organic aerosol, and concentrations of HONO are shown to exceed those that can be explained by previously identified formation pathways. In Chapter V, particle growth events were observed at Summit, Greenland, an extremely remote Arctic site. Particle growth was linked indirectly to condensation of organic compounds because measured concentrations of sulfuric acid could not explain the observed growth rates of up to 0.963 nm hr -1. The snowpack may be the source of condensable organic precursors, and thus organic aerosol, based on prior observations at the site. This pathway represents a source of global SOA currently not taken into account that may have implications for climate regulation

Bromide and other ions in the snow, firn air, and atmospheric boundary layer at Summit during GSHOX

Measurements of gas phase soluble bromide in the boundary layer and in firn air, and Br− in aerosol and snow, were made at Summit, Greenland (72.5° N, 38.4° W, 3200 m a.s.l.) as part of a larger investigation into the influence of Br chemistry on HOx cycling. The soluble bromide measurements confirm that photochemical activation of Br− in the snow causes release of active Br to the overlying air despite trace concentrations of Br− in the snow (means 15 and 8 nmol Br− kg−1 of snow in 2007 and 2008, respectively). Mixing ratios of soluble bromide above the snow were also found to be very small (mean \u3c1 ppt both years, with maxima of 3 and 4 ppt in 2007 and 2008, respectively), but these levels clearly oxidize and deposit long-lived gaseous elemental mercury and may perturb HOx partitioning. Concentrations of Br− in surface snow tended to increase/decrease in parallel with the specific activities of the aerosol-associated radionuclides 7Be and 210Pb. Earlier work has shown that ventilation of the boundary layer causes simultaneous increases in 7Be and 210Pb at Summit, suggesting there is a pool of Br in the free troposphere above Summit in summer time. Speciation and the source of this free tropospheric Br− are not well constrained, but we suggest it may be linked to extensive regions of active Br chemistry in the Arctic basin which are known to cause ozone and mercury depletion events shortly after polar sunrise. If this hypothesis is correct, it implies persistence of the free troposphere Br− for several months after peak Br activation in March/April. Alternatively, there may be a ubiquitous pool of Br− in the free troposphere, sustained by currently unknown sources and processes

On the Stochasticity of Aerosol-Cloud Interactions within a Data-driven Framework

Aerosol-cloud interactions (ACI) pose the largest uncertainty for climate projections. Among many challenges of understanding ACI, the question of whether ACI is deterministic or stochastic has not been explicitly formulated and asked. Here we attempt to answer this question by predicting cloud droplet number concentration Nc from aerosol number concentration Na and ambient conditions. We use aerosol properties, vertical velocity fluctuation w', and meteorological states (temperature T and water vapor mixing ratio q_v) from the ACTIVATE field observations (2020 to 2022) as predictor variables to estimate Nc. We show that the climatological Nc can be successfully predicted using a machine learning model despite the strongly nonlinear and multi-scale nature of ACI. However, the observation-trained machine learning model fails to predict Nc in individual cases while it successfully predicts Nc of randomly selected data points that cover a broad spatiotemporal scale, suggesting the stochastic nature of ACI at fine spatiotemporal scales

Observations of Aerosol‐Cloud Interactions During the North Atlantic Aerosol and Marine Ecosystem Study

Clouds and their response to aerosols constitute the largest uncertainty in our understanding of 20th‐century climate change. We present an investigation that determines linkages between remotely sensed marine cloud properties with in situ measurements of cloud condensation nuclei (CCN) and meteorological properties obtained during the North Atlantic Aerosols and Marine Ecosystems Study. The first two deployments of this campaign have geographically similar domains but occur in different seasons allowing the response of clouds to a range of CCN concentrations and meteorological conditions to be investigated. Well‐defined connections between CCN and cloud microphysical properties consistent with the indirect effect are observed, as well as complex, nonlinear secondary effects that are partially supported by previously proposed mechanisms. Using the Research Scanning Polarimeter's remotely sensed effective variance parameter, correlation is found with liquid water path. In general, cloud macrophysical properties are found to better correlate with atmospheric state parameters than changes in CCN concentrations

