<p>  </p> <p>Atmospheric particles originate from all over the globe with wildly different sources such as sea spray aerosols of the ocean, mineral dust from deserts, biogenic emissions from forests, anthropogenic emissions of urban and industrial areas, volcanic eruptions, and many more. All of these particles can then be transported during which aging can occur where the external and internal chemical composition of particles and drastically be altered in which their physiochemical properties change or new particles as a whole are formed. Understanding what can cause this aging and correctly identifying how these particles change is vital for assessing climate in local areas. </p> <p>Chapter 3 focuses on dry intrusion (DI) and non-DI periods where vertical mixing of air occurs and allows for long range transport of particles. DI periods introduces populations of aged particles from far away sources into local regions. Identification and chemical characterization is performed for both of these periods to highlight the changes the DI period introduces in regards to particle morphology, chemical composition and lifetime. Analysis was performed via computer controlled scanning electron microscopy (CCSEM) for external information of the particles and scanning transmission x-ray microscopy (STXM) was used for internal information. The combination of these two techniques allows for a complete and thorough understanding of the particles during the two periods. </p> <p>Chapter 4 covers the first experiment done on a newly constructed cryogenic cooling cart which was created in the hopes to identify individual ice nucleating events of particles <em>in situ</em> when mimicking real world atmospheric conditions through temperature and humidity control. </p>

<p>The Earth–atmosphere energy balance is dictated by incoming solar radiation and outgoing thermal radiation with greenhouse gases (GHG) and aerosols playing a major role in this effect. The atmospheric abundance and properties of airborne particles and gases lead to the redistribution of radiative energy, resulting in a warming or cooling effect. However, the extent of this effect remains to be insufficiently constrained. Improved quantification and characterization of GHG and aerosols are important requirements to inform current climate models. High-precision instrumentation and thoughtful experimental strategies are necessary to yield various analytical measurement datasets, despite complex meteorological and environmental conditions. This dissertation focuses on the assessment of CO₂and atmospheric particles from aircraft-based measurements enabling representative and spatially sampling of local regions of interest.</p> <p>Chapter 1 provides introductory discussion on the atmospheric implication of GHG and aerosols on the climate and related uncertainties. Chapter 2 summarizes the employed experimental techniques for quantification of GHG and characterization of atmospheric particles. We relied on an aircraft platform equipped with an air turbulence probe for 3D wind vector calculation and a high-precision cavity ring-down spectrometer for the quantification of ambient CO₂, CH₄, and H2O_<em>v</em>. Furthermore, the simultaneous composition and morphological information of aerosol samples were assessed using complementary chemical imaging techniques. Chemical composition of elements with Z > 23 was determined using computer-controlled scanning electron microscopy with energy dispersive X-ray spectroscopy (CCSEM/EDX). Scanning transmission X-ray microscopy coupled with near edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS) was used to determined spatially resolved elemental specific molecular information present in atmospheric particles.</p> <p>Chapter 3 presents our study focused on the characterization of mixed mineral dust and biomass burning (BB) aerosols during an intensive burning event. We identified distinct particle types based on individual elemental contribution pre-, syn-, and post-burning event including highly carbonaceous (54–83%) particles, aged mineral dust (1–6%), and sulfur-containing particles (17–41%). X-ray spectromicroscopy techniques were used to characterize the internal chemical heterogeneity of individual BB particles and the morphology of soot inclusions, as well as changes in the particle organic volume fraction (OVF). An estimation method for particle component masses (i.e., organics, elemental carbon, and inorganics) inferred from STXM measurements was used to determine quantitative mixing state metrics based on entropy-derived diversity measures for particles acquired at different periods of the BB event. In general, there was a small difference in the particle-specific diversity among the samples (<em>D</em>_<em>α</em> = 1.3–1.8). However, the disparity from the bulk population diversity observed during the intense periods was found to have high values of <em>D</em>_<em>γ</em> = 2.5–2.9, while particles collected outside of the burning event displayed lower bulk diversity of <em>D</em>_<em>γ</em> = 1.5–2.0. Quantitative methods obtained from chemical imaging measurements presented here will serve to accurately characterize the evolution of mixed BB aerosols within urban environments.