Extensive Aerosol Optical Properties and Aerosol Mass Related Measurements During TRAMP/TexAQS 2006 – Implications for PM Compliance and Planning

Extensive aerosol optical properties, particle size distributions, and Aerodyne quadrupole aerosol mass spectrometer measurements collected during TRAMP/TexAQS 2006 were examined in light of collocated meteorological and chemical measurements. Much of the evident variability in the observed aerosol-related air quality is due to changing synoptic meteorological situations that direct emissions from various sources to the TRAMP site near the center of the Houston-Galveston-Brazoria (HGB) metropolitan area. In this study, five distinct long-term periods have been identified. During each of these periods, observed aerosol properties have implications that are of interest to environmental quality management agencies. During three of the periods, long range transport (LRT), both intra-continental and intercontinental, appears to have played an important role in producing the observed aerosol. During late August 2006, southerly winds brought super-micron Saharan dust and sea salt to the HGB area, adding mass to fine particulate matter (PM2.5) measurements, but apparently not affecting secondary particle growth or gas-phase air pollution. A second type of LRT was associated with northerly winds in early September 2006 and with increased ozone and sub-micron particulate matter in the HGB area. Later in the study, LRT of emissions from wildfires appeared to increase the abundance of absorbing aerosols (and carbon monoxide and other chemical tracers) in the HGB area. However, the greatest impacts on Houston PM2.5air quality are caused by periods with low-wind-speed sea breeze circulation or winds that directly transport pollutants from major industrial areas, i.e., the Houston Ship Channel, into the city center

Spectral aerosol extinction (SpEx): a new instrument for in situ ambient aerosol extinction measurements across the UV/visible wavelength range

We introduce a new instrument for the measurement of in situ ambient aerosol extinction over the 300– 700 nm wavelength range, the spectral aerosol extinction (SpEx) instrument. This measurement capability is envisioned to complement existing in situ instrumentation, allowing for simultaneous measurement of the evolution of aerosol optical, chemical, and physical characteristics in the ambient environment. In this work, a detailed description of the instrument is provided along with characterization tests performed in the laboratory. Measured spectra of NO2 and polystyrene latex spheres (PSLs) agreed well with theoretical calculations. Good agreement was also found with simultaneous aerosol extinction measurements at 450, 530, and 630 nm using CAPS PMex instruments in a series of 22 tests including nonabsorbing compounds, dusts, soot, and black and brown carbon analogs. SpEx measurements are expected to help identify the presence of ambient brown carbon due to its 300 nm lower wavelength limit compared to measurements limited to longer UV and visible wavelengths. Extinction spectra obtained with SpEx contain more information than can be conveyed by a simple power law fit (typically represented by Ångström exponents). Planned future improvements aim to lower detection limits and ruggedize the instrument for mobile operation

Evolution of brown carbon in wildfire plumes

Particulate brown carbon (BrC) in the atmosphere absorbs light at subvisible wavelengths and has poorly constrained but potentially large climate forcing impacts. BrC from biomass burning has virtually unknown lifecycle and atmospheric stability. Here, BrC emitted from intense wildfires was measured in plumes transported over 2 days from two main fires, during the 2013 NASA SEAC4RS mission. Concurrent measurements of organic aerosol (OA) and black carbon (BC) mass concentration, BC coating thickness, absorption Ångström exponent, and OA oxidation state reveal that the initial BrC emitted from the fires was largely unstable. Using back trajectories to estimate the transport time indicates that BrC aerosol light absorption decayed in the plumes with a half-life of 9 to 15 h, measured over day and night. Although most BrC was lost within a day, possibly through chemical loss and/or evaporation, the remaining persistent fraction likely determines the background BrC levels most relevant for climate forcing