</p> <p>Chapter 4 follows the investigation of the physicochemical properties of atmospheric particles collected onboard a research aircraft flown over the Azores using offline spectromicroscopy techniques. Particles were collected within the marine boundary layer (MBL) and free troposphere (FT) comparing samples after long-range atmospheric transport episodes facilitated by dry intrusion (DI) events. The quantification of the OVF of individual particles derived from X-ray spectromicroscopy, which relates to the multi-component internal composition of individual particles, showed a factor of 2.06±0.16 and 1.11±0.04 increase in the MBL and FT, respectively, among DI samples. We show that supplying particle OVF into the <em>κ</em>-Köhler equation can be used as a good approximation of field-measured <em>in situ</em> CCN concentrations. We also report changes in the <em>κ</em> values in the MBL from <em>κ</em>_{MBL, non-DI} = 0.48 to <em>κ</em>_{MBL, DI} = 0.41, while changes in the FT result in <em>κ</em>_{FT, non-D}_I = 0.36 to <em>κ</em>_{FT, DI} = 0.33, which is consistent with enhancements in OVF followed by the DI episodes. Our observations suggest that the entrainment of particles from long-range continental sources alters the mixing state population and CCN properties of aerosol in the region.</p> <p>Chapter 5 discusses the identification and characterization of fine-mode primary biogenic atmospheric particles (PBAP) from the harvesting of crops. Particle samples were analyzed using complementary chemical imaging techniques to apportion the particle-type population based on their size, morphology, and composition. The contribution of PBAP in the size range of 0.15−1.25 μm is estimated to be 10−12% of ∼39,000 analyzed particles. In addition, particle viscosity and phase state were inferred with X-ray spectromicroscopic analysis has shown that the fine-mode organic particles collected are viscous/semisolid (10²−10¹² Pa s) while the majority of PBAP fragments are solid (>10¹²Pa s). The observation of submicrometer, solid carbonaceous fragments of biogenic origin have implications for the regional CCN and ice nuclei budget. Therefore, the seasonal harvesting of crops may play an important, yet unrecognized, role in regional cloud formation and climate.</p> <p>Chapter 6  explores the measurements and quantification of latent heat, sensible heat, and CO₂ fluxes among different land covers in the surrounding area of urban regions using airborne flux techniques. Cities account for the majority of the global CO₂ emissions due to the consumption of energy, resources, infrastructure, and transportation demands. Accordingly, the accurate quantification of these emissions, with exceptional precision, is necessary so that progress towards emission reduction can be monitored. However, a major challenge in quantifying urban emission estimates arises from accurate background emission definitions and apportionment of emission sources in complex urban environments. Airborne eddy covariance measurements were performed to quantify the bidirectional exchange of latent heat, sensible heat, and CO₂ fluxes in the upwind region of Indianapolis within an active biosphere. Here, we observed differences in fluxes across different days and land covers (e.g., corn, soybean, and forests) allowing us to understand the impact of seasonal variability in urban emissions during the full growing season. These experiments illustrate the capability of a research aircraft to perform technically challenging near-direct measurements of atmosphere–surface exchange over local and regional scales.</p> <p>Chapter 7 presents a new method to spatially allocate airborne mass balance CO₂ emissions. We performed seven aircraft measurements downwind of New York City (NYC) quantifying CO₂ emissions during the non-growing seasons of 2018–2020. A series of prior inventories and footprint transport models were used to account for flux contribution outside the area of interest and attribute emission sources within policy-relevant boundaries of the five boroughs encompassing NYC and then employ the modeled enhancement fraction (Φ) to the bulk emission observations from the mass balance approach. Here, we calculated a campaign-averaged source apportioned mass balance CO₂ emission rate of 56±24 kmol/s. The performance and accuracy of this approach were evaluated against other published works including inventory scaling and inverse modeling, yielding a difference of 5.1% with respect to the average emission rate reported by the two complementary approaches. Utilizing the ensemble of emissions inventories and transport models, we also evaluated the overall sources of variability induced by the prior (1.7%), the transport (4.2%), and the daily variability (42.0%). This approach provides a solution to interpreting aircraft-based mass balance results in complex emission environments.</p> <p>Chapter 8 concludes with a brief discussion of technological advances and research outlooks for X-ray spectromicroscopy analysis on atmospheric particles and the quantification of GHG. Opportunities for future applications and novel development of CCSEM/EDX and STXM/NEXAFS to substantially extend the instrument capabilities and improve our understanding of the physicochemical properties of individual atmospheric particles. Chapter 8 also discusses recent developments in satellite-based CO₂ monitoring to complement direct airborne observations. In recent years, significant progress has been made in satellite-based measurements of CO₂ to reveal the spatio-temporal variation in atmospheric CO₂ concentration. The column-averaged dry air CO₂ mole have reached an accuracy of ~1 ppm with a spatial resolution of less than 4 km. Furthermore, column-averaged retrievals can be used to detect and estimate the surface CO₂ fluxes in an active biosphere, quantify anthropogenic emissions over megacities, and monitor the transport of fossil fuel plumes across different continents and seasons.</p>